CN107774204A - A kind of hollow open lignin nanosphere and preparation method thereof - Google Patents
A kind of hollow open lignin nanosphere and preparation method thereof Download PDFInfo
- Publication number
- CN107774204A CN107774204A CN201610733413.XA CN201610733413A CN107774204A CN 107774204 A CN107774204 A CN 107774204A CN 201610733413 A CN201610733413 A CN 201610733413A CN 107774204 A CN107774204 A CN 107774204A
- Authority
- CN
- China
- Prior art keywords
- lignin
- nanospheres
- hollow open
- hollow
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 69
- 239000002077 nanosphere Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000002245 particle Substances 0.000 claims abstract description 34
- 238000000502 dialysis Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 230000002255 enzymatic effect Effects 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 239000003937 drug carrier Substances 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- -1 coatings Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明公开一种中空开口木质素纳米球的制备方法。步骤为：第一步，将适量的木质素原料加入到有机溶剂中溶解。第二步，在适当的搅拌速度下，将去离子水以适量的速度滴加到有机溶液中，或将溶有木质素的有机溶液以适量的速度滴加到去离子水中，中空开口纳米球缓慢形成。第三步，将悬浮液转移到透析袋中进行透析，除去残余有机溶剂。第四步，将透析后的悬浮液进行冷冻干燥，最终得到中空开口木质素纳米球的粒径为50~600 nm。本发明制备中空开口木质素纳米球可作药物载体。
The invention discloses a method for preparing hollow open lignin nanospheres. The steps are as follows: in the first step, an appropriate amount of lignin raw material is added into an organic solvent to dissolve. In the second step, at an appropriate stirring speed, add deionized water dropwise to the organic solution at an appropriate speed, or add the organic solution dissolved in lignin to the deionized water at an appropriate speed, and the hollow open nanospheres slowly formed. In the third step, the suspension is transferred to a dialysis bag for dialysis to remove residual organic solvents. In the fourth step, the dialyzed suspension is freeze-dried to finally obtain hollow open lignin nanospheres with a particle size of 50-600 nm. The hollow opening lignin nanosphere prepared by the invention can be used as a drug carrier.
Description
技术领域technical field
本发明涉及一种中空开口木质素纳米球的制备方法，以及由该方法制备的中空开口木质素纳米球。The invention relates to a method for preparing hollow open lignin nanospheres and the hollow open lignin nanospheres prepared by the method.
背景技术Background technique
中空纳米或微米球展示较低密度、较高比表面积和较好的表面渗透性能。它们在运输载体、催化剂、涂层和复合材料等方面具有潜在应用价值。当用于药物输送时，相比密实结构的实心球，空心球拥有较高的载药率。许多研究都为了制备可控组成成分、结构和性能的空心球。中空开口球体作为一种新的中空结构受到广泛关注。当前已有制备开口中空球体的报道中，主要采用的是有机聚合物和无机氧化物，例如聚苯乙烯、聚丙烯酰胺-乙二醇二甲基丙烯酸酯、聚苯乙烯/聚二乙烯基苯、聚苯乙烯/聚3,4-乙撑二氧噻吩、聚硅氧烷、二氧化钛和二氧化硅。Hollow nano- or microspheres exhibit lower density, higher specific surface area, and better surface permeability. They have potential applications in transport carriers, catalysts, coatings, and composite materials. When used for drug delivery, hollow spheres have a higher drug loading rate than solid spheres with a dense structure. Much research has been devoted to the preparation of hollow spheres with controllable composition, structure, and properties. Hollow open spheres have attracted extensive attention as a new hollow structure. In the current reports on the preparation of open hollow spheres, organic polymers and inorganic oxides are mainly used, such as polystyrene, polyacrylamide-ethylene glycol dimethacrylate, polystyrene/polydivinylbenzene , polystyrene/poly-3,4-ethylenedioxythiophene, polysiloxane, titanium dioxide and silicon dioxide.
随着能源问题和环境污染问题的突出，开发绿色且来自可再生原料的制备工艺受到广泛关注。木质素作为仅次于纤维素的可再生原料，属于由苯基丙烷结构单元通过醚键和碳-碳键连接构成的具有三维空间结构的高分子聚合物。由于其结构复杂，不同种类木质素结构性能差异大，传统上被认为是一种制浆造纸废料或低价值副产品。然而，由于木质素具有较好的生物降解、生物兼容性和低毒性，木质素作为一种可再生生物质原料日益受到广泛关注。纳米木质素为木质素产品高附加值利用提供了一种新的途径。中国专利CN102002165A、CN 103145999A、CN 103254452A和CN 104497322A分别提出采用超临界反溶剂法、高压均质法、无机酸和交联剂法和液相沉积法制备了纳米木质素，但获得的纳米木质素均为无规形貌，且不具备中空结构。本发明所述方法简单，条件温和，所制备的生物基纳米球具有中空开口结构，且粒径、开口和中空直径可调。With the prominence of energy issues and environmental pollution issues, the development of green preparation processes from renewable raw materials has attracted extensive attention. As a renewable raw material second only to cellulose, lignin belongs to a polymer with a three-dimensional spatial structure composed of phenylpropane structural units connected by ether bonds and carbon-carbon bonds. Due to its complex structure and large differences in the structural properties of different types of lignin, it is traditionally considered a pulp and paper waste or a low-value by-product. However, lignin has attracted increasing attention as a renewable biomass feedstock due to its good biodegradability, biocompatibility, and low toxicity. Nano-lignin provides a new way for high value-added utilization of lignin products. Chinese patents CN102002165A, CN 103145999A, CN 103254452A and CN 104497322A respectively propose to prepare nano-lignin by supercritical anti-solvent method, high-pressure homogenization method, inorganic acid and cross-linking agent method and liquid phase deposition method, but the obtained nano-lignin They are all random in shape and do not have a hollow structure. The method of the invention is simple and the conditions are mild, and the prepared bio-based nanosphere has a hollow opening structure, and the particle size, opening and hollow diameter are adjustable.
发明内容Contents of the invention
本发明的目的是提供一种中空开口木质素纳米球的制备方法。该方法以工业木质素为原料制备中空开口木质素纳米球。该发明制备方法简单，条件温和，所制备的中空开口纳米球具有粒径、开口和中空直径可调。The purpose of the present invention is to provide a method for preparing hollow open lignin nanospheres. The method uses industrial lignin as a raw material to prepare hollow open lignin nanospheres. The invention has a simple preparation method and mild conditions, and the prepared hollow opening nanospheres have adjustable particle diameters, openings and hollow diameters.
本发明的技术方案为：一种中空开口木质素纳米球的制备方法。步骤为：第一步，将适量的木质素原料加入到有机溶剂中溶解。第二步，在适当的搅拌速度下，将去离子水以适量的速度滴加到有机溶液中，或将溶有木质素的有机溶液以适量的速度滴加到去离子水中，中空开口纳米球缓慢形成。第三步，将悬浮液转移到透析袋中进行透析，除去残余有机溶剂。第四步，将透析后的悬浮液进行冷冻干燥，最终得到中空开口木质素纳米球的粒径为50~600 nm。The technical scheme of the invention is: a method for preparing hollow open lignin nanospheres. The steps are as follows: in the first step, an appropriate amount of lignin raw material is added into an organic solvent to dissolve. In the second step, at an appropriate stirring speed, add deionized water dropwise to the organic solution at an appropriate speed, or add the organic solution dissolved in lignin to the deionized water at an appropriate speed, and the hollow open nanospheres slowly formed. In the third step, the suspension is transferred to a dialysis bag for dialysis to remove residual organic solvents. In the fourth step, the dialyzed suspension is freeze-dried to finally obtain hollow open lignin nanospheres with a particle size of 50-600 nm.
所述的木质素原料为酶解木质素、碱木质素、高沸醇木质素、木质素磺酸盐中的任一种。The lignin raw material is any one of enzymatic lignin, alkali lignin, high boiling alcohol lignin and lignosulfonate.
所用有机溶剂为四氢呋喃、二氧六环、二甲基甲酰胺中的任一种。The organic solvent used is any one of tetrahydrofuran, dioxane and dimethylformamide.
第一步中，滴定前木质素的浓度为0.4~6 mg/mL。In the first step, the lignin concentration before titration was 0.4–6 mg/mL.
第二步中，搅拌速度为300~1500 rpm，滴加速度为0.5~6 mL/min，最终溶液中水与有机溶剂的体积比为2~7。In the second step, the stirring speed is 300-1500 rpm, the dropping speed is 0.5-6 mL/min, and the volume ratio of water to organic solvent in the final solution is 2-7.
第三步中，透析时间为12~48 h。In the third step, the dialysis time is 12-48 h.
附图说明Description of drawings
图1是实施例8条件下，激光光粒度仪测得的中空开口木质素纳米球粒径分布图，平均粒径为150.4 nm。Fig. 1 is a particle size distribution diagram of hollow open lignin nanospheres measured by a laser optical particle size analyzer under the conditions of Example 8, and the average particle size is 150.4 nm.
图2是实施例1条件下，激光光粒度仪测得的中空开口木质素纳米球粒径分布图，平均粒径为150.4 nm。Fig. 2 is a particle size distribution diagram of hollow open lignin nanospheres measured by a laser optical particle size analyzer under the conditions of Example 1, and the average particle size is 150.4 nm.
图3是实施例1条件下，中空开口木质素纳米球的扫描电子显微镜照片。3 is a scanning electron micrograph of hollow open lignin nanospheres under the conditions of Example 1.
图4是实施例1条件下，中空开口木质素纳米球的透射电镜照片。Fig. 4 is a transmission electron micrograph of hollow open lignin nanospheres under the conditions of Example 1.
图5是实施例1条件下，中空开口木质素纳米球和木质素原料的红外光谱图，可以看出制备前后特征峰未发生变化，说明制备前后未发生任何化学反应。Figure 5 is the infrared spectrogram of hollow open lignin nanospheres and lignin raw materials under the conditions of Example 1. It can be seen that the characteristic peaks have not changed before and after preparation, indicating that no chemical reaction has occurred before and after preparation.
具体实施方式Detailed ways
将适量的木质素原料加入到有机溶剂中溶解。然后，在适当的搅拌速度下，将去离子水以适量的速度滴加到有机溶液中，中空开口纳米球缓慢形成。随后，将悬浮液转移到透析袋中进行透析，除去残余有机溶剂，最终得到中空开口木质素纳米球的粒径为50~600nm。An appropriate amount of lignin raw material is added into an organic solvent to dissolve. Then, at an appropriate stirring speed, deionized water is added dropwise into the organic solution at an appropriate speed, and hollow open nanospheres are slowly formed. Subsequently, the suspension was transferred to a dialysis bag for dialysis to remove residual organic solvents, and finally hollow open lignin nanospheres were obtained with a particle size of 50-600 nm.
所述的木质素原料为碱木质素、高沸醇木质素、酶解木质素中的任一种。The lignin raw material is any one of alkali lignin, high boiling alcohol lignin and enzymatic lignin.
所用有机溶剂为四氢呋喃、二氧六环、二甲基甲酰胺中的任一种。The organic solvent used is any one of tetrahydrofuran, dioxane and dimethylformamide.
滴定前木质素的浓度为0.4~6 mg/ml, 搅拌速度为300~1500 rpm，滴加水的速度为0.5~6 ml/min，最终溶液中水与有机溶剂的体积比为2~7，透析时间为12~48 h。The concentration of lignin before titration is 0.4-6 mg/ml, the stirring speed is 300-1500 rpm, the speed of adding water is 0.5-6 ml/min, the volume ratio of water and organic solvent in the final solution is 2-7, and the dialyzed The time ranges from 12 to 48 hours.
实施例1：Example 1:
取5 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，在600 rpm下搅拌，随后以2 mL/min速度滴定去离子水40 mL，最后将悬浮液转入透析袋中透析24 h。Take 5 mg of enzymatic lignin in a 250 mL beaker, add 10 mL of tetrahydrofuran, stir at 600 rpm, then titrate with 40 mL of deionized water at a speed of 2 mL/min, and finally transfer the suspension into a dialysis bag for dialysis for 24 h.
图2是激光光粒度仪测得的中空开口木质素纳米球粒径分布图，平均粒径为419.2nm。Figure 2 is a particle size distribution diagram of hollow open lignin nanospheres measured by a laser particle size analyzer, with an average particle size of 419.2nm.
图3是中空开口木质素纳米球的扫描电子显微镜照片。Fig. 3 is a scanning electron micrograph of hollow open lignin nanospheres.
图4是中空开口木质素纳米球的透射电镜照片。Fig. 4 is a transmission electron micrograph of hollow open lignin nanospheres.
图5是中空开口木质素纳米球和木质素原料的红外光谱图，可以看出制备前后特征峰未发生变化，说明制备前后未发生任何化学反应。Figure 5 is the infrared spectrogram of the hollow open lignin nanospheres and the lignin raw material. It can be seen that the characteristic peaks have not changed before and after the preparation, indicating that no chemical reaction has occurred before and after the preparation.
实施例2Example 2
取10 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，在600 rpm下搅拌，随后以2 mL/min速度滴定去离子水40 mL，最后将悬浮液转入透析袋中透析24 h。Take 10 mg of enzymatic lignin in a 250 mL beaker, add 10 mL of tetrahydrofuran, stir at 600 rpm, then titrate 40 mL of deionized water at a speed of 2 mL/min, and finally transfer the suspension into a dialysis bag for dialysis for 24 h.
激光光粒度仪测得平均粒径较实例1增大，为502.4 nm。此外，开口和中空直径较实例1减小。The average particle size measured by the laser optical particle size analyzer is 502.4 nm, which is larger than that in Example 1. In addition, the opening and hollow diameters are reduced compared to Example 1.
实施例3Example 3
取15 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，在600 rpm下搅拌，随后以2 mL/min速度滴定去离子水40 mL，最后将悬浮液转入透析袋中透析24 h。Put 15 mg of enzymatic lignin into a 250 mL beaker, add 10 mL of tetrahydrofuran, stir at 600 rpm, then titrate 40 mL of deionized water at a speed of 2 mL/min, and finally transfer the suspension into a dialysis bag for dialysis for 24 h.
激光光粒度仪测得平均粒径较实例1增大，为515 nm。此外，开口和中空直径较实例1减小。The average particle size measured by the laser optical particle size analyzer is 515 nm, which is larger than that of Example 1. In addition, the opening and hollow diameters are reduced compared to Example 1.
实施例4Example 4
取20 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，在600 rpm下搅拌，随后以2 mL/min速度滴定去离子水40 mL，最后将悬浮液转入透析袋中透析24 h。Put 20 mg of enzymatic lignin into a 250 mL beaker, add 10 mL of tetrahydrofuran, stir at 600 rpm, then titrate 40 mL of deionized water at a speed of 2 mL/min, and finally transfer the suspension into a dialysis bag for dialysis for 24 h.
激光光粒度仪测得平均粒径较实例1增大，为566.9 nm。此外，开口和中空直径较实例1减小。The average particle size measured by the laser optical particle size analyzer is 566.9 nm, which is larger than that in Example 1. In addition, the opening and hollow diameters are reduced compared to Example 1.
实施例5Example 5
取5 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，在500 rpm下搅拌，随后以2 mL/min速度滴定去离子水40 mL，最后将悬浮液转入透析袋中透析24 h。Take 5 mg of enzymatic lignin in a 250 mL beaker, add 10 mL of tetrahydrofuran, stir at 500 rpm, then titrate 40 mL of deionized water at a speed of 2 mL/min, and finally transfer the suspension into a dialysis bag for dialysis for 24 h.
激光光粒度仪测得平均粒径较实例1增大，为480.4 nm。The average particle size measured by the laser optical particle size analyzer is 480.4 nm, which is larger than that of Example 1.
实施例6Example 6
取5 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，在800 rpm下搅拌，随后以2 mL/min速度滴定去离子水40 mL，最后将悬浮液转入透析袋中透析24 h。Take 5 mg of enzymatic lignin in a 250 mL beaker, add 10 mL of tetrahydrofuran, stir at 800 rpm, then titrate 40 mL of deionized water at a speed of 2 mL/min, and finally transfer the suspension into a dialysis bag for dialysis for 24 h.
激光光粒度仪测得平均粒径较实例1减小，为353.5 nm。The average particle size measured by the laser light particle size analyzer is 353.5 nm, which is smaller than that in Example 1.
实施例7Example 7
取5 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，在900 rpm下搅拌，随后以2 mL/min速度滴定去离子水40 mL，最后将悬浮液转入透析袋中透析24 h。Take 5 mg of enzymatic lignin in a 250 mL beaker, add 10 mL of tetrahydrofuran, stir at 900 rpm, then titrate 40 mL of deionized water at a speed of 2 mL/min, and finally transfer the suspension into a dialysis bag for dialysis for 24 h.
激光光粒度仪测得平均粒径较实例1减小，为294.7 nm。Compared with Example 1, the average particle size measured by the laser particle size analyzer is 294.7 nm.
实施例8Example 8
取10 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，制备木质素的四氢呋喃溶液。随后将溶液以2 mL/min速度滴定到搅拌在600 rpm的40 mL去离子水中，得到纳米球的悬浮液。最后将悬浮液转入透析袋中透析24 h。10 mg of enzymatic lignin was placed in a 250 mL beaker, and 10 mL of tetrahydrofuran was added to prepare a tetrahydrofuran solution of lignin. The solution was then titrated at 2 mL/min into 40 mL of deionized water stirred at 600 rpm to obtain a suspension of nanospheres. Finally, the suspension was transferred to a dialysis bag for dialysis for 24 h.
图1是动态光散射仪测得的中空开口木质素纳米球粒径分布图，平均粒径为150.4nm，平均粒径较实例1减小。FIG. 1 is a particle size distribution diagram of hollow open lignin nanospheres measured by a dynamic light scattering instrument. The average particle size is 150.4 nm, and the average particle size is smaller than that of Example 1.
实施例9Example 9
取5 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，在600 rpm下搅拌，随后以1 mL/min速度滴定去离子水40 mL，最后将悬浮液转入透析袋中透析24 h。Take 5 mg of enzymatic lignin in a 250 mL beaker, add 10 mL of tetrahydrofuran, stir at 600 rpm, then titrate 40 mL of deionized water at a speed of 1 mL/min, and finally transfer the suspension into a dialysis bag for dialysis for 24 h.
激光光粒度仪测得平均粒径较实例1增大，为435.8 nm。The average particle size measured by the laser optical particle size analyzer is 435.8 nm, which is larger than that of Example 1.
实施例10Example 10
取5 mg酶解木质素置于250 mL烧杯中，加入10 mL四氢呋喃，在600 rpm下搅拌，随后以4 mL/min速度滴定去离子水40 mL，最后将悬浮液转入透析袋中透析24 h。Take 5 mg of enzymatic lignin in a 250 mL beaker, add 10 mL of tetrahydrofuran, stir at 600 rpm, then titrate 40 mL of deionized water at a speed of 4 mL/min, and finally transfer the suspension into a dialysis bag for dialysis for 24 h.
激光光粒度仪测得平均粒径较实例1减小，为343.9 nm。Compared with Example 1, the average particle size measured by the laser particle size analyzer is 343.9 nm.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610733413.XA CN107774204A (en) | 2016-08-27 | 2016-08-27 | A kind of hollow open lignin nanosphere and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610733413.XA CN107774204A (en) | 2016-08-27 | 2016-08-27 | A kind of hollow open lignin nanosphere and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107774204A true CN107774204A (en) | 2018-03-09 |
Family
ID=61440122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610733413.XA Pending CN107774204A (en) | 2016-08-27 | 2016-08-27 | A kind of hollow open lignin nanosphere and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107774204A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109434098A (en) * | 2018-12-25 | 2019-03-08 | 广西大学 | A kind of method that photocatalysis lignin reduction silver nitrate prepares silver nano-grain |
| CN109621851A (en) * | 2018-12-12 | 2019-04-16 | 天津科技大学 | A kind of preparation method of gamma-valerolactone/glycerol system high yield pulp1 lignin micro-nano ball |
| CN109701462A (en) * | 2018-12-14 | 2019-05-03 | 浙江大学 | Bio-based UV-protected and weather-resistant core-shell micro-nano particles |
| CN110051852A (en) * | 2019-05-24 | 2019-07-26 | 中国林业科学研究院木材工业研究所 | A kind of high encapsulation performance lignin nanosphere as well as preparation method and application thereof |
| CN110387278A (en) * | 2019-07-30 | 2019-10-29 | 中南林业科技大学 | A controllable preparation method of hollow and open structure lignin micro-nanospheres |
| CN110452396A (en) * | 2019-08-20 | 2019-11-15 | 华南农业大学 | A kind of preparation method of lignin micro-/ nano ball |
| CN110857538A (en) * | 2018-08-22 | 2020-03-03 | 中南大学 | Method for synchronously preparing cellulose crystals and lignin nanoparticles |
| CN112646224A (en) * | 2020-11-30 | 2021-04-13 | 中南林业科技大学 | Hollow open-ended lignin-based temperature-sensitive microsphere and preparation method and application thereof |
| CN112646196A (en) * | 2020-12-18 | 2021-04-13 | 安徽工业大学 | Method for preparing nano lignin from lignin extracting solution by utilizing acid sedimentation and dialysis |
| CN113166552A (en) * | 2018-11-29 | 2021-07-23 | 阿尔托大学基金会 | Lignin particle-based hydrogel and method for preparing lignin colloidal particles by solvent evaporation |
| CN113797175A (en) * | 2021-09-08 | 2021-12-17 | 齐鲁工业大学 | Grape seed lignin nanoparticle, preparation method thereof and application thereof in drug loading |
| CN115044107A (en) * | 2022-06-06 | 2022-09-13 | 河南农业大学 | Chitosan-based passive modified atmosphere fresh-keeping film, preparation method and application thereof |
| CN116355251A (en) * | 2023-04-07 | 2023-06-30 | 齐鲁工业大学(山东省科学院) | A kind of lignin micro-nanosphere/PVA composite membrane material and its preparation method and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040023029A1 (en) * | 2001-02-09 | 2004-02-05 | Reika Kogyo Kabushiki Kaisha | Functional particle and preparing/plasma-treating method of the same |
| CN1894027A (en) * | 2003-12-17 | 2007-01-10 | 帝国化学工业公司 | Particulate materials |
| WO2008018716A1 (en) * | 2006-08-09 | 2008-02-14 | Korea Research Institute Of Bioscience And Biotechnology | Sillica capsules having nano-holes or nano-pores on their surfaces and method for preparing the same |
| WO2012142625A2 (en) * | 2011-04-14 | 2012-10-18 | The Regents Of The University Of California | Multifunctional nanoparticle designs and applications |
| CN102764616A (en) * | 2011-05-03 | 2012-11-07 | 中国科学院化学研究所 | Hollow microsphere and its preparation method |
| CN103559973A (en) * | 2013-10-30 | 2014-02-05 | 华南理工大学 | A Fe3O4@SiO2 magnetic single-hole hollow microsphere and its preparation method |
| CN104497322A (en) * | 2014-12-19 | 2015-04-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing nano lignin by use of liquid phase deposition technique |
-
2016
- 2016-08-27 CN CN201610733413.XA patent/CN107774204A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040023029A1 (en) * | 2001-02-09 | 2004-02-05 | Reika Kogyo Kabushiki Kaisha | Functional particle and preparing/plasma-treating method of the same |
| CN1894027A (en) * | 2003-12-17 | 2007-01-10 | 帝国化学工业公司 | Particulate materials |
| WO2008018716A1 (en) * | 2006-08-09 | 2008-02-14 | Korea Research Institute Of Bioscience And Biotechnology | Sillica capsules having nano-holes or nano-pores on their surfaces and method for preparing the same |
| WO2012142625A2 (en) * | 2011-04-14 | 2012-10-18 | The Regents Of The University Of California | Multifunctional nanoparticle designs and applications |
| CN102764616A (en) * | 2011-05-03 | 2012-11-07 | 中国科学院化学研究所 | Hollow microsphere and its preparation method |
| CN103559973A (en) * | 2013-10-30 | 2014-02-05 | 华南理工大学 | A Fe3O4@SiO2 magnetic single-hole hollow microsphere and its preparation method |
| CN104497322A (en) * | 2014-12-19 | 2015-04-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing nano lignin by use of liquid phase deposition technique |
Non-Patent Citations (2)
| Title |
|---|
| HAO LI ET AL.: "Preparation of Nanocapsules via the Self-Assembly of Kraft Lignin: A Totally Green Process with Renewable Resources", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
| YINLIANG LI ET AL.: "Synthesis of Magnetic Lignin-Based Hollow Microspheres: A Highly Adsorptive and Reusable Adsorbent Derived from Renewable Resources", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110857538A (en) * | 2018-08-22 | 2020-03-03 | 中南大学 | Method for synchronously preparing cellulose crystals and lignin nanoparticles |
| CN113166552A (en) * | 2018-11-29 | 2021-07-23 | 阿尔托大学基金会 | Lignin particle-based hydrogel and method for preparing lignin colloidal particles by solvent evaporation |
| CN113166552B (en) * | 2018-11-29 | 2023-04-21 | 阿尔托大学基金会 | Lignin particle-based hydrogels and methods for preparing lignin colloidal particles by solvent evaporation |
| CN109621851A (en) * | 2018-12-12 | 2019-04-16 | 天津科技大学 | A kind of preparation method of gamma-valerolactone/glycerol system high yield pulp1 lignin micro-nano ball |
| CN109621851B (en) * | 2018-12-12 | 2021-04-30 | 天津科技大学 | Preparation method of gamma-valerolactone/glycerol system high-yield lignin micro-nanospheres |
| CN109701462A (en) * | 2018-12-14 | 2019-05-03 | 浙江大学 | Bio-based UV-protected and weather-resistant core-shell micro-nano particles |
| CN109434098A (en) * | 2018-12-25 | 2019-03-08 | 广西大学 | A kind of method that photocatalysis lignin reduction silver nitrate prepares silver nano-grain |
| CN110051852A (en) * | 2019-05-24 | 2019-07-26 | 中国林业科学研究院木材工业研究所 | A kind of high encapsulation performance lignin nanosphere as well as preparation method and application thereof |
| CN110387278A (en) * | 2019-07-30 | 2019-10-29 | 中南林业科技大学 | A controllable preparation method of hollow and open structure lignin micro-nanospheres |
| CN110452396A (en) * | 2019-08-20 | 2019-11-15 | 华南农业大学 | A kind of preparation method of lignin micro-/ nano ball |
| CN110452396B (en) * | 2019-08-20 | 2020-12-29 | 华南农业大学 | A kind of preparation method of lignin micro/nanosphere |
| CN112646224A (en) * | 2020-11-30 | 2021-04-13 | 中南林业科技大学 | Hollow open-ended lignin-based temperature-sensitive microsphere and preparation method and application thereof |
| CN112646224B (en) * | 2020-11-30 | 2022-08-30 | 中南林业科技大学 | Hollow open-ended lignin-based temperature-sensitive microsphere and preparation method and application thereof |
| CN112646196A (en) * | 2020-12-18 | 2021-04-13 | 安徽工业大学 | Method for preparing nano lignin from lignin extracting solution by utilizing acid sedimentation and dialysis |
| CN113797175A (en) * | 2021-09-08 | 2021-12-17 | 齐鲁工业大学 | Grape seed lignin nanoparticle, preparation method thereof and application thereof in drug loading |
| CN115044107A (en) * | 2022-06-06 | 2022-09-13 | 河南农业大学 | Chitosan-based passive modified atmosphere fresh-keeping film, preparation method and application thereof |
| CN116355251A (en) * | 2023-04-07 | 2023-06-30 | 齐鲁工业大学(山东省科学院) | A kind of lignin micro-nanosphere/PVA composite membrane material and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107774204A (en) | A kind of hollow open lignin nanosphere and preparation method thereof | |
| Lu et al. | One-pot assembly of microfibrillated cellulose reinforced PVA–borax hydrogels with self-healing and pH-responsive properties | |
| Cheng et al. | Multifaceted applications of cellulosic porous materials in environment, energy, and health | |
| Huang et al. | Extremely strong and transparent chitin films: a high‐efficiency, energy‐saving, and “Green” route using an aqueous KOH/Urea solution | |
| Ahmed et al. | Green solvent processed cellulose/graphene oxide nanocomposite films with superior mechanical, thermal, and ultraviolet shielding properties | |
| Lin et al. | TEMPO-oxidized nanocellulose participating as crosslinking aid for alginate-based sponges | |
| De France et al. | Review of hydrogels and aerogels containing nanocellulose | |
| Hamedi et al. | Highly conducting, strong nanocomposites based on nanocellulose-assisted aqueous dispersions of single-wall carbon nanotubes | |
| Zhai et al. | Synthesis of polyvinyl alcohol/cellulose nanofibril hybrid aerogel microspheres and their use as oil/solvent superabsorbents | |
| Ye et al. | Cellulose nanocrystal microcapsules as tunable cages for nano-and microparticles | |
| Wu et al. | Facile route to produce chitin nanofibers as precursors for flexible and transparent gas barrier materials | |
| Liu et al. | Chitosan/halloysite nanotubes bionanocomposites: structure, mechanical properties and biocompatibility | |
| CN107973920A (en) | A kind of cellulose/two-dimensional layer Material cladding hydrogel and preparation method thereof | |
| Zhou et al. | Sustainable, high-performance, and biodegradable plastics made from chitin | |
| Roy et al. | A novel approach for fabricating highly tunable and fluffy bioinspired 3D poly (vinyl alcohol)(PVA) fiber scaffolds | |
| CN103642190B (en) | Polyethylene glycol modified cyclodextrin, as well as preparation and application thereof | |
| CN105348548B (en) | A kind of hydrogel microsphere based on glucan and preparation method thereof | |
| Eivazzadeh-Keihan et al. | Synthesis and characterization of cellulose, β-cyclodextrin, silk fibroin-based hydrogel containing copper-doped cobalt ferrite nanospheres and exploration of its biocompatibility | |
| CN101967697B (en) | Preparation method of biodegradable solid-solid phase change nanofiber or fiber membrane | |
| Suenaga et al. | Self-sustaining cellulose nanofiber hydrogel produced by hydrothermal gelation without additives | |
| Xu et al. | Preparation of porous regenerated cellulose microstructures via emulsion-coagulation technique | |
| Liu et al. | Porous starch and its applications | |
| CN112898545B (en) | Solvent-free green method for preparing polylactic acid nano material | |
| Xiong et al. | Nanocellulose implantation enriched the pore structure of aerogel for effective particulate matter removal | |
| Beaumont et al. | Cellulose nanofibrils: From hydrogels to aerogels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |