Journal
LANGMUIR
Volume 30, Issue 47, Pages 14128-14142Publisher
AMER CHEMICAL SOC
DOI: 10.1021/la5008389
Keywords
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Funding
- New Jersey Agriculture Research Station (NJAES)
- U.S. National Science Foundation [CHE-1147353]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1147353] Funding Source: National Science Foundation
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Solvent properties play a central role in mediating the aggregation and self-assembly of molecular gelators and their growth into fibers. Numerous attempts have been made to correlate the solubility parameters of solvents and gelation abilities of molecular gelators, but a comprehensive comparison of the most important parameters has yet to appear. Here, the degree to which partition coefficients (log P), Henrys law constants (HLC), dipole moments, static relative permittivities (epsilon(r)), solvatochromic E-T(30) parameters, Kamlet-Taft parameters (beta, alpha, and pi), Catalans solvatochromic parameters (SPP, SB, and SA), Hildebrand solubility parameters (delta(i)), and Hansen solubility parameters (delta(p), delta(d), delta(h)) and the associated Hansen distance (R-ij) of 62 solvents (covering a wide range of properties) can be correlated with the self-assembly and gelation of 1,3:2,4-dibenzylidene sorbitol (DBS) gelation, a classic molecular gelator, is assessed systematically. The approach presented describes the basis for each of the parameters and how it can be applied. As such, it is an instructional blueprint for how to assess the appropriate type of solvent parameter for use with other molecular gelators as well as with molecules forming other types of self-assembled materials. The results also reveal several important insights into the factors favoring the gelation of solvents by DBS. The ability of a solvent to accept or donate a hydrogen bond is much more important than solvent polarity in determining whether mixtures with DBS become solutions, clear gels, or opaque gels. Thermodynamically derived parameters could not be correlated to the physical properties of the molecular gels unless they were dissected into their individual HSPs. The DBS solvent phases tend to cluster in regions of Hansen space and are highly influenced by the hydrogen-bonding HSP, delta(h). It is also found that the fate of this molecular gelator, unlike that of polymers, is influenced not only by the magnitude of the distance between the HSPs for DBS and the HSPs of the solvent, R-ij, but also by the directionality of Rij: if the solvent has a larger hydrogen-bonding HSP (indicating stronger H-bonding) than that of the DBS, then clear gels are formed; opaque gels form when the solvent has a lower delta(h) than does DBS.
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