To investigate the effect of spatial configuration on the gelation properties of low molecular mass gelators(LMMGs),four novel di-cholesteryl derivatives have been specially designed and synthesized by introducing the cis-/trans-isomers of butene diacid and the optical isomers of D/L-phenylalanine into the linker between two cholesteryl moieties.These isomers have been denoted as MaDC,FaDC,MaLC and FaLC,respectively.The gelation properties of the compounds were examined in 26 organic solvents,and it was found that the trans-configuration is more favorable for the gelation,but the chirality of the linker shows little effect to the gelation.FaDC has the strongest gelation ability among the four isomers.Interestingly,FaDC and FaLC display phase-selective gelation of benzene,toluene and xylene from their mixtures with water at room temperature,which establishes a foundation for the purification of water contaminated by oil or aromatic solvents.SEM and CD spectroscopy studies revealed that the spatial configuration of the linkers of the gelators affects significantly the aggregation mode,the morphologies and the chirality of the network of the gels.Moreover,the different aggregation behaviors also have an impact on mechanical properties of the gels,which are consistent with the results from rheological studies.Furthermore,temperature-and concentration-dependent 1 H NMR and FTIR measurements demonstrated that intermolecular hydrogen bonding and-stacking are the main driving forces for the formation of the gels.
This article is intended to provide an overview of recent progress in the studies of cholesterol-based low-molecular mass gelators (LMMGs) with unusual properties,in particular,gelation and selective gelation at room temperature,gel emulsions and gel film formation,etc.Potential applications of the LMMGs in spilled oil collection and water purification are briefly presented.
LIU KaiQiang,HE PanLi & FANG Yu Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University),Ministry of Education
Five new diacid amides of di-cholesteryl L-glycinates were designed and prepared.The compounds with linkers containing 0,1, 2,3,or 4 methylene units are denoted as 1,2,3,4,and 5,respectively.Their gelation behaviors in 25 solvents were tested as novel low-molecular-mass organic gelators(LMOGs).It was shown that the length of the linker connecting the two-cholesteryl residues in a gelator plays a crucial role in the gelation behavior of the compound.1 gels 11 of the 25 solvents tested at a concentration lower than 1.0%,while 2 gels 17 of the solvents tested.4 and 5,however,gel only 2 and 4 of them,respectively. SEM observation reveals that the lengths of the linkers and the identity of the solvents are the main factors affecting the structures of the aggregates in the gels.Experimentally,a clear linker effect on the microstructures of the gels was observed.As example,the aggregates of 1,2 and 3 in benzene or 1-heptanol adopt structures of thin fibers,rods or lamellas,respectively. Furthermore,it was found that the gelation and aggregation behaviors of 2,3,4,and 5 in DMSO showed an even-odd effect.
LIU KaiQiangPENG JunXiaXUE MinYAN NiLIU JingFANG Yu
