WO2007044473A2

WO2007044473A2 - High gain selective preconcentrators

Info

Publication number: WO2007044473A2
Application number: PCT/US2006/038998
Authority: WO
Inventors: Richard I. Masel; Zheng Ni; Mark A. Shannon
Original assignee: The Board Of Trustees Of The University Of Illinois
Priority date: 2005-10-06
Filing date: 2006-10-06
Publication date: 2007-04-19
Also published as: CA2624959A1; WO2007044473A3; EP1948353A2

Abstract

Novel metal organic framework (MOF) molecules and methods of synthesizing them are described. MOFs are organometallic crystalline structures that have high sorption capacity due to high surface area, tailorable selectivity, an inert nature, and thermal stability at high temperatures. MOFs may be used as sorbents in preconcentrators for analytical devices to provide orders of magnitude of improved sensitivity in analyte detection. MOFs are also useful as sorbents in new compact and portable micropreconcentrator designs such as a modified purge and trap system and a multi-valve microelectromechanical system (MEMS) to achieve high gain in analyte detection. Further, MOFs may be used as coatings for novel microstructure arrays in micropreconcentrators where the microstructures are designed to increase the surface area to volume ratio inside the micropreconcentrator while minimizing the pressure drop across the micropreconcentrator.

Description

HIGH GAIN SELECTIVE PRECONCENTRATORS

STATEMENT REGARDING FEDERALLY-SPONSORED RESEARCH/DEVELOPMENT [0001] This invention was made, at least in part, with U.S. government support under U.S. Air Force Grant No. FA8650-04-1-7121 , awarded by the Defense Advanced Research Projects Agency (DARPA), and under NSF Grant No. DMI 03-28162 and NSF Grant No. CTS 01-20978, awarded by the National Science Foundation. The U.S. government may have certain rights in the invention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

[0002] The invention generally relates to analyte collection and is useful, for example, in analyte detection and analysis systems and methods. In particular, the invention concerns preconcentrators, which are used in a wide variety of collection and analysis systems, and the use of metal organic framework molecules as sorbents in preconcentrators or similar devices, including particularly portable micropreconcentrators.

2. Related Art

[0003] A preconcentrator is a device that is used to collect a sample for analysis of particular constituents in the sample called analytes. A preconcentrator is particularly useful in detecting analytes that are present in very low concentrations in a sample. For example, a preconcentrator may be used in combination with a detection device to collect a sample, thereby increasing its concentration, before transferring it to a detector for analysis of analytes of interest. As a low-concentration sample gas containing a mixture of compounds passes through a preconcentrator, compounds are captured and sorbed by the preconcentrator over time. During preconcentration, the concentration of the analyte may increase by up to over 1000 times the original concentration of the analyte in the sample. The captured compounds are then desorbed, passed out of the preconcenirator, and conducted to the detector for analysis. [0004] For example, a preconcentrator may be used with a gas chromatograph (GC), a vital instrument used to analyze complex compound mixtures in a variety of environments including clinical, aerospace, military, process control, and other applications. A preconcentrator is required in high performance GC systems because the resolving power ofthe GC column or the sensitivity of the sensor is often limited by the low ppb (part-per-billion) concentrations of analytes with a wide range of volatility. When connected to a GC, a discrete sample is first captured in the preconcentrator and then thermally desorbed to a polymer-coated separation column in the GC. The sample is then eluted down the column under a positive pressure of an inert carrier gas to the detector. [0005] Separation of the components of the sample by differential partitioning along the column, which is typically ramped to an elevated temperature range during the analysis, permits the identification and quantification of the components of the sample by their retention times and response profiles. The separated components are subsequently detected and recorded in a detector. Preconcentration increases the sensitivity of the detector by concentrating dilute samples that would normally not be detected.

[0006] Capillary-tube preconcentrators are conventionally used in GCs. Such preconcentrators include a stainless-steel or glass capillary tube packed with one or more granular sorbent materials. These preconcentrators are typically large in size and have significant power requirements, and as a result, the GC systems they are used with are not portable. This makes conventional GCs practically impossible to use in number of settings including subways, airports, and buildings where analysis of air samples must be performed on-site. These preconcentrators also suffer from large dead volume and limited heating efficiency due to their large thermal mass. In addition, conventional GC systems often have a long analysis cycle and require a large sampling volume. This makes them impractical for use in circumstances in which only a small sample is available for testing and rapid analysis is necessary. [0007] Many efforts have gone into the development of portable micropreconcentrators that exhibit sufficiently high performance to be used in portable GC systems. So far, these portable systems have also been relatively large in size or weight (several kg) and have a large power requirement (tens-to-hundreds of Watts). Further, conventional micropreconcentrators have been unable to raise the concentration of dilute samples to a detectable range so that samples can be analyzed accurately. Thus, there are no commercially available fast preconcentrators that are small enough to fit into a microelectromechanical (MEMS) scale gas analysis system. [0008] Common sorbents used in preconcentrators such as activated carbon, Tenax^®, zeolites, carbon nanotubes, Carbopack®, Carbotrap®, Carbosieve®, Carboxen®, Chromosorb®, HayeSep®, silica gel, and glass beads also have several long-standing problems that make them unsuitable or undesirable for use in micropreconcentrators. For example, these sorbents do not have high enough sorption capacity or are not selective enough for specific analytes or and they cause low or incomplete desorption of analyte. In particular, it is known that many toxic gases decompose before they are desorbed from carbon-based sorbents. DB5 is another sorbent in which analytes interfere with each other and make detection difficult. In addition, these sorbents often have slow or incomplete desorption, which makes it very difficult to get accurate concentration readings. [0009] Accordingly, there is a need for improved preconcentrators and, in particular, commercially viable micropreconcentrators, as well as sorbents that provide high gains in concentration of analytes, selective sorption of analytes, allow rapid and complete desorption of analytes, and have high sorption capacities. Further, the sorbent should have thermal stability of to temperatures of up to 300⁰C to 400⁰C and should not interfere with the sample gas or its analytes. In addition, micropreconcentrators should be compact in size so that they can be used wilh a portable analytical instrument and require only a small sample volume.

SUMMARY OF THE INVENTION

[0010] The invention meets the foregoing needs and overcomes the drawbacks and disadvantages of the prior art by providing for a new use of metal organic framework (MOF) molecules as sorbents in preconcentrators, which results in orders of magnitude improvement in the sensitivity in analyte detection in a detection device. The MOFs of the invention may be used in conventional micropreconcentrators with little structural changes. The invention also provides for new micropreconcentrators designs that are more compact and more sensitive through the use of microelectromechanical systems (MEMS) and other technologies that may use MOFs or other sorbents. While the use of MOFs as sorbents is particularly advantageous in micropreconcentrators, the principles of the invention may be used in larger preconcentrator designs with appropriate scale-ups made by the skilled artisan.

[0011] The invention may be implemented in a number of ways. Accordingly, in one aspect of the invention, metal oxide frameworks (MOFs) are used as a sorbent of an analyte in a collection system. The collection system may include one of a preconcentrator, micropreconcentrator, personal respirator and dosimeter. The preconcentrator or micropreconcentrator may be a purge and trap system, microelectromechanical (MEMS) valve system, array of microstructures, dosimeter, disc, pellet, or swab. The preconcentrator or micropreconcentrator may include a MEMS valve system with at least 3 valves. In particular, the MEMS valve system may have 4 or 5 valves. The MOFs may have a thermal stability of up to about 300⁰C to about 400°C. The MOFs also may sorb substantially all of the analyte. After sorbing the analyte, the MOFs may release the analyte, for example, by thermal desorption. The MOF may be in particular form or in a film. The MOF particles may have a diameter of between about 20 nanometers to about 500 microns, and, more particularly, a diameter of between about 100 nanometers to about 50 microns. The MOFs may include one or more of Zn-MOFI , Zn-MOF2, Zn-MOF3, Zn-MOF4, Zn-MOF5, Cu-MOFI , Cu-MOF2, Tb-MOFI , Tb- MOF2, Cd-MOFI , Cd-MOF2, Cd-MOF3, Co-MOFI , Co-MOF2, Zn-MOF6, MOF-5, Cu(4,4- bpy)i.₅NO₃(H₂O)₁.₂₅ IRMOF2, [Cu₃(TMA)₂]_n, [Cu(OH)-(C₅H₄NCO₂], MOF-38 , Ag(4,4'-bpy)NO₃, IRMOF3 and IRMOF7. The MOFs may be selective to a predetermined analyte or group of analytes. This selectively may be enhanced by adjusting the pore size of the MOFs and adding a functional group to the MOFs. The MOFs may sorb analytes including explosives and chemical warfare agents in general and more particularly, analytes such as XV, sarin, DMMP, PMP, diethyl methylphosphonate (DEMP), diisopropyl methylphophonate (DIMP), dichlorohexane, malathion, acetic anhydride, TNT, and RDX.

[0012] According to another aspect of the invention, a method of concentrating an analyte in a sample includes using a sorbentto collect the analyte, wherein the sorbent has high sorption capacity, selective sorptivity, thermal stability at temperatures up to about 30(FC to about

400⁰C, a particle size range from about 20 nm to about 150 microns, and does not substantially decompose the analyte during sorption. The sorbent may include a metal organic framework (MOF) molecule, such as at least one of Zn-MOFI , Zn-MOF2, Zn-MOF3, Zn-MOF4, Zn-MOF5, Cu-MOFI , Cu-MOF2, Tb-MOFI , Tb-MOF2, Cd-MOFI , Cd-MOF2, Cd-MOF3, Co-MOFI , Co- MOF2, Zn-MOF6, MOF-5, Cu(4,4'-bpy)₁.5Nθ3(H₂O)₁.₂5 IRMOF2, [Cu₃(TMA)₂J_n, [Cu(OH)- (C₅H₄NCO₂], MOF-38 , Ag(4,4'-bpy)NO₃, IRMOF3, and IRMOF7.

[0013] In yet another aspect of the invention, a micropreconcentrator includes a sorbent that is highly selective to an analyte or group of analytes. The sorbent may have a thermal stability of up to about 300°C to about 400⁰C, and may include particles having a diameter of between about 20 nanometers to about 500 microns, and, more particularly, a diameter of belween about 100 nanometers to about 150 microns. The sorbent may include a MOF. The sorbent may be adhered ID an array of microstructures, such as microposts.

[0014] In yet another aspect of the invention, a system for collecting an analyte from a sample may include an inlet to receive the sample, a collection chamber containing at least one of i) a sorbent highly selective to the analyte and ii) an array of microstructures having a radius of a, and a half-spacing belween microstructures of s, and wherein adimensionless parameter, β, is defined as a/s such that flow through the collection chamber for β > 0.65 substantially obeys the lubrication Stokes approximation of Navier-Stokes equation, and for/?< 0.65 substantially obeys Oseen's approximation of Navier-Stokes equation, and an outlet to conduct the analyte out of the system. The sorbent may have high sorption capacity, thermal stability at temperatures up to about 300⁰C to about 400⁰C, a particle size range from about 20 nm to about 500 microns, and does not substantially decompose the analyte. The sorbent may include one or more metal oxide frameworks (MOFs). The system may further include at least one valve controlling the flow to or from the collection chamber. The system may be a micropreconcentrator and the valve may be a microelectromechanical (MEMS) valve. The system may include a purge and trap system and the collection chamber may include a groove in a rotary injection valve. The inlet may be coupled to a carrier gas containing the sample, and the analyte may be sorbed onto the sorbent in the collection chamber. The system may also include a release mechanism to desorb the analyte from the sorbent, such as a heater to heat the sorbent. The desorbed analyte may be conducted through the outlet. The outlet may be coupled with a detector. The detector may be coupled with an analytical device, such as a gas chromatograph, surface acoustic wave, evanescent wave detector, a piezoelectric detector, an ion mobility spectrometer, and a chemiresistor detector. The collection chamber may be coupled with a MEMS valve system having a plurality of electrodes and at least one membrane electrode operable to open and close the MEMS valves in a coordinated manner. The membrane electrode may be electrostatically actuated. The MEMS valve system may include at least three valves. The microstructures may be disposed within the collection chamber. The microstructures may be coated with a sorbent selective to the analyte. The sorbent may include one of a low surface area compound and a high surface area compound. The low surface area compounds may include polymers and the high surface area compounds may include MOFs. The microstructures may include generally cylindrical members, and may be arranged in a square array.

[0015] In yet another aspect of the invention, a method of collecting an analyte from a sample for analysis may include concentrating the analyte by sorbing it on a sorbent highly selective to the analyte, desorbing the analyte from the sorbent, and conducting the desorbed analyte to a device for analysis, such as a gas chromatograph, surface acoustic wave, evanescent wave, a piezoelectric detector, an ion mobility spectrometer, or a chemiresistor detector. The concentrating step may include using a sorbent having high selectivity to polar molecules, thermal stability at temperatures up to about 300⁰C to about 400⁰C, a particle size range from about 20 nm to about 500 microns, and which does not substantially decompose the analyte during sorption. The sorbent may include a metal organic framework (MOF) molecule, which may be at least one of Zn-MOFI , Zn-MOF2, Zn-MOF3, Zn-MOF4, Zn-MOF5, Cu-MOFI , Cu- MOF2, Tb-MOFI , Tb-MOF2, Cd-MOFI , Cd-MOF2, Cd-MOF3, Co-MOFI , Co-MOF2, Zn-MOF6, MOF-5, Cu(4,4'-bpy)_{1 5}NO₃(H₂O)_{1 25} IRMOF2, [Cu₃(TMA)₂J_n, [Cu(OH)-(C₅H₄NCO₂], MOF-38 , Ag(4,4'-bpy)NO₃, IRMOF3, and IRMOF7. The method may also include the step of at least one of adjusting the pore size of the MOF and adding a functional group to the MOF. The sorbent may fully sorb the analyte during the collecting step. After the desorbing step, the analyte may be fully released from the sorbent, e.g., by thermal desorption. The MOF may be in particular form or in a film. The analytes may include XV, sarin, DMMP, PMP, diethyl methylphosphonate (DEMP), diisopropyl methylphophonate (DIMP), dichlorohexane, malathion, acetic anhydride, TNT, and RDX. The method may further include the step of synthesizing the sorbent to be selective to a predetermined group of analytes.

[0016] In yet a further aspect of the invention, a process for making a selectively sorbent MOF, Zn-MOFI , having a cubic crystalline structure with crystals in the range of 2 to 4 microns may include (a) dissolving 0.239 g of 4,4', 4",4'"-(21 H, 23H-Porphine-5, 10,15,20- tetrayl)tetrakis(benzoic acid) (H2TPP) and 0.18 g of Zn(NO₃)₂6H₂O in 60 ml_ DEF; (b) stirring the dissolved solution; (c) sealing the dissolved solution in a closed vessel; and (d) heating the vessel to 100⁰C at 2°C/minute. Zn-MOFI may be made by following the above process. [0017] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Zn-MOFI , having a cubic crystalline structure with crystal sizes in the range from about 10 microns to about 30 microns may include (a) dissolving Zn(NO₃)₂*6H₂O (0.18 g, 0.605 mmol ) and 4,4',4",4"'-(21 H,23H-porphine-5-10-15-20-tetrayl)tetrakis(benzoic acid) (0.199 g, 0.252 mmol) in 10 mL diethylformamide; (b) sealing the dissolved solution, and (c) heating in a microwave oven. Zn-MOFI may be made by following the above process. [0018] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Zn-MOF2, having a cubic crystalline structure with crystal sizes in the range from 2 to 4 microns may include (a) mixing Zn(NO₃)₂*6H₂O (0.1 g, 0.336 mmol) and 2-anilino-5-bromoterephthalic acid, (2-anilino-5-BrBDCH2) (0.0847 g, 0.252 mmol; (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating in a microwave oven. Zn- MOF2 may be made by following the above process. [0019] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Zn-MOF3, having a cubic crystalline structure with crystals ranging from 4 to 7 microns, may include (a) mixing Zn(NO₃)₂*6H₂O (0.15 g, 0.504 mmol) with 2-trifluoromethoxy terephthalic acid, (2-trifluoromethoxy-BDCH2) (0.0946 g, 0.378 mmol); (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Zn-MOF3 may be made by following the above process.

[0020] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Zn-MOF4, having crystals of irregular shape may include (a) mixing Zn(NO₃)₂*6H₂O (0.1 g, 0.336 mmol) with nitroterephthalic acid (0.0532 g, 0.252 mmol); (b) dissolving the mixture in 10 mL diethylformamide, sealing the dissolved mixture; and (c) heating the dissolved mixture in a microwave oven. Zn-MOF4 may be made by following the above process.

[0021] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Zn-MOF5, may include (a) mixing Zn(NO₃)₂*6H₂O (0.15 g, 0.504 mmol) with cis-cyclobutane- 1 ,2-dicarboxylic acid (0.0545 g, 0.378 mmol); (b) dissolving the mixture in 1O mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Zn-MOF5 may be made by following the above process.

[0022] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Cu-MOFI ₁ may include (a) mixing Cu(NO₃)₂*2.5H₂O (0.15 g, 0.645 mmol) with 2,5- thiophenedicarboxylic acid (0.0833 g, 0.484 mmol); (b) dissolving the mixture in 10 mL diethylformamide (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Cu-MOFI may be made by following the above process. [0023] In yet another aspect of the invention, a process for making a selectively sorbent MOF, CU-MOF2, may include (a) mixing Cu(NO₃)₂*2.5H₂O (0.1 g, 0.430 mmol) with 2- (trifluoromethoxy) terephthalic acid (2-trifluoromethoxy-BDCH₂) (0.0807 g, 0.322 mmol; (b) dissolving the mixture in 10 ml. diethylformamide; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Cu-MOF2 may be made by following the above process.

[0024] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Tb-MOFI , having a rod-shaped crystalline structure, may include (a) mixing Tb(NO₃)₃*5H₂O, (0.1 g, 0.230 mmol), with terephthalic acid (BDC) (0.0286 g, 0.172 mmol); (b) dissolving the mixture in 10 ml_ diethylformamide; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Tb-MOFI may be made by following the above process.

[0025] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Tb-MOF2, may include (a) mixing Tb(NO₃)₃*5H₂O, (0.1 g, 0.230 mmol), with 2,5- thiophenedicarboxylic acid (0.0297 g, 0.172 mmol); (b) dissolving the mixture in 10 ml_ diethylformamide; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Tb-MOF2 may be made by following the above process. [0026] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Cd-MOFI, may include (a) mixing Cd(NO₃)₂*4H₂O, (0.1 g, 0.324 mmol), with cis-cyclobutane- 1 ,2-dicarboxylic acid (0.0350 g, 0.243 mmol); (b) dissolving the mixture in 10 ml_ diethylformamide; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Cd-MOFI may be made by following the above process. [0027] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Cd-MOF2, may include (a) mixing Cd(NO₃)₂*4H₂O (0.1 g, 0.324 mmol) with nitroterephthalic acid (0.0456 g, 0.216 mmol); (b) dissolving the mixture in 15 ml. diethylformamide; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Cd-MOF2 may be made by following the above process.

[0028] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Cd-MOF3, may include (a) mixing Cd(NO₃)₂*4H₂O (0.1 g, 0.324 mmol) with terephthalic acid (0.0404 g, 0.243 mmol); (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Cd-MOF3 may be made by following the above process.

[0029] In yet another aspect of the invention, a process for making a selectively sorbent MOF, Co-MOFI , may include (a) mixing Co(N0₃)₂*6H₂0, (0.1 g, 0.343 mmol),with terephthalic acid (0.0428 g, 0.258 mmol; (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Co-MOFI may be made by following the above process.

[0030] In yet another aspect of the invention, a process for making a selectively sorbent MOF,

C0-MOF2, may include (a) mixing Co(NO₃)₂*6H₂O, (0.1 g, 0.343 mmol) with 1 ,3,5- benzenetricarboxylic acid (0.0542 g, 0.258 mmol); (b) dissolving the mixture in 10 ml_ diethylformamide; (c) sealing the mixture; and (d) heating in a microwave oven. Co-MOF2 may be made by following the above process.

[0031] In yet another aspect of the invention, a process for making a selectively sorbent MOF,

Zn-MOF6, may include (a) mixing Zn(NO₃)₂*6H₂O (0.05 g, 0.168 mmol) with 3,3- bis(trifluoromethyl)-1-oxo-5-isobenzofurancarboxylic acid (0.0396 g, 0.126 mmol); (b) dissolving the mixture in 7 ml_ diethylformamide/ 3 ml. H₂O; (c) sealing tie dissolved mixture; and (d) heating the dissolved mixture in a microwave oven. Zn-MOF6 may be made by following the above process.

[0032] In yet a further aspect of the invention, a system for collecting an analyte from a sample may include (a) an inlet to receive the sample; (b) a collection chamber containing a sorbent; and (c) a series of at least three valves to control flow of the sample through the system. The series of valves may be microelectromechanical system (MEMS) valves and may include four or five valves.

[0033] Additional features, advantages, and embodiments of the invention may be set forth or apparent from consideration of the following detailed description, drawings, and claims.

Moreover, it is to be understood that both the foregoing summary of the invention and the following detailed description are exemplary and intended to provide further explanation without limiting the scope of the invention as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the detailed desσiption serve to explain the principles of the invention. No attempt is made to show structural details of the invention in more detail than may be necessary for a fundamental understanding of the invention and the various ways in which it may be practiced. In the drawings:

[0035] Figure 1 is a flow chart depicting the basic functional steps carried out by a typical preconcentrator; [0036] Figure 2 is a diagram showing a typical crystalline structure of a MOF; [0037] Figure 3 is a view of the structure and channels of a specific MOF, Zn-MOFI , constructed according to the principles of the invention; [0038] Figure 4 is a graph of the ratio of the weight of an analyte (dimethyl methylphosphonate,

DMMP) to the weight of MOF-5, used as a sorbent in a micropreconcentrator, as a function of temperature;

[0039] Figure 5A and 5B are graphs demonstrating the sorptivity of MOFs as being selective to a polar molecule. Figure 5A shows the difference in signal overtime when MOF-5 is used to sorb 2434 ppb dodecane vapor in helium gas. Figure 5B shows a similar graph when the analyte is 642 ppb DMMP vapor in helium gas;

[0040] Figure 6 is a graph that shows the desorption of DMMP from MOF-5 as a function of temperature; [0041] Figure 7 is a graph that shows the desorption speed of DMMP from MOF-5 of two different particle sizes;

[0042] Figure 8 is a graph depicting the results of a breakdown test in which a signal was obtained by directly injecting DMMP into a GC/MS and another signal was obtained by trapping

DMMP in MOF-5 and desorbing it according to the invention; [0043] Figures 9A₁ 9B, and 10 are graphs demonstrating gains of about 8,000 to 10,000 using

MOF-5 for detecting DMMP in accordance with the invention, compared to conventional detection without use of a MOF micropreconcentrator;

[0044] Figure 11 illustrates a small subset of the chemical structures of various analytes that may be detected according to principles of the invention including VX, sarin, DMMP, and PMP; [0045] Figure 12 shows a plot of an x-ray powder diffraction (XRPD) pattern for the MOF-5 synthesized according to the principles of the invention, along with a simulated pattern obtained from literature;

[0046] Figures 13 and 14 schematically illustrate the loading and operation of a micropreconcentrator in the form of a purge and trap system with a modified rotor design containing MOFs according to the principles of the invention;

[0047] Figure 15A is a conceptual flow diagram that describes the operation of a five microvalve preconcentrator constructed according to the principles of the invention;

[0048] Figure 15B is a diagram that demonstrates an exemplary timing cycle for a five microvalve preconcentrator constructed according to the principles of the invention; [0049] Figure 15C is a conceptual flow diagram that shows the position of the valves during desorption in Stage B at time t₂ according to the timing diagram of Figure 15B;

[0050] Figure 15D is a conceptual flow diagram that shows the positions of the valves when the desorbed analyte is injected out of the preconcentrator and into a GC in Stage C at time t₃ according to the timing diagram of Figure 15B; [0051] Figure 15E is a top view of the upper elecirode of the five microvalve preconcentrator of the invention showing the orientation of valves 1 - 5, the sample gas inlet, carrier gas inlet, vent, and the line to the GC column;

[0052] Figure 15F is a top view of the lower electrode of the five microvalve preconcentrator of the invention showing the orientation of valves 1 - 5, the carrier gas inlet, and the line to the GC column;

[0053] Figure 15G is a cross-sectionai diagram of the five microvalve preconcentrator of the invention taken along line AA' in Figures 15E and 15F showing valves 2 and 4 closed and valve

5 open; [0054] Figure 15H is a cross-sectional diagram of the five microvalve preconcentrator similar to

Figure 15G showing valves 2 and 4 open and valve 5 closed;

[0055] Figure 16A is a photograph of the micropreconcentrator constructed according to the principles of the invention on top of a penny;

[0056] Figure 16B is an SEM photograph of silicon microposts that may be employed in a micropreconcentrator constructed according to the principles of the invention;

[0057] Figure 16C is an SEM photograph of microposts of the invention coated with sorbents;

[0058] Figure 17 is a schematic diagram of a unit cell in a micropost array that is used for modeling fluid flow according to the principles of the invention;

[0059] Figure 18A shows curves for the normalized drag per unit length as a function of the dimensionless parameter, β, that may be employed in modeling the unit cell of Figure 15;

[0060] Figure 18B shows afamily of curves of the dimensionless objective function (DOF) vs. β for a range of aspect ratios of the micropost, that may be employed in modeling the unit cell of the invention;

[0061] Figure 19A is a schematic diagram of a microchannel filled with an N by M array of microposts constructed according to the principles of the inventbn;

[0062] Figure 19B shows optbal microscope images of exemplary silicon micropost arrays constructed according to the principles of the invention;

[0063] Figure 2OA is a graph of the pressure drop per unit cell of the micropost array of the invention vs. the dimensionless parameter/?; [0064] Figure 2OB is a semi-logarithmic version of Figure 18A;

[0065] Figure 21 A is a graph that shows that each theoretical fluid flow model for the unit cell corresponds to the experimental results for its applicable range;

[0066] Figure 21 B is a semi-logarithmic plot of the graph shown in Figure 19A;

[0067] Figure 22A is a cross-sectional view of a micropreconcentrator constructed according to the principles of the invention housing a MEMS valve system incorporating microposts in the collection chamber; and [0068] Figure 22B is an SEM photograph that provides an enlarged view of the microposts present in the collection chamber.

DETAILED DESCRIPTION OF THE INVENTION [0069] The embodiments of the invention and the various features and advantageous details thereof are explained more fully with reference to the non-limiting embodiments and examples that are described and/or illustrated in the accompanying drawings and detailed in tie following description. It should be noted fiat the features illustrated in the drawings are not necessarily drawn to scale, and features of one embodiment may be employed with other embodiments as the skilled artisan would recognize, even if not explicitly stated herein. Descriptions of well- known components and processing techniques may be omitted so as to not unnecessarily obscure the embodiments of the invention. The examples used herein are intended merely to facilitate an understanding of ways in which the invention may be practiced and to further enable those of skill in the art to practice the embodiments of the invention. Accordingly, the examples and embodiments herein should not be construed as limiting the scope of the invention, which is defined solely by the appended claims and applicable law. [0070] Moreover, it is noted that like reference numerals represent similar parts throughout the several views of the drawings. It is understood that the invention is not limited to the particular methodology, protocols, devices, apparatus, materials, and reagents, etc., described herein, as these may vary. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention. It must be noted that as used herein and in the appended claims, the singularforms "a," "an," and "the" include plural reference unless the context clearly dictates otherwise. Thus, for example, a reference to "a MOF" is a reference to one or more MOFs and equivalents thereof known to those skilled in the art and so forth.

[0071] Moreover, provided immediately below is a "Definition" section, where certain terms to the invention are defined specifically for clarity and consistent with the broadest meaning that would be attributed to these terms by an ordinarily skilled artisan. Particular methods, devices, and materials are described, although any method and materials or equivalents to those described herein may be used in the practice or testing of the invention. Words not specifically defined are to be accorded the definition as would be understood by a person skilled in the art consistent with the specification. [0072] Definitions [0073] The term, "preconcentrator" refers to a device that is operable to collect, remove, and/or concentrate a trace component and/or an analyte from a gas or liquid stream. As used herein, preconcentrators include micropreconcentrators, which refer to a preconcentrator that is small enough to be readily portable and capable of being carried by a person from site to site.

Preconcentrators and micropreconcentrators may be used in conjunction with analytical instruments and devices.

[0074] The term "analyte" refers to a substance which a laboratory or other entity seeks to detect and/or identify using analytical procedures or other techniques.

[0075] The term "metal-organic framework" (MOF) refers to a one, two, or three dimensional polymer including bofri organic and metal or metal oxide structural units, where at least one of the metal units is bonded to least one bi-, tri- or poly-dentate organic unit

[0076] The term "adsorption" refers to the adhesion of an extremely thin layer of atoms, molecules, or ions to the surfaces of solid bodies or liquids with which they are in contact.

[0077] The term "absorption" refers to a physical or chemical process by which atoms, molecules, or ions enter the volume of a bulk phase material.

[0078] The term "sorption" is used in its broadest sense to refer to the total effect of atoms, molecules, or ions being incorporated into a material's volume, and/or of atoms, molecules, or ions adhering to a material's surface by any mechanism, including, but not limited to adsorption and absorption.

[0079] The term "sorbent" also is used in its broadest sense to refer to a material that incorporates atoms, molecules, or ions into its volume and/or adheres atoms, molecules, or ions to its surface by "sorption" as defined above. [0080] The term "desorption" refers to a process by which a sorbed material is released from its

"sorbent."

[0081] The term "highly selective" refers to at least about 100 times greater selectivity of a sorbent to a desired analyte in a sample, compared to another substance in the sample being analyzed. [0082] As described earlier, a preconcentrator functions by collecting a sample and raising the concentration of certain analytes of interest that are present in the sample. When used with an analytical instrument such as a GC, this increase in concentration of analytes, referred to herein as "gain," allows a detector to more accurately sense the analytes.

[0083] Common examples of preconcentrators include purge and trap devices used in the front end of analytical instruments, dosimeters used to measure exposure to chemicals, toxins and other components, sample tubes used to collect samples for analysis of air, water, breath, urine, or blood. Further, gas masks and other protective clothing may function as preconcentrators in that they collect and remove trace compounds.

[0084] Figure 1 is a flowchart depicting the basic functional steps carried out by a typical preconcentrator. As shown in Figure 1 , the first step involves collection of a sample containing an analyte in the preconcentrator. For example, the analyte may be collected by sorption on a chemical sorbent contained in the preconcentrator. In the second step, the analyte is released from the preconcentrator. When used with a sorbent, this release may be accomplished by desorbing the analyte from the sorbent. For example, the sorbent may be heated to desorb the analyte. Finally, in step three, the sample and analyte are purged from the preconcentrator and conducted to the detector of an analytical instrument such as a GC, for analysis. The preconcentrator may be purged, for example, by flushing a carrier gas through the preconcentrator.

[0085] This invention provides new ways to collect and release the analyte, as set forth in steps 1 and 2 and novel micropreconcentrator designs in which these steps may be carried out. The micropreconcentrators of the invention may include a high surface area sorbent to selectively sorb analytes. In particular, Applicants discovered that metal-organic framework (MOF) molecules, which area known, but relatively new class of compounds, may be used as sorbents in preconcentrators. [0086] MOFs have been the focus of intense activity in recent years because of their extremely high porosity and tailorable molecular cavities. MOFs have been studied for a variety of applications including hydrogen storage, selective sorption, non-linear optical materials, and as catalysts e.g., catalysts to store H₂ (in fuel cells) or CO₂. Applicants have discovered that MOFs have properties that make them highly advantageous as preconcentrators including, for example, high sorption capacity due to their high surface area, high selectivity to specific analytes, inert nature which does not decompose the analyte, thermal stability, and result in unexpectedly high gains in detection, which will be described in detail later. [0087] Accordingly, in one aspect of the invention, MOFs are used in the collection step of Figure 1 to selectively sorb specific analytes in a preconcentrator. For example, MOFs may be used in particle form, or they may be incorporated into a film inside the preconcentrator. Once the analytes are fully sorbed by the MOFs, the analytes are released in the second step of Figure 1 , e.g., by thermal desorption. Then, they can be purged and transferred from the preconcentrator to a detector, for example. The structure and properties of MOFs that make them highly suitable for use as selective sorbents in preconcentrators are discussed below. [0088] MOFs are organometallic structures with high surface area and tailorable selectivity, which makes them suitable for sorption of selected molecules. They have a cubic crystalline structure that is formed by copolymerizatbn of metals or metal oxides with organic ligands. Figure 2 is a diagram of a typical MOF's crystalline structure 10 including metal or metal oxides, here shown as polyhedrons 12, having polymer ligands 14 extending between them. This highly ordered structure facilitates the creation of interior pores and channels. MOFs are known to have 1 - 3 nanometer (nm) pores. Figure 3 is a view of the structure and channels 16 of one of the new MOFs discovered by Applicants and disclosed herein, Zn-MOF-1. As shown in Figure 3, Zn-MOF-1 has channels 16 of about 10 A x 10 A. MOF crystals are known to have an average diameter of 200 microns.

[0089] The surfaces of MOFs' pores and channels increase the overall surface areas of MOFs and allow them to sorb analytes in the collection step of Figure 1. MOFs have high porosity which is comparable to or larger than that of zeolites. For example, MOF-5, a known MOF, may have a surface area of about 2900 m²/g and IRMOF-177 may have a surface area of about 4500 m²/g. The very high surface area of MOFs thus results in MOFs having very high sorption capacities, which makes them desirable candidates for use in preconcentrators. [0090] Experiments performed by Applicants determined the sorption capacity of certain MOFs. For example, the sorption capacity of MOF-5 was measured using thermal gravimetric analysis (TGA). In order to perform TGA, MOF-5 crystals, prepared as described in Example 18 below, were first ground to a mesh size of less than 120 mesh. The crystals were then evacuated in vacuum at 15O⁰C for one day. Five milligrams of the ground MOF-5 was packed into a 3 mm GC capillary with glass wool. DMMP vapor was carried by15 seem of He gas through a saturator at room temperature (which is 107 ppm) and then passed through the sample capillary at 5O⁰C. After 10 μl_ of solvent loss was observed from the saturator, the samples removed from the system. TGA was then carried out on a Perkin-Elmer TGA7 instrument heating from 25⁰C to 300⁰C at 10°C/min. [0091] Figure 4 is a graph of the ratio of the weight of dimethyl methylphosphonate, DMMP, a substance of interest for detection, to the weight of MOF-5 as a function of temperature, according to the TGA measurement described above. As shown in Figure 4, at 2O⁰C, MOF-5 has tremendous sorption capacity as it is able to sorb almost its own weight of DMMP. The MOF-5 became saturated when the DMMP concentration in the MOF-5 was about 0.7 g/cm³. This compares to a gas phase density at room temperature of 6x10^"7 g/cm³. Thus, MOF-5 raised the DMMP concentration by about 10⁶ in the preconcentrator.

[0092] Further, MOFs are highly advantageous for use in preconcentrators because of their highly selective sorptivity. In particular, MOFs selectively sorb polar compounds. Although the mechanism for this selectivity is currently unknown, the details of the mechanism are not necessary to practice the invention. Figures 5A and 5B demonstrate the highly selective sorptivity of MOFs to a polar molecule measured using a modified purge and trap preconcentrator similar to that shown in Figures 13 and 14 discussed below. [0093] Figure 5A shows he difference in signal overtime between when a MOF-5, synthesized as described below in Example 16, is used to sorb 2434 ppb dodecane vapor in helium gas, designated as "groove with MOF" and when no MOF-5 is used, designated as "empty groove." Dodecane, a non-polar molecule, exhibits limited improvements in gain when used with MOF-5 and Zn-MOF-1. According to Figure 5A, when MOF-5 is used, a signal of 1150 is generated by the detector. When no MOF-5 is used, a signal of 275 is generated by the detector. Thus, the gain for dodecane is only about 4.2 (~1150/275).

[0094] Figure 5B is a graph similar to Figure 5A that shows the signal when the analyte is 642 ppb DMMP vapor in helium gas. As shown in Figure 5B, MOF-5 markedly raises the concentration of DMMP and results in a gain of about 10,000. Thus, although almost 4 times (= 2434/642) more dodecane than DMMP was used in these experϊnents, the selectivity of MOF- 5 to polar molecules resulted in a much higher gain of about 10,000 for DMMP than the gain for dodecane of about 4.2. [0095] Selective sorption in MOFs is significantly better than in previous sorbents, such as activated carbon, which sorb a wide variety of compounds and do not allow a specific analyte to be isolated. Moreover, MOFs may be selectively tailored to detect to specific compounds, which is particularly useful whentrying to isolate a particular analyte. For example, the pore size may be adjusted by replacing a dicarboxylic ligand with one, two or three benzene rings in a row, so that the sorbent is size-selective. Also specific functional groups may be attached to the sorbent. For example, a (CF₃)O functional group may be added to repel water and yet bind analytes of interest.

[0096] As described above in the release step in Figure 1 , the analyte may be released from the MOF in the preconcentrator by desorption. Desorption of the analyte from the MOF is typically achieved by heating the preconcentrator and sorbent to release the sorbed analyte. Other methods of desorption include vacuum and electron or photon stimulated desorption. Figure 6 is a graph that shows the thermal desorption of DMMP from MOF-5 as a function of temperature. As shown in Figure 6, substantially all of the sorbed analyte is desorbed by 23O⁰C. [0097] Experiments conducted by Applicants have shown tiat smaller MOF particles allow faster desorption of sorbed analytes. Figure 7 is a graph showing the desorption speed of

DMMP from MOF-5 particles of two different sizes, <45 μm and 150- 200 μm, as measured in the purge and trap system illustrated in Figures 13 and 14. In the experiment, the DMMP concentration was 642 ppb and the sampling volume was 10 cm³. As shown in Figure 7, the MOF-5 particles with a particle size of <45 μm exhibited a sharp peak that started at about 15 seconds and did not taper off much beyond 30 seconds. In contrast, the desorption peak for the 150 - 200 μm size MOF-5 particles started well before the 45 μm particles (about 9-10 seconds), but the peak was much shorter and it tapered off for longer than 2 minutes. This indicates that mass transfer in the larger MOF particles is much slower. These results confirm that the use of smaller MOF particles in a preconcentrator is preferable because faster desorption allows faster detection of the sample. [0098] Initial observations indicate that for optimal results in the preconcentrators of the invention, MOF particles with a diameter of about 20 nanometers to about 500 microns may be used, preferably between about 20 nanometers and about 150 microns, and more preferably between about 100 nanometers and about 50 microns. If the MOF particles are much smaller than about 100 nanometers, the structures tend to collapse tend to cluster in the preconcentrator, leading to poor mass transfer. Particles larger than about 50 microns give tailing during desorption, as shown in Figure 7. Particles with diameters in the range of about 1 to about 10 microns have been observed to provide favorable results. [0099] Further, tests of various MOFs conducted by Applicants using MOF-5 and Zn-MOF-1 in the modified purge and trap system shown in Figures 13 and 14 demonstrated that MOFs do not decompose analyte while sorbing or desorbing them. Figure 8 is a graph depicting the results of a breakdown test of DMMP during desorption from MOF-5. Peak A and the corresponding mass spectrometer (MS) peaks follow from a direct injection of DMMP into the GC and MS. These peaks coincide well with Peak B and the corresponding MS peaks that follow from a sample in which DMMP was trapped in a MOF and then thermally desorbed. This test demonstrates that MOF-5 did not alter the DMMP molecules as it was sorbed and thermally desorbed on the MOF's surface. Similar results were obtained with similar tests using Zn-MOF-1. This property of MOFs is important for accurate detection of an analyte because if the MOF altered Ihe analyte, the sample could not be analyzed accurately by the GC or MS. [00100] In addition to not decomposing an analyte, MOFs themselves do not decompose at relatively high temperatures. Specifically, MOFs have thermal stability up to temperatures of about 30O⁰C to about 400⁰C. For example, PIZA- 1 MOF begins to decompose at 375⁰C, MOF- 5 is thermally stable up to 350⁰C, and Zn-MOF-1 is thermally stable up to 400⁰C. Having thermal stability up to high temperatures allows use of MOFs in preconcentrators, which are often heated to high temperatures (above 200⁰C) during friermal desorption.

[00101] Figures 9A, 9B, and 10 are graphs that plot GC signals obtained during desorption of DMMP used with the preconcentrator shown in Figures 13 and 14 containing MOF-5 and without any preconcentrators, as a function of time. In particular, Figure 9B is an enlargement of the dotted portion of Figure 9A showing the peak obtained when no preconcentrator was used. Examining Figures 9A, 9B, and 10, it is evident that the peaks obtained when using MOF-5 in the preconcentrator are significantly larger than the peaks obtained with a conventional detector used without a MOF in the preconcentrator. In fact, Figures 9A, 9B, and 10 show that a significant gain of about 8,000 to about 10,000 can be achieved using the MOFs of this inventbn. Similar measurements using Zn-MOF-1 demonstrate a similar trend. This unexpectedly high gain demonstrates that use of a MOF in accordance with the invention greatly improves sensitivity of the GC detector. [00102] In accordance with principles of the invention, MOFs may be used as sorbents in preconcentrators to detect various chemical substances and/or their precursors. Figure 11 illustrates the chemical structures of various substances including VX, sarin, DMMP, and PMP that can be sorbed by MOFs during preconcentration and subsequently detected. Other suitable substances that have chemical structures that would be concentrated by MOFs may include, but are not limited to, diethyl methylphosphonate (DEMP), diisopropyl methylphophonate(DIMP), dichlorohexane, malathion, acetic anhydride, TNT, RDX, and other explosives or chemical warfare agents. As described earlier, MOFs may be tailored to selectively detect specific compounds for use in various applicatons. [00103] Numerous methods have been developed for synthesizing MOFs using precursors including a metal precursor and corresponding spacing ligand. The MOFs of the invention may be made according to any method known in the art, in addition to proprietary microwave methods developed by Applicants described subsequently. Solvothermal and hydrothermal synthesis methods using these precursors have conventionally been employed to form MOF crystals. Solvothermal synthesis is a method where precursors for MOF crystal formation are heated in a solvent other than water. In hydrothermal synthesis, precursors for MOF crystals are heated in water. Hydrothermal synthesis is suitable when the ligand precursor is soluble in water. [00104] In solvothermal and hydrothermal synthesis, a solution with MOF precursors is typically maintained at a predetermined equilibrium temperature for an extended period to induce crystallization. Solvothermal and hydrothermal synthesis methods are typically slow, often taking hours and even days.

[00105] General information on different known MOFs and conventional synthesis methods are reported in a number of publications, including, "Design and Synthesis of an Exceptionally Stable and Highly Porous Metal-Organic Framework," Yaghi et al., Nature 402 (1999) 276-279; "Interwoven Metal-Organic Framework on a Periodic Minimal Surface with Extra-Large Pores, B. Chen, M. Eddaoudi," Yaghi et al. Science 291 (2001) 1021 - 1023; "Systematic Design of Pore Size and Functionality in lsoreticular MOFs and Their Application and Methane Storage," Yaghi et al, Science 295 (2002) 469 - 472; "Reticular Synthesis and Design of New Materials, Yaghi et al., Nature 423 (2003) 705 - 714; "Hydrogen Storage in Microporous Metal-Organic Frameworks, Yaghi et al., Science 300 (2003) 1127- 1129. [00106] Reported solvothermal synthesis methods are slow, typically taking a day or more. U.S. Published Application No. 2003/0004364 discloses a solvothermal process to form MOF materials that takes about one day to several days. In the synthesis method of the above- referenced application, a metal salt and a linear ditropic carboxylate are dissolved in a solvent to form a solution. The solution is then crystallized, which involves at leastone of leaving 1he solution at room temperature, adding a diluted base to the solution to initiate the crystallization, diffusing a diluted base into the solution to initiate the crystallization, and transferring the solution to a closed vessel and heating to a predetermined temperature. [00107] A multi-day hydrothermal synthesis process has also been proposed for the production of nonlinear optically active MOF material. (See e.g., "A Novel Optical Metal- Organic NLO Material Based on a Chiral 2D Coordination Network," Lin, et al., J. Am. Chem. Soc, 1999, 121, 11249-11250.) Others have reported a thermally stable [Cu₃(TMA)₂(H₂O)₃I_n framework structure produced through a 12 hour solvothermal synthesis. (See e.g., "A Chemically Functionalizable Nanoporous Material [Cu₃(TMA)₂(H₂O)₃]_n," Chui, et al., Science, 1999, 283, 1148.) Catalytic active homochiral metal-organic materials formed by a two-day liquid diffusion method or solvothermal method have been reported. (See e.g., "A Homochiral Meta-organic Porous Material for Enantioselective Separation and Catalysis," Seo, et al., Nature, 2000, 404, 982-986; "A Homochiral Metal-Organic Material with Permanent Porosity, Enantioselective Sorption Properties, and Catalytic Activity", Dybtsev, et al., Angew. Chem. Int. Ed., 2006, 45, 916-920.) Others have reported porphyrin MOF structures by a two-day solvothermal synthesis. (See e.g., "A functional zeolite analogue assembled from metalloporphyrins," Kosal, M. E.; Chou, J.-H., Wilson, S. R.; Suslick, K. S. Nature Materials, 2002, 1, 118-121.) Synthesis by one-week deprotonating vapor diffusion has also been reported. (See e.g., "A Robust Microporous Zinc Porphyrin Framework Solid", Smithenry, D. W. et al. Inorg. Chem. 2003, 42, 7719.)

[00108] As an alternative to the solvothermal and hydrothermal synthesis methods, a microwave-assisted process has been developed by the Applicants to rapidly produce a metal organic framework (MOF) material. According to this method, a reactant solution including MOF precursors is exposed to microwaves for a period sufficient to achieve crystallization. The time period required may be, for example, a few seconds to a few minutes or more. The time period required for crystallization depends upon tie microwave power andthe solution concentration. Example formation times have ranged from about 5 seconds to about 2.5 minutes, which is a significant improvement over the conventional synthesis methods that typically take several hours or days. [00109] Microwave-assisted MOF synthesis methods such as those described above may be particularly advantageous to the synthesis of MOFs for purposes of the invention. For example, the microwave-assisted MOF synthesis method described above provides materials with uniform crystal size and well-defined shape. The resulting micro-sized or nano-sized crystals produced by these methods can be engineered for use in preconcentrators. Reaction conditions may be tailored to provide, for example, particle size control, larger functioning surfaces, or faster sorption kinetics. In addition, post-processing after initial synthesis may be conducted to provide larger crystals. For example, these synthesis methods provide well- defined crystals that may serve as seeds for the synthesis of larger crystals through a secondary growth process. [00110] Another advantage of microwave-assisted MOF synthesis is that it allows one to determine the optimum conditions for crystal growth in a short amount of time. For example, one can use the microwave synthesis method to determine the conditions at which crystals of the desired structure grow, and then repeat the crystal growth under those conditions using published methods to obtain larger crystals for other purposes. [00111] Several new MOFs were synthesized by Applicants according to the microwave- assisted method, as described in the following Examples 1 - 16, for use as sorbents in preconcentrators, but they may also be made by any other methods known in the art. [00112] Example 1

[00113] Zn-MOFI synthesis: An exact amount of zinc nitrate hexahydrate,

Zn(NO₃)₂*6H₂O, (0.18 g, 0.605 mmol) and 4,4',4",4'"-(21 H,23H-porphine-5-10-15-20- tetrayl)tetrakis(benzoic acid), (0.199 g, 0.252 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 80 seconds. The crystals obtained were dark purple with a cubic shape with sizes ranging from about 10 to about 30 microns. [00114] Example 2 [00115] Zn-MOF2 synthesis: An exact amount of zinc nitrate hexahydrate,

Zn(NO₃)₂*6H₂O, (0.1 g, 0.336 mmol) and 2-anilino-5-bromoterephthalic acid, (2-anilino-5- BrBDCH2) (0.0847 g, 0.252 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 80 seconds. The obtained crystals were light yellow with a cubic shape with sizes ranging from 2 to 4 microns. [00116] Example 3

[00117] Zn-MOF3 synthesis: An exact amount of zinc nitrate hexahydrate,

Zn(NO₃)₂*6H₂O, (0.15 g, 0.504 mmol) and 2-trifluoromethoxy terephthalic acid, (2- trifluoromethoxy-BDCH2) (0.0946 g, 0.378 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 80 seconds. The obtained crystals were yellow with a cubic shape, with sizes ranging from about 4 to about 7 microns. [00118] Example 4

[00119] Zn-MOF4 synthesis: An exact amount of zinc nitrate hexahydrate, Zn(NO₃)₂*6H₂O, (0.1 g, 0.336 mmol) and nitroterephthalicacid, (0.0532 g, 0.252 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800W) for a reaction time of 80 seconds. The obtained crystals had an irregular shape.

[00120] Example 5

[00121] Zn-MOF5 synthesis: An exact amount of zinc nitrate hexahydrate, 2n(NO₃)₂*6H₂O, (0.15 g, 0.504 mmol) and cis-cyclobutane-1,2-dicarboxylic acid (0.0545 g, 0.378 mmol) were dissolved in 10 ml_ diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 105 seconds. The obtained crystals had a square plate shape. [00122] Example 6 [00123] Cu-MOFI synthesis: An exact amount of cupric nitrate, Cu(NO₃)₂*2.5H₂O, (0.15 g, 0.645 mmol) and 2,5-thiophenedicarboxylic acid, (0.0833 g, 0.484 mmol) were dissolved h 1O mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 80 seconds. [00124] Example 7 [00125] CU-MOF2 synthesis: An exactamount of cupric nitrate, Cu(NO₃)₂*2.5H₂O, (0.1 g,

0.430 mmol) and 2-(trifluoromethoxy)terephthalic acid (2-trifluoromethoxy-BDCH₂) (0.0807 g, 0.322 mmol) were dissolved in 10 ml_ diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 80 seconds. [00126] Example 8

[00127] Tb-MOFI synthesis: An exact amount of terbium (III) nitrate pentahydrate,

Tb(NO₃)₃*5H₂O, (0.1 g, 0.230 mmol) and terephthalic acid (BDC) (0.0286 g, 0.172 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800W) for a reaction time of 80 seconds. The obtained crystals had a rod shape. [00128] Example 9

[00129] Tb-MOF2 synthesis: An exact amount of terbium (III) nitrate pentahydrate,

Tb(NO₃)₃*5H₂O, (0.1 g, 0.230 mmol) and 2,5-thiophenedicarboxylic acid (0.0297 g, 0.172 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 80 seconds.

[00130] Example 10

[00131] Cd-MOFI synthesis: An exactamount of cadmium nitrate hexahydrate,

Cd(NO₃)₂*4H₂O, (0.1 g, 0.324 mmol) and cis-cyclobutane-1 ,2-dicarboxylic acid (0.035Og, 0.243 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 60 seconds.

[00132] Example 11

[00133] Cd-MOF2 synthesis: An exact amount of cadmium nitrate tetrahydrate, Cd(NO₃)₂*4H₂O, (0.1 g, 0.324 mmo!) and nitroterephthalic acid (0.0456 g, 0.216 mmol) were dissolved in 15 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 60 seconds.

[00134] Example 12

[00135] Cd-MOF3 synthesis: An exact amount of cadmium nitrate tetrahydrate, Cd(NO₃)₂*4H₂O, (0.1 g, 0.324 mmol) and terephthalic acid (0.0404 g, 0.243 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800W) for a reaction time of 90 seconds.

[00136] Example 13

[00137] Co-MOFI synthesis: An exact amount of cobalt (II) nitrate hexahydrate, Co(NO₃)₂*6H₂O, (0.1 g, 0.343 mmol) and terephthalic acid (0.0428 g, 0.258 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800W) for a reaction time of 60 seconds.

[00138] Example 14

[00139] Co-MOF2 synthesis: An exact amount of cobalt (II) nitrate hexahydrate, Co(N0₃)₂*6H₂0, (0.1 g, 0.343 mmol) and 1 ,3,5-benzenetricarboxylic acid (0.0542 g, 0.258 mmol) were dissolved in 10 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of 60 seconds.

[00140] Example 15 [00141] Zn-MOF6 synthesis: An exact amount of zinc nitrate hexahydrate,

Zn(NO₃)₂*6H₂O, (0.05 g, 0.168 mmol) and 3,3-bis(trifluoromethyl)-1-oxo-5- isobenzofurancarboxylic acid (0.0396 g, 0.126 mmol) were dissolved in7 mL diethylformamide/

3 mL H₂O. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800W) for a reaction time of 120 seconds. The obtained crystals had a hexagonal cylinder shape, with size ranging from about 2 to about 4 microns.

[00142] In addition, new MOFs were synthesized according to the methods described in

U.S. Patent Publication No. 2005/0192175, as described in the following Example 16, for use as sorbents in preconcentrators.

[00143] Example 16 [00144] Zn-MOFI synthesis: 0.239 g of 4,4' ,4",4'"-(21 H₁ 23H-Porphine-5, 10,15,20- tetrayl)tetrakis(benzoic acid) (H2TPP) and 0.18 g of Zn(NO₃)₂6H₂O were dissolved in 60 mL DEF. The solution was stirred for 3 hours and then sealed in a closed vessel. The vessel was heated to 100⁰C at 2°C/minute. Dark purple crystals were collected after 3 days for a yield of 40%.

[00145] Specific known MOFs were synthesized either using microwave synthesis or according to the methods described in U.S. Patent Publication No. 2005/0192175, asdescribed in the following Examples 17 - 35. [00146] Example 17

[00147] 50 - 1 ,000 micron MOF-5 synthesis: 0.200 g Zn(NO₃)₂6H₂O and 0.084 g 1 , 4- dibenzenedicarboxylate (H₂BDC) ligand in were dissolved 2O mL N,N'diethylformamide (DEF). The solution was stirred for 30 minutes and then heated in a closed vessel at 8O⁰C. After 1-3 days, small transparent crystals were obtained with a size distribution between about 50 and about 1 ,000 microns. [00148] Example 18

[00149] 30-50 micron MOF-5 synthesis: The MOF-5 crystals in Example 17 were ground with a mortar and pestle. They were then sorted with a 120 mesh sieve to produce particles that were between about 30 and about 45 microns in diameter. [00150] Example 19

[00151] 4-6 micron MOF-5 synthesis: An exact amount of Zn(NO₃)₂.6H₂O (0.2g, 0.67 mmol) and 1 ,4-benzenedicarboxylate acid (BDCH2) (0.083g, 0.50 mmol) were dissolved in 10 mL of the N,N'-diethylformamide (DEF) resulting in a clear solution. One ml_ of the solution was sealed h a 4-mL Pyrex sample vial. The vial was then placed inside a hood behind a blast shield and heated by a microwave synthesizer (Resonance Instrument Inc. Model 520A) at 150 W for about 25 seconds. A yellow suspension formed after the microwave treatment. The product was rinsed (centrifuged and re-dispersed in DEF by sonicating) for 3 times before analysis. Light yellow crystals with a particle size of about 4-6 microns were observed. [00152] Example 20

[00153] 3 micron MOF-5 synthesis: An exact amount of Zn(NO₃)₂.6H₂O (0.2 g, 0.67 mmol) and 1 ,4-benzenedicarboxylate acid (BDCH2) (0.083 g, 0.50 mmol) were dissolved in 10 mL of the N.N'-diethylformamide (DEF) resulting in a clear solution. The solution was diluted with DEF until the BDCH₂ concentration was approximately 25 mmol/L. One mL of the solution was sealed in a 4-mL Pyrex sample vial. The vial was then placed inside a hood behind a blast shield and heated by a microwave synthesizer (Resonance Instrument Inc. Model 520A) at 150 W for about 33 seconds. A yellow suspension formed after the microwave treatment. The product was rinsed (centrifuged and re-dispersed in DEF by sonicating) for 3 times before analysis. Light yellow crystals with average particle size of about 3 micron were observed. [00154] Example 21 [00155] 1.5 micron MOF-5 synthesis: An exact amount of Zn(NO₃)₂.6H₂O (0.2 g, 0.67 mmol) and 1 ,4-benzenedicarboxylate acid (BDCH2) (0.083 g, 0.50 mmol) were dissolved in 10 ml_ of the N,N'-diethylformamide (DEF) resulting in a clear solution. The solution was diluted with DEF until the BDCH₂ concentration was approximately 12.5 mmol/L One mL of the solution was sealed h a 4-mL Pyrex sample vial. The vial was then placed inside a hood behind a blast shield and heated by a microwave synthesizer (Resonance Instrument Inc. Model 520A) at 150 W for about 41 seconds. A yellow suspension formed after the microwave treatment. The product was rinsed (centrifuged and re-dispersed in DEF by sonicating) for 3 times before analysis. Light yellow crystals with average particle size of about 1.5 micron were observed.

[00156] Example 22

[00157] 0.75 micron MOF-5 synthesis: An exact amount of Zn(NO₃)₂.6H₂O (0.2 g, 0.67 mmol) and 1 ,4-benzenedicarboxylate acid (BDCH2) (0.083g, 0.50mmol) were dissolved in 10 mL of the N,N'-diethylformamide (DEF) resulting in a clear solution. The solution was diluted with DEF until the BDCH₂ concentration was approximately 6.25 mmol/L. One mL of the solution was sealed in a 4-mL Pyrex sample vial. The vial was then placed inside a hood behind a blast shield and heated by a microwave synthesizer (Resonance Instrument Inc. Model 520A) at 150 W for about 49 seconds. A yellow suspension formed after the microwave treatment. The product was rinsed (centrifuged and re-dispersed in DEF by sonicating) for 3 times before analysis. Light yellow crystals with average particle size of about 0.75 micron were observed. [00158] Example 23

[00159] MOF-5 synthesis: An exact amount of Zn(NO₃)₂.6H₂O (0.2 g, 0.67 mmol) and

1 ,4-benzenedicarboxylate acid (BDCH2) (0.083 g, 0.50 mmol) were dissolved in 10 mL of the N,N'-diethylformamide (DEF) resulting in a clear solution. The solution was diluted with DEF until the BDCH₂ concentration was approximately 3.13 mmol/L. One mL of the solution was sealed in a 4-mL Pyrex sample vial. The vial was then placed inside a hood behind a blast shield and heated by a microwave synthesizer (Resonance Instrument Inc. Model 520A) at 150 W for about 57 seconds. A yellow suspension formed after the microwave treatment. The product was rinsed (centrifuged and re-dispersed in DEF by sonicating) for 3 times before analysis. Light yellow crystals with average particle size of about 0.5 micron were observed. [00160] Example 24

[00161] MOF-5 synthesis: An exact amount of Zn(NO₃)₂.6H₂O (0.2 g, 0.67 mmol) and

1 ,4-benzenedicarboxylate acid (BDCH2) (0.083 g, 0.50 mmol) were dissolved in 10 mL of the N,N'-diethylformamide (DEF) resulting in a clear solution. The solution was diluted with DEF until the BDCH₂ concentration was approximately 1.56 mmol/L. One mL of the solution was sealed in a 4-mL Pyrex sample vial. The vial was then placed inside a hood behind a blast shield and heated by a microwave synthesizer (Resonance Instrument Inc. Model 520A) at 150 W for about 65 seconds. A yellow suspension formed after the microwave treatment. The product was rinsed (centrifuged and re-dispersed in DEF by sonicating) for 3 times before analysis. Light yellow crystals with an average particle size of about 0.5 micron were observed. [00162] Example 25

[00163] 0.4 micron MOF-5 synthesis: An exact amount of Zn(NO₃)₂.6H₂O (0.2 g, 0.67 mmol) and 1 ,4-benzenedicarboxylate acid (BDCH2) (0.083 g, 0.50 mmol) were dissolved in 10 mL of the N,N'-diethylformamide (DEF) resulting in a clear solution. The solution was diluted with DEF until the BDCH₂ concentration was approximately 0.78 mmol/L. One mL of the solution was sealed h a 4-mL Pyrex sample vial. The vial was then placed inside a hood behind a blast shield and heated by a microwave synthesizer (Resonance Instrument Inc. Model 520A) at 150 W for about 73 seconds. A yellow suspension formed after the microwave treatment. The product was rinsed (centrifuged and re-dispersed in DEF by sonicating) for 3 times before analysis. Light yellow crystals with average particle size of 0.4 micron were observed.

[00164] Example 26

[00165] 0.3 micron MOF-5 synthesis: An exact amount of Zn(NO₃)₂.6H₂O (0.2 g, 0.67 mmol) and 1 ,4-benzenedicarboxylate acid (BDCH2) (0.083 g, 0.50 mmol) were dissolved in 10 mL of the N,N'-diethylformamide (DEF) resulting in a clear solution. The solution was diluted with DEF until the BDCH₂ concentration was approximately 0.39 mmol/L. One mL of the solution was sealed h a 4-mL Pyrex sample vial. The vial was then placed inside a hood behind a blast shield and heated by a microwave synthesizer (Resonance Instrument Inc. Model 520A) at 150 W for about 81 seconds. A yellow suspension formed after the microwave treatment. The product was rinsed (centrifuged and re-dispersed in DEF by sonicating) for 3 times before analysis. Light yellow crystals with average particle size of 0.3 micron were observed.

[00166] Example 27

[00167] 100-300 nm MOF-5 synthesis: An exact amount of Zn(NO₃)₂.6H₂O (0.2 g, 0.67 mmol) and 1 ,4-benzenedicarboxylate acid (BDCH2) (0.083 g, 0.50 mmol) were dissolved in 10 mL of the N,N'-diethylformamide (DEF) resulting in a clear solution. The solution was diluted with DEF until the BDCH₂ concentration was approximately 0.20 mmol/L. One mL of the solution was sealed h a 4-mL Pyrex sample vial. The vial was then placed inside a hood behind a blast shield and heated by a microwave synthesizer (Resonance Instrument Inc. Model 520A) at 150 W for about 90 seconds. A yellow suspension formed after the microwave treatment. The product was rinsed (centrifuged and re-dispersed in DEF by sonicating) for 3 times before analysis. Light yellow crystals with average particle size of about 0.1 to about 0.3 microns (i.e. 100 to 300 nm) were observed.

[00168] Example 28

[00169] IRMOF2 synthesis: An exact amount of 2-bromoterephthalfc acid, (2-BrBDCH2) (0.040 g, 0.160 mmol), and zinc nitrate hexahydrate, Zn(NO₃)₂.6H₂O, (0.0594 g, 0.20 mmol) were dissolved in 15 ml_ diethylformamide. The solution was then sealed with a Pyrex sample vial and heated at 150 W for a reaction time of about 40 seconds. A yellow suspension formed after the microwave treatment. [00170] Example 29 [00171] IRMOF3 synthesis: An exact amount of 2-aminoterephthalic acid, (2-Amino-

BDCH2) (0.2 g, 0.67 mmol) and zinc nitrate hexahydrate, Zn(NO₃)₂.6H₂O, (0.0913 g, 0.504 mmol) were dissolved in a mixture of 39 mL diethylformamide and 3 mL ethanol. The solution was then sealed with a Pyrex sample vial and heated at 150 W for a reaction time of about 35 seconds. An orange suspension formed after the microwave treatment. [00172] Example 30

[00173] Cu(4,4^>-bpy)₁.₅NO3(H₂O)₁.25 synthesis described in detail in JACS 1995,

117,10401-10402: An exact amount of Cu(NO₃)₂.2.5H₂O (0.1133 g, 0.487 mmol), 4,4'-dipyridyl (0.114 g, 0.730 mmol), and 1 ,3,5-triazine (0.026 g, 0.323 mmol) were dissolved in 15 mL of deionized water. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of about 60 seconds. [00174] Example 31

[00175] [Cu₃(TMA)₂J_n synthesis described in detail in Science 1999, 283,1148-1150: An exact amount of cupric nitrate Cu(NO₃)₂.2.5H₂O (0.1 g, 0.430 mmol) and 1 ,3,5-benzene- tricarboxylic acid (0.05 g, 0.239 mmol) were dissolved in 10 mL of DEF. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of about 60 seconds. [00176] Example 32

[00177] [Cu(OH)-(C₅H₄NCO₂]_n synthesis described in detail in Inorg. Chem. 2005, 44,

6192-6196: An exact amount of cupric nitrate Cu(NO₃)₂.2.5H₂O (0.1 g, 0.430 mmol) and isonicotinic acid (0.067 g, 0.430 mmol) were dissolved in 4 mL of deionized water. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of about 60 seconds. [00178] Example 33

[00179] MOF-38 synthesis in detail in JACS, 2001 , 123,8239-8247: An exact amount of zinc nitrate hexahydrate, Zn(NO₃)₂.6H₂O (0.1 g, 0.336 mmol) and 1 ,3,5-benzene-tricarboxylic acid (0.039 g, 0.187 mmol) were dissolved in 10 mL of DEF. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800 W) for a reaction time of about 60 seconds. [00180] Example 34

[00181] Ag(4,4'-bpy)NO₃ synthesis described in detail in JACS, 1996, 118, 295-296: An exact amount of silver nitrate, Ag(NO₃) (0.050 g, 0.294 mmol) and 4,4'-dipyridyl (0.051 g, 0.325 mmol) were dissolved in 10 mL of deionized water. The solution was then sealed with a Pyrex sample vial and heated with a household microwave oven (800W) for a reaction time of about 60 seconds. [00182] Example 35 [00183] IRMOF7 synthesis: An exact amount of 1,4 naphthalene dicarboxylic acid,

(0.109 g, 0.504 mmol) and zinc nitrate hexahydrate, Zn(NO₃)₂.6H₂O, (0.2 g, 0.673 mmol) were dissolved in a 15 mL diethylformamide. The solution was then sealed with a Pyrex sample vial and heated at 150 W for a reaction time of about 60 seconds. [00184] Of the MOF-5 samples prepared by the procedures described above, those in Examples 21 , 22 and 23 worked better in sorption experiments than those prepared by the procedures in Examples 20, 24, 25, 26, and 27. MOF-5 with particle sizes above 10 microns showed slower sorptionand desorption, which limited their utility in experiments where the sorption/desorption time needed to be under 4 seconds. The particles with sizes below 1 micron gave high pressure drops. In addition, the weight of MOF that adhered to the epoxy (discussed below) in the preconcentrator in Figure 14, decreased as the particle size was reduced, thus reducing the preconcenirators' effectiveness. Thus, the particles that were smaller than 1 micron were less effective in the preconcentrator design of Figures 13 and 14. [00185] Once the MOFs were formed, they were characterized using x-ray powder diffraction (XRPD) to confirm their composition. XRPD patterns were collected on a Bruker General Area Detector Diffraction System for 900 seconds with an 8.5 cm sample-to-detector distance. Solvated crystals used for XRPD measurements were transferred along with a mother liquor into a 0.7 mm capillary tube. For example, Figure 12 plots an XRPD pattern for the MOF-5 obtained in Example 16 along with a simulated pattern obtained from literature. It is evident from Figure 12 that the XRPD pattern for laboratory-synthesized MOF-5 and the simulated pattern coincide closely, indicating that the laboratory-synthesized MOF-5 was formed correctly.

[00186] As mentioned previously, the MOFs described in this invention can be used in various known or new types of preconcentrators for use in a wide range of analytical instruments and detectors. Specific embodiments of preconcentrators of the invention that may employ MOFs include a conventional purge and trap system using a modified rotor (such as that described in connection with Figures 13-14), a MEMS valve system (such as the valve designs described in Figures 15-22B which may or may not include microposts), vacuum cleaner assisted preconcentrator, dosimeter, swab, and disc or pellet, as described in more detail below. While the detailed embodiments disclosed herein are directed to micropreconcentrators, the skilled artisan will recognize that the principles of the invention may be scaled up and practiced as a preconcentrator.

[00187] Figure 13 and 14 schematically illustrate the loading and operation of a purge and trap micropreconcentrator system, 100, with a modified rotor design containing MOFs, according to an embodiment of the invention. This system provides high gain because most of the analyte is collected from a large volume sample and is then trapped in a small space. As shown in Figure 13, MOF crystals are mounted into the rotor of a conventional Valco® injector valve 110. Specifically, the rotor has four 0.05 μl_ grooves and the MOF is loaded into one of the grooves referred to as the sample groove 112.

[00188] Three methods were used to hold the MOF in the grooves. In the first method,

MOF particles that were approximately the same diameter as the groove were placed in the groove and held via friction. In a second method, a thin layer of Locktite quickset epoxy was placed in the groove. Then, MOF powder was pressed into the grove on top of the epoxy, the epoxy was allowed to dry, and then any loose particles were blown off of the groove using a nitrogen stream. According to a third method, particles were put in a small capillary which was then placed or glued into the groove. [00189] During the operation of the purge and trap micropreconcentrator 100, the sample groove 112 is rotated to each of the four positions labeled A-D in Figure 13 and 14. Position A couples the sample groove 112 to the sample and carrier gas inlet 114 and the vent 116. Position B has no connections, so when the sample groove 112 is in this position, its contents have no outlet. Position C couples the sample groove 112 to a heater 118, for example, for the desorption step. Position D couples the sample groove 112 to a purge gas inlet 132 and to a detector through a GC column 130, for example.

[00190] As described in more detail below, a carrier gas is supplied from a carrier gas cylinder 120, for example, and may pass through a mass flow controller 122 before being supplied to the valve 110 at position A. A purge gas may be supplied from a purge gas cylinder 124, for example, through a purge gas pressure gauge 126 before being supplied to the valve 110 at position D.

[00191] As shown in Figure 13, the sample groove 112, shown at position A, may be loaded with MOFs in any suitable manner. For example, the sample groove may be loaded with a predetermined number, e.g., five cubic MOF crystals, or the sample groove 112 may also be covered with 1-10 micron MOF particles. Referring to Step 1 of Figure 14, tie sample groove 112 is in or is moved to position A where a sample gas from the sample and carrier gas inlet 114 containing an analyte such as DMMP vapor is allowed to flow from an ice-bath bubbler 128 (as shown in Figure 13) to the sample groove 112 at 20 seem, for example, at room temperature for about one minute, for example. The MOFs in the sample groove 112 sorb and trap the analyte in the sample groove 112 at position A. Excess gas is allowed to leave through the vent 116.

[00192] Next, in Step 2, the valve 110 is rotated so that the sample groove 112 is in position B. The MOF and analyte stay trapped in sample groove 112 because position B provides no connections to the outside. Then in Step 3, the sample groove 112 containing the analyte and MOF are rotated to position C where they are heated by means known in the art, such as a suitable healer 118, to a temperature to cause desorption of the analyte, e.g., to about 22O⁰C. In this step, the analyte desorbs from the MOF but stays trapped in the sample groove 112.

[00193] Last, in Step 4, the valve 110 is rotated such that the sample groove 112 is in position D and is thus coupled to the GC column 130. During Step 4, the desorbed analyte leaves the sample groove 112 and a purge gas such as hydrogen or helium may be introduced to assist in injecting or pushing the analyte out of the sample groove from the purge gas inlet 132 at position D. As known in the art, the flow rate of the purge gas is adjusted to avoid diluting the analyte. After the analyte are purge gas are transferred from the sample groove 112 in Step 4, to the column 130, they then flow to a detector (not shown). For example, the injected vapor may be passed from the column to a flame ionization detector (FID) of a GC. [00194] Another embodiment of a preconcentrator according to the invention involves use of multiple electrostatically actuated MEMS valves. In one embodiment, a preconcentrator includes five microvalves that may be constructed as described below, and which work together to supply a concentrated analyte to a detector. The five microvalve system may be used with MOFs as well as ottier high surface area sorbents, as described below. In addition to the five microvalve configuration, the preconcentrator may be actuated with only two valves, inlet and outlet valves, as well as without an active valve in the split "Y" valve configuration more commonly found in large scale preconcentrator systems. [00195] Figures 15A - 15H are schematic diagrams illustrating the operation of the five microvalve preconcentrator of the invention. Figure 15A is a conceptual flow diagram that describes the operation of a five microvalve preconcentrator. Valve 1 is the sample gas input valve through which the sample gas is supplied to the preconcenirator. Valve 2 is the carrier gas input valve that is used to introduce carrier gas through the preconcentrator. Valve 3 is the vent valve, through which sample gas and carrier gas are vented to the atmosphere. Valve 4 is the column injection valve from the preconcentrator through which the sample gas passes. Valve 5 is an optional bypass valve for carrier gas that bypasses the preconcentrator and goes directly from the carrier gas inlet to the column. In Figures 15A-H, the valves shown without cross-hatching are open and those with cross-hatching are closed.

[00196] If valve 5 is not used for the bypass, valve 4 may simply feed a split "Y" valve with carrier gas continually flowing. The addition of valve 5 allows sharper insertion of the desorbed gas into a separation column. In one embodiment, valves 1 , 2, and 3 may have the same structure. In a second embodiment, valves 4 and 5 are integrated and operated opposite each other such that when one valve is closed, the other valve is open. [00197] Figure 15B is a diagram that demonstrates an exemplary timing of the five microvalves. Referring to Figure 15B, there are three main stages, A, B, and C and two optional purge stages. In Stage A, which begins attime to, the preconcentrator is loaded with the sample gas. Loading is accomplished by suppling the sample gas through the preconcentrator by opening sampling valve 1 , as shown in Figure 15A. The sorbent is contained in a collection chamber 236 which communicates with and/or is integrated with the valves as shown in Figures 15G and 15H. Vent valve 3 is also open during Stage A, as shown in Figure 15A, allowing sample gas to exit the preconcentrator through the vent, after passing by the sorbent in the collection chamber 236. The duration of loading, to- t_{i 7} determines the amount of analyte carried in the sample gas that is sorbed withh the preconcentrator by the sorbent. The longerthe duration of loading for a given flow rate, the more the desired species are sorbed, and the higher the gain, up to saturation of the sorbent. Carrier gas valve 2 and injection valve 4 are closed and bypass valve 5 is open during Stage A, as shown in Figure 15A.

[00198] Figure 15C illustrates desorption in Stage B at time t₂. As shown in Figure 15B, valves 1 , 2, 3, and 4 are closed and the preconcentrator is heated to a temperature sufficient to desorb all or most of the analyte off the sorbent. Pressure rises in the preconcentrator during Stage B.

[00199] Stage C begins attime t₃ and is illustrated in Figure 15D. Figure 15D shows how the sample gas is injected out of the preconcentrator and into a column, for example. Injection valve 4 is opened and bypass valve 5 is closed, starting the flow of gas in the preconcentrator. Shortly thereafter, carrier gas valve 2 is opened, allowing the carrier gas to be passed through the preconcentrator to the detector, such as a FID, through the column of a GC. The injection from the preconcentrator is stopped by closing valve 4 and reopening bypass valve 5 after time 1». If an optional purge is not used, valve 2 is also closed at U- [00200] There are two optional purge stages that may be taken between Stage A and

Stage B at time t_{1 ?} and then again at time t* between Stage C and the next Stage A. These steps can be added to prevent the sample gas from being eluted into the column and so that analyte from a sample gas is eliminated from the preconcentrator to avoid cross-contamination of consecutive samples. The purge gas also reduces the impact of dead volume between the preconcentrator and the valves, since this volume is filled with carrier gas, and not sample gases.

[00201] In addition to Stages A, B, C, and the two optional purge stages, offset times, δ, may be added to the stage timing so that the valve pairs 1 and 3, 2 and 4, and 4 and 5 are not opened and closed at exactly the same time. This is illustrated in Figure 15B. These offsets may be employed to reduce crossover between sample and carrier gases, column and vent, etc., as well as to reduce fluid flow surges between valve switching. [00202] Valves 1 , 2, 3, and 4 may have substantially the same design as described above, while valve 5 may have a different design. Valves 1 , 2, 3, and 4 are normally closed valves, and only open on actuation. Valve 5 is a normally open valve that only closes on actuation to allow bypass of the carrier gas past the preconcentrator, except during the injection stage. Valve 4 and valve 5 may be combined together into a single unit such that when valve 4 opens, valve 5 closes, and vice versa. [00203] The ports in valves 1 and 3 are matched in size and are typically larger than the ports in valves 2 and 4, which are also matched in size. Alternatively, all the valves may be the same size or different sizes. The valve ports have approximately the same dimensions in terms of hydraulic diameter as the column into which the gases are being injected. Capillary columns used in separations often range from 50 to 500 microns in diameter. If the ports are much smaller, i.e. more than one order of magnitude, the pressure drop across the valves may be too high for suitable performance. If the ports are much larger, i.e. more than one order of magnitude, the valves will be unnecessarily large and require more space and power to operate. [00204] Valves 1 - 5 of the five microvalve system may be opened and closed by an electrostatically actuated MEMS employing three electrodes. The electrodes include an upper electrode, a membrane electrode, and a lower electrode. Figure 15E is a top plan view of the upper electrode showing the orientation of valves 1 - 5 the sample gas inlet 20, carrier gas inlet 22, vent 24, and the line to column 26. Figure 15F is a top plan view of the lower electrode showing the orientation of valves 1 - 5, the carrier gas inlet 22, and the line to column 26. [00205] Figures 15G and 15H are cross-sectional diagrams of the five microvalve preconcentrator 200 taken along line AA', as shown in Figures 15E and 15F. Figure 15G illustrates that during desorption in Stage B, valve 2 and valve 4 are closed and valve 5 is open. In Figure 15H, valve 2 and valve 4 are open and valve 5 is closed. [00206] As illustrated in Figures 15G and 15H, the five microvalve system includes an upper fixed electrode 210, a movable membrane electrode 212, and a lower fixed electrode 214. The upper fixed elecirode 210 defines transverse fluid ports including an inlet 220 and an outlet 222 with microfluidic channels leading to and from the ports. The membrane electrode 212 is positioned against the inlet 220 and outlet 222. While a single inlet and outlet are illustrated in the upper fixed electrode 210, that electrode may include multiple inlets and outlets which can be controlled by the membrane electrode 212. The lower fixed electrode 214 defines a microcavity 224 to accommodate deformation of the membrane electrode 212.

[00207] As shown in Figures 15G and 15H, the five microvalve system includes a collection chamber 236 to direct flow between microchannels valves. In addition, sorbents such as MOFs or other materials suitable as sorbente in micropreconcentrators may be placed inside the collection chamber 236. The microvalve is symmetrical about a post 238 that separates two separate microcavities 224. Operation on the left and right sides of the microvalve may be independent or may be synchronized as the membrane electrode 212 may have multiple metal patterns. In Figure 15G, valve 2 and valve 4 are closed (and valve 5 is open). In Figure 15H, the membrane electrode 212 is fully open into both of the left and right microcavities 224 and in contact with the central pads 228. [00208] A pressure balance layer 226 is disposed at the lower portion of the lower fixed electrode 214 and providesfluid channels in communication with the inlet 220. In addition, the pressure balance layer 226 provides a pressure balance port 225 communicating with one of the microcavities 224, which provides a space into which the membrane electrode 212 may deform, as shown in Figure 15H. The pressure balance port 225 is maintained at a pressure near that of the inlet 220 pressure. When the pressure in the pressure balance port 225 is exactly the same as the pressure on the inlet 220, the pressure is balanced and the electrostatic force needed to open the valve by overcoming the sticking force of the membrane electrode 212 on the upper electrode 210 is reduced. In addition, to counteract the pressure on the membrane electrode 212, the electrostatic force must counteract any tension in the membrane electrode 212 and the pressure differential between the pressure balance layer 226 and the outlet 222. Thus, if the pressure in the pressure balance port 225 is less than the pressure on the inlet 220, less electrostatic force is required to move the membrane electrode 212, and vice versa. In particular, the pressure balance layer 226 allows the electrostatic force required to hold the membrane electrode 212 to the upper electrode 210 to be adjusted to be zero when the pressures balance. By adjusting the pressure within the pressure balance port 225, the operational speed of the microvalves may be adjusted.

[00209] A central pad 228 reduces a gap between a portion of the lower fixed electrode

14 and the membrane electrode212. The central pad 228 is aligned between the inlet 220 and outlet 222 and with the central portion of the membrane electrode 212 as it is most readily pulled away from its seated position. The central portion of the membrane electrode 212 is the least resilient portion as it is farthest from fixed ends of the membrane electrode 212. Also, fluid pressure from the inlet 220 is nearby. The central pad 228 reduces the gap but also allows the membrane electrode 212 to deform sufficiently into the microcavites 224 for fluid flow.

[00210] In the embodiment shown in Figures 15G and 15H, the five microvalve system has a normally closed position and will also fail in the closed position. Typically, the fluid will flow from the inlet 220 to the outlet 222, but different flow paths and bi-directional configurations may be made by moving the location of the inlet 220 and outlet 222 and center pad 228 as needed. The membrane electrode 212 will be attracted to the upper fixed electrode 210 or lower fixed electrode 214 depending on which side has a voltage potential applied between the membrane electrode 212 and the upper fixed electrode 210 or lower fixed electrode 214. The upper fixed electrode 210 normally touches the membrane electrode 212, blocking flow from the inlet 220 to the outlet 222. Fluid pressure from the pressure balance layer 226 assists in maintaining this position and may be sufficient to maintain the closed position in the absence of applied voltage. [00211] When a potential, V1 , is applied to the membrane electrode 212 wit) respect to the upper fixed electrode 210, an electrostatic force attracts the membrane electrode to the upper fixed electrode 210, and the membrane electrode 212 will seat tightly and can hold off very large forward pressures at the inlet 220 (up to more than 20 atm or higher depending on the area of the inlet 220 vs. the surrounding membrane electrode area). When the voltage is equalized between the membrane electrode 212 and the upper fixed electrode 210, and a potential, V2, is applied to the lower fixed electrode 214 with respect to the membrane electrode, an electrostatic force pulls the membrane electrode 212 away from the upper fixed electrode 210 towards the lower fixed electrode 214. [00212] The lower fixed electrocfe 214 may have the central pad 228 disposed centrally in the microcavity 224. The pad 228 may be much closer (about 10 microns or less versus about 100 microns for the microcavity 224) to the membrane electrode 212 than the remaining portions of lower fixed electrode 214 that define the microcavity 224. From the closed position, the central pad 228 generates a much stronger force (up to the order of 100 times stronger) on the central portion of the membrane electrode 212 than the remaining portions lower electrode 214 do because of the increased force caused by the decreased gap. The stronger force pops the membrane electrode 212 off the upper electrode 210, creating a faster response for fluid to flow between the inlet 220 and the outlet 222. The larger volume beneath the membrane electrode 212 in the lower electrode microcavity 224 between the central pad 228 and edge of the lower electrode microcavity 224 allows the fluid to flow more easily, and reduces the squeeze film damping that occurs between the membrane electrode 212 and lower electrode 214. [00213] The size of the central pad 228 also determines how much pressure the lower electrode microcavity 224 can have with respect to the inlet 220 and outlet 222 in order to open and close quickly. In general, the larger the central pad 228, the faster the opening time for a given applied voltage, gap distance, and pressure at the pressure balance layer 226. However, for the same conditions, the closing time will slow with increasing central pad size. Preferably, the central pad 228 and microcavity 224 are sized to produce comparable fast open and close times.

[00214] The depth of the microcavity 224 into which portions of the membrane electrode move is also determined in part by the flow rate of the fluid moving through the device. Making the microcavity 224 surrounding the central pad 228 deeper than the gap between the membrane electrode 212 and the central pad 228 creates a larger cross-sectional area for fluid to flow between the inlet and outlet, than that permitted by the distance to the central pad 228 itself. This feature prevents excessive pressure drop across the device, and permits variable flows to be controlled by adjusting the voltage. Higher voltages will pull the membrane electrode 212 further into the microcavity 224 by capacitive action without touch-mode actuation, creating a larger cross-sectional area and thus a lower pressure drop. However, if the depth of the microcavity 224 creates a much larger cross-sectional area than that of the inlet and outlet ports, the benefit of further increases diminishes. In addition, a greater depth requires a higher voltage to pull the membrane electrode 212 into the microcavity 224, requiring higher voltages to adjust the flow rates. Therefore, microcavity depths much more than 500 microns have little practical use for microscale fluid flows.

[00215] The upperfixed electrode 210, membrane electrode 212, and the lower fixed electrode 214 have substantially flat surfaces and are preferably semiconductor fabricated layers. The lack of curves and complicated shapes permits the use of semiconductor materials and semiconductor fabrication techniques.

[00216] The membrane electrode 212 may include a Cr/Au/Cr imbedded metal layer in polyimide, for example. Other flexible polymers may be used including, but not limited to parylene, Teflon®, Nafion®, Viton®, polyester, polybutylene, PDMS, and other dielectric polymers with reasonable electrical breakdown strength. In addition, other suitable polymer dielectrics for imbedding the metal layer of the membrane electrode 212 may include, but are not limited to parylene, Teflon^®, Nafion^®, polyester, polybutylene, and polydimethylsiloxane (PDMS).

[00217] For example, the membrane electrode 212 may be fabricated using a polyimide polymer that is spun on and cured in a low pressure environment absent of any water vapor, referred to as vacuum cure, on a separate glass carrier plate. Vacuum curing is found to substantially enhance breakdown voltage. Curing of polyimide may be performed from about 350⁰C to about 450°C. The membrane electrode 212 may be at least 0.1 microns thick to avoid premature failure. For example, the membrane electrode 212 may be between 1 and 3 microns thick. Membrane electrodes 212 thicker than about 20 microns are typically too stiff for the five microvalve system, but larger devices may utilize thicker membranes. [00218] The polyimide polymer may be metallized with thin layers of chrome, gold, and then chrome, which are then paterned to provide an electrically conductive layer within the membrane. A second polyimide polymer layer is spun on and vacuum cured over the metal layer. Holes are patterned with photoresist and etched using oxygen plasma to open up electrical contacts to the metal layer within the stack. The oxygen etches down and stops on the upper chrome layer, which is subsequently removed using a commercially available chrome etchant, exposing the gold layer to allow electrical contact. The polymer/metal/polymer sandwich stack is then transferred, aligned, bonded, and released Io a silicon layer using an adhesive that may be applied to the silicon via contact printing, for example. [00219] The bonding of the layers together enables higher pressures to be switched, since without the adhesive bonding, eakage from the inlet 220 to the outlet 222, as well to the outside environment can occur more easily. For example, the adhesive layer may be an epoxy adhesive made from a mixture of Dow Corning solid epoxy novolac-modified resin with curing agent in a 2.5:1 mass ratio, and various solvents (2-methoxyethanol 15 to 50% by mass range, anisole 15 to 50% by mass range, and PGMEA 0 to 10% by mass range, the exact amounts depend upon the adhesive layer thickness desired). Most often, the solvents are selected to modify the viscosity of the adhesive in order to achieve a thickness of 1 μm via spin coating and to achieve sharp interfaces. For a complete description of the spin coating process, see Flachsbart, B.R., K. Wong, J. M. lannacone, E.N. Abante, R.L. Vlach, PA Rauchfuss, P.W. Bohn, J.V. Sweedler, and M.A. Shannon, "Design and fabrication of a multilayered polymer microfluidic chip with nanofluidic interconnects via adhesive contact printing," Lab-On-A-Chip, 6, 667-674, 2006.

[00220] Other adhesives may be used, including those made from biphenol compounds which cure at a higher temperature and demonstrate higher bond strengths. The key issues of the adhesive layer are that it is thin (less than 20 microns and in a range of 1- 3 microns), it bonds the interfaces together to enable the device to sustain high pressures, it is aligned and contact printed on the microvalve interfaces and the membrane electrode is free to move from the upper fixed electrode210 toward the lower fixed electrode 214, and so that the low surface energy and low surface charge trapping coatings are not affected by the adhesive layer. [00221] The adhesive may be applied by contact printing, or any other method known in the art. Steps for contact printing may include first coating a temporary carrier with adhesive (e.g., a PDMS (Polydimethylsiloxane) stamp). The adhesive is then pressed onto the upper fixed electrode 210 or the lower fixed electrode214 to be bonded with the membrane electrode 212 and is cured under pressure with heat. During the process, the adhesive is contact printed only onto the areas of the fixed electrodes 210 and 214 that have been patterned to not have a low surface energy film coating, which is discussed further below. The adhesive may be applied first to the upper fixed electrode 210 (by pressing the compliant PDMS stamp that has the adhesive spun onto it), and then the membrane assembly is pressed onto the upper fixed electrode 210 and is cured underpressure and heat. Then the adhesive is applied to the PDMS stamp again, and it is pressed onto the lower fixed electrode 214. The lower fixed electrode 214 is then pressed onto the upper fixed electrode 210 and membrane electrode 212 and is cured.

[00222] Solvents may be used to modify the viscosity of the adhesive in order to achieve a thickness of preferably less than 10 μm, and most preferably about 1 μm via spin coating and to achieve sharp interfaces between the those areas printed with the adhesive, and those areas without adhesive. In other embodiments, the adhesive may be applied to the membrane electrode 212.

[00223] The adhesive may bond the layers together by covalent bonding or by being physically keyed into the layer (for example, by the adhesive flowing into a pore having an opening smaller than the interior, prior to curing). Since the layers are held on the carrier plate by non-covalent forces, for example by hydrogen bonding, they can be released from the carrier plate without affecting the adhesive. The adhesive preferably forms a solid resin, such as a bisphenol, a resin-based adhesive. Examples include DER 642U, DER 662, DER 663U, DER 664U, DER 665U, DER 667 and DER 672U, all from Dow Corning. These adhesives use a hardener, such as DEH 82, DEH 84, DEH 85 and DEH 87, all from Dow Corning. The adhesive may also be an epoxy adhesive mixture of solid epoxy novolac modified resin with curing agent in a 2.5:1 mass ratio.

[00224] A solvent may be added to the adhesive to control the viscosity, for example 2- methoxyethanol (15 to 50% by mass), anisole (15 to 50% by mass), and PGMEA (0 to 10% by mass) range. The layers may be bonded by heating and applying pressure to cure the adhesive, for example at 130⁰C and 5.2 MPa under vacuum for 10 minutes. The temporary adhesive carrier is an elastic polymer, such as a 3 mm thick 50 mm diameter PDMS disk. The carrier plate may be released from the layer using a hot water bath at approximately 50°C for 5 minutes. The adhesive may be given a final cure, for example by heating the completed device for 12 hours at 13O⁰C. Then the silicon layer may be bonded to the membrane using the same process. [00225] The resulting microvalve is then placed in a plastic package developed to apply pressure and electrical potentials using standard fittings. The plastic package may also be used to hold the pieces together instead of bonding, particularly for lower operating pressure devices.

[00226] The upper fixed electrode 210 and the lower fixed electrode 214 may include a semiconductor and its oxide with an additional nitride film, for example. The nitride film may only be a few monolayers thick. This film provides low surface charge trapping and is preferably used with a low surface energy film, e.g., Teflon^®, and such a thin multi-layer is effective both in preventing stiction and surface charge build up. In another embodiment, a dielectric oxide and nitride monolayers may be used to isolate the metal layer of the membrane electrode 212. Additionally, low surface charge trapping and low surface energy coatings may be added to the electrodes during semiconductor fabrication techniques.

[00227] The microcavity 224, central pad 228, upper fixed electrode 210, and membrane electrode 212 have flat surfaces. The flat surfaces are readily fabricated by conventional semiconductor microfabrication techniques, without resort to machining steps. Machining steps, such as those required for curved or arched surfaces increase the lowest possible size limit and do not readily translate to mass fabrication techniques.

[00228] In the five microvalve system, voltage rises rapidly as the gap between the central pad 228 and the membrane electrode 212 increases. High voltages may create difficulty because they create a large electric field when the microvalve opens and the membrane electrode 212 touches the central pad 228. With a gap of about 250 microns, the electric field exceeds the breakdown voltage of most polymers. For example, the electric field may be below 200 V/micron and preferably below 50 V/micron to prevent long-term degradation of the membrane. That limits the distance to be below about 150 microns and preferably below about 25 microns. Fabrication may be difficult if the distance is less than about 1 micron. 0.1 microns represents a practical lower limit with conventional MEMS fabrication tools. [00229] The time response of the microvalve is determined by the specific application, in particular which are much more important factors in gas chromatograph injector microvalve, chemical analysis, and etc. The important factors can be injector pressure (which depends on the pressure across the microvalve), flow rate (which depends on both the pressure across the microvalve, the microvalve orifice size, the membrane electrode 212 thickness and size), and the microcavity 224 size, the voltage across the membrane electrode 212, and the current through the microvalve (which depends on the applied voltage, the capacitance and resistance of the microvalve and circuit). Pressure from the pressure balance layer 226 also factors into response time. The balance pressure is added to balance pressure on both sides of the membrane electrode 212, thereby decreasing the net pressure across the membrane electrode 212 to increase both the pressure the microvalve can handle and speed of opening and closing. The pressure can be adjusted to be different on both sides of the membrane electrode 212 to apply a pneumatic actuation in addition to the electrostatic force, to control open and closing times, as well as to determine if the device fails open or closed. [00230] This allows, for example, the pneumatic action across the microvalve to be adjusted as desired to create faster opening microvalves (by reducing tie pressure in the pressure balance layer 226 on the lower electrode 214 side) or faster closing microvalves with lower leakage of fluid from the inlet 220 to the outlet 222 (by increasing the pressure at the pressure balance layer 226 on the lower electrode 214 side). For the embodiment shown in Figures 15G and 15H, even when the pressure is initially equal on both sides of the membrane when the microvalve is closed, once fluid starts flowing from the inlet 220 to the outlet 222, the pressure acting on the upper side of the membrane electrode 212 will decrease due to Bernoulli forces and the pressure at the pressure balance layer 226 will be higher than at the inlet 220, acting to help close the microvalve. A regulator and/or orifice may also be added to either the inlet 220, outlet 222, or at the pressure balance layer 226 to adjust the pneumatic actuation to the value desired for other embodiments of this inventbn. [00231] Another embodiment of a micropreconcentrator of the invention features high surface area micropost structures that may be coated with sorbents to form a micropreconcentrator. Microposts are three-dimensional structures that increase the surface area of the substrate they are formed on due to their geometry. In particular, the microposts may be cylindrical in shape and thus have surface area along their cylindrical wall and top. [00232] Micropost structures are arranged in an array within the micropreconcentrator and they are coated with a sorbent. For example, in one embodiment of the inventbn, micropost arrays may be used to increase the surface area of a sorbent when they are deposited inside the surface of a collection chamber of a microvalve preconcentrator of the invention, as described in detail below. Alternatively, microposts may be deposited on intermediate structures and then placed inside the collection chamber. The microposts may be aligned in a staggered configuration, for example, as shown in Figure 19A and 19B, below, or in other spacing configurations. The sorbent coating allows the microposts to collect and trap analytes that pass through the micropost array. Since the surface area of a micropost array is itself very high, this embodiment of the invention can be used with sorbents that have lower surface areas than MOFs.

[00233] The micropreconcentrators of the invention may release molecules in milliseconds and may selectively provide high gain (about 1000 times) for analytes of interests and little gain for common interferents, depending on the sorbent used. The micropost arrangement has been developed to provide a comparable surface-area-to-volume-ratio to microporous media, but with a shorter effective path length and lower pressure drop per unit length. A smaller pressure drop in the micropreconcentrator implies faster response time and less power consumption.

[00234] Figure 16A is a photograph of a micropreconcentrator constructed according to an embodiment of the invention on top of a standard U.S. penny. As is evident from the picture, the entire micropreconcentrator is a fraction of the size of a penny and has a correspondingly low volume, which makes it highly suitable for use in a micro GC. [00235] Micropost structures are formed on a substrate using any method known in the art to increase its surface area and allow higher sorption of the analyte. Using a highly controlled inductively coupled plasma deep reactive ion etching (ICP-DRIE) process, for example, highly anisotropic structures can be etched into the silicon. The ICP-DRIE process may employ a well-known SF₆ etching gas step followed by a C₄F₈ passivation step, which are repeated for many cycles until the desired depth is achieved. In addition, silicon microposts may also be grown using welhknown thermally-initiated chemical vapor deposition processes on catalysts, such as NiFe or Pd/Au patterned or deposited on the silicon substrates. [00236] For example, using any method known in the art, densely packed micron diameter silicon posts of predetermined dimensions may be formed uniformly over a micropreconcentrator, such as shown in the SEM photograph of Figure 16B. The microposts may then be doped and electrochemically etched to produce nanometer size etch pits within the microposts. These nanometer size etch pits further enhance the inherently high surface area of the microposts without increasing the pressure drop. The combination of high sorbent capacity due to high surface area and a very small volume allow for high-gains in concentration that improve sensitivity of analyte detection.

[00237] The microposts may be coated with a wide range of sorbents such as low surface area compounds including polymers. In addition, high surface area compounds such as MOFs may be coated on the microposts, although the use of MOFs is not required since the micropost array itself produces very high surface areas for enhanced sorption, as described earlier. Figure 16C is an SEM photograph of silicon microposts coated with sorbents according to the invention. Thus, the micropost structures of the invention can provide high surface area instead of requiring the sorbent to have an inherently high surface area. [00238] Sorbents may be coated on the microposts by any method known to one skilled in the art. One particularly novel and advantageous coating method has been developed by Applicants to coat the micropost structures with selective sorbents, as described in detail below. This method involves surface modification to covalently attach preformed sorbents to a micropost surface. For example, a polymer layer may be deposited on the micropost by providing an anchor on the micropost surface to attach the polymer by nucleophillic substitution. As a result, adherent polymer layers provide the ability to control fluid transport characteristics within micro- and nano-channels.

[00239] This surface modification method involves four main steps. First, surface activation of the preconcentrator substrate with water-vapor plasma introduces surface hydroxylation that is chemically bonded to the surface. Next, treatment of the plasma-treated substrate with a solution containing trichlorosilane or trimethoxysilane forms a functional surface layer that reacts with the hydroxyl groups. The reaction between the trichorosilane or the trimethoxysilane, or any other reactive silane forms a covalenfly bonded silicon compound at the surface of the preconcentrator. Bromoalkyltrichlorosilane may be used as the initial functional surface layer, for example.

[00240] After this functional layer is formed, surface azides are then introduced via a S_N2 nucleophilic substitution with the azides. Finally, functionalized alkynes may be added to modify the surface through to 1 , 2, 3,-triazole linkages. This method allows rapid and facile modification of a wide range of surfaces including glass, silicon, silicon oxide and nitride, alumina, and other ceramics. The key step for the substrate material is that it can be hydroxylated. Preconcentrator substrates can also be made from polymers that may include, but are not limited to, polymethyl methacrylate (PMMA), polyethylene glycol (PEG), polyamido amine (PAMAM), polyimide, polyethylene, polypropylene, polystyrene, polyoxymethylene, polyethylene terephthalate (PET), and silicone rubber. [00241] Typically, preconcentrators with high-surface area to volume ratios also have high pressure drops across the system, which require more power to move gases through it. Such systems also often have relatively long sorption and desorption times, leading to longer and less sensitive detection by a GC or other analytical instrument. The pressure drop across the micropreconcentrator of this invention, however, is very small due to the low fluid resistance enabled by its open structure. The micropost packing density increases continuously as the diameter of the posts scales down to nanometer size, but the pressure drop does not increase. [00242] These unique features allow the micropreconcentrator to have a very small volume while maintaining low power consumption and shorter analysis cycles and still providing high concentration gain and higher sensitivity of the GC. In particular, according to one embodiment, the micropreconcentrator of the invention may consume only 1 μl of sample for each analysis and B able to complete at least 4 analyses per minute using 40 cc of analyte. Further, only one (1) J is required for each analysis, thus minimizing the power consumption. [00243] This design also albws the micropreconcentrator to have low dead volume, which provides a sharper desorption peak and accordingly boosts the performance of the micropreconcentrator preconcentrator and the GC system. To minimize the volume of the micropreconcentrator and achieve low power consumption, short analysis cycles, and high gain, the dimensions of the microposts and the geometry of channel may be carefully designed. In particular, design parameters including the radius-half spacing ratio, β, and the aspect ratio, which will be defined later, may be optimized according to the principles of the invention. Using these design parameters, a dimensionless objective function (DOF) may be derived to minimize the pressure drop while maximizing the surface area-to-volume ratio for a given channel geometry of the micropost-filled preconcentrator. As a result of the optimization achieved by the invention, the number of molecules sorbed and desorbed for a given flow rate and channel geometry is maximized. Applying the optimization techniques of the invention, it was found that as the number of microposts increases for a given channel size, a higher surface area-to- volume ratio is available fora fixed pressure drop.

[00244] To begin the mathematical optimization of the surface area-to-volume ratio for a given pressure drop according to the invention, the dimensions of the microposts and geometry of the channel must be considered. Figure 17 is a schematic diagram of a unit cell in a square micropost array includes cylindrical microposts with circular cross section. As shown in Figure 17, each micropost has a radius of a, a half-spacing between adjacent posts of s, and a height of H. The aspect ratio, AR, is defined as the ratio of the height, H, of the posts to the half spacing, s, between adjacent posts, which thus may be expressed as H/s. [00245] The pressure drop can be expressed solely as a function of a dimensionless parameter, β(= a/s), which is the ratio of the radius of each post to the half-spacing between two adjacent posts, β is then used to estimate the drag per unit length of the cylinder. Two independent models from literature, the lubrication Stokes model and the Oseen approximation of the Navier-Stokes equation for fluid flow, were used by Applicants to predict the pressure drop across the micropost-filled channels with low Reynolds number flow past a square array of the circular cylinders, as shown in Figure 17. The model was extrapolated from one unit cell to arrays of unit cells.

[00246] In the first mathematical model, Keller (Joseph B. Keller, "Viscous flow through a grating or lattice of cylinders", J. Fluid Mech. 18 (1964) 94-96) assumed that most of the flow resistance came from the narrow gap between adjacent cylinders and applied the lubrication model derived from the Navier-Stokes equation to determine the flow in the gap. With a few more approximations, the normalized drag per unit length (D) on each cylinder can be then expressed as a function of /? in Equation 1 below:

where U is a uniform upstream velocity per unit cell and μ is fluid viscosity. Equation 1 is more accurate as β approaches unity. Since a large value of β means a closely spaced array of cylinders, the viscous effect of the flow on a cylinder readily interferes with its adjacent ones and dominates over the inertia effect.

[00247] As β gets smaller, however, the inertia term in the Navier-Stokes equation becomes more significant and can no longer be ignored. Thus, others skilled in the art have used Oseen's linearized equations of motion to study a 2-D steady flow past an array of cylinders at low Reynolds numbers. (See, e.g., K. Tamada and H. Fujikawa, "The steady two dimensional flow of viscous fluid at low Reynolds numbers passing through an infinite row of equal parallel circular cylinders", Quart. J. Mech. Appl. Math., 10 (1957) 425-432) and H. Hasimoto, "On the periodic fundamental solutions of the Stokes equations and their application to viscous flow pasta cubic array of spheres", J. Fluid Mech., 5 (1959) 317-328). As both the Tamada and Fujikawa method and the Hasimoto method suggest solutions that coincide relatively well, one of their approaches can be taken as an example. Applying the Tamada and Fujikawa method, the Applicants applied Oseen's equations and calculated the drag per unit length of a cylinder in the form of power series function of β, as shown below in Equation 2. D ~+ O(Re²) (2)

Where A₀ = l-2ln(πβ)+^πβ)² -^(πj3)" + J^(πβ)⁶ +O((πβ)')

[00248] This solution is true only for small β values. Figure 18A shows curves for the normalized drag per unit length as a function of the dimensionless parameter β. As the normalized drag per unit length on a cylinder is plotted with β, as shown in Figure 18A, both solutions correctly predict the limiting case of β approaching zero. Howe\er, in the other extreme case (β-> 1) only Keller's model shows the diverging trend mi) . The intersection of two curves at /?~ 0.65 is shown in Figure 18A and the valid region of each model is indicated by a solid line. [00249] Using these drag models, the calculation of the surface area-to-volume ratio (SAV) per unit cell is straightforward exceptfor whether or not the upper and lower bounded walls should be included in calculating the surface area of the unit cell. The SAV per unit cell is a function of not only the radius-half spacing ratio, β, but also the aspect ratio of the channel, i.e., Ar? (= H/s). From Figure 17, the SAV per unit cell can be written as Equation 3 below.

^ce" As¹H- Ka¹H H {4- πβ² J Note that the SAV per unit cell has a unit of inverse length and the term '2' in the bracket is the contribution from the top and bottom of the bounded walls.

[00250] An objective function for the minimal pressure drop and maximal surface area-to- volume ratio is defined by dividing the normalized drag per unit length on a cylinder, b , by the SAV per unit cell. This function is not yet dimensionless so further manipulation is required to obtain a unitless objective function. The pressure drop per unit cell, AP_ceιι, can be written according to Equation 4 below.

^- ⁼έ ^<4) [00251] Setting D equal to in f(β) in Equation 1 and Equation 2 and plugging Equation 4 into Equation 1 , the normalized pressure drop per unit cell is written as in Equation 5 below.

[00252] Finally, a dimensionless objective function (DOF) can be written as the ratio of the normalized pressure drop to the SAV in a unit cell, as shown in Equation 6 below:

DOF ^-U ^-U ₈, MIW ₍₆₎

SA I V_M 4πβAR/ (4- πβ²) + 4 ^K ' with f(β) being ό_Keto for /?> 0.65 and D_1nJoX β < 0.65.

[00253] Figure 18B shows a family of curves of the DOF vs. β for a range of aspect ratios. The DOF curves with higher aspect ratios (represented by darker thin lines) asymptotically approach frie thick solid line of the DOF with an infinite aspect ratio, where the contribution to the SAA/ per unit cell from the top and bottom of the walls becomes negligible, and Equation 6 can be reduced to Equation 7 below.

[00254] An optimal design of the microposts may be achieved if β is selected such that

DOF is at a minimum for a given desired surface area to volume ratio, which is determined by the desired gain of the preconcentrator. The smaller DOF becomes, the less pressure drop is present, or the more SAV available per unit cell. Figure 18B demonstrates that all DOF curves monotonically increase except the infinite aspect ratio case in which a minimum exits. According to these findings, arrays of posts with nanometer diameters and spacing can be an optimal structure for a micropreconcentrator with high surface area yet small flow resistance. [00255] To experimentally verify the results of the analytical optimizations, a number of millimeter channels filled with DRIE-etched microposts of various Rvalues were fabricated. Figure 19A is a schematic diagram of a microchannel filled with an N by M array of microposts. Figure 19A shows the configuration of 2-D fluid flow across the channel and an N by M array of microposts. The diameter of the microposts ranges from 200 μm to less than 10 μm, and the spacing between them from 400 μm to 40 μm. In these experiments, AR_Q = 0.1. These dimensions are chosen to allow β to vary between 0.2 and 0.95 and are recorded using the calibrated optical microscope to account for any discrepancy that may arise during the lithographic and efching processes. Figure 19B shows optical microscope images of the exemplary silicon (Si) micropost arrays constructed according to principles of the inventbn. The optical microscope images of an array of the microposts with different Rvalues are shown Figure 17B. In total, 27 devices were fabricated on a 100 mm diameter Si wafer (Silicon Quest International^®, N-type <100>, 1-10 Ω-cm) using a conventional double-sided photolithography and subsequent DRIE etching (Plasma-Therm^® SLR770). Each Si die was etched to a uniform depth (c.a. 200 μm) and bonded with a 1 mm-thick microscope slide that had been cut in the same size of a Si die. A thermally curable epoxy based adhesive was transferred to a Si die via the contact printing, and a glass top was then pressed down to the adhesive-coated Si die on 13O⁰C hotplate for a gas-tight seal.

[00256] All bonded samples were housed h the SLA packages that provide a leak-free fluidic connection to via holes in a Si die. High purity N₂ gas (S. Smith^®, 99.9%) from the high pressure source tank was filtered and fed to the flow meter (MKS^®, 2179A) which regulates flow rate of the gas via the computer software of the data acquisition system. Two commercial pressure sensors (Omega Engineering Inc.^®, PX142) that have a linear response up to 7000 Pa with a 5 V span (meaning the resolution of about 1.4 Pa/mV) were placed in the inlet and outlet of the SLA package to measure pressure at each point. First, the pressure drop (ΔP = P -

P_oul|et) in all 24 samples was measured individually at a flow rate of 10 seem. Then, the pressure drop across a dummy sample of the same channel dimensions but with no micropost structures was measured as a control and later subtracted from the previous pressure drop measurements of the channel with microp ^rost structures. Therefore, ΔP corrected = ΔP - ΔP control

The pressure drop measurements were repeated five times to provide a statistical basis on the error analysis. [00257] The Reynolds number of the flow depends on which dimension is chosen as a characteristic length for calculation. A diameter of each post, a center-distance between two adjacent posts, and the height of the channel may all be the characteristic length. With 10 seem of a fixed flow rate, the Reynolds number depending on the choice of the characteristic length ranges from 0.1 to 0.5, in which the Stokes approximation is valid. [00258] Since the number of microposts varies sample by sample along with different β values, a direct comparison of these pressure drop measurements with the analytical solutions would not be appropriate. The pressure drop per unit cell, i.e., the contribution of each micropost to the overall pressure drop, can be calculated by dividing the corrected pressure drop by the number of the microposts in the channel. From Figure 15 and 19A, the pressure drop in the cell can be written as shown below in Equation 8. A D _ corrected cell, measured ΛfM

The measured pressure drop per unit cell can be directly compared to the theoretical solutions using the following relationship, derived from Equation 5, as shown below in Equation 9.

Δ/L, =/*/ f(β)

W (9) where U= U_ceιιN. Figure 2OA and Rgure 2OB show that each theoretical model well represents the experimental results for its applicable/? range.

[00259] For β greater than 0.65, the agreement of the pressure drop data to Keller's model using the Stokes equation suggests that the viscous effect is indeed prevailing inthe pressure drop of the closely spaced posts. As β gets smaller, both viscous and inertial components of the pressure drop in the channel become important. Therefore, Tamada's solution to Oseen's equation better predicts the pressure drop behaviorfor lower/? values. It is evident from Figure 18A that Keller's model underestimates the pressure drop for β less than 0.65 because it includes the viscous component of the flow only. Due to the fabrication challenges faced when etching very small diameter post structures, samples with β< 0.2 were unavailable.

[00260] When an array of the posts is considered as shown in Figure 19A, it is more instructive to express the SAV per unit cell and DOF in terms of the number of posts in a column, N, rather than aspect ratio, AR. Equation 3 and Equation 6 can be rewritten using the geometrical identities, W= 2sN and L=2sM(see Figure 19A),

FOM = WW (11)

AπβAR^N I{A- πβ²) + 2 where AR = HAA/ , fixed by the geometry of the channel.

[00261] Note that the pressure drop per unit cell is independent of the number of posts,

Λ/, and a function of only β. The dependence of the DOF on Λ/ stems purely from SA/V. Therefore, the N dependence of the DOF disappears as N goes to infinity, and Equation 11 is reduced to Equation 7. As shown in Figure 21 A and Figure 21 B, the DOF is plotted with β for a wide range of N. The solid lines represent the calculations based on the Keller and Tamada models, and data points for two different N values exhibit basic agreement of the calculated DOF. [00262] In sum, based on the Keller and Tamada models, the mathematical findings indicate that the DOF decreases with increasing Λ/. Therefore, for fixed /? value and channel geometry, microposts should be packed densely for minimal pressure drop and maximal surface-area-to-volume-ratio. In order to increase N with a fixed /?, the size of the post has to be smaller and smaller.

[00263] In another embodiment of the invention, microposts may be disposed inside the collection chamber of a MEMS valve system, such as the five microvalve system used as a micropreconcentrator, as described earlier. For example, the microposts may be disposed on the inner walls of the collection chamber so that the sample gas can pass through it. The microposts may line the microchannel in which the sample gas passes through from valve 1 to valve 3, while loading the preconcentrator. [00264] More particularly, Figure 22A is a cross-sectional schematic view of a micropreconcentrator 300 constructed according to principles of the invention housing a MEEMS valve system incorporating microposts. In this embodiment, the micropreconcentrator is located between two microvalves that open and close to admit sample gas and carrier gases that are routed from a trap and purge system shown in Figure 14. As shown in Figure 22A, the carrier gas 312 enters the system through the carrier gas inlet 314. Sample gas enters the system through the sampling gas inlet 316 and is directed to collection chamber 310, which contains microposts constructed according to the principles of the invention as shown in Figure 22B described below. The membrane electrode 318 is electrostatically actuated to allow flow through a first valve 320 and a second valve 322. For desorption, a microheater 324, such as a nickel-chromium (NiCr) microheater is positioned near the collection chamber 310, which contains microposts constructed according to the principles of the invention as shown in Figure 22B. Desorbed analyte flows to the column of an analytical instrument through the outlet 326. [00265] Figure 22B is an SEM photograph that provides an expanded view of the microposts 328 present in the collection chamber 310. The design of the microposts and the micropost array may be optmized according to the principles discussed above to produce a high surface area to volume ratio and a low pressure drop across the micropost array. The microposts may be coated with a suitable sorbentfor collection of analyte using any method known in the art, including those discussed above. With this configuration, use of a high surface area sorbent, such as a MOF, is not necessary since the microposts provides an inherently high surface area for the analyte to be collected in the collection chamber. However, the chamber may also be designed to have a lower density of microposts to permit MOF's to be inserted into the preconcentrator.

[00266] In addition to the advantageous design and optimizatbn of microposts in the micropreconcentrator discussed above, preconcentrators of the invention may also utilize catalytic heater technology for desorbing the analyte to substantially reduce the electricity needed in the device, such as a nickel-chromium microheater known in the art. Hydrides may also be used for heating the micropreconcentrator during desorption since hydrides can be stored at the equivalent of 1000 w-hr/L and the hydrogen can act as a carrier and then be reused to provide heat. Other techniques known in the art for desorption may also be employed. [00267] Other embodiments of micropreconcentrators that may incorporate the use of

MOFs and/or MEMS valves and micropost arrays according to the principles of the invention include a dosimeter, which is any device used to measure an individual's exposire to a hazardous environment and is often portable. Examples include the dosimeters described in U.S. Patent Nos. 4,235,097, 4,040,085, 3,985,017, 6,607,700, 5,482,677, 5,110,551 and U.S. Patent Application No. 2005/0101027. In addition, the preconcentrators may be in disc or pellet form as described in U.S. Patents Nos. 3,925,022, 4,301,114, 5,014,541 , and 6,978,657, for example. Additional examples of preconcentrators that may use the principles of the invention are given in U.S. Patent Nos. 3,168,823, 3,345,858, 3,357,232, 3,568,411, 3,585,863, 3,769,837, 3,797,318, 3,807,217, 3,897,679, 3,923,461 , 3,950,980, 4,084,440, 4,128,008, 4,180,389, 4,293,316, 4,399,688, 4,451 ,816, 4,541 ,268, 4,599,095, 4,698,071, 4,701,306, 4,759,210, 4,805,441 , 4,819,477, 4,915,051, 4,915,843, 4,977,095, 5,083,019, 5,092,155, 5,092,218, 5,123,276, 5,142,143, 5,162,652, 5,173,264, 5,224,972, 5,288,310, 5,294,418, 5,328,851 , 5,395,589, 5,465,607, 5,551 ,278, 5,585,575, 5,753,832, 5,763,360, 5,795,368, 5,854,431 , 5,970,804, 6,085,601 , 6,165,254, 6,223,584, 6,345,545, 6,455,003, 6,523,393, 6,604,406, 6,610,125, 6,656,738, 6,814,781, 6,910,394, 6,984,524, RE38,797, 6,749,826, 5,465,607, 5,092,217, 6,848,325.

[00268] Yet, further embodiments of the micropreconcentration systems of the invention may be designed to detect substances using an integrated cartridge that is attached to a handheld vacuum-like device, such as for non-contact gas sampling of explosives. The handheld vacuum may draw sample particles and other molecules off of a person or object and trap them on a filter that contains special sorbents, such as MOFs. These sorbents catch and grab the sample particles and molecules out of the air. The filter may then be manually transferred to a commercial off-the-shelf ion mobility spectrometer (COTS IMS) based detector for analysis. Examples of possible substances that may be detected by a COTS IMS may include, but are not limited to dimethyl dinitrobutane (DMNB), triperoxides, TATP and HMTD. [00269] Although the various micropreconcentrator embodiments have been described for use in a gas chromatograph, micropreconcentrators of the invention may also be used in a number of different detection devices, including, but not limited to a surface acoustic wave (SAW), an evanescent wave detector, a piezoelectric detector, an ion mobility spectrometer, and a chemiresistor detector. Examples of these devices are given in U.S. Patent Nos. 3,168,823, 3,345,858, 3,357,232, 3,568,411, 3,585,863, 3,769,837, 3,797,318, 3,807,217, 3,897,679, 3,923,461 , 3,950,980, 4,084,440, 4,128,008, 4,180,389, 4,293,316, 4,399,688, 4,451 ,816, 4,541 ,268, 4,599,095, 4,698,071 , 4,701 ,306, 4,759,210, 4,805,441 , 4,819,477, 4,915,051 , 4,915,843, 4,977,095, 5,083,019, 5,092,155, 5,092,218, 5,123,276, 5,142,143, 5,162,652, 5,173,264, 5,224,972, 5,288,310, 5,294,418, 5,328,851, 5,395,589, 5,465,607, 5,551 ,278, 5,585,575, 5,753,832, 5,763,360, 5,795,368, 5,854,431 , 5,970,804, 6,085,601 , 6,165,254, 6,223,584, 6,345,545, 6,455,003, 6,523,393, 6,604,406, 6,610,125, 6,656,738, 6,814,781 , 6,910,394, 3,925,022, 4,301 ,114, 5,014,541 , 6,978,657, RE38.797. 6,967,193, 6,840,120, and 6,773,674. [00270] The micropreconcentrators of the invention may be used with detection devices for a variety of applications, including, but not limited to air quality, water quality, pollution monitoring, process monitoring, breath analysis, personal health monitoring and protection, food monitoring, and security. These security applications include passenger screening in schools, airports, subways, train stations, buses, shipping containers/truck screening, building security, first responder sensors, sensors for water and food safety, and the military. [00271] While the invention has been described in terms of exemplary embodiments, those skilled in the art will recognize that the invention can be practiced with modifications in the spirit and scope of the appended darns. These examples given above are merely illustrative and are not meant to be an exhaustive list of all possible designs, embodiments, applications or modifications of the invention.

Claims

WHAT IS CLAIMED:

1. A method of using metal oxide frameworks (MOFs) as a sorbent of an analyte in a collection system.

2. The method of claim 1 , wherein the collection system comprises one of a preconcentrator, micropreconcentrator, personal respirator and dosimeter.

3. The method of claim 2, wherein one of the preconcenirator or micropreconcentrator is a purge and trap system, microelectromechanical (MEMS) valve system, array of microstructures, dosimeter, disc, pellet, or swab.

4. The method of claim 3 wherein the preconcentrator or micropreconcentrator comprises a MEMS valve system with at least 3 valves.

5. The method of claim 4, wherein the said MEMS valve system has 4 or 5 valves.

6. The method of claim 1 , wherein the MOFs have a thermal stability of up to about 300⁰C to about 400⁰C.

7. The method of claim 1 , wherein the MOFs sorb substantially all of the analyte.

8. The method of claim 1 , wherein after sorbing the analyte, the MOFs release the analyte.

9. The method of claim 8, wherein the MOFs release the analyte by thermal desorption.

10. The method of claim 1 , wherein the MOFs comprise particles or a film.

11. The method of claim 10, wherein the MOF particles have a diameter of between about 20 nanometers to about 500 microns.

12. The method of claim 11 , wherein the MOF particles have a diameter of between about 100 nanometers to about 50 microns.

13. The method of claim 1 , wherein the MOFs comprise one or more selected from the group consisting of Zn-MOFI , Zn-MOF2, Zn-MOF3, Zn-MOF4, Zn-MOF5, Cu-MOFI , Cu- MOF2, Tb-MOFI , Tb-MOF2, Cd-MOFI , Cd-MOF2, Cd-MOF3, Co-MOFI , Co-MOF2, Zn- MOF6, MOF-5, Cu(4,4'-bpy)₁.₅NO₃(H₂O)₁.₂₅ IRMOF2, [Cu₃(TMA)₂]_n, [Cu(OHHC₅H₄NCO₂],

MOF-38 , Ag(4,4'-bpy)NO₃, IRMOF3 and IRMOF7.

14. The method of claim 1 , further comprising the step of synthesizing the MOFs to be selective to a predetermined analyte or group of analytes.

15. The method of claim 14, wherein said synthesizing step comprises at least one of adjusting the pore size of the MOFs and adding a functional group to the MOFs.

16. The method of claim 1 , wherein the MOFs sorb analytes selected from the group consisting of explosives and chemical warfare agents.

17. The method of claim 1 , wherein the MOFs sorb analytes selected from the group consisting of XV, sarin, DMMP, PMP, diethyl methylphosphonate (DEMP), diisopropyl methylphophonate (DIMP), dichlorohexane, malathion, acetic anhydride, TNT, and RDX.

18. A method of concentrating an analyte in a sample comprising using a sorbent to collect the analyte, wherein the sorbent has high sorption capacity, selective sorptivity, thermal stability at temperatures up to about 300⁰C to about 40O⁰C, a particle size range from about 20 nm to about 150 microns, and does not substantially decompose the analyte during

5 sorption.

19. The method of claim 18, wherein the sorbent comprises a metal organic framework (MOF) molecule.

20. The method of claim 19, wherein the MOF is at least one MOF selected from the group consisting of Zn-MOFI , Zn-MOF2, Zn-MOF3, Zn-MOF4, Zn-MOF5, Cu-MOFI, Cu-MOF2, 0 Tb-MOFI , Tb-MOF2, Cd-MOFI , Cd-MOF2, Cd-MOF3, Co-MOFI , Co-MOF2, Zn-MOF6,

MOF-5, Cu(4,4'-bpy)₁.5Nθ3(H₂O)₁.25 IRMOF2, [Cu₃(TMA)₂Jn₁ [Cu(OH)-(C₅H₄NCO₂], MOF-38 , Ag(4,4'-bpy)NO₃, IRMOF3, and IRMOF7.

21. A micropreconcentrator comprising a sorbent that is highly selective to an analyte or group of analytes. 5

22. The micropreconcentrator of claim 21 , wherein said sorbent has a thermal stability of up to about 300⁰C to about 400⁰C.

23. The micropreconcentrator of claim 21 , wherein said sorbent comprises particles having a diameter of between about 20 nanometers to about 500 microns.

24. The micropreconcentrator of claim 23, wherein said sorbent comprises particles having 0 a diameter of between about 100 nanometers to about 150 microns.

25. The micropreconcentrator of claim 21 , wherein said sorbent comprises a MOF.

26. The micropreconcentrator of claim 21 , wherein said sorbent comprises an array of microstructures.

27. The micropreconcentrator of claim 26, wherein said microstructures comprise 5 microposts.

28. The micropreconcentrator of claim 26, wherein said sorbent is adhered to the microstructures.

29. A system for collecting an analyte from a sample, said system comprising: an inlet to receive the sample; o a collection chamber containing at least one of i) a sorbent highly selective to the analyte and ii) an array of microstructures having a radius of a, and a half-spacing between microstructures of s, and wherein a dimensionless parameter, β, is defined as a/s such that flow through the collection chamber for β> 0.65 substantially obeys the lubrication Stokes approximation of Navier-Stokes equation, and for/?< 0.65 substantially obeys Oseen's 5 approximation of Navier-Stokes equation; and an outlet to conduct the analyte out of said system.

30. The system of claim 29, wherein said sorbent has high sorption capacity, thermal stability at temperatures up to about 300⁰C to about 400⁰C, a particle size range from about 20 nm to about 500 microns, and does not substantially decompose the analyte.

31. The system of claim 29, wherein said sorbent comprises one or more metal oxide frameworks (MOFs).

32. The system of claim 29, further comprising at least one valve controlling the flow to or from said collection chamber.

33. The system of claim 32, wherein said system is a micropreconcentrator and said valve is a microelectromechanical (MEMS) valve.

34. The system of claim 33, wherein said system comprises a purge and trap system and said collection chamber comprises a groove in a rotary injection valve.

35. The system of claim 29, wherein said inlet is coupled to a carrier gas containing the sample, and the analyte is sorbed onto the sorbent in said collection chamber.

36. The system of claim 35, further comprising a release mechanism to desorb the analyte from the sorbent.

37. The system of claim 36, wherein said release mechanism comprises a heater to heat the sorbent.

38. The system of claim 36, wherein the desorbed analyte is conducted through said outlet.

39. The system of claim 38, wherein said outlet is coupled with a detector.

40. The system of claim 39, wherein said detector is coupled with an analytical device.

41. The system of claim 40, wherein said analytical device is one of a gas chromatograph, surface acoustic wave, evanescent wave detector, a piezoelectric detector, an ion mobility spectrometer, and a chemiresistor detector.

42. The system of claim 29, wherein said collection chamber is coupled with a MEMS valve system having a plurality of electrodes and at least one membrane electrode operable to open and close the MEMS valves in a coordinated manner.

43. The system of claim 42, wherein said membrane electrode is electrostatically actuated.

44. The system of claim 42 wherein said MEMS valve system comprises at least three valves.

45. The system of claim 43, wherein said microstructures are disposed within said collection chamber.

46. The system of claim 29, wherein said microstructures are coated with a sorbent selective to the analyte.

47. The system of claim 46, wherein said sorbent comprises one of a low surface area compound and a high surface area compound.

48. The system of claim 47, wherein said low surface area compounds comprise polymers and said high surface area compounds comprise MOFs.

49. The system of claim 29, wherein said microstructures comprise generally cylindrical members.

50. The system of claim 29, wherein said microstructures are arranged in a square array.

51. A method of collecting an analyte from a sample for analysis comprising: concentrating the analyte by sorbing it on a sorbent highly selective to the analyte; desorbing the analyte from the sorbent; and conducting the desorbed analyte to a device for analysis.

52. The method of claim 51 , wherein said concentrating step comprising using a sorbent having high selectivity to polar molecules, thermal stability at temperatures up to about 300⁰C to about 400⁰C, a particle size range from about 20 nm to about 500 microns, and which does not substantially decompose the analyte during sorption.

53. The method of claim 52, wherein the sorbent comprises a metal organic framework (MOF) molecule.

54. The method of claim 53, wherein the MOF is at least one MOF selected from the group consisting of Zn-MOFI , Zn-MOF2, Zn-MOF3, Zn-MOF4, Zn-MOF5, Cu-MOFI , Cu-MOF2, Tb-MOFI , Tb-MOF2, Cd-MOFI , Cd-MOF2, Cd-MOF3, Co-MOFI , Co-MOF2, Zn-MOF6, MOF-5, Cu(4,4'-bpy)₁.5Nθ3(H₂O)₁.25 IRMOF2, [Cu₃(TMA)₂],,, [Cu(OH)-(C₅H₄NCO₂], MOF-38 , Ag(4,4'-bpy)NO₃, IRMOF3, and IRMOF7.

55. The method of claim 53, further comprising the step of at least one of adjusting the pore size of the MOF and adding a functional group to the MOF.

56. The method of claim 51 , wherein the sorbent fully sorbs the analyte during said collecting step.

57. The method of claim 51 , wherein after said desorbing step, the analyte is fully released from the sorbent.

58. The method of claim 51 , wherein said desorbing step comprises thermal desorption.

59. The method of claim 57, wherein the MOF comprises particles or a film.

60. The method of claim 51 , wherein the analytes are selected from the group consisting of XV, sarin, DMMP, PMP, diethyl methylphosphonate(DEMP), diisopropyl methylphophonate

(DIMP), dichlorohexane, malathion, acetic anhydride, TNT, and RDX.

61. The method of claim 51 , further comprising the step of synthesizing the sorbent to be selective to a predetermined group of analytes.

62. The method of claim 51 , wherein said conducting step comprises conducting the analyte to one of a gas chromatograph, surface acoustic wave, evanescent wave, a piezoelectric detector, an ion mobility spectrometer, and a chemiresistor detector.

63. A process for making a selectively sorbent MOF, Zn-MOFI , having a cubic crystalline structure with crystals in the range of 2 to 4 microns, comprising

(a) dissolving 0.239 g of 4,4', 4",4"'-(21 H₁ 23H-Porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid) (H2TPP) and 0.18 g of Zn(NO₃)₂6H₂O in 60 ml. DEF; (b) stirring the dissolved solution; (c) sealing the dissolved solution in a closed vessel; and (d) heating said vessel to

100°C at 2°C/minute.

64. The product made by the process of claim 63.

65. A process for making a selectively sorbent MOF, Zn-MOFI , having a cubic crystalline structure with crystal sizes in the range from about 10 microns to about 30 microns, comprising (a) dissolving Zn(NO₃)₂*6H₂O (0.18 g, 0.605 mmol ) and 4,4',4",4'"-(21 H,23H- porphine-5-10-15-20-tetrayl)tetrakis(benzoic acid) (0.199 g, 0.252 mmol) in 10 mL diethylformamide; (b) sealing the dissolved solution, and (c) heating in a microwave oven.

66. The product made by the process of claim 65.

67. A process for making a selectively sorbent MOF, Zn-MOF2, having a cubic crystalline structure with crystal sizes in the range from 2 to 4 microns, comprising (a) mixing

Zn(NO₃)₂*6H₂O (0.1 g, 0.336 mmol) and 2-anilino-5-bromoterephthalic acid, (2-anilino-5- BrBDCH2) (0.0847 g, 0.252 mmol; (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing tie dissolved mixture; and (d) heating in a microwave oven.

68. The product made by the process of claim 67.

69. A process for making a selectively sorbent MOF, Zn-MOF3, having a cubic crystalline structure with crystals ranging from 4 to 7 microns, comprising (a) mixing Zn(NO₃)₂*6H₂O (0.15 g, 0.504 mmol) with 2-trifluoromethoxy terephthalic acid, (2-trifluoromethoxy-BDCH2) (0.0946 g, 0.378 mmol); (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

70. The product made by the process of claim 69.

71. A process for making a selectively sorbent MOF, Zn-MOF4, having crystals of irregular shape, comprising (a) mixing Zn(NO₃)₂*6H₂O (0.1 g, 0.336 mmol) with nitroterephthalic acid (0.0532 g, 0.252 mmol); (b) dissolving the mixture in 10 mL diethylformamide, sealing the dissolved mixture; and (c) heating said dissolved mixture in a microwave oven.

72. The product made by the process of claim 71.

73. A process for making a selectively sorbent MOF, Zn-MOF5, comprising (a) mixing Zn(NO₃)₂*6H₂O (0.15 g, 0.504 mmol) with cis-cyclobutane-1 ,2-dicarboxylic acid (0.0545 g, 0.378 mmol); (b) dissolving the mixture in 1O mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

74. The product made by the process of claim 73.

75. A process for making a selectively sorbent MOF, Cu-MOFI , comprising (a) mixing Cu(NO₃)₂*2.5H₂O (0.15 g, 0.645 mmol) with 2,5-thiophenedicarboxylic acid (0.0833 g, 0.484 mmol); (b) dissolving the mixture in 10 mL diethylformamide (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

76. The product made by the process of claim 75.

77. A process for making a selectively sorbent MOF, Cu-MOF2, comprising (a) mixing Cu(NO₃)₂*2.5H₂O (0.1 g, 0.430 mmol) with 2-(trifluoromethoxy) terephthalic acid (2- trifIuoromethoxy-BDCH₂) (0.0807 g, 0.322 mmol; (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

78. The product made by the process of claim 77.

79. A process for making a selectively sorbent MOF, Tb-MOFI , having a rod-shaped crystalline structure, comprising (a) mixing Tb(NO₃)₃*5H₂O, (0.1 g, 0.230 mmol), with terephthalic acid (BDC) (0.0286 g, 0.172 mmol); (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

80. The product made by the process of claim 79.

81. A process for making a selectively sorbent MOF, Tb-MOF2 , comprising (a) mixing Tb(NO₃)₃*5H₂O, (0.1 g, 0.230 mmol), with 2,5-thiophenedicarboxylic acid (0.0297 g, 0.172 mmol); (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

82. The product made by the process of claim 81.

83. A process for making a selectively sorbent MOF, Cd-MOFI , comprising (a) mixing Cd(NO₃)₂*4H₂O, (0.1 g, 0.324 mmol), with cis-cyclobutane-1 ,2-dicarboxylic acid (0.035O g, 0.243 mmol); (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

84. The product made by the process of claim 83.

85. A process for making a selectively sorbent MOF, Cd-MOF2, comprising (a) mixing Cd(NO₃)₂*4H₂O (0.1 g, 0.324 mmol) with nitroterephthalic acid (0.0456 g, 0.216 mmol); (b) dissolving the mixture in 15 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

86. The product made by the process of claim 85.

87. A process for making a selectively sorbent MOF, Cd-MOF3, comprising (a) mixing Cd(NO₃)₂*4H₂O (0.1 g, 0.324 mmol) with terephthalic acid (0.0404 g, 0.243 mmol); (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

88. The product made by the process of claim 87.

89. A process for making a selectively sorbent MOF, Co-MOFI , comprising (a) mixing Co(NO₃)₂*6H₂O, (0.1 g, 0.343 mmo!),with terephthalic acid (00428 g, 0.258 mmol; (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the dissolved mixture; and (d) heating said dissolved mixture in a microwave oven.

90. The product made by the process of claim 89.

91. A process for making a selectively sorbent MOF, Co-MOF2, comprising (a) mixing Co(NO₃)₂*6H₂O, (0.1 g, 0.343 mmol) with 1 ,3,5-benzenetricarboxylic acid (0.0542 g, 0.258 mmol); (b) dissolving the mixture in 10 mL diethylformamide; (c) sealing the mixture; and (d) heating in a microwave oven.

92. The product made by the process of claim 91.

93. A process for making a selectively sorbent MOF, Zn-MOF6, comprising (a) mixing Zn(NO₃)₂*6H₂O (0.05 g, 0.168 mmol) with 3,3-bis(trifluoromethyl)-1-oxo-5- isobenzofurancarboxylic acid (0.0396 g, 0.126 mmol); (b) dissolving the mixture in 7 mL diethylformamide/ 3 mL H₂O; (c) sealing the dissolved mixture; and (d) heating the dissolved mixture in a microwave oven.

94. The product made by the process of claim 93.

95. A system for collecting an analyte from a sample, said system comprising:

(a) an inlet to receive the sample; (b) a collection chamber containing a sorbent; and (c) a series of at least three valves to control flow of the sample through the system.

96. The system of claim 95 wherein said series of valves are microelectromechanical system (MEMS) valves.

97. The system of claim 95 wherein said series of at least three valves comprises four or five valves.