CN117304365A - Synthesis method of hydrophobically modified sodium alginate - Google Patents
Synthesis method of hydrophobically modified sodium alginate Download PDFInfo
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- CN117304365A CN117304365A CN202311429071.9A CN202311429071A CN117304365A CN 117304365 A CN117304365 A CN 117304365A CN 202311429071 A CN202311429071 A CN 202311429071A CN 117304365 A CN117304365 A CN 117304365A
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical class CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 239000000661 sodium alginate Substances 0.000 claims abstract description 51
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 51
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 29
- 229920000615 alginic acid Polymers 0.000 claims abstract description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- MZFGYVZYLMNXGL-UHFFFAOYSA-N undec-10-enoyl chloride Chemical compound ClC(=O)CCCCCCCCC=C MZFGYVZYLMNXGL-UHFFFAOYSA-N 0.000 claims abstract description 18
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229940072056 alginate Drugs 0.000 claims abstract description 17
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229960001126 alginic acid Drugs 0.000 claims abstract description 12
- 239000000783 alginic acid Substances 0.000 claims abstract description 12
- 150000004781 alginic acids Chemical class 0.000 claims abstract description 12
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims abstract description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229960002703 undecylenic acid Drugs 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005457 ice water Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019253 formic acid Nutrition 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 57
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 12
- 238000005063 solubilization Methods 0.000 description 9
- 230000007928 solubilization Effects 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- 229940109262 curcumin Drugs 0.000 description 6
- 235000012754 curcumin Nutrition 0.000 description 6
- 239000004148 curcumin Substances 0.000 description 6
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 description 6
- ITYXXSSJBOAGAR-UHFFFAOYSA-N 1-(methylamino)-4-(4-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=C(C)C=C1 ITYXXSSJBOAGAR-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
Abstract
The invention belongs to the technical field of biological materials, and particularly discloses a synthesis method of hydrophobically modified sodium alginate. For supporting hydrophobic substances. The method comprises the following steps: sodium alginate was dispersed in formic acid solution under ice water bath, after 1h the ice bath was removed and reacted overnight at room temperature. Adding 70% ethanol for washing and suction filtering to obtain alginic acid. Adding water into alginic acid, neutralizing with tetrabutylammonium hydroxide solution, and freeze drying to obtain tetrabutylammonium alginate. After undecylenic acid and excessive thionyl chloride react, the solvent is dried by spin, and the undecylenic acid chloride is obtained by vacuum pumping to constant weight. Adding tetrabutylammonium alginate and 4-dimethylaminopyridine into a three-necked bottle, vacuumizing, introducing nitrogen, injecting dimethyl sulfoxide and triethylamine, adding undecylenoyl chloride in an ice water bath, reacting for 1h at 0 ℃, and heating to room temperature for continuous reaction for 24h. After the saturated sodium chloride solution is added for reaction, the mixture is dialyzed in 0.1mol/L sodium chloride solution and deionized water in sequence, and freeze-dried.
Description
Technical Field
The invention belongs to the technical field of biological materials, and particularly relates to a synthesis method of hydrophobically modified sodium alginate.
Background
Sodium alginate is a hydrophilic natural polysaccharide existing in brown algae plants and bacteria, has good biocompatibility and no toxicity, and can be crosslinked with divalent cations to form gel under mild conditions, and is widely applied to the fields of biomedicine, food engineering, textile printing and dyeing and the like. However, sodium alginate has the problems of poor stability, insufficient water resistance, incapability of loading hydrophobic substances and the like, so that the application range is limited.
The molecular chain of sodium alginate has a large number of hydroxyl and carboxyl groups, and provides a modifiable site. If the sodium alginate is subjected to hydrophobic modification, the problem of over-strong hydrophilicity of the sodium alginate can be solved, and the load of the sodium alginate on hydrophobic substances can be improved. However, sodium alginate is a water-soluble material that is insoluble in organic solvents and grafting water-insoluble functional groups presents great difficulty if it is chemically modified in a water-solvent system.
In order to enable the sodium alginate to be dissolved in an organic medium, it is generally acidified to alginic acid and then neutralised to tetrabutylammonium alginate by tetrabutylammonium hydroxide. However, the conventional tetrabutylammonium alginate prepared by the hydrochloric acid acidification method cannot be completely dissolved in an organic solvent.
Disclosure of Invention
The invention aims to provide a synthesis method of hydrophobically modified sodium alginate, which effectively solves the problem that tetrabutylammonium alginate prepared by a hydrochloric acid acidification method cannot be completely dissolved in an organic solvent.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthesis method of hydrophobically modified sodium alginate comprises the following steps: (1) Sodium alginate was dispersed in 70% formic acid aqueous solution at 2wt% in ice water bath, after 1h the ice bath was removed and reacted overnight at room temperature to give reaction solution I.
(2) Adding 70% ethanol water solution into the reaction solution I for washing and suction filtration, repeating for a plurality of times to obtain alginic acid, and placing the alginic acid into a fume hood for drying overnight.
(3) And adding water to the alginic acid, neutralizing with tetrabutylammonium hydroxide solution until the pH value is 7 to obtain tetrabutylammonium alginate solution, and freeze-drying the tetrabutylammonium alginate solution to obtain tetrabutylammonium alginate.
(4) Adding a certain amount of undecylenic acid and excessive sulfoxide chloride into a dry single-mouth bottle, reacting for a period of time at room temperature to obtain a product I, spin-drying the solvent of the product I, and vacuumizing to constant weight to obtain undecylenoyl chloride.
(5) Adding tetrabutylammonium alginate and 4-dimethylaminopyridine prepared in the step (3) into a dry three-necked bottle, vacuumizing, introducing nitrogen, repeating the steps for a plurality of times, injecting dimethyl sulfoxide and dry triethylamine into the three-necked bottle, slowly dropwise adding undecylenoyl chloride prepared in the step (4) into the three-necked bottle under ice water bath, reacting for 1h at 0 ℃, and then, heating to room temperature for continuous reaction for 24h to obtain a reaction solution II. The molar ratio of undecylenoyl chloride, 4-dimethylaminopyridine and triethylamine is 8.5:1:8.5.
(6) Adding saturated sodium chloride solution into the reaction solution II for reaction for 30min, then placing the reaction solution into a dialysis bag, dialyzing the reaction solution in 0.1mol/L sodium chloride solution for 1 day, dialyzing the reaction solution in deionized water for 2 to 3 days, and finally freeze-drying the reaction solution to obtain a sample SA-C11.
Further, in the step (5), SA-C11 having different grafting ratios was prepared by varying the addition amount of undecylenoyl chloride.
Further, in the step (2), the volume of the 70% aqueous ethanol solution is 2 to 3 times the volume of the reaction solution I.
Further, in the step (4), the reaction time period at room temperature is 4 hours.
Further, in the step (5), the molar ratio of the undecylenoyl chloride to the structural unit of sodium alginate is 0.1-0.4.
The beneficial technical effects of the invention are as follows:
(1) The invention successfully prepares tetrabutylammonium alginate which can be uniformly dissolved in an organic solvent by using a formic acid acidification method, and the tetrabutylammonium alginate reacts with undecylenic acid in the organic solvent in a homogeneous way, so that the undecylenic acid is successfully grafted onto a molecular chain of sodium alginate.
(2) According to the invention, the hydroxyl of the sodium alginate is modified, and long-chain hydrophobic molecules are grafted onto the molecular chains of the sodium alginate through homogeneous reaction in an organic solvent system, so that the modified sodium alginate with amphipathy is obtained, and the solubilization of hydrophobic substances is improved.
Drawings
The invention will be described in further detail below with reference to the drawings and the detailed description.
FIG. 1 is a schematic diagram of the synthesis reaction of SA-C11 of the invention;
FIG. 2 is an infrared spectrum of SA-C11 prepared in example 1 of the present invention with the starting materials SA and SA-TBA;
FIG. 3 is a solid state nuclear magnetic resonance carbon spectrum of SA-C11 and raw material SA prepared in example 1 of the invention;
FIG. 4 is an XRD diffraction pattern of the starting materials SA of the invention and SA-C11-1, SA-C11-2, SA-C11-3 and SA-C11-4 of varying grafting ratios;
FIG. 5 is a graph showing the concentration of curcumin as a function of SA solution and SA-C11 solution concentration for test example 1 according to the invention;
FIG. 6 is a graph showing the concentration of Sudan blue II as a function of the concentration of SA solution and SA-C11 solution according to test example 2 of the invention.
Detailed Description
Example 1
A synthesis method of hydrophobically modified sodium alginate comprises the following steps: (1) Sodium Alginate (SA) was dispersed in 70% formic acid aqueous solution at 2wt% in ice water bath, after 1h the ice bath was removed and reacted overnight at room temperature to give reaction solution I.
(2) 70% ethanol aqueous solution was added to the reaction solution I to perform washing and suction filtration, and the reaction was repeated 3 times to obtain alginic acid, and the alginic acid was placed in a fume hood to be dried overnight. The volume of the 70% ethanol aqueous solution is 2-3 times of the volume of the reaction solution I.
(3) Adding a proper amount of water to the alginic acid, and neutralizing with tetrabutylammonium hydroxide (TBA-OH) solution until the pH value is 7 to obtain tetrabutylammonium alginate (SA-TBA) solution, and then freeze-drying the tetrabutylammonium alginate (SA-TBA) solution to obtain tetrabutylammonium alginate (SA-TBA).
(4) A certain amount of undecylenic acid and excessive thionyl chloride are added into a dry single-mouth bottle to react for 4 hours at room temperature, so that a product I is obtained, the solvent of the product I is dried in a spinning way, and then the product I is vacuumized to constant weight, so that undecylenoyl chloride (C11-COCl) is obtained.
(5) Adding SA-TBA and 4-Dimethylaminopyridine (DMAP) prepared in the step (3) into a dry three-necked bottle, vacuumizing, introducing nitrogen, repeating the operation for 3 times, injecting dimethyl sulfoxide (DMSO) and dry triethylamine into the three-necked bottle, slowly dropwise adding C11-COCl prepared in the step (4) into the three-necked bottle under ice water bath, reacting for 1h at 0 ℃, and then, heating to room temperature, and continuing to react for 24h to obtain a reaction solution II. The molar ratio of the C11-COCl, the DMAP and the triethylamine is C11-COCl: DMAP: triethylamine = 8.5:1:8.5.
(6) Adding saturated sodium chloride solution into the reaction solution II for reaction for 30min, then placing the reaction solution II into a dialysis bag, dialyzing the reaction solution in 0.1mol/L sodium chloride solution for 1 day, dialyzing the reaction solution in deionized water for 2 to 3 days, and finally freeze-drying the reaction solution II to obtain the sample SA-C11. A schematic of the SA-C11 synthesis reaction is shown in FIG. 1.
In the step (5), SA-C11 having different grafting ratios can be prepared by changing the addition amount of undecylenoyl chloride. When the molar ratio of undecylenoyl chloride to the structural unit of sodium alginate was 0.1, the prepared SA-C11 sample was designated SA-C11-1. When the molar ratio of undecylenoyl chloride to the structural unit of sodium alginate was 0.15, the prepared SA-C11 sample was designated SA-C11-2. When the molar ratio of undecylenoyl chloride to the structural unit of sodium alginate was 0.2, the prepared SA-C11 sample was designated SA-C11-3. When the molar ratio of undecylenoyl chloride to the structural unit of sodium alginate was 0.4, the prepared SA-C11 sample was designated SA-C11-4.
To demonstrate the successful synthesis of SA-C11 using the procedure of example 1, characterization was performed by IR, nuclear magnetic and XRD, respectively.
The infrared spectra of SA-C11 and the raw materials SA and SA-TBA are shown in FIG. 2 at 3234cm -1 The broad and strong absorption peak at the location is caused by the stretching vibration of-OH on SA. SA-TBA and SA-C11 at 2959cm compared to the starting material SA -1 And 2873cm -1 The new absorption band at this point is due to the C-H vibration of the methylene group. SA-C11 at 1741cm -1 A new absorption peak is generatedThis is the stretching vibration peak of the ester group after grafting, demonstrating successful grafting of undecylenic acid onto the molecular chain of SA using the procedure of example 1.
As shown in FIG. 3, the solid nuclear magnetic resonance carbon spectra of SA-C11 and SA show that the absorption peak at 175ppm of SA is assigned to the carbon atom of carboxyl group, the formants of terminal carbon are observed at 100ppm, and the peaks at 65 to 85ppm are all formants of the carbon atom to which the hydroxyl group on the SA pyranose ring is attached. SA-C11 showed coincidence of two peaks at 175ppm, as compared to SA, which was a new peak generated after grafting undecylenic acid onto SA. And (3) carrying out integral calculation after peak-by-peak fitting, roughly calculating the amount of the undecylenic acid grafted on each structural unit of SA, and marking as the grafting rate. Through tests, the grafting amount of SA-C11-1 is less, and the characteristic peak of the nuclear magnetic spectrogram is not obvious, so that the grafting rate is not calculated; the grafting ratio of SA-C11-2 is about 4.3%; the grafting rate of SA-C11-3 is 7%; the grafting ratio of SA-C11-4 was 14.8%.
As shown in the XRD diffraction patterns of the raw material SA and SA-C11-1, SA-C11-2, SA-C11-3 and SA-C11-4 with different grafting rates, as shown in figure 4, the XRD patterns are dispersive because SA is in an amorphous state, the intensity of diffraction peaks of SA is reduced after grafting undecylenic acid on SA, and the peaks at 13.6 DEG disappear because the grafting undecylenic acid affects the state of the molecular chains of SA, the hydrogen bond density among molecules is reduced, thereby affecting the distribution of chain segments of SA, and simultaneously proving that undecylenic acid is successfully grafted on the molecular chains of SA.
Test example 1
A series of SA aqueous solution and SA-C11 aqueous solution with concentration of 2-12 mg/mL are respectively prepared, excessive curcumin is added into each solution, the solutions are mixed for 24 hours under shaking at normal temperature, then the mixture is filtered by a 22 mu m filter head, the obtained filtrate is diluted by 20 times by absolute ethyl alcohol, and the absorbance is measured at the wavelength of 422 nm.
FIG. 5 is a graph showing the concentration of curcumin as a function of concentration of SA solution and SA-C11 solution, and as can be seen from FIG. 5, SA-C11 has obvious solubilization effect on curcumin relative to unmodified SA, SA-C11 obtained after hydrophobically modifying SA is amphiphilic, hydrophobic drug curcumin can interact with the hydrophobic chain of SA-C11, so that the solubilization of curcumin is increased, and the solubilization effect is improved along with the enhancement of hydrophobic association.
Test example 2
A series of SA aqueous solution and SA-C11 aqueous solution with concentration of 2-12 mg/mL are respectively prepared, excessive Sudan blue II is added into each solution, the solutions are mixed for 24 hours under shaking at normal temperature, then the mixture is filtered by a 22 mu m filter head, the obtained filtrate is diluted by 20 times by absolute ethyl alcohol, and the absorbance is measured at 644nm wavelength.
FIG. 6 is a plot of Sudan blue II concentration versus SA solution and SA-C11 solution concentration, as can be seen from FIG. 6, unmodified SA has less solubilization of Sudan blue II, SA-C11 has significant solubilization of Sudan blue II and solubilization is more pronounced with increasing solution concentration, indicating that SA-C11 has good solubilization of hydrophobic dyes.
According to the invention, tetrabutylammonium alginate which can be uniformly dissolved in an organic solvent is successfully prepared by a formic acid acidification method, and simultaneously, through modifying the hydroxyl of sodium alginate, long-chain hydrophobic molecules are grafted onto the molecular chain of the sodium alginate through homogeneous reaction in an organic solvent system to obtain the modified sodium alginate with amphipathy, so that the solubilization of hydrophobic substances is improved.
It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications, adaptations, additions and alternatives falling within the spirit and scope of the invention.
Claims (5)
1. The synthesis method of the hydrophobically modified sodium alginate is characterized by comprising the following steps of:
s1, dispersing sodium alginate in 70% formic acid aqueous solution according to 2wt% under ice water bath, removing the ice water bath after 1h, and reacting overnight at room temperature to obtain a reaction solution I;
s2, adding 70% ethanol water solution into the reaction solution I for washing and suction filtration, repeating for a plurality of times to obtain alginic acid, and drying the alginic acid overnight;
s3, adding water to the alginic acid, neutralizing with tetrabutylammonium hydroxide solution until the pH value is 7, and then freeze-drying to obtain tetrabutylammonium alginate;
s4, reacting a certain amount of undecylenic acid with excessive thionyl chloride at room temperature to obtain a product I, spin-drying the solvent of the product I, and vacuumizing to constant weight to obtain undecylenoyl chloride;
s5, adding tetrabutylammonium alginate and 4-dimethylaminopyridine which are prepared in the step S3 into a dry three-necked bottle, vacuumizing, introducing nitrogen, repeating for a plurality of times, injecting dimethyl sulfoxide and dry triethylamine into the three-necked bottle, slowly dropwise adding undecylenoyl chloride prepared in the step S4 into the three-necked bottle under ice water bath, reacting for 1h at 0 ℃, and then, heating to room temperature for continuous reaction for 24h to obtain a reaction solution II, wherein the molar ratio of undecylenoyl chloride to 4-dimethylaminopyridine to triethylamine is 8.5:1:8.5;
s6, adding saturated sodium chloride solution into the reaction solution II for reaction for 30min, then placing the reaction solution II into a dialysis bag, dialyzing the reaction solution in 0.1mol/L sodium chloride solution for 1 day, dialyzing the reaction solution in deionized water for 2 to 3 days, and finally freeze-drying the reaction solution II to obtain the sample SA-C11.
2. The method for synthesizing hydrophobically modified sodium alginate according to claim 1, wherein in step S5, SA-C11 having different grafting ratios is prepared by varying the amount of undecylenoyl chloride added.
3. The method for synthesizing hydrophobically modified sodium alginate as defined in claim 2, wherein in step S2, the volume of the 70% aqueous ethanol solution is 2-3 times the volume of the reaction solution I.
4. The method for synthesizing hydrophobically modified sodium alginate as defined in claim 3, wherein in step S4, the reaction time period at room temperature is 4 hours.
5. The method for synthesizing hydrophobically modified sodium alginate according to claim 2, wherein in step S5, the molar ratio of undecylenoyl chloride to structural units of sodium alginate is 0.1 to 0.4.
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| CN202311429071.9A CN117304365A (en) | 2023-10-31 | 2023-10-31 | Synthesis method of hydrophobically modified sodium alginate |
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| CN116082534A (en) * | 2022-12-26 | 2023-05-09 | 临沂大学 | Alginic acid derivative, alginic acid derivative ammonium salt/graphene composite material and preparation method and application thereof |
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