Exploring the Tunable Optical and Mechanical Properties of Multicomponent Low-Molecular-Weight Gelators.

A class of amino acid-based low-molecular-weight gelators (LMWGs) was used for single and multicomponent gel studies to investigate their tunable optical properties and their self-assembly process. The optical properties of multicomponent gels were found to be easily tuned by changing the proportion of the components, varying from opaque to highly transparent gels as analyzed using ultraviolet-visible spectroscopy. This phenomenon allows tunability without introducing another variable into the system. Scanning electron microscopy, differential scanning calorimetry, and small-angle X-ray scattering (SAXS) were used to investigate the structures of the gels. It was found that because of the structural similarities of the molecules, the gelators favor coassembly packing over self-sorting. The emergence of transparency was ascribed to changes in the fiber diameters. Moreover, analysis of the SAXS data allowed us to compare the molecular order present in the gel phase with single-crystal X-ray diffraction (SCXRD) data. Our analysis suggests that the packing of molecules seen in the crystalline phase is translated into the gel network. This reveals that the structure of the crystalline phase seen through SCXRD is a useful tool to aid in understanding the molecular packing in the gel phase.

Amino Acid-Containing Phase-Selective Organogelators: A Water-Based Delivery System for Oil Spill Treatment.

The simple structural modification of replacing a terminal carboxylic acid with a primary amide group was found to lower the minimum gelation concentration (MGC), by at least an order of magnitude, for a series of N-lauroyl-l-amino acid phase-selective organogelators in decane. The amide-functionalized analogue N-lauroyl-l-alanine-CONH2 was demonstrated to gel a broad range of solvents from diesel to THF at MGCs of 2.5% w/v or less, as well as to produce gels with a higher thermal stability (ca. 30 °C) and enhanced mechanical properties (5 times increase in complex modulus), compared to the carboxylic acid analogue, N-lauroyl-l-alanine-COOH. These improved properties may be due to the additional hydrogen bonding in the primary amide analogue as revealed by SCXRD. Most significantly for this study, the introduction of the primary amide functionality enabled N-lauroyl-l-alanine-CONH2 to form a self-assembled fibrillar network in water. The aqueous network could then actively uptake and rapidly gel decane, diesel, and diluted bitumen ("dilbit") with MGCs of 2.5% w/v or less. This aqueous delivery method is advantageous for oil-remediation applications as no harmful carrier solvents are required and the gel can be easily separated from the water, allowing the oil to be recovered and the gelator recycled.

Demonstrating Aqueous-Phase Low-Molecular-Weight-Gel Wicking of Oil for the Remediation of Oil Spilled into Surface Water.

Oils spilled into surface water require effective and timely treatment. In this paper, we report on a low-molecular-weight gelator that can form gels in organic and aqueous phases. The aqueous gel was observed to absorb oils, which is proposed as a new class of materials for remediating oil spilled into surface water. The gels and the low-molecular-weight gelator have both fundamental and applied significance. Fundamentally, identifying the mechanisms that govern the formation of these gels and their resultant mechanical properties is of interest. Subsequently, these fundamental insights aid in the optimization of these gels for addressing spilled oil. First, we briefly compare the organic and aqueous gels qualitatively before focusing on the aqueous gel. Second, we demonstrate the ability of the aqueous gel to wick oils through experiments in a Hele-Shaw cell and compare our results to the Washburn equation for porous media. The Washburn equation is not entirely adequate in describing our results due to the change in volume of the porous media during the wicking process. Finally, we investigate mechanisms proposed to govern the formation of low-molecular-weight gels in the literature through rheological shear measurements during gel formation. Our experiments suggest that the proposed mechanisms are applicable to our aqueous gels, growing as anisotropic crystal networks with fractal dimensions between one and two dimensions from temporally sporadic nucleation sites.

Synthesis of [difluoro-(3-alkenylphenyl)-methyl]-phosphonic acids on non-crosslinked polystyrene and their evaluation as inhibitors of PTP1B.

A series of [difluoro-(3-alkenylphenyl)-methyl]-phosphonates were prepared on non-crosslinked polystyrene, a soluble polymer support. After cleavage from the support, the resulting phosphonic acids were examined for inhibition with protein tyrosine phosphatase 1B. Compound 20, bearing an alpha,beta-unsaturated allyl ester moiety, was the most potent of this series of compounds, being a reversible, competitive inhibitor with a K(i) of 8.0+/-1.4 microM.

The difluoromethylenesulfonic acid group as a monoanionic phosphate surrogate for obtaining PTP1B inhibitors.

Three peptides, 7-9, bearing sulfono(difluoromethyl)phenylalanine (F(2)Smp, 2), a nonhydrolyzable, monoanionic phosphotyrosine mimetic, were prepared and evaluated as PTP1B inhibitors. The most effective inhibitor was the nonapeptide, ELEF(F(2)Smp)MDYE-NH(2), (9) which exhibited a K(i) of 360 nM. A comparison of F(2)Smp-bearing peptides 7 [DADE(F(2)Smp)LNH(2), K(i)=3.4 microM] and 8 [EEDE(F(2)Smp)LNH(2), K(i)=0.74 microM] with their phosphono(difluoromethyl)phenylalanine (F(2)Pmp)-bearing analogues indicated that F(2)Smp is not as effective a pTyr mimetic as F(2)Pmp by 100- to 130-fold. Although F(2)Smp is not as effective as F(2)Pmp, a comparison of peptide 7 with analagous peptides bearing other monoanionic pTyr mimetics recently reported in the literature indicates that F(2)Smp is about 65-fold more effective than any other non-hydrolyzable, monanionic pTyr mimetic reported to date. To further assess the difluoromethylenesulfonic acid (DFMS) group as a monoanionic phosphate mimetic, a series of 24 nonpeptidyl biaryl compounds bearing the DFMS group were prepared using polymer-supported methodologies and screened for PTP1B inhibition. Several of these compounds were selected for further study and their IC(50)'s compared to their difluoromethylenephosphonic (DFMP) analogues. The differences in IC(50)'s between the DFMS and DFMP non-peptidyl compounds was not as great as with the F(2)Smp- and F(2)Pmp-bearing peptides. Possible reasons for this and its implication to the design of small molecule PTP1B inhibitors is discussed.