CN105948086B - Citric acid pillared hydrotalcite supramolecular materials and its intercalation assemble method - Google Patents
Citric acid pillared hydrotalcite supramolecular materials and its intercalation assemble method Download PDFInfo
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Abstract
The invention discloses a kind of citric acid pillared hydrotalcite supramolecular materials and its intercalation assemble method, belong to supramolecular materials technical field, with CO3 2‑Magnalium hydrotalcite is precursor, and citric acid pillared hydrotalcite is successfully prepared for the back-mixing precipitation method.Pass through X-ray powder diffraction (XRD), infrared spectrum analysis (IR), three kinds of methods of differential thermal analysis (DTA) are characterized and determined to crystal structure, chemical constitution and the heat endurance of prepared citric acid pillared hydrotalcite；Interfloor distance expands, i.e., intercalation assembles successfully citric acid, and with individual layer, perpendicular acting in interlayer；The drug release rate of citric acid pillared hydrotalcite determines under the conditions of pH3.6 acetate buffer, as a result the reduction of citric acid pillared hydrotalcite rate of release is shown, with slow releasing function, illustrate that citric acid-inorganic mixture material can act as effective drug delivery system.
Description
Technical field
The invention belongs to supramolecular materials technical field, is related to a kind of citric acid pillared hydrotalcite supramolecular materials and its inserts
Layer assemble method.
Background technology
Hydrotalcite (Layered Double Hydroxides, abbreviation LDHs) formula is [M2+ 1-xM3+ x(OH)2](An-)x/
n·mH2O, wherein M2+(M3+), An-, x, m are respectively divalence or trivalent metal cation, interlayer anion, M3+/(M2++M3+) rub
Your when crystallization water quantity.The structure of such material is by positively charged class shepardite layer and the exchangeable anions and moisture of interlayer
Son is formed.Strong covalent bond effect in LDHs laminates be present, interlayer then has a kind of weak interaction force, i.e. interlayer object anion
It is connected between main layer board with weak chemical bonds such as electrostatic attraction, hydrogen bond or Van der Waals forces, and main, object is all in an orderly way
Arrangement form supramolecular structure (compound) compound.Interlayer, which introduces new object anion, can make layer structure and composition produce phase
The change answered, many organic intercalation hydrotalcite materials with specific function or structure novelty are prepared, extensively should
Used in the field such as catalysis, absorption, medicine, photoelectricity, environmental protection and agricultural chemicals.
In controlled drug delivery system, except medicine in itself in addition to, pharmaceutical carrier plays key player.Current medicine carries
Body is mostly that research of the developed country such as high polymer material, America and Europe to slow/controlled release material is very active, especially with regard to can biology drop
The research of solution property polymeric material turns into current research emphasis and development trend.It is but this with specific function polymer
Preparation difficulty is larger, and cost is higher.Therefore, at present to the pharmaceutical dosage form transformation also progress of not making a breakthrough property.In recent years, including
Inorganic material including mesoporous material, stratified material replaces polymeric material to be used for the carrier of medicine slow/controlled release system increasingly
It is valued by people.
Supermolecular intercalation structure slow/controlled release drug system integrates the advantage of LDHs carriers and polymer support, can be more
To be accurately controlled release of the oral slow/controlled release medicine in gastrointestinal region.
The limitation that medicine uses, it is small etc. to be not only present in poorly efficient and therapeutic domain, be more present in can not gram
In terms of the toxic side effect of clothes.Control delivery for reduce drug dose, the control medicine zone of action, improve medicine action potency,
Reduce toxic side effect etc., undoubtedly a kind of very effective approach.Supermolecular intercalation structure slow/controlled release drug system is ground
The development of slow/controlled release preparation can be promoted in terms of practical application by studying carefully, and the exploitation of development and use of approved drugs for nonapproved uses for new drug provides more
For wide application prospect；It can further promote the development of supermolecular intercalation chemistry even supramolecular chemistry in theoretical side.
Citric acid obtains a wide range of applications in field of medicaments.JairoTnirto is introduced citrate with coprecipitation
LDHs interlayers prepare intercalation configuration LDHs as sustained release sex medicine, show good application effect.But coprecipitation is not only
Experiment condition is harsh, and course of reaction needs N2Protection, and precipitation process citrate can form complex compound with Mg and Al so that
Intercalation assembling becomes very difficult, and obtained intercalation product crystallinity is low, and crystal structure is imperfect, is not easy to obtain complete intercalation
Product.
The content of the invention
To achieve the above object, the present invention provides a kind of citric acid pillared hydrotalcite supramolecular materials, energy control release, tool
There is slow releasing function；Solve in the prior art that citric acid effect is low, therapeutic domain is small, the zone of action is uncontrollable, can not overcome
The problem of toxic side effect.
It is another object of the invention to provide a kind of intercalation assemble method of citric acid pillared hydrotalcite.
The technical solution adopted in the present invention is a kind of citric acid pillared hydrotalcite supramolecular materials, and chemical molecular formula is：
Mg6Al2(OH)15C6H5O7。
A kind of intercalation assemble method of citric acid pillared hydrotalcite supramolecular materials, is specifically followed the steps below：
Step 1：Magnalium LDHs is prepared using nucleation/crystallization isolation method：Weigh 6.4g NaOH and 1.1g anhydrous Nas2CO3Add
Enter proportionaling alkali-forming solution A in 60ml deionized waters to be put into 500ml beakers；The another MgSO for taking 14.8g4·7H2O、13.3gAl2
(SO4)3·18H2O is added in 80ml deionized waters and is made into salting liquid B；B solution is added in solution A under fierce magnetic agitation,
Then it is heat-treated 20h in 62-66 DEG C of water；PH value is washed to less than 8,70 DEG C of oven drying 18h are put into after centrifugation, are obtained
Magnalium LDHs；
Step 2：4.5g magnaliums LDHs made from step 1 method is added in the beaker for filling 100mL deionized waters, room
The lower magnetic agitation of temperature, excessive citric acid 7.5g is added until turbid solution is changed into settled solution in beaker, it is standby；
Step 3：CO is eliminated with 100mL2Deionized water dissolving 2gNaOH, be subsequently poured into there-necked flask, magnetic agitation
While, the settled solution that step 2 obtains is added dropwise, pH is kept during dropwise addition>9, pH is adjusted with NaOH, until in settled solution
Precipitation is engendered, after completion of dropwise addition, oil bath heating backflow 6h, is fully washed to pH with 40-50 DEG C of hot water<8, centrifuge
The obtained pillared LDHs of citric acid produces in 75 DEG C of dry 14h.
The invention has the advantages that the present invention has advantages below：
(1) present invention is with CO3 2Magnalium hydrotalcite is precursor, and the intercalation assembling chemical reaction carried out with the back-mixing precipitation method can
Obtain the pillared LDHs of supramolecular structure citric acid.
(2) the pillared LDHs interlamellar spacings of citric acid are 1.25nm, and citrate is that with two there is symmetrical carboxyl to be mutually one
Determine a slab effect of angle and hydrotalcite, and another carboxyl relies on ionic bond perpendicular to another laminate of hydrotalcite
Function.
(3) citrate ion enters hydrotalcite layers, and intercalation assembling improves the heat endurance of citric acid, decomposes temperature
Degree is 439 DEG C.
(4) the pillared LDHs supramolecular structures medicine sustained release agent of citric acid is prepared by the back-mixing precipitation method, can controls and release
Put, there is slow releasing function.
The course of reaction of the intercalation assemble method of citric acid pillared hydrotalcite of the present invention does not need N2Protection, citric acid are pillared
The intercalation assemble method of hydrotalcite is simple, and obtained citric acid pillared hydrotalcite passes through X-ray powder diffraction (XRD), infrared light
Spectrum analysis (IR), three kinds of methods of differential thermal analysis (DTA) are characterized and surveyed to its crystal structure, chemical constitution and heat endurance
It is fixed；Citric acid is in interfloor height ordered arrangement, crystal formation is complete, without dephasign, can obtain the product of complete intercalation；Interfloor distance
Expanding, i.e., intercalation assembles successfully citric acid, and with individual layer, perpendicular acting in interlayer；Citric acid pillared hydrotalcite
Drug release rate determines under the conditions of pH3.6 acetate buffer, the results showed that citric acid pillared hydrotalcite rate of release drops
It is low, there is slow releasing function, illustrate that citric acid-inorganic mixture material can act as effective drug delivery system.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is magnalium LDHs XRD spectra.
Fig. 2 is the pillared LDHs of citric acid XRD spectra.
Fig. 3 is magnalium LDHs IR spectrograms.
Fig. 4 is the pillared LDHs of citric acid IR spectrograms.
Fig. 5 is the pillared LDHs of citric acid DTA curve.
Fig. 6 is magnalium LDHs DTA curve.
Fig. 7 is the supramolecular structure model schematic of citric acid pillared hydrotalcite prepared by the back-mixing precipitation method.
Fig. 8 is that the pillared LDHs of citric acid, citric acid+LDHs physical mixture, citric acid are molten in pH3.6 acetate salt buffers
Releasing curve diagram in liquid.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
Material and instrument：
MgSO4·7H2O (Shantou, Guangdong city Xi Long chemical plant), Al2(SO4)3·18H2O (Tianjin Ke Miou chemical reagent
Development centre), NaOH (Tianjin Ke Miou chemical reagent development centre), anhydrous Na2CO3, (Tianjin section is close europeanized for citric acid
Learn reagent development centre), copper sulphate (Yantai three and chemical reagent Co., Ltd), acetic acid (Shanghai Nuo Tai Chemical Co., Ltd.s),
Sodium acetate (Langfang Asia-Pacific Long Xing Chemical Co., Ltd.s).
Infrared spectrum is determined with AVATAR360 (Nicolet companies of the U.S.) type FTIS, KBr pressures
Piece.
Differential thermal (DTA) analysis of sample is combined in Chemistry and Chemical Engineering College of Central South University and Hunan Bo Di Electric Applicance Co., Ltd grinds
Carried out on the differential thermal analysis system of system, heating rate is 10 DEG C/min, is operated in air atmosphere.
Thermogravimetric (TG) analysis of sample is carried out on WRT-3P types micro thermal balance (Shanghai balance factory).
X-ray powder diffraction determines on the x ray diffractometer xs of D-MAX 2500 (Rigaku company), CuK α 1.
UV scanning and absorbance determine on UV-3802 types ultraviolet-uisible spectrophotometer (Shanghai analytical instrument factory).
Drug dissolution determines on RCZ-6B drug dissolutions instrument (Shanghai Huanghai Sea medicine inspection Instrument Ltd.).
Drug dissolution determines on RCZ-6B drug dissolution instrument.
Magnalium LDHs (Mg-Al-CO3- LDHs) preparation：
Magnalium LDHs precursors are prepared using nucleation/crystallization isolation method：Weigh 6.4g NaOH and 1.1g anhydrous Nas2CO3Add
Proportionaling alkali-forming solution A is put into 500ml cups in 60ml deionized waters；The another MgSO for taking 14.8g4·7H2O、13.3gAl2(SO4)3·
18H2O adds 80ml deionized waters and is made into salting liquid B；B solution is added in solution A under fierce magnetic agitation, then in 62-
20h is heat-treated in 66 DEG C of water；PH value is washed to less than 8,70 DEG C of oven drying 18h are put into after centrifugation, obtain magnalium LDHs.
The back-mixing precipitation method prepare the pillared LDHs of citric acid (hydrotalcite)：
4.5g magnalium LDHs is added in the beaker for filling 100mL deionized waters, magnetic agitation, was added at room temperature
Amount citric acid 7.5g until beaker in turbid solution be changed into settled solution, it is standby；CO is eliminated with 100mL2Deionized water dissolving
2gNaOH, it is subsequently poured into there-necked flask, while magnetic agitation, the settled solution that step 2 obtains is added dropwise, is kept during dropwise addition
pH>9, pH is adjusted with NaOH, until engendering precipitation in settled solution；After completion of dropwise addition, oil bath heating backflow 6h, 40- is used
50 DEG C of hot water is fully washed to pH<8, the pillared LDHs of citric acid being centrifugally separating to obtain produce in 75 DEG C of dry 14h.
Vitro release determines：
(1) wavelength selects：
Precision weigh dry to constant weight Acidum Citricum sodium and appropriate copper sulphate, respectively using pH3.6 acetate buffer as
Medium, the copper-bath for being configured to 1826 μ g/ml Acidum Citricums sodium solutions and 1323 μ g/ml are standby.Precision measures Acidum Citricum sodium
Solution 3ml is put in l00ml volumetric flasks, is added copper-bath 5ml, is added pH3.6 acetate buffer to be shaken up to scale, put
Put 5min.Copper-bath 5ml separately is taken in l00ml volumetric flasks, adds pH3.6 acetate buffer to shake up, place to scale
5min, as blank, scanned in 200-350nm wave-length coverages, measure a length of 240 ± 0.5nm of maximum absorption wave.
(2) standard curve：
Precision measures sodium citrate solution 2ml, 2.5ml, 3ml, 3.5ml, 4ml, 4.5ml and put respectively in 100ml volumetric flasks,
Add copper-bath 5ml；PH3.6 acetate buffers are added to be surveyed to the scale of volumetric flask according to maximum absorption wavelength determination method
Determine trap.5ml copper-baths are taken, add pH3.6 acetate buffers into 100ml volumetric flasks, as blank.It is in wavelength
Trap is determined at 240 ± 0.5nm, with A2With C (ug/m1) return regression equation is：
A2=-0.11977+0.00792C, r=0.9999, (n=6) wherein, A is absorbance, and C is solution concentration；
As a result show, sodium citrate concentration A in the range of 40~80 μ g/ml2It is good with C linear relationships.
(3) drug release determination：
By version in 2005《Chinese Pharmacopoeia (two)》The methods of annex XC first, using pH3.6 acetate buffers 900mL as dissolution
Medium, 37 ± 0.5 DEG C of temperature, rotating speed 50r/min, samples take solution 8ml respectively at regular intervals, with 0.8 μm of miillpore filter
Filtration, and distilled water 8ml is supplemented in process container in time.Primary filtrate is discarded, precision measures subsequent filtrate 2ml, puts 50ml capacity
In bottle, after adding copper-bath 3ml, add pH3.6 acetate buffer constant volume, stand 5min.According to UV-vis spectroscopy light
Degree method, see version in 2005《Chinese Pharmacopoeia (two)》The A of annex IV), at 240 ± 0.5nm wavelength, after diluting identical multiple
Copper-bath makees blank, surveys its absorbance with ultraviolet-visible spectrophotometer, calculates the cumulative release amount of citric acid.Sampling
Time：Citric acid, citric acid+LDHs physical mixture are 1min, 3min, 10min, 40min, 80min, 100min；Lemon
The pillared LDHs of acid is 5min, 10min, 15min, 20min, 30min, 40min, 60min, 80min, 100min.
XRD analysis：
From Fig. 1-2 and table 1 as can be seen that the pillared LDHs of citric acid synthesized with the inventive method characteristic diffraction peak all to
Low-angle moves, and the characteristic diffraction peak for representing interfloor height is 003, and 2 θ are reduced to 7.0 ° by 11.5 °, correspondence interlamellar spacing by
0.76nm is increased to 1.25nm, because shepardite laminate thickness is 0.48nm, interlamellar spacing subtracts laminate thickness and obtains citric acid post
Interlayer object is highly 0.77nm after support.Illustrate that intercalation enters hydrotalcite layers to citrate ion, passes through carboxylic in interlayer
Base is connected with laminate, and individual layer, perpendicular acting are in interlayer.
The magnalium LDHs of the table 1 and pillared LDHs of citric acid XRD diffraction peak datas
Fig. 3 is in 3448cm-1Place is OH in magnalium LDHs-Stretching band, in 3448cm-1Locating wider bands of a spectrum is
The stretching band of-the OH of physical absorption water or crystallization water vibrational bands and M-OH, in addition in 1637cm-1Also there is the weak of water at place
Flexural vibrations bands of a spectrum.1363cm-1Left and right is CO3 2-Symmetric vibration bands of a spectrum, in 1040~1100cm-1With 780~890cm-1Place
It is CO3 2-Weak stretching band outside in face and face；Less than 1000cm-1Other bands of a spectrum be M-O vibrational bands.
As seen from Figure 4,3450cm-1The absworption peak at place belongs to the stretching vibration of OH- in the pillared LDHs of citric acid, with
3600cm-1Free state-the OH at place is compared, and between interlayer anion and/or laminate hydroxyl hydrogen may occur for interlayer hydrone
Key acts on, thus this peak is to lower wave number displacement.
After the pillared LDHs of citric acid, CO3 2-Absworption peak disappears；1637cm-1There is the absworption peak of the last one at place, belongs to the crystallization water
- OH vibration, due to containing a molecular water in citric acid molecule, make to contain more water in the pillared LDHs of citric acid, thus this
Corresponding peak intensity of the peak compared with magnalium LDHs in Fig. 3；Due to containing three carboxyls in citric acid molecule, in 1400cm-1Place occurs strong
The asymmetric absworption peak of carboxylic acid ion.
Fig. 3 and Fig. 4 IR spectrograms illustrate that citric acid instead of the CO in magnalium LDHs3 2-, realize the pillared LDHs of citric acid
The intercalation assembling of Supramolecular layered material.
The pillared LDHs of citric acid heat endurance：
Fig. 5 is the pillared LDHs of citric acid DTA curve, occurs endothermic peak mainly absorption and intermediary water at 100~200 DEG C
Removing；Occurs obviously exothermic peak at 400~500 DEG C, the summit temperature of corresponding exothermic peak is about 439 DEG C, and this is main
It is that organic matter (citric acid) aoxidizes caused by (burning) in atmosphere.
Compare Fig. 5 and Fig. 6 to understand：There is no exothermic peak on magnalium LDHs DTA curve, and occur after inserting citric acid bright
Aobvious exothermic peak, illustrate that citrate enters hydrotalcite layers.
The decomposition temperature of citric acid is between 160~250 DEG C.After citrate pillared hydrotalcite, the decomposition temperature of citric acid
Degree is 400~500 DEG C by 160~207 DEG C of rises, after illustrating that citrate enters LDHs interlayers, due to interlayer object citric acid
Interaction between root and main body LDHs laminates be present, the heat endurance of citric acid is improved.
XRD, IR, DTA characterization result explanation are reacted assembling by intercalation chemistry and obtained by main body (LDHs), object (lemon
Acid) a variety of primitives composition pillared hydrotalcite, a variety of of bondings such as ionic bond and main layer board covalent bond between main body, object, visitor
Supramolecular layered material of the body in interfloor height ordered arrangement.
The pillared LDHs of citric acid supramolecular structure, as shown in fig. 7, citrate has 3 carboxyls, 2 carboxyls therein
With certain symmetry, and citrate is to be present in hydrotalcite layers in the form of negative trivalent anion, so citric acid
Root should have the mutual angled and slab effect of hydrotalcite of symmetrical carboxyl with two.And another carboxyl
Another laminate perpendicular to hydrotalcite functions by ionic bond, and such arrangement is just most stable and meets what experiment obtained
Interlamellar spacing numerical value.It is 1.25nm by the interlamellar spacing being calculated of XRD spectrum, it is contemplated that laminate height (thickness) degree has 0.48nm, lemon
Lemon acid molecule should be 0.77nm in the height of interlayer, due to there is 0.27nm hydrogen bond region between Subjective and Objective, so citrate
Numerical value after the real height of interlayer should be removing hydrogen bond region distance, i.e. 0.50nm.
As shown in figure 8, citric acid+LDHs physical mixture, citric acid, it is impossible to control release, without slow releasing function,
Just discharged in 4min completely.And the pillared LDHs energy control release of citric acid, there is slow releasing function, 89% is discharged in 20min,
100min is needed just to discharge completely.Releasing Mechanisms of the pillared LDHs of citric acid in acetate buffer solution is the acetic acid in solution
The Citrate anions of radical ion and the pillared LDHs interlayers of citric acid swap, and acetate ion enters LDHs interlayers, and lemon
Lemon acid anion enters solution, and the incipient stage, ion-exchange speed is very fast, with the progress of ion exchange, ion-exchange speed
Progressively increase, after reaching maximum, with the progress of ion exchange, ion-exchange speed gradually reduces again.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent substitution and improvements made within the spirit and principles in the present invention etc., are all contained in protection scope of the present invention
It is interior.
Claims (1)
1. a kind of intercalation assemble method of citric acid pillared hydrotalcite supramolecular materials, it is characterised in that specifically according to following step
It is rapid to carry out：
Step 1：Magnalium LDHs is prepared using nucleation/crystallization isolation method：Weigh 6.4g NaOH and 1.1g anhydrous Nas2CO3Add
Proportionaling alkali-forming solution A is put into 500ml beakers in 60ml deionized waters；The another MgSO for taking 14.8g4·7H2O、13.3gAl2
(SO4)3·18H2O is added in 80ml deionized waters and is made into salting liquid B；B solution is added in solution A under fierce magnetic agitation,
Then it is heat-treated 20h in 62-66 DEG C of water；PH value is washed to less than 8,70 DEG C of oven drying 18h are put into after centrifugation, are obtained
Magnalium LDHs；
Step 2：4.5g magnaliums LDHs made from step 1 method is added in the beaker for filling 100mL deionized waters, at room temperature
Magnetic agitation, add excessive citric acid 7.5g until beaker in turbid solution be changed into settled solution, it is standby；
Step 3：CO is eliminated with 100mL2Deionized water dissolving 2gNaOH, be subsequently poured into there-necked flask, magnetic agitation it is same
When, the settled solution that step 2 obtains is added dropwise, pH is kept during dropwise addition>9, pH is adjusted with NaOH, until in settled solution gradually
Precipitate, after completion of dropwise addition, oil bath heating backflow 6h, fully washed to pH with 40-50 DEG C of hot water<8, it is centrifugally separating to obtain
The pillared LDHs of citric acid in 75 DEG C of dry 14h, produce；
The chemical molecular formula of obtained citric acid pillared hydrotalcite supramolecular materials is：Mg6Al2(OH)15C6H5O7。
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| CN108517561B (en) * | 2018-03-30 | 2019-10-29 | 岭南师范学院 | A kind of layered double hydroxide LDH-Cl3The preparation method and applications of-I whisker |
| CN109502656B (en) * | 2018-11-29 | 2021-02-19 | 兰州金通储能动力新材料有限公司 | Spherical Co (II) Co (III) hydrotalcite-like material and preparation method thereof |
| CN112080263B (en) * | 2020-09-21 | 2022-05-20 | 西南石油大学 | Preparation method of slow-release retarder for well cementation |
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| CN1467177A (en) * | 2002-06-24 | 2004-01-14 | 北京化工大学 | Method for assembling anion type supramolecular intercalation structure material |
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