Mechanistic Insight into Supramolecular Polymerization in Water Tunable by Molecular Geometry

作     者：Fan Xu Stefano Crespi Lukas Pfeifer Marc C.A.Stuart Ben L.Feringa 

作者机构：Stratingh Institute for ChemistryUniversity of GroningenGroningen 9747 AG Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular EngineeringFeringa Nobel Prize Scientist Joint Research CenterFrontiers Science Center for Materiobiology and Dynamic ChemistryInstitute of Fine ChemicalsSchool of Chemistry and Molecular EngineeringEast China University of Science and TechnologyShanghai 200237 Angstrom LaboratoryDepartment of ChemistryUppsala UniversityUppsala 75120 Laboratory of Photonics and InterfacesDepartment of Chemistry and Chemical EngineeringÉcole Polytechnique Fédérale de LausanneLausanne CH-1015 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2022年第4卷第7期

页      面：2212-2220页

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：Financial support from the Netherlands Organization for Scientific Research(NWO-CW) the European Research Council(ERC,advanced grant no.694345 to B.L.F.) the Dutch Ministry of Education,Culture and Science(Gravitation program no.024.001.035) the China Scholarship Council(CSC,no.201707040064 to F.X.) the Marie Skłodowska-Curie Actions(Individual Fellowships no.838280 to S.C.and no.793082 to L.P.)is gratefully acknowledged 

主　　题：supramolecular polymerization stiff-stil-bene bis-urea hydrogen bonding π-stacking hydro-phobic effects 

摘      要：Supramolecular self-assembly in water based on non-covalent bonding is attracting major attention due to the potential of hydrogels and aqueous polymers in biomedical *** supramolecular polymerization in organic solvents is well established,the key design features,the assembly mechanisms in water and achieving control over the aggregate structures remain ***,we present the assembly and disassembly of geometrical isomers of a stiff-stilbene bis-urea amphiphile(SA)in pure water.A remarkable feature of this system is that the(E)-isomer forms supramolecular polymers in both pure water and organic *** advantage of this unique property,the hydrophobic effect was studied by comparing the supramolecular assembly in both *** assembly process inwater follows an enthalpy-driven nucleation-elongation(cooperative)supramolecular polymerization mechanism with a standard Gibbs free energy(ΔG°=−53 kJ mol^(−1))double the value of the one found in *** attributed this distinctive feature to the hydrophobic effect in ***,we discovered an isomer-dependent assembly process,which can be used to control aggregation in aqueous *** to the substantial geometric difference between(E)-SA and(Z)-SA,we compared their assembly in water to study the influence of different driving forces involved in the *** supramolecular polymerization of(E)-SA was cooperatively influenced by hydrogen bonding,π-stacking,and hydrophobic effects,whereas the assembly of(Z)-SAwasmainly driven by hydrophobic *** a result,the fiber length of(E)-SA in water is much longer than that of(Z)-SA,presenting opportunities for geometrical control of aggregation in aqueousmedia.