JP2012180455A - Low molecular weight hydrogelling agent originating from sugar, and hydrogel with the hydrogelling agent as active ingredient - Google Patents
Low molecular weight hydrogelling agent originating from sugar, and hydrogel with the hydrogelling agent as active ingredient Download PDFInfo
- Publication number
- JP2012180455A JP2012180455A JP2011044445A JP2011044445A JP2012180455A JP 2012180455 A JP2012180455 A JP 2012180455A JP 2011044445 A JP2011044445 A JP 2011044445A JP 2011044445 A JP2011044445 A JP 2011044445A JP 2012180455 A JP2012180455 A JP 2012180455A
- Authority
- JP
- Japan
- Prior art keywords
- low molecular
- water
- hydroxy
- molecular weight
- hydrogelator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 235000000346 sugar Nutrition 0.000 title claims abstract description 13
- 239000000017 hydrogel Substances 0.000 title claims description 8
- 239000004480 active ingredient Substances 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 18
- 229930195729 fatty acid Natural products 0.000 claims abstract description 18
- 239000000194 fatty acid Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- -1 hydroxy fatty acid Chemical class 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 125000002252 acyl group Chemical group 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical group OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- LSYICPNAJSMBIC-UHFFFAOYSA-N hydroxymethyl hypofluorite Chemical compound OCOF LSYICPNAJSMBIC-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 150000008163 sugars Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000499 gel Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229940125904 compound 1 Drugs 0.000 description 8
- NEZJDVYDSZTRFS-RMPHRYRLSA-N Phenyl beta-D-glucopyranoside Chemical class O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC=C1 NEZJDVYDSZTRFS-RMPHRYRLSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000002772 monosaccharides Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ATRNZOYKSNPPBF-CYBMUJFWSA-N (R)-3-hydroxytetradecanoic acid Chemical compound CCCCCCCCCCC[C@@H](O)CC(O)=O ATRNZOYKSNPPBF-CYBMUJFWSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ATRNZOYKSNPPBF-UHFFFAOYSA-N D-beta-hydroxymyristic acid Natural products CCCCCCCCCCCC(O)CC(O)=O ATRNZOYKSNPPBF-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229960002246 beta-d-glucopyranose Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003349 gelling agent Substances 0.000 description 3
- MIAKOEWBCMPCQR-RMPHRYRLSA-N p-aminophenyl-α-d-galactopyranoside Chemical compound C1=CC(N)=CC=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 MIAKOEWBCMPCQR-RMPHRYRLSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- WQZGKKKJIJFFOK-UHFFFAOYSA-N alpha-D-glucopyranose Natural products OCC1OC(O)C(O)C(O)C1O WQZGKKKJIJFFOK-UHFFFAOYSA-N 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000002158 endotoxin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229960003082 galactose Drugs 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920006008 lipopolysaccharide Polymers 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UHZWUNLTEZCDMA-UHFFFAOYSA-N (10r)-10-hydroxyundecanoic acid Chemical compound CC(O)CCCCCCCCC(O)=O UHZWUNLTEZCDMA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- JTGHBEFBQXGABE-UHFFFAOYSA-N 2,2-dihydroxyheptanoic acid Chemical compound CCCCCC(O)(O)C(O)=O JTGHBEFBQXGABE-UHFFFAOYSA-N 0.000 description 1
- CGPYJCKJLKTKAR-UHFFFAOYSA-N 2,2-dihydroxynonanoic acid Chemical compound CCCCCCCC(O)(O)C(O)=O CGPYJCKJLKTKAR-UHFFFAOYSA-N 0.000 description 1
- TVBMLKMGUIJSIR-UHFFFAOYSA-N 2,2-dihydroxyoctanoic acid Chemical compound CCCCCCC(O)(O)C(O)=O TVBMLKMGUIJSIR-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- CPLYLXYEVLGWFJ-UHFFFAOYSA-N 2-hydroxyarachidic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)C(O)=O CPLYLXYEVLGWFJ-UHFFFAOYSA-N 0.000 description 1
- RPGJJWLCCOPDAZ-UHFFFAOYSA-N 2-hydroxybehenic acid Chemical compound CCCCCCCCCCCCCCCCCCCCC(O)C(O)=O RPGJJWLCCOPDAZ-UHFFFAOYSA-N 0.000 description 1
- GHPVDCPCKSNJDR-UHFFFAOYSA-N 2-hydroxydecanoic acid Chemical compound CCCCCCCCC(O)C(O)=O GHPVDCPCKSNJDR-UHFFFAOYSA-N 0.000 description 1
- YDZIJQXINJLRLL-UHFFFAOYSA-N 2-hydroxydodecanoic acid Chemical compound CCCCCCCCCCC(O)C(O)=O YDZIJQXINJLRLL-UHFFFAOYSA-N 0.000 description 1
- KUZABABLVHWUGR-UHFFFAOYSA-N 2-hydroxyheptadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)C(O)=O KUZABABLVHWUGR-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- JYZJYKOZGGEXSX-UHFFFAOYSA-N 2-hydroxymyristic acid Chemical compound CCCCCCCCCCCCC(O)C(O)=O JYZJYKOZGGEXSX-UHFFFAOYSA-N 0.000 description 1
- PYNCEZHRMYECCB-UHFFFAOYSA-N 2-hydroxynonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)C(O)=O PYNCEZHRMYECCB-UHFFFAOYSA-N 0.000 description 1
- NKASEPJANRVKDD-UHFFFAOYSA-N 2-hydroxypentadecanoic acid Chemical compound CCCCCCCCCCCCCC(O)C(O)=O NKASEPJANRVKDD-UHFFFAOYSA-N 0.000 description 1
- KCEUZVYQPROALO-UHFFFAOYSA-N 2-hydroxytridecanoic acid Chemical compound CCCCCCCCCCCC(O)C(O)=O KCEUZVYQPROALO-UHFFFAOYSA-N 0.000 description 1
- UNSAJINGUOTTRA-UHFFFAOYSA-N 3-(3-bromophenyl)prop-2-yn-1-ol Chemical compound OCC#CC1=CC=CC(Br)=C1 UNSAJINGUOTTRA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 150000008211 L-arabinosides Chemical class 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 description 1
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 1
- MBLBDJOUHNCFQT-LXGUWJNJSA-N N-acetylglucosamine Natural products CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- GZCGUPFRVQAUEE-UHFFFAOYSA-N alpha-D-galactose Natural products OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-DVKNGEFBSA-N alpha-D-glucose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-DVKNGEFBSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- WQZGKKKJIJFFOK-FPRJBGLDSA-N beta-D-galactose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-FPRJBGLDSA-N 0.000 description 1
- WQZGKKKJIJFFOK-RWOPYEJCSA-N beta-D-mannose Chemical compound OC[C@H]1O[C@@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-RWOPYEJCSA-N 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- GZQKNULLWNGMCW-PWQABINMSA-N lipid A (E. coli) Chemical compound O1[C@H](CO)[C@@H](OP(O)(O)=O)[C@H](OC(=O)C[C@@H](CCCCCCCCCCC)OC(=O)CCCCCCCCCCCCC)[C@@H](NC(=O)C[C@@H](CCCCCCCCCCC)OC(=O)CCCCCCCCCCC)[C@@H]1OC[C@@H]1[C@@H](O)[C@H](OC(=O)C[C@H](O)CCCCCCCCCCC)[C@@H](NC(=O)C[C@H](O)CCCCCCCCCCC)[C@@H](OP(O)(O)=O)O1 GZQKNULLWNGMCW-PWQABINMSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229950006780 n-acetylglucosamine Drugs 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
Abstract
Description
本発明は、糖由来の低分子ヒドロゲル化剤に関し、特に、水及び親水性有機溶媒を含む水の両方に対しゲル化能を有する低分子ヒドロゲル化剤に関する。本発明はまた新規化合物に関する。 The present invention relates to a sugar-derived low-molecular hydrogelator, and more particularly to a low-molecular hydrogelator that has a gelling ability with respect to both water and water containing a hydrophilic organic solvent. The invention also relates to novel compounds.
水をゲル化するヒドロゲル化剤は衛生用品、化粧品、食品、医薬品、分析科学の分野を含む様々な分野で注目を集めている材料である。 Hydrogelators that gel water are materials that are attracting attention in a variety of fields, including hygiene products, cosmetics, foods, pharmaceuticals, and analytical science.
従来実用的に用いられているヒドロゲル化剤は、ほとんどが天然あるいは人工の高分子由来であった。天然由来の高分子は多糖類、コラーゲンなどがあげられるが種類、機能が限られている。人工高分子はポリアクリルアミドなどがあげられ、優れた生体適合性を示すものもあるが、生分解性などに問題がある。また、高分子ヒドロゲル化剤は一般的に１wt％以下の濃度でゲル化することが少なく、ゲル化には高濃度、すなわち多量のゲル化剤が必要であった。
これに対して優れた生分解性、生体適合性を期待できる低分子ヒドロゲル化剤が近年研究されている。また低分子ヒドロゲル化剤は１wt％以下の低濃度でゲル化するものも多い。しかしながら、これまでに報告されている低分子化合物は合成が煩雑であり、実用化に向けてはコスト面で問題があった（特許文献１）。一方、低分子ヒドロゲル化剤の例として、フェニル-β-グルコピラノシド誘導体は、比較的安価な原料から簡便に合成することができる。さらに、この化合物は水−親水性有機溶媒の混合液をゲル化することが報告されている（特許文献２）。
Conventionally, most of the hydrogelators that have been practically used are derived from natural or artificial polymers. Naturally-derived polymers include polysaccharides and collagen, but have limited types and functions. Artificial polymers include polyacrylamide, and some have excellent biocompatibility, but there are problems with biodegradability and the like. Further, the polymer hydrogelator generally hardly gels at a concentration of 1 wt% or less, and high concentration, that is, a large amount of gelling agent is necessary for gelation.
On the other hand, low molecular hydrogelators that can be expected to have excellent biodegradability and biocompatibility have been recently studied. Many low-molecular hydrogelators gel at a low concentration of 1 wt% or less. However, the low molecular weight compounds reported so far are complicated to synthesize, and have a problem in terms of cost for practical use (Patent Document 1). On the other hand, as an example of a low-molecular hydrogelator, a phenyl-β-glucopyranoside derivative can be easily synthesized from a relatively inexpensive raw material. Furthermore, this compound has been reported to gel a mixed solution of water-hydrophilic organic solvent (Patent Document 2).
しかし、上述のフェニル-β-グルコピラノシド誘導体は、溶媒が水だけではゲル化機能を示さず、有機溶媒の添加が必須であった。その理由として、フェニル-β-グルコピラノシド誘導体の親水性の低さにより、純水への溶解性が極めて低く、かつ結晶化が極めて速く進んでしまうということが挙げられる。
本発明は、このような従来技術の有する課題を鑑みてなされたものであり、フェニル-β-グルコピラノシド誘導体の分子構造を見直し、分子の親水性を向上させることにより、水−親水性有機溶媒の混合液だけでなく、水だけでもゲル化機能を示す安価な新規低分子ヒドロゲル化剤を提供することを目的とするものである。
However, the above-mentioned phenyl-β-glucopyranoside derivative does not exhibit a gelling function only with water as a solvent, and an organic solvent must be added. The reason for this is that due to the low hydrophilicity of the phenyl-β-glucopyranoside derivative, the solubility in pure water is extremely low and crystallization proceeds very rapidly.
The present invention has been made in view of such problems of the prior art, and by reviewing the molecular structure of the phenyl-β-glucopyranoside derivative and improving the hydrophilicity of the molecule, the water-hydrophilic organic solvent An object of the present invention is to provide an inexpensive new low-molecular hydrogelator that exhibits a gelling function not only with a mixed solution but also with water alone.
本発明者らは、かかる課題に対して鋭意検討を重ねた結果、フェニル-β-グルコピラノシド誘導体の親水性、流動性を向上させるために、疎水基である脂肪酸に親水性の官能基として水酸基が少なくとも一つ導入されたヒドロキシ脂肪酸を用いることを検討した。例えばヒドロキシ脂肪酸である３-ヒドロキシミリスチン酸は、グラム陰性菌細胞壁外膜の構成成分であるリポ多糖（LPS）リピッドAに含まれる部分構造として知られ、水酸基の影響により常温でリピッドAの全体流動性を維持するという特性をもつことから、脂肪酸部位に水酸基を少なくとも一つ導入することにより水中での流動性を改善できるのではないかと考えた。そこで、ヒドロキシ脂肪酸をフェニル-β-グルコピラノシド誘導体に組み込んだ結果、有機溶媒を加えることなく純水中での低分子ヒドロゲル化剤の結晶化を阻害し、極めて少量の添加で水−親水性有機溶媒の混合液だけでなく、溶媒が水だけでもゲル化可能な新規な低分子ヒドロゲル化剤を提供できることが判明した。上記のようなヒドロキシ脂肪酸は、安価に入手可能あるいは低価格の原料を用いて容易に合成することが可能である（上記特許文献３参照）。 As a result of intensive studies on such problems, the present inventors have found that a hydroxyl group as a hydrophilic functional group is added to a fatty acid that is a hydrophobic group in order to improve the hydrophilicity and fluidity of the phenyl-β-glucopyranoside derivative. The use of at least one introduced hydroxy fatty acid was studied. For example, 3-hydroxymyristic acid, a hydroxy fatty acid, is known as a partial structure contained in lipopolysaccharide (LPS) lipid A, which is a constituent of the outer membrane of Gram-negative bacteria. Therefore, it was thought that the fluidity in water could be improved by introducing at least one hydroxyl group at the fatty acid site. Therefore, as a result of incorporating a hydroxy fatty acid into the phenyl-β-glucopyranoside derivative, the crystallization of the low molecular weight hydrogelator in pure water is inhibited without adding an organic solvent. It has been found that it is possible to provide a novel low-molecular hydrogelling agent that can be gelled not only by the mixed solution but also by using only water as a solvent. Such hydroxy fatty acids can be obtained at low cost or can be easily synthesized using low-cost raw materials (see Patent Document 3).
本発明で得られた低分子ゲル化剤は、上記の知見に基づいて完成したものであり、本発明によれば、以下の発明が提供される。
（１）下記一般式（I）（式中、Aは糖の残基を表し、R1及びR2は独立して水素、メチル、ヒドロキシ、メトキシ、フッ素、クロル、ブロム、またはヨウ素を表し、-C(O)-Rはヒドロキシ脂肪酸から誘導されるアシル基を表す）で表される低分子ヒドロゲル化剤。
（３）Aが、アルドピラノースの６員環に結合するいずれか一つの水酸基を除いた残基を表す前記（１）または（２）に記載の低分子ヒドロゲル化剤。
（４）前記Ａが、β-D-グルコピラノース残基である前記（３）に記載の低分子ヒドロゲル化剤。
（５）ヒドロキシ脂肪酸の炭素数が６−２０である前記（１）〜（４）のいずれか一項に記載の低分子ヒドロゲル化剤。
（６）前記（１）〜（５）のいずれかに記載のヒドロゲル化剤によって、水または親水性有機溶媒を含む水がゲル化されたことを特徴とするヒドロゲル。
（７）下記一般式（I）
The low molecular gelling agent obtained in the present invention has been completed based on the above findings, and according to the present invention, the following inventions are provided.
(1) The following general formula (I) (wherein A represents a sugar residue, R 1 and R 2 independently represent hydrogen, methyl, hydroxy, methoxy, fluorine, chloro, bromine, or iodine; -C (O) -R represents an acyl group derived from a hydroxy fatty acid).
(3) The low molecular hydrogelator according to (1) or (2), wherein A represents a residue excluding any one hydroxyl group bonded to the 6-membered ring of aldopyranose.
(4) The low molecular hydrogelator according to (3), wherein A is a β-D-glucopyranose residue.
(5) The low molecular hydrogelator according to any one of (1) to (4), wherein the hydroxy fatty acid has 6 to 20 carbon atoms.
(6) A hydrogel characterized in that water or water containing a hydrophilic organic solvent is gelled by the hydrogelator according to any one of (1) to (5).
(7) The following general formula (I)
本発明の低分子ヒドロゲル化剤は、ゲル化する溶媒が水と親水性有機溶媒の混合液のみならず、水だけの場合でも良好なゲル化機能を有し、さらに少量のゲル化剤によって大量の溶媒を固化することができるので、保水剤、水分の吸収剤、家庭用汚水廃液固化剤等として、更に水分を多く含む柔軟な材料として生体適合性材料、体内で刺激応答性薬物徐放キャリア、組織・細胞培養の固体培地、蛋白質や核酸などの生体材料分離材などへ応用できる。 The low molecular hydrogelator of the present invention has a good gelling function not only when the solvent to be gelated is a mixture of water and a hydrophilic organic solvent, but also with water alone. As a water retaining agent, moisture absorbent, household wastewater waste liquid solidifying agent, etc., biocompatible material as a flexible material containing more water, stimulating drug sustained release carrier in the body It can be applied to solid media for tissue / cell culture, biomaterial separators such as proteins and nucleic acids.
本発明で得られた低分子ゲル化剤は、水-親水性有機溶媒の混合液のみならず、溶媒が水だけでも良好なゲル化機能を有し、さらに少量（例えば１ｗｔ％以下）で透明もしくは無色のゲルを得る事ができる。親水性有機溶媒の例として、メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、グリセリン、アセトン、テトラヒドロフラン、ジオキサン、アセトニトリル等が挙げられる。水-親水性有機溶媒の混合液を用いる場合、水と親水性有機溶媒の混合比は親水性有機溶媒の含有率が体積百分率で50%以下であることが望ましい。またゲル化能が阻害されない限り水あるいは、水-親水性有機溶媒の混合液に他成分を加えてもよい。このような他成分としては染料、香料、電解質、医療用薬剤などが例として挙げられる。 The low-molecular gelling agent obtained in the present invention has a good gelling function not only in a mixed solution of water-hydrophilic organic solvent but also in water alone, and is transparent in a small amount (for example, 1 wt% or less). Or a colorless gel can be obtained. Examples of the hydrophilic organic solvent include methanol, ethanol, propanol, butanol, ethylene glycol, glycerin, acetone, tetrahydrofuran, dioxane, acetonitrile and the like. When a water-hydrophilic organic solvent mixture is used, the mixing ratio of water and the hydrophilic organic solvent is preferably such that the content of the hydrophilic organic solvent is 50% or less by volume. Further, other components may be added to water or a mixed solution of water-hydrophilic organic solvent as long as the gelling ability is not inhibited. Examples of such other components include dyes, fragrances, electrolytes, medical drugs and the like.
本発明で得られた低分子ヒドロゲル化剤は、一般式（I）（式中、Aは糖の残基を表し、R1及びR2は独立して水素、メチル、ヒドロキシ、メトキシ、フッ素、クロル、ブロム、またはヨウ素を表し、Ｒはアルキル基を表す）で表され、低分子ヒドロゲル化剤の全構成部位が協奏的に作用し、安定なヒドロゲルを形成できる。 The low molecular hydrogelator obtained in the present invention has a general formula (I) (wherein A represents a sugar residue, R 1 and R 2 are independently hydrogen, methyl, hydroxy, methoxy, fluorine, Chloro, bromo, or iodine, and R represents an alkyl group), and all the components of the low-molecular hydrogelator act in concert to form a stable hydrogel.
一般式（Ｉ）中のAは分子中で親水性官能基として機能する糖の残基を表す。この糖は単糖類、オリゴ糖類、又は多糖類のいかなる糖であってもよいが、単糖類であることが好ましい。残基とはこの糖に結合するいずれか一つの水酸基を除いた部位を表す。この単糖類としては、グルコース、ガラクトース、N-アセチルグルコサミン等のヘキソース、Lアラビノシドやヘキシロースのペントース等いずれでもよいが、特にアルドピラノースが好ましい。アルドピラノースとして、α-D-グルコピラノース、α-D-ガラクトピラノース、α-D-マンノピラノース、β-D-グルコピラノース、β-D-ガラクトピラノース、β-D-マンノピラノース等が挙げられるが、より好ましい例としてβ-D-グルコピラノースが挙げられる。 A in the general formula (I) represents a sugar residue that functions as a hydrophilic functional group in the molecule. The sugar may be any sugar of monosaccharide, oligosaccharide, or polysaccharide, but is preferably a monosaccharide. The residue represents a site excluding any one hydroxyl group bonded to this sugar. The monosaccharide may be any of hexoses such as glucose, galactose and N-acetylglucosamine, L-arabinoside and pentose of hexylose, but aldopyranose is particularly preferable. Examples of aldopyranose include α-D-glucopyranose, α-D-galactopyranose, α-D-mannopyranose, β-D-glucopyranose, β-D-galactopyranose, β-D-mannopyranose, etc. More preferred examples include β-D-glucopyranose.
一方、上記一般式（I）中、-C(O)-Rはヒドロキシ脂肪酸から誘導されるアシル基を表す。このアシル基の疎水的相互作用によりファイバーを形成して安定したゲルが得られる。このアシル基は直鎖であっても、分枝鎖を有するものであってもよいが、直鎖が好ましい。ただし、Rの炭素鎖が短すぎると水素結合がより支配的になり、結晶性を強く示す。また長すぎると親水性が低下し、水に分散しなくなる。かくしてアシル基の炭素数は６〜２０が好ましく１０〜１５がより好ましい。そのようなヒドロキシ脂肪酸として、ヒドロキシカプロン酸、ジヒドロキシエナント酸、ジヒドロキシカプリル酸、ジヒドロキシペラルゴン酸、ヒドロキシカプリン酸、ヒドロキシウンデカン酸、ヒドロキシラウリン酸、ヒドロキシトリデカン酸、ヒドロキシミリスチン酸、ヒドロキシペンタデカン酸、ヒドロキシパルミチン酸、ヒドロキシマルガリン酸、ヒドロキシステアリン酸、ヒドロキシノナデカン酸、ヒドロキシアラキジン酸、ヒドロキシベヘン酸などが挙げられる。ヒドロキシ基の位置は限定しないがβ位が好ましい。そのなかでより好ましい例として３−ヒドロキシミリスチン酸が挙げられる。ヒドロキシ脂肪酸は水酸基が結合した炭素は不斉となるため、Ｒ，Ｓ体の光学異性体、およびその混合物が存在し、そのいずれでもよいが、より好ましくはラセミ体である。 On the other hand, in the general formula (I), -C (O) -R represents an acyl group derived from a hydroxy fatty acid. A stable gel is obtained by forming fibers by the hydrophobic interaction of the acyl groups. This acyl group may be linear or branched, but is preferably linear. However, if the carbon chain of R is too short, the hydrogen bonds become more dominant and show strong crystallinity. On the other hand, if it is too long, the hydrophilicity is lowered and it is not dispersed in water. Thus, the acyl group preferably has 6 to 20 carbon atoms, more preferably 10 to 15 carbon atoms. Such hydroxy fatty acids include hydroxycaproic acid, dihydroxyenanthic acid, dihydroxycaprylic acid, dihydroxypelargonic acid, hydroxycapric acid, hydroxyundecanoic acid, hydroxylauric acid, hydroxytridecanoic acid, hydroxymyristic acid, hydroxypentadecanoic acid, hydroxypalmitin Examples thereof include acid, hydroxymargaric acid, hydroxystearic acid, hydroxynonadecanoic acid, hydroxyarachidic acid, and hydroxybehenic acid. The position of the hydroxy group is not limited, but the β position is preferred. Among them, 3-hydroxymyristic acid is a more preferable example. Since the hydroxy fatty acid has an asymmetric carbon atom to which the hydroxyl group is bonded, there are R, S isomers and mixtures thereof, and any of them may be used, but a racemate is more preferable.
水又は水-親水性有機溶媒の混合液のゲル化に用いられる、低分子ヒドロゲル化剤の濃度は溶媒の重量に対して0.01−5ｗｔ％が好ましく、より好ましくは0.02−3ｗｔ％である。低分子ヒドロゲル化剤を溶解させるために水又は水-親水性有機溶媒の混合液を加熱することが好ましく、温度は好ましくは60〜100℃である。 The concentration of the low molecular hydrogelator used for gelation of water or a water-hydrophilic organic solvent mixture is preferably 0.01-5 wt%, more preferably 0.02-3 wt%, based on the weight of the solvent. In order to dissolve the low molecular weight hydrogelator, it is preferable to heat water or a mixed solution of water-hydrophilic organic solvent, and the temperature is preferably 60 to 100 ° C.
次に、本発明を実施例からさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。
（実施例１）低分子ヒドロゲル化剤化合物の合成
親水部としての単糖がβ-D-グルコピラノース、疎水部としてRが炭素数１３のヒドロキシ脂肪酸を有する低分子ヒドロゲル化剤化合物（化合物１）を下記の反応式にしたがって合成した。なお、4-アミノフェニル-β-D-グルコピラノシドは、特開２００３−４９１５４号公報に記載の方法で合成した。
Example 1 Synthesis of Low-Molecular Hydrogelator Compound Low-molecular hydrogelator compound in which monosaccharide as a hydrophilic part is β-D-glucopyranose and R is a hydroxy fatty acid having 13 carbon atoms as a hydrophobic part (Compound 1) Was synthesized according to the following reaction formula. 4-Aminophenyl-β-D-glucopyranoside was synthesized by the method described in JP-A-2003-49154.
化合物1（本発明）の合成
アルゴン雰囲気下、4-アミノフェニル-β-D-グルコピラノシド 0.29 g (1.10 mmol), 3-ヒドロキシミリスチン酸 0.26g (1.10 mmol) （東京化成工業（株）製）, 1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩（WSC・HClと略記する） 1.01 g (5.28 mmol) （国産化学（株）製）を無水テトラヒドロフラン 50 mL に溶解させ、室温で8時間攪拌した。有機溶媒を減圧留去後、粗生成物を得た。得られた粗生成物を、シリカゲルクロマトグラフィー（メタノール）で精製し、乾燥させて白色固体の目的物0.29ｇを得た（収率54％）。
1H NMR (CD3OD) :・0.99 (t, 3H, J = 7.08 Hz) ; 1.38 (m, 18H) ; 1.60 (m, 2H) ; 2.55 (m, 2H) ; 3.40-4.14 (m, 8H) ; 7.15 (d, 2H, J = 9.0 Hz) ; 7.55 (d, 2H, J = 9.0 Hz). +ESI-LC-MS m/z = 497+23(M+Na).
Synthesis of Compound 1 (Invention) 4-Aminophenyl-β-D-glucopyranoside 0.29 g (1.10 mmol), 3-hydroxymyristic acid 0.26 g (1.10 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.), under argon atmosphere 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (abbreviated as WSC · HCl) 1.01 g (5.28 mmol) (manufactured by Kokusan Chemical Co., Ltd.) was dissolved in 50 mL of anhydrous tetrahydrofuran and stirred at room temperature. Stir for hours. After distilling off the organic solvent under reduced pressure, a crude product was obtained. The obtained crude product was purified by silica gel chromatography (methanol) and dried to obtain 0.29 g of the desired product as a white solid (yield 54%).
1 H NMR (CD 3 OD): 0.99 (t, 3H, J = 7.08 Hz); 1.38 (m, 18H); 1.60 (m, 2H); 2.55 (m, 2H); 3.40-4.14 (m, 8H ); 7.15 (d, 2H, J = 9.0 Hz); 7.55 (d, 2H, J = 9.0 Hz). + ESI-LC-MS m / z = 497 + 23 (M + Na).
化合物２（比較例）の合成
4-アミノフェニル-β-D-グルコピラノシドとミリストイルクロリドから、特開２００３−４９１５４号公報の合成と同等の方法を用いて化合物２を合成した（収率66.5％）。
1H NMR (DMSO-d6) :・0.98 (t, 3H) ; 1.48 (m, 20H) ; 1.83 (m, 2H) ; 2.49 (t, 2H, J
= 7.4 Hz,) ; 3.28-3.99 (m, 7H) ; 7.15 (d, 2H, J = 8.6 Hz) ; 7.54 (d, 2H, J = 8.6 Hz). +ESI-LC-MS m/z = 481+23(M+Na).
Synthesis of Compound 2 (Comparative Example)
Compound 2 was synthesized from 4-aminophenyl-β-D-glucopyranoside and myristoyl chloride using a method equivalent to the synthesis of JP-A-2003-49154 (yield 66.5%).
1 H NMR (DMSO-d6): 0.98 (t, 3H); 1.48 (m, 20H); 1.83 (m, 2H); 2.49 (t, 2H, J
= 7.4 Hz,); 3.28-3.99 (m, 7H); 7.15 (d, 2H, J = 8.6 Hz); 7.54 (d, 2H, J = 8.6 Hz). + ESI-LC-MS m / z = 481 +23 (M + Na).
（実施例２）ゲル形成能力の評価
実施例１で得られた低分子ヒドロゲル化剤化合物のヒドロゲル化能を以下のように評価した。
実施例１で作成した低分子ヒドロゲル化剤の濃度を0.1−1.0wt％となるように、純水あるいは水-アルコールの混合液に混合し、この混合物を固形成分が溶解するまで加熱する。生成した溶液を室温まで冷却後、放置した。ヒドロゲルの形成は、得られたサンプルを倒立させた際に、ゲルが流れ落ちないことを基準とした。
(Example 2) Evaluation of gel forming ability The hydrogelation ability of the low molecular weight hydrogelator compound obtained in Example 1 was evaluated as follows.
The low molecular weight hydrogelling agent prepared in Example 1 is mixed with pure water or a water-alcohol mixture so that the concentration of the low molecular hydrogelling agent is 0.1 to 1.0 wt%, and this mixture is heated until the solid components are dissolved. The resulting solution was cooled to room temperature and allowed to stand. The formation of the hydrogel was based on the fact that the gel did not run down when the obtained sample was inverted.
以下の一覧表に化合物１、２のゲル化能力の評価結果を示す。表中、PGは部分的ゲル化、Gは完全にゲル化したことを示す。また、1wt%/waterの行中のカッコ内は1wt%以下でゲル化を確認した最低濃度を示している。
ヒドロキシ脂肪酸から誘導されるアシル基を有する化合物１は、水-親水性有機溶媒（エタノール、メタノール）の混合液、および純水に対して良好なゲル化機能を示した。とくに純水については0.05wt%と、極めて少量でヒドロゲルを与えた。一方、水酸基を有しないアシル基を有する化合物２については、水-親水性有機溶媒（エタノール、メタノール）の混合溶媒をゲル化するが、純水に対しては部分的にしかゲル化能を示さなかった。以上の結果から、化合物１が水-エタノール混合溶媒に対してゲル化能を示し、かつ純水に対して優れたゲル化能を有していることが分かった。 Compound 1 having an acyl group derived from a hydroxy fatty acid showed a good gelling function with respect to a mixed solution of water-hydrophilic organic solvent (ethanol, methanol) and pure water. In particular, pure water gave a hydrogel in an extremely small amount of 0.05 wt%. On the other hand, the compound 2 having an acyl group having no hydroxyl group gels a mixed solvent of water-hydrophilic organic solvent (ethanol, methanol), but exhibits a gelling ability only partially with respect to pure water. There wasn't. From the above results, it was found that Compound 1 exhibited a gelling ability with respect to a water-ethanol mixed solvent and had an excellent gelling ability with respect to pure water.
図１に化合物１を用いて得られたゲルの写真を示す。
また、化合物１と純水から得られた（１ｗt％）ヒドロゲルを凍結乾燥して作成したキセロゲルの電界放出型走査電子顕微鏡(FE-SEM)観察を行ったところ、繊維状構造体からなる網目構造が観察された（図２）。すなわち、化合物１が純水中で溶解した後、繊維状に自己集合し、この繊維の網目の中に溶媒分子が取り込まれることで、ヒドロゲルが形成した。
FIG. 1 shows a photograph of a gel obtained using Compound 1.
In addition, a field emission scanning electron microscope (FE-SEM) observation of a xerogel prepared by freeze-drying (1 wt%) hydrogel obtained from Compound 1 and pure water revealed a network structure composed of a fibrous structure. Was observed (FIG. 2). That is, after the compound 1 was dissolved in pure water, it self-assembled into a fibrous form, and a solvent molecule was taken into the fiber network to form a hydrogel.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011044445A JP5750798B2 (en) | 2011-03-01 | 2011-03-01 | Sugar-derived low-molecular hydrogelator and hydrogel containing the hydrogelator as an active ingredient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011044445A JP5750798B2 (en) | 2011-03-01 | 2011-03-01 | Sugar-derived low-molecular hydrogelator and hydrogel containing the hydrogelator as an active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012180455A true JP2012180455A (en) | 2012-09-20 |
| JP5750798B2 JP5750798B2 (en) | 2015-07-22 |
Family
ID=47011921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011044445A Active JP5750798B2 (en) | 2011-03-01 | 2011-03-01 | Sugar-derived low-molecular hydrogelator and hydrogel containing the hydrogelator as an active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5750798B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018070546A1 (en) * | 2016-10-14 | 2018-04-19 | 国立大学法人静岡大学 | Novel hydrogelator |
| JPWO2017034004A1 (en) * | 2015-08-25 | 2018-08-30 | 国立大学法人九州大学 | Novel sugar derivative gelling agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247847A (en) * | 2000-03-03 | 2001-09-14 | Nisshin Oil Mills Ltd:The | Aqueous gelling agent |
| JP2002249756A (en) * | 2001-02-23 | 2002-09-06 | Japan Science & Technology Corp | New gelling agent consisting of saccharide derivative |
| JP2003049154A (en) * | 2001-08-07 | 2003-02-21 | Japan Science & Technology Corp | Hydrogel-forming agent derived from sugar |
-
2011
- 2011-03-01 JP JP2011044445A patent/JP5750798B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247847A (en) * | 2000-03-03 | 2001-09-14 | Nisshin Oil Mills Ltd:The | Aqueous gelling agent |
| JP2002249756A (en) * | 2001-02-23 | 2002-09-06 | Japan Science & Technology Corp | New gelling agent consisting of saccharide derivative |
| JP2003049154A (en) * | 2001-08-07 | 2003-02-21 | Japan Science & Technology Corp | Hydrogel-forming agent derived from sugar |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2017034004A1 (en) * | 2015-08-25 | 2018-08-30 | 国立大学法人九州大学 | Novel sugar derivative gelling agent |
| WO2018070546A1 (en) * | 2016-10-14 | 2018-04-19 | 国立大学法人静岡大学 | Novel hydrogelator |
| CN109790439A (en) * | 2016-10-14 | 2019-05-21 | 国立大学法人静冈大学 | New hydrogel agent |
| JPWO2018070546A1 (en) * | 2016-10-14 | 2019-09-05 | 国立大学法人静岡大学 | Novel hydrogelator |
| JP7133174B2 (en) | 2016-10-14 | 2022-09-08 | 国立大学法人静岡大学 | New hydrogelator |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5750798B2 (en) | 2015-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peng et al. | Cyclodextrin–dextran based in situ hydrogel formation: a carrier for hydrophobic drugs | |
| Dahlmann et al. | Fully defined in situ cross-linkable alginate and hyaluronic acid hydrogels for myocardial tissue engineering | |
| CA2887324C (en) | Glucose responsive hydrogel comprising pba-grafted hyaluronic acid (ha) | |
| NO305369B1 (en) | Hyaluronic acid esters and process for their preparation | |
| JP6347742B2 (en) | Novel sugar derivative gelling agent | |
| WO2006043705A1 (en) | Type ii cubic liquid crystal composition | |
| WO2011078383A1 (en) | Low-viscosity liquid-crystal compound | |
| AU2020203078A1 (en) | Substituted anionic compounds consisting of a backbone consisting of a discrete number of saccharide units | |
| RU2006134015A (en) | COMPLEX ETHERS OF HYALURONIC ACID WITH RHINE, METHOD FOR PRODUCING THEM AND COMPOSITIONS CONTAINING THESE ETHERS | |
| JP5907489B2 (en) | Hydrogels derived from chitosan derivatives | |
| CN1492760A (en) | Cyclodextrin preparation | |
| ES2261681T3 (en) | NEW DERIVATIVES OF THE HIALURONAN. | |
| JP5750798B2 (en) | Sugar-derived low-molecular hydrogelator and hydrogel containing the hydrogelator as an active ingredient | |
| WO2014190849A1 (en) | Doxorubicin prodrug, method of preparing same, and injectable combination | |
| CN1568999A (en) | Stable freeze dried formulation of spheroidine for medical use | |
| JP2011057620A (en) | Gelling agent of lipid histidine | |
| EP3320342B1 (en) | New hydrogels having a silylated structure, and method for obtaining same | |
| França et al. | Oxi-HA/ADH hydrogels: a novel approach in tissue engineering and regenerative medicine | |
| Tsupko et al. | Self‐assembled trehalose amphiphiles as molecular gels: A unique formulation to wax‐free cosmetics | |
| JP5447967B2 (en) | Reverse vesicle composed of biosurfactant | |
| Zhuang et al. | Properties of gelatin films cross–linked by N-hydroxysuccinimide–activated furandicarboxylic acid (NHS-FDCA) | |
| CN112704662A (en) | Lidocaine cream, preparation method and application thereof | |
| JP2007099902A (en) | Alginic acid derivatives, polyacrylic acid derivatives, and production methods thereof | |
| JP3898897B2 (en) | Novel gelling agent comprising a sugar derivative | |
| JP6193278B2 (en) | Vitamin C complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140128 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140120 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20141217 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150203 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150323 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150414 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150501 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5750798 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |