CN105111466A - Environmentally-sensitive hydrogel and method and application for preparing hydrogel by using bamboo shoot scraps - Google Patents
Environmentally-sensitive hydrogel and method and application for preparing hydrogel by using bamboo shoot scraps Download PDFInfo
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Abstract
The invention belongs to the technical field of composite hydrogel and discloses environmentally-sensitive hydrogel and a method and application for preparing the hydrogel by using bamboo shoot scraps. The method for preparing the environmentally-sensitive hydrogel comprises the steps that firstly, cellulose is extracted from bamboo shoot craps, and then sodium chloroacetate is adopted for carboxymethylation modification; secondly, the carboxymethylated bamboo shoot cellulose and beta-cyclodextrin are added into an aqueous solution of 12% Urea/7%NaOH; thirdly, epoxy chloropropane is added for cross-linking reaction; finally, unreacted reagents are washed away through subsequent treatment, and freeze drying is performed, so that the hydrogel is prepared. The prepared hydrogel is sensitive to temperature, pH, saline solutions and organic solvent, and therefore the hydrogel can be applied in the field of cationic dye or the field of drug slow release materials. Besides, according to the method, the reaction conditions are mild, process routes are simple and practicable, and industrialized operation is easy.
Description
Technical field
The invention belongs to the technical field of composite aquogel, be specifically related to a kind of environment sensitive type hydrogel and utilize bamboo shoots tankage to prepare method and the application of environment sensitive type hydrogel.
Background technology
Qingyuan City sinocalamus latiflorus bamboo shoot (Dendrocalamuslatiflorus, DL) is a kind of aboundresources, the edible plants that output is higher.The sinocalamus latiflorus bamboo shoot uniqueness that to be bamboos have in early days of growth expand bud stem, its matter is tender delicious, containing abundant essential amino acid, mineral element, VITAMIN and be difficult to the fibre composition etc. that digests by human body, be that one has the natural food materials of nutritive value.Because the plantation of forest land bamboo shoots in recent years is constantly applied, since 2010, often produced 5000000-600 ten thousand tons, bamboo shoots per year, except 40% marketing fresh, all the other are all for the processing of can bamboo shoot and dried bamboo shoots.
The complete processings such as the main processing mode of bamboo shoots is mainly pickled, dry, fermentation, freezing.Bamboo shoots its young tender part in the course of processing compares edibility, and the aging part of fiber discards in the course of processing of being everlasting, and therefore bamboo shoot product processed output is low, wastes very serious.The bamboo shoot meat being generally used for making the bamboo shoot product such as Bamboo shoots, dry bamboo shoot only accounts for the comparatively small part of whole bamboo shoot body, for moso bamboo shoot, its bamboo shoot meat accounts for 28%, all the other are the tankage such as bamboo shoot head and bamboo shoot shell, it is because rough wearing fiber composition is up to 72%, therefore be discarded in the course of processing, and these tankage Middle nutrition not yet effectively utilized and health-care components also lower comparatively speaking, be not processed to food.So, in the course of processing of bamboo shoot process, all can produce a large amount of processing waste-tankage, if these by product process is bad, the wasting of resources and environmental pollution will be caused, will have a negative impact to the production of people, life and health, and cause the waste of biomass resource.So, the research of the recycling of processing waste is just seemed extremely important.Therefore, the utilisation technology studying bamboo shoot process waste just has possibility.
China remains a developing large agricultural country at present, the minimizing of what the carrying out along with Rural Urbanization Construction brought is arable area, and the primary agricultural products that still added value is extremely low produced on this limited soil, and a large amount of processing of farm products waste residues is discarded or is burned, this not only contaminate environment also waste resource, cause a large amount of CO
2with PM2.5 particulate emission.Therefore, China, as large agricultural country, is necessary agricultural-food industrial chain to develop to high value added products such as Biomass Industries, produces the biomass product improved People's livelihood more.Therefore, bamboo shoots tankage skin slag in processing of farm products is carried out modification, synthesis of natural macromolecule hydrogel material, for curbing environmental pollution, drug controlled release, to a certain extent for the processing treatment of asparagus tankage gives certain terms of settlement, significant.
Summary of the invention
In order to overcome shortcoming and defect in prior art, the object of the present invention is to provide a kind of method utilizing bamboo shoots tankage to prepare environment sensitive type hydrogel.The present invention is intended to carry out higher value application to agricultural-food bamboo shoots tankage, by extracting bamboo shoots Mierocrystalline cellulose from bamboo shoots tankage, then carry out carboxymethyl-modification and carry out being cross-linked with beta-cyclodextrin preparing multiple environment response type hydrogel, this hydrogel is to pH, temperature, ionic strength, organic solvent all has environmental response.
Another object of the present invention is to provide the environment sensitive type prepared by aforesaid method hydrogel.
Another object of the present invention is the application providing above-mentioned environment sensitive type hydrogel.
Object of the present invention is achieved through the following technical solutions:
A kind of bamboo shoots tankage prepare the method for environment sensitive type hydrogel, extracted after Mierocrystalline cellulose by bamboo shoots tankage and carry out carboxymethyl-modification with sodium chloroacetate, and carry out epoxy chloropropane with beta-cyclodextrin and be cross-linked, wash away unreacting reagent afterwards, finally carry out lyophilize to form, concrete steps are:
(1) bamboo shoots tankage are carried out wash, dry, pulverize, obtain bamboo shoots ground-slag;
(2) distilled water is added in the bamboo shoots ground-slag of step (1) and carry out the process that completes, then regulate pH, then carry out bleaching, filter, washing, dry, obtain pre-treatment bamboo shoots fiber, be denoted as PBSC (PretreatmentBambooShootCellulose);
(3) pre-treatment bamboo shoots fiber added in alkaline solution carry out alkalinisation treatment, then wash, dry, obtain bamboo shoots Mierocrystalline cellulose after de-hemicellulose, be denoted as BSC (BambooSheetCellulose);
(4) in the cellulosic reactor of bamboo shoots after de-hemicellulose is housed, add isopropanol water solution and hydrogen peroxide solution successively, mixing, adds sodium hydroxide solution 1 and carries out alkalinisation treatment, obtains alkalization bamboo shoots Mierocrystalline cellulose; Add sodium chloroacetate solution 1 again, carry out first time gradient increased temperature etherificate, after gradient increased temperature etherificate completes for the first time, recover room temperature, add sodium hydroxide solution 2 and carry out double alkalisation, alkalize complete, add sodium chloroacetate solution 2 and carry out second time gradient increased temperature etherificate; Described sodium hydroxide solution 1 and sodium hydroxide solution 2 are all sodium hydroxide solution; Described sodium chloroacetate solution 1 and sodium chloroacetate solution 2 are all the alcoholic solution of sodium chloroacetate;
(5) after etherificate completes, be cooled to room temperature, remove supernatant liquor, add methyl alcohol to process, then adopt ethanolic soln to wash, dry, obtain the carboxymethylation bamboo shoots Mierocrystalline cellulose of modification, be denoted as MBSC (ModifiedBambooSheetCellulose);
(6) aqueous solution (12% and 7% is massfraction) of 12%Urea/7%NaOH is carried out freezing, take out, when aqueous temperature is-12 to-15 DEG C, the carboxymethylation bamboo shoots Mierocrystalline cellulose (MBSC) of modification and beta-cyclodextrin are added in the aqueous solution of 12%Urea/7%NaOH, stirring and evenly mixing, add epoxy chloropropane again, ultrasonic deaeration, fluid-tight, left at room temperature 36-48h, removes fluid-tight, washing, soak, dry, obtain environment sensitive type hydrogel and loose porous modification bamboo shoots Mierocrystalline cellulose/beta-cyclodextrin water-setting blob of viscose.
Washing described in step (1) adopts clear water to wash, and described drying is for drying or drying, and the condition of described oven dry is the temperature of drying is 70 ~ 80 DEG C, and drying time is 12 ~ 16h;
The condition processed that completes described in step (2) processes 2h-2.5h for completing in 65-80 DEG C; Described bamboo shoots ground-slag end is 1:20-1:25 with the mass ratio of distilled water; Described pH is 3.8-4.0, and the material of described adjustment pH is the glacial acetic acid solution of massfraction 10%-15%; The SYNTHETIC OPTICAL WHITNER of described bleaching is Textone, and the temperature of described bleaching is 75-80 DEG C; Described in step (2), the mass ratio of bamboo shoots powder and Textone is 1:1-1:0.8, and bleaching time is 2-3h.
Washing described in step (2) refers to and first adopts distilled water to wash until filtrate is colourless the insoluble floss after filtration, then adopts ethanolic soln to carry out alcohol wash, alcohol wash 3 ~ 5 times; The mass percent of described ethanolic soln is 85% ~ 95%; The condition of described drying is in 50-70 DEG C of drying treatment 16-20h;
Described in step (3), the mass volume ratio of pre-treatment bamboo shoots fiber and alkaline solution is 1g:(15-20) ml; Described in step (3), strong base solution is potassium hydroxide solution, and mass percent concentration is 10%-15%; The time of described alkalinisation treatment is 12 ~ 20h; Condition dry described in step (3) is dry 16-20h at 50-70 DEG C; Described in step (3), the concrete grammar of washing is: first use distilled water wash filtrate pH to neutral, use volume fraction to be that 95% ethanolic soln and dehydrated alcohol respectively wash 1 time afterwards.
After de-hemicellulose described in step (4), the amount ratio of bamboo shoots Mierocrystalline cellulose, isopropanol water solution, hydrogen peroxide solution and sodium hydroxide solution 1 is (10 ~ 12) g:200mL:(80 ~ 100) uL:(16 ~ 20) mL;
In aqueous isopropanol described in step (4), the volume ratio of distilled water and Virahol is 1:(8.5 ~ 10); The mass percent concentration of described hydrogen peroxide solution is 30% ~ 35%; Described sodium hydroxide solution 1 for mass percent be the sodium hydroxide solution of 40%-50%; Described in step (4), alkalization time is 2 ~ 3h;
First time described in step (4) heat up etherificate, second time intensification etherificate processing condition be: by reaction solution first under the condition of magnetic agitation in room temperature treatment 30 ~ 50min, then shaking table is transferred in 40 ~ 45 DEG C of shaking water bath 30 ~ 40min, be warming up to 55 ~ 60 DEG C and continue shaking water bath 30 ~ 40min, then be warming up to 75 ~ 80 DEG C of pyroprocessing 80 ~ 90min; The rotating speed of described magnetic agitation is 30 ~ 40r/min, and the rotating speed of shaking water bath is 120 ~ 135r/min, and the rotating speed continuing shaking water bath is 100 ~ 120r/min;
After de-hemicellulose described in step (4), the mass volume ratio of bamboo shoots Mierocrystalline cellulose and sodium hydroxide solution 2 is (10 ~ 12) g:(6 ~ 10) mL, sodium hydroxide solution 2 for mass percent be the sodium hydroxide solution of 50%; The time of double alkalisation is 30min;
Described in step (4), sodium chloroacetate solution 1 and sodium chloroacetate solution 2 are all the ethanolic soln of sodium chloroacetate, and the concentration of two solution is identical; In the ethanolic soln of described sodium chloroacetate, the mass volume ratio of the ethanolic soln of sodium chloroacetate and sodium chloroacetate is 1g:2mL; After de-hemicellulose described in step (4), the mass volume ratio of bamboo shoots Mierocrystalline cellulose and sodium chloroacetate solution 1 is (10 ~ 12) g:(12 ~ 16) mL.
The consumption of described sodium chloroacetate solution 2 is 0.25 ~ 0.29 times of sodium chloroacetate solution 1.
Described in step (5), drying conditions is: in 45-50 DEG C of dry 16-20h; After methyl alcohol process refers to and adds methyl alcohol described in step (5), in room temperature shaker concussion 30 ~ 40min, filter, again add methyl alcohol and carry out concussion 20 ~ 50min, after leaving standstill 12 ~ 16h, be adjusted to neutrality with Glacial acetic acid, stir, leave standstill, remove upper liquid; After described methyl alcohol and de-hemicellulose, the cellulosic magnitude relation of bamboo shoots is (300 ~ 500) mL:(10 ~ 12) g; Described ethanolic soln carries out washing and refers to that employing volume fraction is that 75%, 85%, 95% ethanolic soln washs product successively; The speed of described shaking table vibration is 100 ~ 140r/min.
The carboxymethylation bamboo shoots Mierocrystalline cellulose (MBSC) of modification described in step (6) and beta-cyclodextrin need to adopt dehydrated alcohol to carry out moistening before use, carboxymethylation bamboo shoots Mierocrystalline cellulose (MBSC) and the beta-cyclodextrin mass ratio 6:4 ~ 9:1 of described modification; Described MBSC and the total consumption of beta-cyclodextrin are the 5%-7% of the aqueous solution quality of 12%Urea/7%NaOH; The aqueous solution of described 12%Urea/7%NaOH and the mass volume ratio of epoxy chloropropane are 100g:(5 ~ 10) mL; The rotating speed of described stirring is 800 ~ 1000rpm, and the time of stirring is 3 ~ 5min.
Condition freezing described in step (6) is preserve 12-18h in-20 DEG C; The condition of ultrasonic deaeration described in step (6) is ultrasonic power is 300 ~ 600W, and ultrasonic time is 1 ~ 3min.
Fluid-tight described in step (6) adopts whiteruss to carry out fluid-tight, described washing refer to adopt deionized water successively, volume fraction 95% ethanolic soln washs; Described immersion refers to and adopts distilled water to soak, and soak time is 3 ~ 7d, repeatedly changes water to hydrogel and remove unreacted reagent in immersion process; Described drying is vacuum lyophilization, and temperature is-58 ~-50 DEG C, and the time is 30 ~ 35h.
Bamboo shoots tankage described in step (1) refer to the more waste being unfavorable for processing of aged fiber that bamboo shoots work in-process abandons, and are that the rear portion bamboo shoot root of bamboo shoots divides; The bamboo shoots tankage slag powder diameter obtained is 0.1-0.6mm.
Described environment sensitive type hydrogel is prepared by above-mentioned preparation method.
Described environment sensitive type hydrogel is applied to the absorption of cationic dyestuff molecule, controlled fertilising material and Thermosensitive Material Used for Controlled Releasing of Medicine field.
The present invention is using natural biomass Qingyuan City bamboo shoots waste residue as raw material, after carboxymethyl-modification is carried out to it, under green solvent NaOH/Urea system, chemically crosslinked is carried out by linking agent epoxy chloropropane (ECH) and beta-cyclodextrin, utilize the inner cavity of relative hydrophobic of beta-cyclodextrin and the interaction of Subjective and Objective, prepare bamboo shoots carboxymethyl cellulose/beta-cyclodextrin hydrogel, and various sign is carried out to the composite aquogel prepared, prepare the composite aquogel possessing environmental response characteristic, and in the intelligent behavior that varying environment produces, mechanism explaination is carried out to hydrogel.
Sorbent material of the present invention compared with prior art has following feature:
(1) hydrogel of the present invention main raw material used is discarded bamboo shoots tankage slag, and abundance is cheap, and this hydrogel can as sorbent material, and to dye molecule high adsorption capacity, absorption property is stablized;
(2) in preparation method of the present invention, bamboo shoots Mierocrystalline cellulose only needs the modification of carboxymethylation one step, and modified technique is fairly simple; By adding cyclic polysaccharide beta-cyclodextrin, hydrogen bond action is different at different temperatures to utilize beta-cyclodextrin shell hydroxyl and hydroxyl on modification bamboo shoots fiber reinforcement, thus makes the hydrogel prepared produce temperature sensitivity;
(3) the present invention is by introducing carboxyl to the cellulosic carboxymethylation of bamboo shoots, and on hydrogel, carboxyl ionizes in aqueous, the electronegative carboxylic ions of generating strap, makes composite aquogel have pH susceptibility equally;
(4) the responsive responsiveness of pH that the hydrogel that prepared by the present invention is had by bury function and its of beta-cyclodextrin, hydrogel can be carried out medicine carrying, make it at duodenum, small intestine, the varying environments such as colon make medicine targeted release, thus site-specific delivery of drugs is realized to focus, increase the drug level of medicine in affected part, reduce the side effect that medicine brings, improve the bioavailability of medicine, number of times and the quantity of drug administration can be reduced simultaneously, improve the result for the treatment of of medicine;
(5) composite aquogel reaction conditions of the present invention is gentle, and use green non-pollution Urea/NaOH system to carry out hydrogel preparation, operational path is simple, is easy to industrial operation.
Accompanying drawing explanation
Fig. 1 is the FTIR spectrogram of environment sensitive type hydrogel prepared by embodiment 1 ~ 4; In figure 1 ~ 4 is respectively the spectrogram of environment sensitive type hydrogel prepared by embodiment 1 ~ 4;
Fig. 2 is the SEM figure of environment sensitive type hydrogel prepared by embodiment 2; The SEM that wherein (a) is environment sensitive type hydrogel schemes, and (b) is the SEM figure after hydrogel Adsorption Model medicine sodium salicylate;
Fig. 3 is the X diffractogram of environment sensitive type hydrogel prepared by embodiment 1 ~ 3; In figure 1 ~ 3 is respectively the spectrogram of environment sensitive type hydrogel prepared by embodiment 1 ~ 3;
Fig. 4 is histogram and the graphic representation of environment sensitive type hydrogel temperature sensitivity prepared by embodiment 2; Wherein (a) is the histogram of environment sensitive type hydrogel swelling ratio at different temperatures, and (b), under differing temps, the swelling ratio of environment sensitive type hydrogel is along with the graphic representation of time variations;
Fig. 5 is the salts solution sensitivity curves figure of environment sensitive type hydrogel prepared by embodiment 2; Wherein (a) for environment sensitive type hydrogel in 0.1mol/L various salts swelling ratio along with the graphic representation of time variations, (b) for environment sensitive type hydrogel in 0.01mol/L various salts swelling ratio along with the graphic representation of time variations;
Fig. 6 is the pH sensitivity curves figure of environment sensitive type hydrogel prepared by embodiment 2; Wherein (a) is the histogram of environment sensitive type hydrogel swelling ratio under different pH, the reversible responsiveness curve of the pH that (b) is environment sensitive type hydrogel;
Fig. 7 is that the environment sensitive type hydrogel of embodiment 2 preparation is to the sensitivity curves figure of organic solvent.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described and describe, but embodiments of the present invention are not limited thereto.
Embodiment 1
Bamboo shoots tankage prepare a method for environment sensitive type hydrogel, specifically comprise the following steps:
(1) bamboo shoots tankage are after distilled water wash, and in 70 DEG C of dry 12h, be cut into small pieces shape, and 80 mesh sieves pulverized by pulverizer, and obtain bamboo shoots ground-slag end, its powder diameter is 0.1-0.6mm;
(2) in bamboo shoots ground-slag end, add distilled water, the mass ratio of bamboo shoots ground-slag and distilled water is 1:20, and complete process 2h under 70 DEG C of conditions, passivation bamboo shoots active enzyme; Add the Glacial acetic acid adjustment pH to 3.8 that massfraction is 10%, add Textone in 80 DEG C of bleaching 2h (mass ratio of Textone and bamboo shoots ground-slag is 1:1);
(3) after bleaching, insoluble flocculent substance in filtering solution, and with distilled water wash, it is colourless to filtrate, massfraction 90% ethanolic soln is adopted to carry out alcohol wash 4 times, last in 60 DEG C of drying treatment 20h, obtain pre-treatment bamboo shoots fiber, be denoted as PBSC (PretreatmentBambooShootCellulose);
(4) pre-treatment bamboo shoots Mierocrystalline cellulose was pulverized 80 mesh sieves, joining massfraction is alkalinisation treatment 16h in 10% potassium hydroxide solution, wherein the amount ratio of pre-treatment bamboo shoots Mierocrystalline cellulose and potassium hydroxide aqueous solution is 1g:15ml, it is neutral for carrying out washing to filtrate with distilled water after alkalization, then volume fraction is used to be that 95% ethanol and dehydrated alcohol respectively wash 1 time, in 50 DEG C of dry 16h, obtain bamboo shoots Mierocrystalline cellulose after de-hemicellulose, be denoted as BSC (BambooShootCellulose);
(5) cross 80 mesh sieves after being pulverized by bamboo shoots Mierocrystalline cellulose after de-hemicellulose and carry out carboxymethyl-modification, modified condition is as follows: be added to by 10g bamboo shoots Mierocrystalline cellulose (in aqueous isopropanol, the mass ratio of distilled water and Virahol is 1:9) in the aqueous solution of 200ml Virahol, the mass percent adding 80ul is more successively the hydrogen peroxide of 30%, 16ml mass percent is the NaOH solution of 50%, alkalinisation treatment 2h; Alkalize complete, add the ethanolic soln of the sodium chloroacetate of the concentration 50% (w/v) of 14ml, carry out first time gradient increased temperature etherificate, recover room temperature, add the NaOH solution that 6ml mass percent is 50%, carry out double alkalisation 30min, alkalize complete, add the ethanolic soln of the sodium chloroacetate of the concentration 50% (w/v) of 3.5ml, carry out second time gradient increased temperature etherificate; The processing condition of gradient increased temperature etherificate and second time intensification etherificate for the first time: with 40r/min rotating speed stir process 30min under room temperature, with the rotating speed shaking water bath 30min of 130r/min at 45 DEG C, shaking water bath 30min is continued with the rotating speed of 110r/min again, finally in 75 DEG C of process 80min at 60 DEG C;
(6), after etherificate, abandoning supernatant, adds 300ml methyl alcohol room temperature concussion 30min (rotating speed is 130r/min), after filtration, after again adding 300ml methyl alcohol, shake 30min, leave standstill 12h, pH is regulated to be neutral with Glacial acetic acid, stir, leave standstill abandoning supernatant, use the ethanolic soln of volume fraction 75%, 85%, 95% to carry out cleaning 3 times to precipitation successively successively, filter, dry 16h at 50 DEG C, the carboxymethylation bamboo shoots Mierocrystalline cellulose after obtaining modification, is designated as MBSC;
(7) by the 12%Urea/7%NaOH aqueous solution, take out preserve 12h in-20 DEG C of refrigerators after, treat that thermometer instruction solution temperature is-12 DEG C, solution presents mixture of ice and water state, MBSC and beta-cyclodextrin are carried out in dehydrated alcohol moistening after, by MBSC and beta-cyclodextrin (MBSC and beta-cyclodextrin mass ratio 6:4, total consumption of MBSC and beta-cyclodextrin is 7% of 12%Urea/7%NaOH aqueous solution quality) join in the 12%Urea/7%NaOH aqueous solution of 100g, stir 5min with 800rpm rotating speed; Add 10ml epoxy chloropropane, carry out ultrasonic deaeration process 2min, ultrasonic power is 400W, obtains mixed glue solution; Slowly be poured on culture dish by mixed glue solution, carry out fluid-tight with whiteruss, enter to prevent the oxygen in air and the generation of bubble, room temperature leaves standstill 36h, and modification bamboo shoots Mierocrystalline cellulose and beta-cyclodextrin are fully cross-linked; Remove whiteruss, use deionized water, percent by volume be 95% ethanolic soln the hydrogel prepared is washed, obtain water white hydrogel nahlock; Hydrogel nahlock is put into distilled water and soaks 7d, the reticulated structure of hydrogel stretches to allow moisture fully promote, repeatedly changes water to hydrogel and remove unreacted reagent in immersion process; After immersion, dry the moisture of hydrogel surface with qualitative filter paper, pre-freeze final vacuum lyophilize (temperature-50 DEG C, the time is 30h), obtains loose porous modification bamboo shoots Mierocrystalline cellulose/beta-cyclodextrin water-setting blob of viscose and environment sensitive type hydrogel.
Embodiment 2
Bamboo shoots tankage prepare a method for environment sensitive type hydrogel, specifically comprise the following steps:
(1) bamboo shoots tankage are after washing, and in 70 DEG C of dry 12h, be cut into small pieces shape, and 80 mesh sieves pulverized by pulverizer, and obtain bamboo shoots ground-slag end, its powder diameter is 0.1-0.6mm;
(2) in bamboo shoots ground-slag end, add distilled water, the mass ratio of bamboo shoots ground-slag and distilled water is 1:20, and complete process 2h under 70 DEG C of conditions, passivation bamboo shoots active enzyme; Add the Glacial acetic acid adjustment pH to 3.8 that massfraction is 10%, add Textone in 80 DEG C of bleaching 2h (mass ratio of Textone and bamboo shoots ground-slag is 1:1);
(3) after bleaching, insoluble flocculent substance in filtering solution, and with distilled water wash, it is colourless to filtrate, massfraction 90% ethanolic soln is adopted to carry out alcohol wash 4 times, last in 60 DEG C of drying treatment 20h, obtain pre-treatment bamboo shoots fiber, be denoted as PBSC (PretreatmentBambooShootCellulose);
(4) pre-treatment bamboo shoots Mierocrystalline cellulose was pulverized 80 mesh sieves, joining massfraction is alkalinisation treatment 16h in 10% potassium hydroxide solution, wherein the amount ratio of pre-treatment bamboo shoots Mierocrystalline cellulose and potassium hydroxide aqueous solution is 1g:15ml, it is neutral for carrying out washing to filtrate with distilled water after alkalization, then volume fraction is used to be that 95% ethanol and dehydrated alcohol respectively wash 1 time, in 50 DEG C of dry 16h, obtain bamboo shoots Mierocrystalline cellulose after de-hemicellulose, be denoted as BSC (BambooShootCellulose);
(5) cross 80 mesh sieves after being pulverized by bamboo shoots Mierocrystalline cellulose after de-hemicellulose and carry out carboxymethyl-modification, modified condition is as follows: be added to by 10g bamboo shoots Mierocrystalline cellulose (in aqueous isopropanol, the mass ratio of distilled water and Virahol is 1:9) in the aqueous solution of 200ml Virahol, the mass percent adding 80ul is more successively the hydrogen peroxide of 30%, 16ml mass percent is the NaOH solution of 50%, alkalinisation treatment 2h; Alkalize complete, add the ethanolic soln of the sodium chloroacetate of the concentration 50% (w/v) of 14ml, carry out first time gradient increased temperature etherificate, recover room temperature, add the NaOH solution that 6ml mass percent is 50%, carry out double alkalisation 30min, alkalize complete, add the ethanolic soln of the sodium chloroacetate of the concentration 50% (w/v) of 3.5ml, carry out second time gradient increased temperature etherificate; The processing condition of gradient increased temperature etherificate and second time intensification etherificate for the first time: with 40r/min rotating speed stir process 30min under room temperature, with the rotating speed shaking water bath 30min of 130r/min at 45 DEG C, shaking water bath 30min is continued with the rotating speed of 110r/min again, finally in 75 DEG C of process 80min at 60 DEG C;
(6), after etherificate, abandoning supernatant, adds 300ml methyl alcohol room temperature concussion 30min (rotating speed is 130r/min), after filtration, after again adding 300ml methyl alcohol, shake 30min, leave standstill 12h, pH is regulated to be neutral with Glacial acetic acid, stir, leave standstill abandoning supernatant, use the ethanolic soln of volume fraction 75%, 85%, 95% to carry out cleaning 3 times to precipitation successively successively, filter, dry 16h at 50 DEG C, the carboxymethylation bamboo shoots Mierocrystalline cellulose after obtaining modification, is designated as MBSC;
(7) by the aqueous solution of 12%Urea/7%NaOH, take out preserve 12h in-20 DEG C of refrigerators after, treat that thermometer instruction solution temperature is-12 DEG C, solution presents mixture of ice and water state, MBSC and beta-cyclodextrin are carried out in dehydrated alcohol moistening after, by MBSC and beta-cyclodextrin (MBSC and beta-cyclodextrin mass ratio 7:3, total consumption of MBSC and beta-cyclodextrin is 7% of 12%Urea/7%NaOH aqueous solution quality) join in the 12%Urea/7%NaOH aqueous solution of 100g, stir 5min with 1000rpm rotating speed; Add 10ml epoxy chloropropane and carry out ultrasonic deaeration process 3min, ultrasonic power is 300W, obtains mixed glue solution; After being disposed, mixed glue solution is slowly poured on culture dish, fluid-tight is carried out with whiteruss, enter to prevent the oxygen in air and the generation of bubble, room temperature leaves standstill 36h, and modification bamboo shoots Mierocrystalline cellulose and beta-cyclodextrin are fully cross-linked, and removes whiteruss, use deionized water, 95% ethanol wash, and obtain water white hydrogel nahlock; Afterwards, hydrogel nahlock is put into distilled water and soaks 7d, the reticulated structure of hydrogel stretches to allow moisture fully promote, repeatedly changes water to hydrogel and remove unreacted reagent in immersion process; After immersion, dry the moisture of hydrogel surface with qualitative filter paper, pre-freeze final vacuum lyophilize (temperature-50 DEG C, the time is 30h), obtains loose porous modification bamboo shoots Mierocrystalline cellulose/beta-cyclodextrin water-setting blob of viscose and environment sensitive type hydrogel.
Embodiment 3
Bamboo shoots tankage prepare a method for environment sensitive type hydrogel, specifically comprise the following steps:
(1) bamboo shoots tankage are after washing, and after carrying out dry 12h in 70 DEG C, be cut into small pieces shape, and 80 mesh sieves pulverized by pulverizer, and obtain bamboo shoots ground-slag end, its powder diameter is 0.1-0.6mm;
(2) in bamboo shoots ground-slag end, add distilled water, the mass ratio of bamboo shoots ground-slag and distilled water is 1:20, and complete process 2h under 70 DEG C of conditions, passivation bamboo shoots active enzyme; Add the Glacial acetic acid adjustment pH to 3.8 that massfraction is 10%, add Textone in 80 DEG C of bleaching 2h (mass ratio of Textone and bamboo shoots ground-slag is 1:1);
(3) after bleaching, insoluble flocculent substance in filtering solution, and with distilled water wash, it is colourless to filtrate, massfraction 90% ethanolic soln is adopted to carry out alcohol wash 4 times, last in 60 DEG C of drying treatment 20h, obtain pre-treatment bamboo shoots fiber, be denoted as PBSC (PretreatmentBambooShootCellulose);
(4) pre-treatment bamboo shoots Mierocrystalline cellulose was pulverized 80 mesh sieves, joining massfraction is alkalinisation treatment 16h in 10% potassium hydroxide solution, wherein the amount ratio of pre-treatment bamboo shoots Mierocrystalline cellulose and potassium hydroxide aqueous solution is 1g:15ml, it is neutral for carrying out washing to filtrate with distilled water after alkalization, then volume fraction is used to be that 95% ethanol and dehydrated alcohol respectively wash 1 time, in 50 DEG C of dry 16h, obtain bamboo shoots Mierocrystalline cellulose after de-hemicellulose, be denoted as BSC (BambooShootCellulose);
(5) cross 80 mesh sieves after being pulverized by bamboo shoots Mierocrystalline cellulose after de-hemicellulose and carry out carboxymethyl-modification, modified condition is as follows: be added to by 10g bamboo shoots Mierocrystalline cellulose (in aqueous isopropanol, the mass ratio of distilled water and Virahol is 1:9) in the aqueous solution of 200ml Virahol, the mass percent adding 80ul is more successively the hydrogen peroxide of 30%, 16ml mass percent is the NaOH solution of 50%, alkalinisation treatment 2h; Alkalize complete, add the ethanolic soln of the sodium chloroacetate of the concentration 50% (w/v) of 14ml, carry out first time gradient increased temperature etherificate, recover room temperature, add the NaOH solution that 6ml mass percent is 50%, carry out double alkalisation 30min, alkalize complete, add the ethanolic soln of the sodium chloroacetate of the concentration 50% (w/v) of 4ml, carry out second time gradient increased temperature etherificate; The processing condition of gradient increased temperature etherificate and second time intensification etherificate for the first time: with 40r/min rotating speed stir process 30min under room temperature, with the rotating speed shaking water bath 30min of 130r/min at 45 DEG C, shaking water bath 30min is continued with the rotating speed of 110r/min again, finally in 75 DEG C of process 80min at 60 DEG C;
(6), after etherificate, abandoning supernatant, adds 300ml methyl alcohol room temperature concussion 30min (rotating speed is 130r/min), after filtration, shake 30min after again adding 300ml methyl alcohol, leave standstill 12h, regulate pH to be neutral with Glacial acetic acid, stir, leave standstill abandoning supernatant, use the ethanolic soln of volume fraction 75%, 85%, 95% to carry out cleaning 3 times to precipitation successively successively, filter, dry 16h at 50 DEG C, the carboxymethylation bamboo shoots Mierocrystalline cellulose after obtaining modification is designated as MBSC;
(7) by the aqueous solution of 12%Urea/7%NaOH, take out preserve 12h in-20 DEG C of refrigerators after, treat that thermometer instruction solution temperature is-12 DEG C, solution presents mixture of ice and water state, by MBSC and beta-cyclodextrin (MBSC and beta-cyclodextrin mass ratio 8:2, total consumption of MBSC and beta-cyclodextrin is 7% of 12%Urea/7%NaOH aqueous solution quality) join in the 12%Urea/7%NaOH aqueous solution of 100g, stir 5min with 1000rpm rotating speed; Add 10ml epoxy chloropropane and carry out ultrasonic deaeration process 1min, ultrasonic power is 400W, obtains mixed glue solution; After being disposed, mixed glue solution is slowly poured on culture dish, fluid-tight is carried out with whiteruss, enter to prevent the oxygen in air and the generation of bubble, room temperature leaves standstill 36h, and modification bamboo shoots Mierocrystalline cellulose and beta-cyclodextrin are fully cross-linked, and removes whiteruss, use deionized water, 95% ethanol wash, and obtain water white hydrogel nahlock; Afterwards, hydrogel nahlock is put into distilled water and soaks 7d, the reticulated structure of hydrogel stretches to allow moisture fully promote, repeatedly changes water to hydrogel and remove unreacted reagent in immersion process; After immersion, dry the moisture of hydrogel surface with qualitative filter paper, pre-freeze final vacuum lyophilize (temperature-50 DEG C, the time is 30h), obtains loose porous modification bamboo shoots Mierocrystalline cellulose/beta-cyclodextrin water-setting blob of viscose and environment sensitive type hydrogel.
Embodiment 4
Bamboo shoots tankage prepare a method for environment sensitive type hydrogel, specifically comprise the following steps:
(1) bamboo shoots tankage are after washing, and after carrying out dry 12h in 70 DEG C, be cut into small pieces shape, and 80 mesh sieves pulverized by pulverizer, and obtain bamboo shoots ground-slag end, its powder diameter is 0.1-0.6mm.
(2) in bamboo shoots ground-slag end, add distilled water, the mass ratio of bamboo shoots ground-slag and distilled water is 1:20, and complete process 2h under 70 DEG C of conditions, passivation bamboo shoots active enzyme; Add the Glacial acetic acid adjustment pH to 3.8 that massfraction is 10%, add Textone in 80 DEG C of bleaching 2h (mass ratio of Textone and bamboo shoots ground-slag is 1:1);
(3) after bleaching, insoluble flocculent substance in filtering solution, and with distilled water wash, it is colourless to filtrate, massfraction 90% ethanolic soln is adopted to carry out alcohol wash 4 times, last in 60 DEG C of drying treatment 20h, obtain pre-treatment bamboo shoots fiber, be denoted as PBSC (PretreatmentBambooShootCellulose);
(4) pre-treatment bamboo shoots Mierocrystalline cellulose was pulverized 80 mesh sieves, joining massfraction is alkalinisation treatment 16h in 10% potassium hydroxide solution, wherein the amount ratio of pre-treatment bamboo shoots Mierocrystalline cellulose and potassium hydroxide aqueous solution is 1g:15ml, it is neutral for carrying out washing to filtrate with distilled water after alkalization, then volume fraction is used to be that 95% ethanolic soln and dehydrated alcohol respectively wash 1 time, in 50 DEG C of dry 16h, obtain bamboo shoots Mierocrystalline cellulose after de-hemicellulose, be denoted as BSC (BambooShootCellulose);
(5) cross 80 mesh sieves after being pulverized by bamboo shoots Mierocrystalline cellulose after de-hemicellulose and carry out carboxymethyl-modification, modified condition is as follows: be added to by 10g bamboo shoots Mierocrystalline cellulose (in aqueous isopropanol, the mass ratio of distilled water and Virahol is 1:9) in the aqueous solution of 200ml Virahol, the mass percent adding 80ul is more successively the hydrogen peroxide of 30%, 16ml mass percent is the NaOH solution of 50%, alkalinisation treatment 2h; Alkalize complete, add the ethanolic soln of the sodium chloroacetate of the concentration 50% (w/v) of 14ml, carry out first time gradient increased temperature etherificate, recover room temperature, add the NaOH solution that 6ml mass percent is 50%, carry out double alkalisation 30min, alkalize complete, add the ethanolic soln of the sodium chloroacetate of the concentration 50% (w/v) of 4ml, carry out second time gradient increased temperature etherificate; The processing condition of gradient increased temperature etherificate and second time intensification etherificate for the first time: with 40r/min rotating speed stir process 30min under room temperature, with the rotating speed shaking water bath 30min of 130r/min at 45 DEG C, shaking water bath 30min is continued with the rotating speed of 110r/min again, finally in 75 DEG C of process 80min at 60 DEG C;
(6), after etherificate, abandoning supernatant, adds 300ml methyl alcohol room temperature concussion 30min (rotating speed is 130r/min), after filtration, shake 30min after again adding 300ml methyl alcohol, leave standstill 12h, regulate pH to be neutral with Glacial acetic acid, stir, leave standstill abandoning supernatant, use the ethanolic soln of volume fraction 75%, 85%, 95% to carry out cleaning 3 times to precipitation successively successively, filter, dry 16h at 50 DEG C, the carboxymethylation bamboo shoots Mierocrystalline cellulose after obtaining modification;
(7) take out after the aqueous solution of 12%Urea/7%NaOH being preserved 12h in-20 DEG C of refrigerators, treat that thermometer instruction solution temperature is-12 DEG C, solution presents mixture of ice and water state, by MBSC and beta-cyclodextrin (MBSC and beta-cyclodextrin mass ratio 9:1, total consumption of MBSC and beta-cyclodextrin is 7% of 12%Urea/7%NaOH aqueous solution quality) join in the 12%Urea/7%NaOH aqueous solution of 100g, stir 5min with 1000rpm rotating speed; Add 10ml epoxy chloropropane and carry out ultrasonic deaeration process 1min, ultrasonic power is 400W, obtains mixed glue solution; After being disposed, mixed glue solution is slowly poured on culture dish, fluid-tight is carried out with whiteruss, enter to prevent the oxygen in air and the generation of bubble, room temperature leaves standstill 48h, and modification bamboo shoots Mierocrystalline cellulose and beta-cyclodextrin are fully cross-linked, and removes whiteruss, use deionized water, 95% ethanol wash, and obtain water white hydrogel nahlock; Afterwards, hydrogel nahlock is put into distilled water and soaks 7d, the reticulated structure of hydrogel stretches to allow moisture fully promote, repeatedly changes water to hydrogel and remove unreacted reagent in immersion process; After immersion, dry the moisture of hydrogel surface with qualitative filter paper, pre-freeze final vacuum lyophilize (temperature-50 DEG C, the time is 30h), obtains loose porous modification bamboo shoots Mierocrystalline cellulose/beta-cyclodextrin water-setting blob of viscose and environment sensitive type hydrogel.
Performance test:
(1) the FTIR spectrum analysis of the i.e. environment sensitive type hydrogel prepared of embodiment 1-4 and bamboo shoots fiber/beta-cyclodextrin composite aquogel:
Get a certain amount of embodiment 1-4 freeze-drying hydrogel, use KBr (spectroscopically pure) compressing tablet, then scan, the sweep limit of FT-IR spectrum: 4000cm
-1-400cm
-1, resolving power is 2cm
-1.The FT-IR spectrogram of composite aquogel as shown in Figure 1, is found out, 3430-3440cm from infrared spectrum
-1near and 2920cm
-1vicinity shows the absorption peak of O – H stretching vibration and the stretching vibration of C-H feature in representation polymer respectively, simultaneously at 1630cm
-1and 1430cm
-1there is absorption peak position, this is that carboxyl carries out symmetry and asymmetric vibrations cause, this is due to the hydroxyl generation hydrogen bond action on the hydroxyl of cyclodextrin hydrophilic end and bamboo shoots carboxymethyl cellulose, cause the absorption peak of carboxyl on bamboo shoots carboxymethylcellulose backbone to there occurs displacement, this proves the physical action occurred therebetween.In addition at 1115cm
-1, 1120cm
-1there is the flexible vibrations of C-O and the flexible vibrations peak of C-O-C in place, this is the vibrations of C-O singly-bound in beta cyclo dextrin polymer inner chamber, shows that composite aquogel is successful and connect with beta-cyclodextrin, and 1045cm
-1and 1060cm
-1place's absorption peak should be that the ehter bond that epoxy chloropropane and the two polymkeric substance are cross-linked to form caused, and overall peak shape is wider than bamboo shoots carboxymethyl cellulose peak shape.At 624cm
-1, 587cm
-1-CH in beta-cyclodextrin
2c-H rocking vibration absorption peak, along with the increase of its content, this peak is also subjected to displacement.Same displacement also occurs in the flexible vibrations of O-H on polymer backbone, and the O – H stretching vibration of bamboo shoots carboxymethyl cellulose is at 3385cm
-1place.But in composite aquogel, along with the content of beta-cyclodextrin constantly increases, its absorption peak is past high wave-number migration constantly, from 3431cm
-1be offset to 3441cm
-1, illustrate that beta-cyclodextrin content can affect the power of Hyarogen-bonding between it and bamboo shoots carboxymethyl cellulose in hydrogel.
(2) the environment sensitive type hydrogel of embodiment 2 preparation and the sem analysis of modification bamboo shoots fiber/beta-cyclodextrin composite aquogel:
Freeze-drying hydrogel film sample conductive resin embodiment 2 prepared sticks on copper dish, after metal spraying process, under 10k acceleration voltage, the surface topography of hydrogel is observed by scanning electron microscope, its result as shown in Fig. 2 (a), when after hydrogel Adsorption Model medicine sodium salicylate in embodiment 2 its SEM scheme as shown in Fig. 2 (b).
Hydrogel surface is observed slightly coarse from Fig. 2 (a), this determined by bamboo shoots carboxymethyl cellulose structure, be dispersed with diameter in the above at about 5-10 μm, compact construction, in picturesque disorder intensive porous, and the distinctive acicular structure of more bamboo shoots carboxymethyl cellulose can be observed around it.The hole wall that can be observed composite aquogel from Fig. 2 (a) is equally in fibrous texture, and the path micropore just in the existence of these structures and composite aquogel gives the ability that hydrogel adsorbs swelling behavior and slow releasing pharmaceutical preferably.Composite aquogel mesoporous be formed with two reasons, first: the carboxylate anion (COO in composite aquogel
-) there is electrostatic repulsion, under electrostatic repulsion effect, cause gel aperture to increase, but due to the hydrogen bond action of beta-cyclodextrin shell hydroxyl and bamboo shoots cellulose skeleton in composite aquogel, cut down electrostatic tension to a certain extent, make the aperture of this composite aquogel less, the raising of restriction swelling ratio, but be beneficial to the absorption of drug model molecule; The second, composite aquogel circulates through multigelation, and on polymer backbone, molecular chain constantly tangles at random, making polymer network after cross-linking from concluding, carrying out the directional realignment of molecular chain, makes hydrogel produce Process.
Fig. 2 (b) compares Fig. 2 (a) original intensive vesicular structure major part and shrinkage occurs, only deposit the pore of a small amount of diameter less than 0.8 μm, the fibrous texture that hole wall presents also goes to pot, this is mainly due to when carrying medicament, namely hydrogel micropore starts to shrink, hole diminishes gradually, and even the shrinkage of generation hole causes.Hydrogel has carrying medicament ability mainly because its electrostatic repulsion causes targeted drug by outside to inside carrying out absorption and diffusion, and in this process, hydrogel provides a large amount of ducts for it, is conducive to the carrying out adsorbed.By SEM, composite aquogel is characterized, from microscopic appearance aspect for hydrogel possesses swelling behavior and medicament slow release performance provides a strong circumstantial evidence.
(3) the X diffraction analysis of the environment sensitive type hydrogel prepared of embodiment 1-3 and modification bamboo shoots fiber/beta-cyclodextrin composite aquogel.
Carry out X diffraction analysis to hydrogel in embodiment 1-3, concrete operations condition is as follows: copper target, 40KV, and step-length is 0.02 °, and sweep velocity is 18s/ step, and scanning angle scope is 5-60 °, and its result as shown in Figure 3.The X-ray diffraction spectrum form of the composite aquogel of embodiment 1-3 is substantially identical, respectively at 32 °, there are three obvious diffraction peaks at 45 ° and 56 ° of places, this is due between composite aquogel internal fiber element skeleton carboxyl, beta-cyclodextrin shell hydroxyl and cellulose hydroxyl group, the peak crystallization that the hydrogen bond association occurred between beta-cyclodextrin shell hydroxyl and carboxyl causes.The Intermolecular Forces of beta-cyclodextrin shell hydroxyl and cellulose hydroxyl group is the major cause causing composite aquogel to produce crystalline texture, and the diffraction peak of original bamboo shoots fiber 17 ° and 22 ° obviously disappears, illustrate that bamboo shoots fiber is after modification is also crosslinked, there is obvious change in its crystalline texture, and diffraction peak disappear degree and composite aquogel in beta-cyclodextrin content be negative correlation.On composite aquogel, the intensity of three diffraction peaks but has significant difference along with the change of MBSC in composite aquogel and beta-cyclodextrin mass ratio, this causes the carboxyl in itself and cellulose skeleton and hydroxyl hydrogen bond action constantly to strengthen caused mainly along with the increase of beta-cyclodextrin content in composite aquogel.
(4) the environment sensitive type hydrogel prepared of embodiment 2 and modification bamboo shoots fiber/beta-cyclodextrin composite aquogel temperature sensitivity detect, and test result as shown in Figure 4.
Hydrogel goes swelling ratio measuring method as follows in deionized water at different temperatures: the dried hydrogel of accurate weighing certain mass is in beaker, be allowed to condition in differing temps deionised water water and reach swelling equilibrium (180min), dry hydrogel surface with filter paper afterwards, measure its swelling ratio; The Swelling Dynamics of hydrogel be measure at different temperatures hydrogel at the swelling ratio of different time, the following formula of basis of concrete swelling behavior rate: SW=(W
t-W
d)/W
d, in formula: W
twith W
drepresent swelling behavior process moment quality and vacuum-freeze-dry hydrogel quality (g) respectively; The equilibrium swelling ratio (g/g) of what SW represented is hydrogel.
The relation of composite aquogel swelling ratio and temperature is as shown in Fig. 4 (a), swelling ratio general trend along with the rising composite aquogel of temperature constantly declines, wherein swelling behavior rate the biggest drop within the scope of 10 DEG C-30 DEG C, when envrionment temperature is 10 DEG C, the swelling ratio of hydrogel is 203.05g/g, and when envrionment temperature is increased to 80 DEG C, swelling behavior rate obviously declines, only reach 79.37g/g, illustrate that this glue is to temperature sensitive.
Next 15 DEG C are chosen, 30 DEG C, 4 temperature such as 45 DEG C and 60 DEG C make a concrete analysis of the Swelling Dynamics difference of hydrogel, its result is as shown in Fig. 4 (b), can find out that composite aquogel is swelling early stage in 0-60min, the construction stretch speed of composite aquogel is very fast, the most finally swelling equilibrium is substantially reached after 360min, temperature sensitive performance is presented in the swelling process of hydrogel, namely along with temperature reduces the swelling ratio increase of this composite aquogel, when temperature is at 15 DEG C, the equilibrium swelling ratio of this composite aquogel reaches 233.38g/g, and when temperature rises to 70 DEG C, the swelling ratio of composite aquogel only has 102.30g/g.
The temperature sensitivity major cause that has of composite aquogel is: in hydrogel on beta-cyclodextrin-OH to the hydrophilic interaction of water molecules in solution, and-OH on itself and bamboo shoots carboxymethylcellulose backbone and-COOH also exists hydrogen bond and intermolecular reactive force, maintain the tridimensional network of hydrogel, along with the continuous rising of system temperature, tridimensional network hydrogen bond action is constantly weakened, the macromolecular chain of whole tridimensional network gradually loose opening is distributed in the middle of solution system, and hydrogel to be increased and swelling ratio declines along with envrionment temperature.
(5) the salts solution deswelling dynamics research of the environment sensitive type hydrogel of embodiment 2 preparation:
Hydrogel deswelling dynamics measuring method in salts solution is as follows: the dried hydrogel of accurate weighing certain mass is in beaker, be allowed to condition in deionized water and reach swelling equilibrium (360min), hydrogel surface is dried afterwards with filter paper, then put it in the salts solution of different concns and different ions kind, at once deswelling is there is in hydrogel in beaker, measure the swelling ratio of hydrogel different time in salts solution, the following formula of basis of concrete swelling behavior rate: SW=(W
t-W
d)/W
d, in formula: W
twith W
drepresent swelling behavior process moment quality and vacuum-freeze-dry hydrogel quality (g) respectively; The equilibrium swelling ratio (g/g) of what SW represented is hydrogel.Composite aquogel different concns (0.1M, 0.01M) salts solution deswelling dynamics as shown in Figure 5.Experimental result shows, for four in Fig. 5 kind of salts solution (NaCl, CaCl
2, FeCl
3, KCl), the hydrogel after swelling equilibrium all can present the performance of fast response, and along with the raising of salts solution ionic strength, the responsiveness of this composite aquogel is more obvious.By contrast, after composite aquogel reaches salts solution Deswelling equilibrium after 360min, at the FeCl of the maximum 0.1M of ionic strength
3in solution, its water-retention value is only 7.35%.This composite aquogel occurs that such swelling behavior is the increase due to the ionic strength along with salts solution, cause the osmotic pressure between aquogel polymer inside configuration and solution to reduce, greatly weaken water molecules enters into hydrogel inside ability by the partial potential that osmotic pressure produces.When concentration of salt solution is larger (0.1M), solution ion strength improves (Fe along with the increase of metal ion valence state
3+> Ca
2+> K
+≈ Na
+), the inside and outside partial potential produced of composite aquogel also declines because of the raising of ionic strength, and therefore swelling ratio order (descending) of composite aquogel in salts solution is NaCl, CaCl respectively
2, FeCl
3.This have the ionic strength sensibility hydrogel well removing swelling behavior, may have potential using value in the controlled fertilising material in modern agriculture.
(6) the environment sensitive type hydrogel of embodiment 2 preparation and the pH sensitivity tests of modification bamboo shoots fiber/beta-cyclodextrin composite aquogel:
The swelling ratio of hydrogel is measured by quality change before and after swelling behavior, the swelling process of hydrogel carries out in different pH buffer solution system, concrete operations are as follows: the dried hydrogel of certain mass is in 100ml beaker, the freeze-drying hydrogel weighed is kept to be independent monoblock, then, different pH damping fluid is poured in beaker, hydrogel at once occurs swelling in beaker, measure hydrogel different pH equilibrium swelling ratio (after 360min), when the reversible response type of the pH measuring hydrogel, first hydrogel is placed in pH1.8 damping fluid, separated in time measures the swelling ratio of hydrogel, afterwards hydrogel surface filter paper is dried.
The reversible responsiveness of hydrogel to pH is measured by quality change before and after swelling behavior, concrete operations are as follows: the dried hydrogel of certain mass is in 100ml beaker, the freeze-drying hydrogel weighed is kept to be independent monoblock, then, different pH damping fluid is poured in beaker, hydrogel at once occurs swelling in beaker, measure hydrogel different pH equilibrium swelling ratio (after 360min), when the reversible response type of the pH measuring hydrogel, first hydrogel is placed in pH1.8 damping fluid, separated in time measures the swelling ratio of hydrogel, afterwards hydrogel surface filter paper is dried, proceed in pH7.4 damping fluid, continue separated in time and measure swelling behavior rate, circulation like this, measure the reversible response performance of pH of hydrogel, the following formula of basis of concrete swelling behavior rate: SW=(W
t-W
d)/W
d, in formula: W
twith W
drepresent swelling behavior process moment quality and vacuum-freeze-dry hydrogel quality (g) respectively, the equilibrium swelling ratio (g/g) of what SW represented is hydrogel.The pH susceptibility of composite aquogel and can reverse response as shown in Figure 6, owing to composite aquogel there being-COOH functional group, it can produce the respondent behavior of pH value in the solution due to electrostatic repulsion, this point is confirmed by experiment.Experimental result finds that this composite aquogel water-retaining capacity in different pH solution can produce notable difference, as shown in Fig. 6 (a), as pH < 4, or under 7 < pH < 8 conditions, composite aquogel affects larger by pH.As pH < 4 ,-COO in molecule
-group proton turns to-COOH, due to its hydrogen bond action, hydrogel network is shunk and strengthens gel network structure, greatly reducing equilibrium swelling ratio, and as pH > 7, in hydrogel ,-COOH ionization occurs for-COO
-, under the effect of electrostatic tension, make hydrogel three-dimensional reticulated structure launch, improve its swelling ratio.In addition, owing to being flooded with a large amount of ion in this pH damping fluid, the Na in swelling media
+and K
+ion can make the swelling ratio of composite aquogel not as the equilibrium swelling ratio in pure water due to the effect of osmotic pressure and electron screening.
Due to the pH susceptibility of this composite aquogel, therefore this experimental simulation human gastric juice (pH1.8) and human body intestinal juice (pH7.4) study the reversible responsiveness of pH of composite aquogel, as the reversible responsiveness curve of pH that Fig. 6 (b) is hydrogel, when in the simulated gastric fluid of composite aquogel at pH1.8, swelling ratio is 22.09g/g, show as volumetric shrinkage, and when composite aquogel being proceeded to pH7.4 solution, the hydrogel shunk starts again swelling, equilibrium swelling ratio reaches 63.09g/g, front and back difference 2.856 times, so repeatedly, formed interesting, fast, the response phenomenon of circulating and reversible.The reversible response cycle of this kind of pH of composite aquogel has good theory significance and using value as medicine carrying material: when medicine needs to discharge at enteron aisle, can by Drug absorbability in this composite aquogel, when medicine carrying hydrogel is by gastric juice, its swelling behavior is very little, medicine can not be released, and when it arrives enteron aisle time, this hydrogel starts response, as Fig. 6 (b), just complete a circulation, realize the Targeting delivery of medicine, improve the bioavailability of medicine.
(7) the environment sensitive type hydrogel of embodiment 2 preparation and the organic solvent sensitivity tests of modification bamboo shoots fiber/beta-cyclodextrin composite aquogel.
The swelling ratio of hydrogel is measured by quality change before and after swelling behavior, the swelling process of hydrogel carries out in different organic solvents system, concrete operations are as follows: the dried hydrogel of certain mass is in 100ml beaker, the freeze-drying hydrogel weighed is kept to be independent monoblock, then, different organic solvents is poured in beaker, hydrogel at once occurs swelling in beaker, separated in time measures swelling behavior rate, again hydrogel surface filter paper is dried afterwards, proceed in distilled water, continue separated in time and measure swelling behavior rate, circulation like this, measure the reversible response performance of organic solvent of hydrogel, the following formula of basis of concrete swelling behavior rate: SW=(W
t-W
d)/W
d, in formula: W
twith W
drepresent swelling behavior process moment quality and vacuum-freeze-dry hydrogel quality (g) respectively, the equilibrium swelling ratio (g/g) of what SW represented is hydrogel.
Through experiment, as shown in Figure 7, hydrogel in organic solvent can rapid dehydration for the reversible swelling curve of composite aquogel in water-organic solvent, and network structure is shunk.Making hydrogel shrink the most significantly organic solvent is acetone, minimum swelling ratio only reaches 2.74g/g, but the composite aquogel shunk in organic solvent is immersed in deionized water again, hydrogel can be swelling rapidly, volume increases, and returns to original swelling levels (about 206g/g).Cause composite aquogel to occur so significantly organic solvent susceptibility, with the solubility parameters of hydrogel, the polar group of specific inductivity and solvent and the molecular interaction of hydrogel have direct relation.Analyze from the angle of Intermolecular Forces, basic structure due to composite aquogel is the macromolecular structure of bamboo modification bamboo shoot fibres sugars unit and beta-cyclodextrin composition, be flooded with a large amount of hydrogen bonds in such an embodiment, ensure the cancellated formation of hydrogel three-dimensional, when hydrogel absorbs water time, water molecules can enter hydrogel space, with-the OH on polymer backbone and-CH
2the groups such as OH form hydrogen bond, the final hydrogel formed macroscopically.And for most organic solvent, polarity is more weak than water molecules, cannot grab and replace the hydrogen bond that original copolymer skeleton has been formed, therefore hydrogel fast dewatering can be made after it enters hydrogel inside, on protofibril element skeleton, hydrogen bond recovers again, makes hydrogel structure shrinkage in organic solvent.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (10)
1. bamboo shoots tankage prepare a method for environment sensitive type hydrogel, it is characterized in that: concrete steps are:
(1) bamboo shoots tankage are carried out wash, dry, pulverize, obtain bamboo shoots ground-slag;
(2) distilled water is added in the bamboo shoots ground-slag of step (1) and carry out the process that completes, then regulate pH, then carry out bleaching, filter, washing, dry, obtain pre-treatment bamboo shoots fiber, be denoted as PBSC;
(3) pre-treatment bamboo shoots fiber added in alkaline solution carry out alkalinisation treatment, then wash, dry, obtain bamboo shoots Mierocrystalline cellulose after de-hemicellulose, be denoted as BSC;
(4) in the cellulosic reactor of bamboo shoots after de-hemicellulose is housed, add isopropanol water solution and hydrogen peroxide solution successively, mixing, adds sodium hydroxide solution 1 and carries out alkalinisation treatment, obtains alkalization bamboo shoots Mierocrystalline cellulose; Add sodium chloroacetate solution 1 again, carry out first time gradient increased temperature etherificate, after gradient increased temperature etherificate completes for the first time, recover room temperature, add sodium hydroxide solution 2 and carry out double alkalisation, alkalize complete, add sodium chloroacetate solution 2 and carry out second time gradient increased temperature etherificate; Described sodium hydroxide solution 1 and sodium hydroxide solution 2 are all sodium hydroxide solution; Described sodium chloroacetate solution 1 and sodium chloroacetate solution 2 are all the alcoholic solution of sodium chloroacetate;
(5) after etherificate completes, be cooled to room temperature, remove supernatant liquor, add methyl alcohol and process, then adopt ethanolic soln to wash, dry, obtain the carboxymethylation bamboo shoots Mierocrystalline cellulose of modification, be denoted as MBSC;
(6) aqueous solution of 12%Urea/7%NaOH is carried out freezing, take out, when aqueous temperature is-12 to-15 DEG C, MBSC and beta-cyclodextrin are added in the aqueous solution of 12%Urea/7%NaOH, stirring and evenly mixing, then add epoxy chloropropane, ultrasonic deaeration, fluid-tight, left at room temperature 36-48h, removes fluid-tight, washing, soak, dry, obtain environment sensitive type hydrogel and loose porous modification bamboo shoots Mierocrystalline cellulose/beta-cyclodextrin water-setting blob of viscose.
2. bamboo shoots tankage prepare the method for environment sensitive type hydrogel according to claim 1, it is characterized in that: MBSC and beta-cyclodextrin described in step (6) need to adopt dehydrated alcohol to carry out moistening before use, described MBSC and beta-cyclodextrin mass ratio 6:4 ~ 9:1; Described MBSC and the total consumption of beta-cyclodextrin are 5% ~ 7% of the aqueous solution quality of 12%Urea/7%NaOH; The aqueous solution of described 12%Urea/7%NaOH and the mass volume ratio of epoxy chloropropane are 100g:(5 ~ 10) mL; The rotating speed of described stirring is 800 ~ 1000rpm, and the time of stirring is 3 ~ 5min;
The condition of ultrasonic deaeration described in step (6) is ultrasonic power is 300 ~ 600W, and ultrasonic time is 1 ~ 3min.
3. bamboo shoots tankage prepare the method for environment sensitive type hydrogel according to claim 1, it is characterized in that: after de-hemicellulose described in step (4), the amount ratio of bamboo shoots Mierocrystalline cellulose, isopropanol water solution, hydrogen peroxide solution and sodium hydroxide solution 1 is (10 ~ 12) g:200mL:(80 ~ 100) uL:(16 ~ 20) mL;
In aqueous isopropanol described in step (4), the volume ratio of distilled water and Virahol is 1:(8.5 ~ 10); The mass percent concentration of described hydrogen peroxide solution is 30% ~ 35%; Described sodium hydroxide solution 1 for mass percent be the sodium hydroxide solution of 40%-50%; Described in step (4), alkalization time is 2 ~ 3h;
After de-hemicellulose described in step (4), the mass volume ratio of bamboo shoots Mierocrystalline cellulose and sodium hydroxide solution 2 is (10 ~ 12) g:(6 ~ 10) mL, sodium hydroxide solution 2 for mass percent be the sodium hydroxide solution of 50%; The time of double alkalisation is 30min.
4. bamboo shoots tankage prepare the method for environment sensitive type hydrogel according to claim 1, it is characterized in that: first time described in step (4) heat up etherificate, second time intensification etherificate processing condition be: by reaction solution first under the condition of magnetic agitation in room temperature treatment 30 ~ 50min, then shaking table is transferred in 40 ~ 45 DEG C of shaking water bath 30 ~ 40min, be warming up to 55 ~ 60 DEG C and continue shaking water bath 30 ~ 40min, then be warming up to 75 ~ 80 DEG C of pyroprocessing 80 ~ 90min; The rotating speed of described magnetic agitation is 30 ~ 40r/min, and the rotating speed of shaking water bath is 120 ~ 135r/min, and the rotating speed continuing shaking water bath is 100 ~ 120r/min.
5. bamboo shoots tankage prepare the method for environment sensitive type hydrogel according to claim 1, it is characterized in that:
Described in step (4), sodium chloroacetate solution 1 and sodium chloroacetate solution 2 are all the ethanolic soln of sodium chloroacetate, and the concentration of two solution is identical; In the ethanolic soln of described sodium chloroacetate, the mass volume ratio of the ethanolic soln of sodium chloroacetate and sodium chloroacetate is 1g:2mL;
After de-hemicellulose described in step (4), the mass volume ratio of bamboo shoots Mierocrystalline cellulose and sodium chloroacetate solution 1 is (10 ~ 12) g:(12 ~ 16) mL;
The consumption of described sodium chloroacetate solution 2 is 0.25 ~ 0.29 times of sodium chloroacetate solution 1.
6. bamboo shoots tankage prepare the method for environment sensitive type hydrogel according to claim 1, it is characterized in that: the condition of the process that completes described in step (2) processes 2h ~ 2.5h for completing in 65 ~ 80 DEG C; Described bamboo shoots ground-slag end is 1:20 ~ 1:25 with the mass ratio of distilled water; Described pH is 3.8 ~ 4.0, and the material of described adjustment pH is the glacial acetic acid solution of massfraction 10% ~ 15%;
Described in step (2), the SYNTHETIC OPTICAL WHITNER of bleaching is Textone, and the mass ratio of described bamboo shoots powder and Textone is 1:1 ~ 1:0.8; Described in step (2), the temperature of bleaching is 75 ~ 80 DEG C, and described bleaching time is 2 ~ 3h;
Described in step (3), the mass volume ratio of pre-treatment bamboo shoots fiber and alkaline solution is 1g:(15 ~ 20) ml; Described in step (3), the mass percent concentration of alkaline solution is 10% ~ 15%; The time of described alkalinisation treatment is 12 ~ 20h;
Drying conditions described in step (5) is in 45 ~ 50 DEG C of drying 16 ~ 20h.
7. bamboo shoots tankage prepare the method for environment sensitive type hydrogel according to claim 1, it is characterized in that: described in step (3), alkaline solution is potassium hydroxide solution; Condition dry described in step (3) is dry 16 ~ 20h at 50 ~ 70 DEG C; Described in step (3), the concrete grammar of washing is: first use distilled water wash filtrate pH to neutral, use afterwards volume fraction be 95% ethanolic soln and dehydrated alcohol respectively wash 1 time;
Washing described in step (2) refers to and first adopts distilled water to wash until filtrate is colourless the insoluble floss after filtration, then adopts ethanolic soln to carry out alcohol wash, alcohol wash 3 ~ 5 times; The mass percent of described ethanolic soln is 85% ~ 95%; The condition of described drying is in 50 ~ 70 DEG C of drying treatment 16 ~ 20h;
After methyl alcohol process refers to and adds methyl alcohol described in step (5), in room temperature shaker concussion 30 ~ 40min, filter, again add methyl alcohol and carry out concussion 20 ~ 50min, after leaving standstill 12 ~ 16h, be adjusted to neutrality with Glacial acetic acid, stir, leave standstill, remove upper liquid; Described ethanolic soln carries out washing and refers to that employing volume fraction is that 75%, 85%, 95% ethanolic soln washs product successively; The speed of described shaking table vibration is 100 ~ 140r/min.
8. bamboo shoots tankage prepare the method for environment sensitive type hydrogel according to claim 1, it is characterized in that: washing described in step (1) adopts clear water to wash, described drying is for drying or drying, the condition of described oven dry is the temperature of drying is 70 ~ 80 DEG C, and drying time is 12 ~ 16h;
Described in step (6), freezing conditions is: preserve 12 ~ 18h in-20 DEG C; Described fluid-tight adopts whiteruss to carry out fluid-tight, and described washing refers to and adopts deionized water, volume fraction 95% ethanol successively; Described immersion refers to and adopts distilled water to soak, and soak time is 3 ~ 7d, repeatedly changes water to hydrogel and remove unreacted reagent in immersion process; Described drying is vacuum lyophilization.
9. one kind prepares environment sensitive type hydrogel by the method described in any one of claim 1 ~ 8.
10. according to claim 9 environment sensitive type hydrogel in the application in the absorption of cationic dyestuff molecule, controlled fertilising material and Thermosensitive Material Used for Controlled Releasing of Medicine field.
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