Combining low molecular weight gelators (LMWGs) with polymers is a broad yet relatively recent field, in a phase of rapid expansion and with huge potential for exploitation. This review provides an overview of the state-of-the-art and reflects on new technologies that might be unlocked. We divide LMWG-polymer systems into five categories: (i) polymerisation of self-assembled LMWG fibres, (ii) capture of LMWG fibres in a polymer matrix, (iii) addition of non-gelling polymer solutions to LMWGs, (iv) systems with directed interactions between polymers and LMWGs, and (v) hybrid gels containing both LMWGs and polymer gels (PGs). Polymers can have significant impacts on the nanoscale morphology and materials performance of LMWGs, and conversely LMWGs can have a major effect on the rheological properties of polymers. By combining different types of gelation system, it is possible to harness the advantages of both LMWGs and PGs, whilst avoiding their drawbacks. Combining LMWG and polymer technologies enhances materials performance which is useful in traditional applications, but it may also yield major steps forward in high-tech areas including environmental remediation, drug delivery, microfluidics and tissue engineering.

Dibenzylidene-D-sorbitol (DBS) has been a well-known low-molecular-weight gelator of organic solvents for over 100 years. As such, it constitutes a very early example of a supramolecular gel--a research field which has recently developed into one of intense interest. The ability of DBS to self-assemble into sample-spanning networks in numerous solvents is predicated upon its 'butterfly-like' structure, whereby the benzylidene groups constitute the 'wings' and the sorbitol backbone the 'body'--the two parts representing the molecular recognition motifs underpinning its gelation mechanism, with the nature of solvent playing a key role in controlling the precise assembly mode. This gelator has found widespread applications in areas as diverse as personal care products and polymer nucleation/clarification, and has considerable potential in applications such as dental composites, energy technology and liquid crystalline materials. Some derivatives of DBS have also been reported which offer the potential to expand the scope and range of applications of this family of gelators and endow the nansocale network with additional functionality. This review aims to explain current trends in DBS research, and provide insight into how by combining a long history of application, with modern methods of derivatisation and analysis, the future for this family of gelators is bright, with an increasing number of high-tech applications, from environmental remediation to tissue engineering, being within reach.

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ABSTRACT:We report a multi-component self-assembling system based on 1,3:2,4-dibenzyldene-D-sorbitol (DBS) derivatives which form gels as the pH is lowered in a controlled way. The two DBS gelators are functionalized with carboxylic acids the first in the 4-position of the aromatic rings (DBS-CO 2 H), the second having glycine connected through an amide bond and displaying a terminal carboxylic acid (DBS-Gly). Importantly, these two self-assembling DBS-acids have different pK a values, and as such, their self-assembly is triggered at different pHs. Slowly lowering the pH of a mixture of gelators using glucono--lactone (GdL) initially triggers assembly of DBS-CO 2 H, followed by DBS-Gly a good degree of kinetic self-sorting is achieved. Gel formation can also be triggered in the presence of diphenyliodonium nitrate (DPIN) as a photoacid under UV irradiation. Two-step acidification of a mixture of gelators using (a) GdL and (b) DPIN assembles the two networks sequentially. By combining this approach with a mask during step (b), multidomain gels are formed, in which the network based on DBS-Gly is positively patterned into a pre-existing network based on DBS-CO 2 H. This innovative approach yields spatially-resolved multidomain multi-component gels based on programmable lowmolecular-weight gelators, with one network being positively written into another.

A simple approach to a patterned multidomain gel is reported, combining a pH-responsive low-molecular-weight gelator (LMWG) and a photoinducible polymer gelator (PG). Using SEM (scanning electron microscopy), NMR spectroscopy, and CD, we demonstrate that self-assembly of the LMWG network occurs in the presence of the PG network, but that the PG has an influence on LMWG assembly kinetics and morphology. The application of a mask during photoirradiation allows patterning of the PG network; we define the resulting system as a "multidomain gel"-one domain consists of a LMWG, whereas the patterned region contains both LMWG and PG networks. The different domains have different properties with regard to diffusion of small molecules, and both gelator networks can control diffusion rates to give systems capable of controlled release. Such materials may have future applications in multikinetic control of drug release, or as patterned scaffolds for directed tissue engineering.