Versatile low-molecular-weight hydrogelators: achieving multiresponsiveness through a modular design.

Multiresponsive low-molecular-weight hydrogelators (LMWHs) are ideal candidates for the development of smart, soft, nanotechnology materials. The synthesis is however very challenging. On the one hand, de novo design is hampered by our limited ability to predict the assembly of small molecules in water. On the other hand, modification of pre-existing LMWHs is limited by the number of different stimuli-sensitive chemical moieties that can be introduced into a small molecule without seriously disrupting the ability to gelate water. Herein we report the synthesis and characterization of multistimuli LMWHs, based on a modular design, composed of a hydrophobic, disulfide, aromatic moiety, a maleimide linker, and a hydrophilic section based on an amino acid, here N-acetyl-L-cysteine (NAC). As most LMWHs, these gelators experience reversible gel-to-sol transition following temperature changes. Additionally, the NAC moiety allows reversible control of the assembly of the gel by pH changes. The reduction of the aromatic disulfide triggers a gel-to-sol transition that, depending on the design of the particular LMWH, can be reverted by reoxidation of the resulting thiol. Finally, the hydrolysis of the cyclic imide moieties provides an additional trigger for the gel-to-sol transition with a timescale that is appropriate for use in drug-delivery applications. The efficient response to the multiple external stimuli, coupled to the modular design makes these LMWHs an excellent starting point for the development of smart nanomaterials with applications that include controlled drug release. These hydrogelators, which were discovered by serendipity rather than design, suggest nonetheless a general strategy for the introduction of multiple stimuli-sensitive chemical moieties, to offset the introduction of hydrophilic moieties with additional hydrophobic ones, in order to minimize the upsetting of the critical hydrophobic-hydrophilic balance of the LMWH.

Shear ordered diblock copolymers with tuneable optical properties.

A series of high molecular weight poly(styrene-b-isoprene) block copolymers with optical properties defined by composition in a non-selective solvent were studied using simultaneous ultra small angle X-ray scattering (USAXS) and optical spectrometry. A small magnitude shear produces ordered and oriented states in the copolymer solutions that persist for extended periods of time, and also have superior optical properties that are directly attributable to the mesoscopic block copolymer (BCP) morphology. We have demonstrated that the optical transmission of these materials can be tuned by the addition of low molecular weight poly(isoprene) and poly(styrene) to swell their respective domains within the diblock copolymer. The optical transmission peak for the diblocks could be tuned; from 380 nm-440 nm for the 670k diblock, 425 nm-540 nm for the 850k diblock and 541 nm-625 nm for the 1 million diblock by altering the solution concentration and composition. The full width at half maximum that can be achieved for the optical transmission peaks is as small as 15 nm at 473 nm with a Δλ/λ of 0.03, highlighting the high quality ordering in these systems. Also a small shift in the transmission peak wavelength was observed across a wide angle of view (15 nm at 30°) suggesting that these materials could be used for large area narrow band optical filters.