A supramolecular hydrogel as a reusable heterogeneous catalyst for the direct aldol reaction

An L-proline based supramolecular hydrogel is used as an efficient heterogeneous organocatalyst for the direct aldol reaction with high stereoselectivity (up to 90% ee) and recyclability (up to 3 runs). The reversible nature of this self-assembled supramolecular system allows for easy recovery and regeneration of the catalys

Supramolecular gel formation and self-correction induced by aggregation-driven conformational changes

The formation of self-assembled fibrillar networks by low molecular weight peptidomimetics containing a Pro-Val moiety is reported; insight into the aggregation mechanism is provided revealing that it is associated to an unfolding process and that a fibrillar network formed under kinetic control can self-correct into a thermodynamically stable on

Remarkable increase in basicity associated with supramolecular gelation

L-Proline derivatives which are able to form supramolecular gels show an amazing basicity increase in the aggregated (gel) state as compared to solution. As a result they behave as enantioselective catalysts for the aldol reaction in solution but produce a base-catalyzed aldol racemisation in the gel stat

Structure and adhesion properties before and after hydrolytic ageing of polyurethane urea adhesives made with mixtures of waterborne polyurethane dispersions

Several waterborne polyurethane urea dispersions (WPUUs) were prepared by mixing different amounts of two waterborne polyurethane urea dispersions made with polyester (WPUU-Polyester) and polycarbonate diol (WPUU-PCD). Their crystallinity, thermal, rheological, viscoelastic and adhesion properties depended on the segmented structure and degree of phase separation which were determined by the different content of the parent dispersions. The PUU films made with WPUU-Polyester+WPUU-PCD mixtures containing more than 50 wt% of WPUU-PCD showed higher hard segments content and lower degree of phase separation, and the addition of 25 wt% of WPUU-Polyester imparted crystallinity to the polyurethane urea due to the interactions between the carbonate groups in the soft segments. The differences in the degree of phase separation and crystallinity of the PUU films made with WPUU-Polyester+WPUU-PCD mixtures were evidenced by the increase in the glass transition temperature associated to the alpha relaxation of the soft segments, and the higher modulus at the cross-over between the storage and loss moduli. Excellent adhesion was obtained in plasticized PVC/WPUU/plasticized PVC joints, and a cohesive failure of PVC was always obtained, irrespective of the composition of WPUU-Polyester+WPUU-PCD mixtures. Furthermore, the adhesion of surface-chlorinated vulcanized styrene-butadiene (SBR) rubber/WPUU+5 wt% hardener/roughened leather joints were high and similar in all joints and a dominant cohesive failure in the rubber substrate was produced. The accelerated ageing by immersion in water at 70 °C during different times showed that the polyurethane urea film and the surface-chlorinated vulcanized SBR rubber/WPUU+5 wt% hardener/roughened leather joint made with WPUU-PCD dispersion were not affected, but noticeable hydrolytic degradation of the ester units in the soft segments was produced in PUU-Polyester and, to a less extent, in PUU-50Polyester/50PCD films and adhesive joints.Financial support by UBE CHEMICAL EUROPE (Grant no. UBE1-15ID) is acknowledged

HRMAS 1H NMR as a tool for the study of supramolecular gels

HRMAS 1H NMR is reported for the first time as a useful technique to gain insight into the dynamic properties of aggregates present in supramolecular gels. The study of several low molecular weight gelators with this technique in toluene and acetonitrile is described

Microfluidic Assisted Self-Assembly of pH-Sensitive Low-Molecular Weight Hydrogelators Close to the Minimum Gelation Concentration

\u3cp\u3eThe fibrillation and subsequent gelation of low molecular hydrogelators is usually triggered by external stimuli. Generally, strong acids are employed to trigger the self-assembly mechanism in pH-responsive supramolecular systems. However, the generation and design of novel stable gels with performing mechanical properties is a challenging task as a result of the uneven self-assembled networks formed. Here, we report the study of the self-assembly process of a low molecular weight hydrogelator (LMWG) in the proximity of its minimum gelation concentration (MGC = 0.3 mg/ml). At such high dilution, the generation of homogeneous gels with good mechanical properties by turning pH by strong acids is a demanding task as a result of the lack of monodisperse 1D self-assembled rod-like aggregates. A microfluidic device is employed here to gradually and homogeneously change the pH. We show that self-assembly of LMWG in well-defined structures can be enhanced by using the diffusive mixing occurring in the microfluidic reactor channel. For very short mixing times, aggregates with 2 nm cross-section are found in the region adjacent to the focused LMWG solution in contact with the low pH buffer solution streams, where the pH reaches values below the pKa of the LMWG and triggers the supramolecular self-assembly. For longer mixing times, aggregates grow in size and occupy homogeneously the micro channel. The results presented here show that better controlled self-assembly can be achieved using microfluidic mixing devices and early stages of self-assembly can be efficiently studied by coupling synchrotron SAXS with microfluidics.\u3c/p\u3

Selective and highly efficient dye scavenging by a pH-responsive molecular hydrogelator

A structurally simple low molecular weight hydrogelator derived from isophthalic acid forms robust pH-responsive hydrogels capable of highly efficient and selective dye adsorption

An Engineered extraplastidial pathway for carotenoid biofortification of leaves

Carotenoids are lipophilic plastidial isoprenoids highly valued as nutrients and natural pigments. A correct balance of chlorophylls and carotenoids is required for photosynthesis and therefore highly regulated, making carotenoid enrichment of green tissues challenging. Here we show that leaf carotenoid levels can be boosted through engineering their biosynthesis outside the chloroplast. Transient expression experiments in Nicotiana benthamiana leaves indicated that high extraplastidial production of carotenoids requires an enhanced supply of their isoprenoid precursors in the cytosol, which was achieved using a deregulated form of the main ratedetermining enzyme of the mevalonic acid (MVA) pathway. Constructs encoding bacterial enzymes were used to convert these MVA-derived precursors into carotenoid biosynthetic intermediates that do not normally accumulate in leaves, such as phytoene and lycopene. Cytosolic versions of these enzymes produced extraplastidial carotenoids at levels similar to those of total endogenous (i.e. chloroplast) carotenoids. Strategies to enhance the development of endomembrane structures and lipid bodies as potential extraplastidial carotenoid storage systems were not successful to further increase carotenoid contents. Phytoene was found to be more bioaccessible when accumulated outside plastids, whereas lycopene formed cytosolic crystalloids very similar to those found in the chromoplasts of ripe tomatoes. This extraplastidial production of phytoene and lycopene led to an increased antioxidant capacity of leaves. Finally, we demonstrate that our system can be adapted for the biofortification of leafy vegetables such as lettuce

Selective Extraction and in Situ Reduction of Precious Metal Salts from Model Waste to Generate Hybrid Gels with Embedded Electrocatalytic Nanoparticles

A hydrogel based on 1,3:2,4-dibenzylidenesorbitol (DBS), modified with acyl hydrazides which extracts gold/silver salts from model waste is reported, with preferential uptake of precious heavy metals over other common metals. Reduction of gold/silver salts occurs spontaneously in the gel to yield metal nanoparticles located on the gel nanofibers. High nanoparticle loadings can be achieved, endowing the gel with electrochemical activity. These hybrid gels exhibit higher conductances than gels doped with carbon nanotubes, and can be used to modify electrode surfaces, enhancing electrocatalysis. We reason this simple, industrially and environmentally relevant approach to conducting materials is of considerable significance

Applying low-molecular weight supramolecular gelators in an environmental setting – self-assembled gels as smart materials for pollutant removal

This review explores supramolecular gels as materials for environmental remediation. These soft materials are formed by self-assembling low-molecular-weight building blocks, which can be programmed with molecular-scale information by simple organic synthesis. The resulting gels often have nanoscale ‘solid-like’ networks which are sample-spanning within a ‘liquid-like’ solvent phase. There is intimate contact between the solvent and the gel nanostructure, which has a very high effective surface area as a result of its dimensions. As such, these materials have the ability to bring a solid-like phase into contact with liquids in an environmental setting. Such materials can therefore remediate unwanted pollutants from the environment including: immobilisation of oil spills, removal of dyes, extraction of heavy metals or toxic anions, and the detection or removal of chemical weapons. Controlling the interactions between the gel nanofibres and pollutants can lead to selective uptake and extraction. Furthermore, if suitably designed, such materials can be recyclable and environmentally benign, while the responsive and tunable nature of the self-assembled network offers significant advantages over other materials solutions to problems caused by pollution in an environmental setting