含苯环结构的糖类小分子胶凝剂的合成及其自组装行为研究
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摘要
以(邻、间、对)苯二胺为连接臂将葡萄糖酸与胆固醇相连接,设计合成了3种含苯环结构的糖类小分子胶凝剂.通过核磁、质谱、红外光谱、元素分析对所得化合物进行了结构表征,系统考察了3种胶凝剂分子在常见30种溶剂中的胶凝行为.实验结果表明,间位连接的胶凝剂C2G的胶凝能力明显优于邻位和对位连接的胶凝剂C1G和胶凝剂C3G,且C2G在DMSO中最低胶凝浓度可达0.06%(w/v).胶凝剂的分子结构及浓度,以及溶剂极性对胶凝剂在溶剂中的胶凝行为、自组装聚集体的形貌和流变学性能均有显著影响.流变学结果表明C2G/DMSO凝胶体系具有较好的机械稳定性和剪切触变性.红外光谱和变温、变浓度核磁表明胶凝剂分子中葡萄糖酸残基之间的氢键及胆固醇和苯环之间的π-π堆积作用是该类超分子凝胶形成的两大驱动力.XRD结果表明胶凝剂C2G在DMSO中以层状模型堆积.
Three glucose derivatives containing benzene rings were designed and prepared by using(o-,m-,p-) phenylenediamine as linkers to connect gluconic acid with cholesterol.The structures and compositions of all these compounds are characterized by ~1H NMR,MS(ESI),FTIR spectroscopy,and elemental analysis.Their gelation abilities were evaluated in 30 commonly used solvents.It can be seen that the gelation abilities of the compounds are dependent strongly on the spacer structures of them,compound C2G with a critical gelation concentration(CGC) of 0.06%(w/v) in DMSO.The spacer structure,the concentration of the gelator and the nature of the solvent play a crucial role in the morphologies and rheological properties of their xerogels.It is worth mentioning that C2G/DMSO gel possesses smart and reversible thixotropic property.As revealed by FT-IR and ~1H NMR,hydrogen-bonding between glucono units and π-π stacking between cholesteryl and benzene groups are important in the formation of the gels.XRD study revealed that C2G assembled into a layered structure in its DMSO gel.
Three glucose derivatives containing benzene rings were designed and prepared by using(o-,m-,p-) phenylenediamine as linkers to connect gluconic acid with cholesterol.The structures and compositions of all these compounds are characterized by ~1H NMR,MS(ESI),FTIR spectroscopy,and elemental analysis.Their gelation abilities were evaluated in 30 commonly used solvents.It can be seen that the gelation abilities of the compounds are dependent strongly on the spacer structures of them,compound C2G with a critical gelation concentration(CGC) of 0.06%(w/v) in DMSO.The spacer structure,the concentration of the gelator and the nature of the solvent play a crucial role in the morphologies and rheological properties of their xerogels.It is worth mentioning that C2G/DMSO gel possesses smart and reversible thixotropic property.As revealed by FT-IR and ~1H NMR,hydrogen-bonding between glucono units and π-π stacking between cholesteryl and benzene groups are important in the formation of the gels.XRD study revealed that C2G assembled into a layered structure in its DMSO gel.
引文
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[2] P.Terech,R.G.Weiss.Low molecular mass gelators of organic liquids and the properties of their gels[J].Chem.Rev.,1997,97:3 133-3 159.
[3] X.W.Chen,Y.J.Chen,J.M.Wang,et al.Tunable volatile release from organogel-emulsions based on the self-assembly of β-sitosterol and γ-oryzanol[J].Food Chem.,2017,221:1 491-1 498.
[4] H.Yang,S.F.Zhang,K.Q.Liu,et al.Calix[4]arene-based low molecular mass gelators to form gels in organoalkoxysilanes[J].RSC Advances,2016,6:109 969-109 977.
[5] A.Aggeli,M.Bell,N.Boden,et al.Responsive gels formed by the spontaneous self-assembly of peptides into polymeric β-sheet tapes[J].Nature,1997,386:259-262.
[6] J.Liu,P.He,J.Yan,et al.An organometallic super-gelator with multiple-stimulus responsive properties[J].Adv.Mater.,2008,20:2 508-2 511.
[7] L.Henrik,M.O.Elena,V.D.Max.Self-assembled orthoester cryptands:Orthoester scope,post-functionalization,kinetic locking and tunable degradation kinetics[J].Chem.Sci.,2018,9:4 785-4 793.
[8] F.Ono,S.Shinkai,H.Watanabe.High internal phase water/oil and oil/water gel emulsions formed using a glucose-based low-molecular-weight gelator[J].N.J.Chem.,2018,42(9):6 601-6 603.
[9] L.A.Estroff,A.D.Hamilton.Water gelation by small organic molecules[J].Chem.Rev.,2004,104:1 201-1 218.
[10] O.Gronwald,S.Shinkai.Sugar-integrated gelators of organic solvents[J].Chem.Eur.J.,2001,7:4 328-4 334.
[11] P.K.Vemula,J.Li,G.John.Enzyme catalysis:Tool to make and break amygdalin hydrogelators from renewable resources:A delivery model for hydrophobic drugs[J].J.Am.Chem.Soc.,2006,128:8 932-8 938.
[12] J.H.Jung,S.Shinkai,T.Shimizu.Spectral characterization of self-assemblies of aldopyranoside amphiphilicgelators:What is the essential structural difference between simple amphiphiles and bolaamphiphiles[J].Chem.Eur.J.,2002,8:2 684-2 690.
[13] X.Y.Hou,D.Gao,J.L.Yan,et al.Novel dimeric cholesteryl derivatives and their smart thixotropic gels[J].Langmuir,2011,27:12 156-12 163.
[14] 刘硕,聚天冬氨酸水凝胶的分子模拟与性能预测[D].北京:北京化工大学,2018.
[15] M.G.Page,G.Gregory,G.G.Warr.Structure and dynamics of self-assembling aluminum didodecyl phosphate organogels[J].J.Phys.Chem.B.,2004,108:16 983-16 989.
[16] M.Lescanne,P.Grondin,A.d′Aléo,et al.Thixotropic organogels based on a simple N-hydroxyalkyl amide:Rheological and aging properties[J].Langmuir,2004,20:3 032- 3 041.
[17] M.George,G.P.Funkhouser,P.Terech,et al.Organogels with Fe(III) complexes of phosphorus-containing amphiphiles as two-component isothermal gelators[J].Langmuir,2006,22:7 885-7 893.
[18] V.Trappe,D.A.Weitz.Phys.Scaling of the viscoelasticity of weakly attracttive particles[J].Phys.ReV.Lett.,2000,85(2):449-452.
[19] M.C.Yang,L.E.Scriven,C.W.Macosko.Some rheological measurements on magnetic iron oxide suspensions in silicone oil[J].J.Rheol.,1986,30:1 015-1 029.
[20] W.G.Weng,J.B.Beck,A.M.Jamieson,et al.Understanding the mechanism of gelation and stimuli-responsive nature of a class of metallo-supramolecular gels[J].J.Am.Chem.Soc.,2006,128(35):11 663-11 672.
[21] P.Terech,D.Pasquier,V.Bordas,et al.Rheological properties and structural correlations in molecular organogels[J].Langmuir,2000,16:4 485-4 494.
[22] J.Brinksma,B.L.Feringa,R.M.Kellogg,et al.Rheology and thermotropic properties of bis-urea-based organogels in various primary alcohols[J].Langmuir,2000,16:9 249-9 255.
[23] N.Yamada,T.Imai,E.Koyama.Lyotropic aggregate of tripeptide derivatives within organic solvents:Relationship between interpeptide hydrogen bonding and packing arrangements of components[J].Langmuir,2001,17(4):961-963.
[24] A.Ballabh,D.R.Trivedi,P.Dastidar.New series of organogelators derived from a combinatorial library of primary ammonium monocarboxylate salts[J].Chem.Mater.,2006,18(16):3 795-3 800.
[25] S.R.Jadhav,P.K.Vemula,R.Kumar,et al.Sugar-derived phase-selective molecular gelators as model solidifiers for oil spills[J].Angew.Chem.Int.Ed.,2010,49:1-5.
[26] J.X.Peng,K.Q.Liu,X.F.Liu,et al.New dicholesteryl- based gelators:Gelling ability and selective gelation of organic solvents from their mixtures with water at room temperature[J].New.J.Chem.,2008,32:2 218-2 224.
[27] M.Xue,D.Gao,K.Q.Liu,et al.Cholesteryl derivatives as phase-selective gelators at room temperature[J].Tetrahedron,2009,65:3 369-3 377.
[28] F.S.Schoonbeek,J.van Esch,R.Hulst,et al.Geminal bis-ureas as gelators for organic solvent:Gelation properties and structural studies in solution and in the gel state[J].Chem.Eur.J.,2000,6:2 633-2 643.
[29] E.Snip,S.Shinkai,D.N.Reinhoudt.Organogels of a nucleobase-bearing gelator and the remarkable effects of nucleoside derivatives and a porphyrin derivative on the gel stability[J].Tetrahedron Lett.,2001,42:2 153-2 156.
[30] C.C.Tsou,S.S.Sun.New fluorescent amide-functionalized phenylethynylthiophene low molecular weight gelator[J].Org.Lett.,2006,8:387-390.
[31] D.H.Kumar,D.A.Jose,P.Dastidar,et al.Nonpolymeric hydrogelator derived from N-(4-pyridyl)isonicotinamide[J].Langmuir,2004,20:10 413- 10 418.
[32] K.Hanabusa,M.Matsumoto,M.Kimura,et al.Low molecular weight gelators for organic fluids:Gelation using a family of cyclo(dipeptide)s[J].J.Colloid Interface Sci.,2000,224:231-244.
[33] D.J.Abdallah,S.Sirchio,R.G.Weiss.Hexatriacontane organogels:The first deter-mination of the conformation and molecular packing of a low-molecular-mass organogelator in its gelled state[J].Langmuir,2000,16:7 558-7 561.
[34] M.Himabindu,A.Palanisamy.Ultrasound and temperature-induced gelation of gluconosemicarbazide gelator in DMSO and water mixtures[J].Gels,2017,3(2):12.
[35] M.Xue,K.Q.Liu,J.X.Peng,et al.Novel dimeric cholesteryl based A(LS)2 low-molecular-mass gelators with a benzene ring in the linker[J].J.Colloid Interface Sci.,2008,327:94-101.