Naked-Eye Thiol Analyte Detection via Self-Propagating, Amplified Reaction Cycle.

We present an approach for detecting thiol analytes through a self-propagating amplification cycle that triggers the macroscopic degradation of a hydrogel scaffold. The amplification system consists of an allylic phosphonium salt that upon reaction with the thiol analyte releases a phosphine, which reduces a disulfide to form two thiols, closing the cycle and ultimately resulting in exponential amplification of the thiol input. When integrated in a disulfide cross-linked hydrogel, the amplification process leads to physical degradation of the hydrogel in response to thiol analytes.

Dynamic Growth of Macroscopically Structured Supramolecular Hydrogels through Orchestrated Reaction-Diffusion.

Living organisms are capable of dynamically changing their structures for adaptive functions through sophisticated reaction-diffusion processes. Here we show how active supramolecular hydrogels with programmable lifetimes and macroscopic structures can be created by relying on a simple reaction-diffusion strategy. Two hydrogel precursors (poly(acrylic acid) PAA/CaCl and Na CO ) diffuse from different locations and generate amorphous calcium carbonate (ACC) nanoparticles at the diffusional fronts, leading to the formation of hydrogel structures driven by electrostatic interactions between PAA and ACC nanoparticles.

Design Rules for Binary Bisamide Gelators: toward Gels with Tailor-Made Structures and Properties.

This study intends to develop design rules for binary mixture of gelators that govern their assembly behavior and subsequently explore the impact of their supramolecular assembly patterns on the gels' rheological properties. To achieve these goals, BA gelators with odd and even parities [-methylene spacers between the amide groups ( = 5-10) and 17 carbons at each end] were blended at different ratios. Such bisamides with simple structures were selected to study because their different spacer lengths offer the possibility to have matching or non-matching hydrogen bonds.

Supramolecular Arrangement and Rheological Properties of Bisamide Gels.

We report a systematic study of the gelation behavior of BA gelators in xylene, with odd and even -methylene spacers between the amide groups ( = 5-10) and 17 carbons at each end. The melting temperatures () of BA gels are obtained from fitting our DSC(T) model to the experimental DSC data. The found of BA gels is about 35 °C lower than of the pure BA gelators.

Dynamics of hydroxide-ion-driven reversible autocatalytic networks.

In living systems adaptive regulation requires the presence of nonlinear responses in the underlying chemical networks. Positive feedbacks, for example, can lead to autocatalytic bursts that provide switches between two stable states or to oscillatory dynamics. The stereostructure stabilized by hydrogen bonds provides an enzyme its selectivity, rendering pH regulation essential for its functioning.

Plaque burden is associated with minimal intimal coverage following drug-eluting stent implantation in an adult familial hypercholesterolemia swine model.

Safety and efficacy of coronary drug-eluting stents (DES) are often preclinically tested using healthy or minimally diseased swine. These generally show significant fibrotic neointima at follow-up, while in patients, incomplete healing is often observed. The aim of this study was to investigate neointima responses to DES in swine with significant coronary atherosclerosis.

Molecular Arrangement and Thermal Properties of Bisamide Organogelators in the Solid State.

The crystal structure and phase behavior of bisamide gelators are investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy, X-ray diffraction (XRD), and molecular modeling, aiming at a better understanding of bisamide gel systems. A homologous series of bisamide model compounds (BAs) was prepared with the (CH) spacer between the two amide groups, where varies from 5 to 10, and with two symmetric C17 alkyl tails. With increasing spacer length, the thermal properties show a clear odd-even effect, which was characterized using our newly developed analytical model DSC(T).

How the Choice of Force-Field Affects the Stability and Self-Assembly Process of Supramolecular CTA Fibers.

In recent years, computational methods have become an essential element of studies focusing on the self-assembly process. Although they provide unique insights, they face challenges, from which two are the most often mentioned in the literature: the temporal and spatial scale of the self-assembly. A less often mentioned issue, but not less important, is the choice of the force-field.

Gelation Kinetics-Structure Analysis of pH-triggered Low Molecular Weight Hydrogelators.

Properties such as shear modulus, gelation time, structure of supramolecular hydrogels are strongly dependent on self-assembly, gelation triggering mechanism and processes used to form the gel. In our work we extend reported rheology analysis methodologies to pH-triggered supramolecular gels to understand structural insight using a model system based on N-N' Dibenzoyl-L-Cystine pH-triggered hydrogelator and Glucono-δ-Lactone as the trigger. We observed that Avrami growth model when applied to time-sweep rheological data of gels formed at lower trigger concentrations provide estimates of fractal dimension which agree well compared with visualization of the microstructure as seen via Confocal Laser Scanning Microscopy, for a range of gelator concentrations.

Transient supramolecular hydrogels formed by catalytic control over molecular self-assembly.

The present work shows how transient supramolecular hydrogels can be formed by catalytically controlled molecular self-assembly. Catalysis formation of molecular gelators leads the self-assembly along a kinetically favored pathway, resulting in transient hydrogels. This work demonstrates an effective approach towards pathway-dependent supramolecular materials.

Interfacial Microcompartmentalization by Kinetic Control of Selective Interfacial Accumulation.

Reported here is a 2D, interfacial microcompartmentalization strategy governed by 3D phase separation. In aqueous polyethylene glycol (PEG) solutions doped with biotinylated polymers, the polymers spontaneously accumulate in the interfacial layer between the oil-surfactant-water interface and the adjacent polymer phase. In aqueous two-phase systems, these polymers first accumulated in the interfacial layer separating two polymer solutions and then selectively migrated to the oil-PEG interfacial layer.

Dual-Functionalized Crescent Microgels for Selectively Capturing and Killing Cancer Cells.

In cancer therapy, the selective targeting of cancer cells while avoiding side effects to normal cells is still full of challenges. Here, we developed dual-functionalized crescent microgels, which selectively captured and killed lung cancer cells in situ without killing other cells. Crescent microgels with the inner surface of the cavity functionalized with antibody and containing glucose oxidase (GOX) in the gel matrix have been produced in a microfluidic device.

Imaging-assisted hydrogel formation for single cell isolation.

We report a flexible single-cell isolation method by imaging-assisted hydrogel formation. Our approach consists of imaging-aided selective capture of cells of interest by encasing them into a polymeric hydrogel, followed by removal of unwanted cells and subsequent release of isolated cells by enzymatic hydrogel degradation, thus offering an opportunity for further analysis or cultivation of selected cells. We achieved high sorting efficiency and observed excellent viability rates (>98%) for NIH/3T3 fibroblasts and A549 carcinoma cells isolated using this procedure.

Transient Supramolecular Hydrogels Formed by Aging-Induced Seeded Self-Assembly of Molecular Hydrogelators.

Here, transient supramolecular hydrogels that are formed through simple aging-induced seeded self-assembly of molecular gelators are reported. In the involved molecular self-assembly system, multicomponent gelators are formed from a mixture of precursor molecules and, typically, can spontaneously self-assemble into thermodynamically more stable hydrogels through a multilevel self-sorting process. In the present work, it is surprisingly found that one of the precursor molecules is capable of self-assembling into nano-sized aggregates upon a gentle aging treatment.

Spatial Manipulation and Integration of Supramolecular Filaments on Hydrogel Substrates towards Advanced Soft Devices.

Supramolecular assemblies are promising building blocks for the fabrication of functional soft devices for high-tech applications. However, there is a lack of effective methods for large-scale manipulation and integration of nano-sized supramolecular structures on soft substrate. Now, functional soft devices composed of micellar filaments and hydrogels can be created through a versatile approach involving guided dewetting, transfer-printing, and laser-assisted patterning.

Biomimetic Strain-Stiffening Self-Assembled Hydrogels.

Supramolecular structures with strain-stiffening properties are ubiquitous in nature but remain rare in the lab. Herein, we report on strain-stiffening supramolecular hydrogels that are entirely produced through the self-assembly of synthetic molecular gelators. The involved gelators self-assemble into semi-flexible fibers, which thereby crosslink into hydrogels.

Non-marking Collection of Amino Acids from Fingerprints Using Hydrogels.

The amino acid profile obtained from a fingerprint may provide valuable information on its donor. Unfortunately, the collection of chemicals from the fingerprint is often destructive to the fingerprint ridge detail. Herein we detail the use of cross-linkable solutions of dextran-methacrylate to form hydrogels capable of collecting amino acids from surfaces followed by extraction and quantification with UPLC-MS.

Locally pH controlled and directed growth of supramolecular gel microshapes using electrocatalytic nanoparticles.

Controlled localization of platinum nanoparticles (Pt NPs) at a solid support assisted by a polarized liquid-liquid interface is reported. Electrocatalytic water oxidation resulted in local pH modulation followed by the directed self-assembly of a dibenzoyl-l-cystine hydrogelator forming a structured hydrogel retaining the shape of the Pt NP deposit.

Control over the formation of supramolecular material objects using reaction-diffusion.

Controlled diffusion, reaction and assembly of hydrogelator precursors can be used to create soft hydrogel objects of defined shape and size. In this study we show that controlling local reaction kinetics by means of pH, diffusion length and the concentrations of reactants allows control over the dimensions of formed supramolecular structures. By correlating a reaction diffusion model to experimental results, we show that the influence of all these control parameters can be unified using the Damköhler number, thus providing an easy-to-use relation between experimental parameters and structure dimensions.

Crystallization of Sodium Salt of Organic Acid as Example for Neutral Salt Recovery of Bio Acids.

The optimization of an organic acid production process downstream of fermentation is presented. Sodium salt solution of the organic acid (Na salt) solution is the product in the industrial fermentation process for the organic acid production and until today, it has not been attempted to directly crystallize/isolate the Na salt under these circumstances. Evaporation crystallization of Na salt directly from the solid-free fermentation broth without purification can be realized with high product purity.

Membrane-Freeze Concentration Hybrid for Temperature-Sensitive Biomolecules. Investigation, Application, and Techno-Economic Benefits.

In order to close the technology gap between membrane technologies and spray/freeze-drying ideally with a technology that avoids thermal stress to sensitive enzyme solutions, the limits of freeze concentration for this application have been investigated. On laboratory scale it was found that average crystal sizes are > 300 µm despite high viscosity and ice separation is possible up to 42 % solids and > 1000 mms viscosity. No activity loss was observed during concentration.

Silk Fluorescence Collimator for Ultrasensitive Humidity Sensing and Light-Harvesting in Semitransparent Dye-Sensitized Solar Cells.

This work examines the self-collimation effect of silk materials on fluorescence emission/detection. A macroscopic regulation strategy, coupled with meso-reconstruction and meso-functionalization, is adopted to amplify the fluorescence emission of organic fluorescent dyes (i.e.