Design principles for a nanoconfined enzyme cascade electrode reaction-diffusion modelling.

The study of enzymes by direct electrochemistry has been extended to enzyme cascades, with a key development being the 'electrochemical leaf': an electroactive enzyme is immobilized within a porous electrode, providing cofactor (NADP(H)) regeneration for a co-immobilized downstream enzyme. This system has been further developed to include multiple downstream enzymes, and it has become an important tool in biocatalysis, however, the local environment within the porous electrode has not been investigated in detail. Here, we constructed a 1D reaction-diffusion model, comprising the porous electrode with 2 kinds of enzymes immobilized, and an enzyme-free electrolyte diffusion layer.

The Growing Importance of Chirality in 3D Chemical Space Exploration and Modern Drug Discovery Approaches for Hit-ID: Topical Innovations.

Modern-day drug discovery is now blessed with a wide range of high-throughput hit identification (hit-ID) strategies that have been successfully validated in recent years, with particular success coming from high-throughput screening, fragment-based lead discovery, and DNA-encoded library screening. As screening efficiency and throughput increases, this enables the viable exploration of increasingly complex three-dimensional (3D) chemical structure space, with a realistic chance of identifying highly specific hit ligands with increased target specificity and reduced attrition rates in preclinical and clinical development. This minireview will explore the impact of an improved design of multifunctionalized, sp-rich, stereodefined scaffolds on the (virtual) exploration of 3D chemical space and the specific requirements for different hit-ID technologies.

High sulfur content polymers: The effect of crosslinker structure on inverse vulcanization.

The discovery of inverse vulcanization has allowed polymers to be made using elemental sulfur as the major component. However, until now, there has been little discussion of why seemingly similar crosslinkers result in polymers with radically different properties. Combining synthesis, spectroscopy, and modeling, this study reveals the structure-property relationships of sulfur polymers and reports a new system using 5-ethylidene-2-norbornene as a crosslinker that can stabilize up to 90 wt % of elemental sulfur.

Electrodeposition of Gold Nanostructures at the Interface of a Pickering Emulsion.

The controlled electrodeposition of nanoparticles at the surface of an emulsion droplet offers enticing possibilities in regards to the formation of intricate structures or fine control over the locus or duration of nanoparticle growth. In this work we develop electrochemical control over the spontaneous reduction of aqueous phase Au(III) by heterogeneous electron transfer from decamethylferrocene present in an emulsion droplet - resulting in the growth of nanoparticles. As gold is a highly effective conduit for the passage of electrical current, even on the nanoscale, the deposition significantly enhances the current response for the single electron transfer of decamethylferrocene when acting as a redox indicator.

Modulated release from implantable ocular silicone oil tamponade drug reservoirs.

Complicated cases of retinal detachment can be treated with silicone oil tamponades. There is the potential for silicone oil tamponades to have adjunctive drug releasing behaviour within the eye, however the lipophilic nature of silicone oil limits the number of drugs that are suitable, and drug release from the hydrophobic reservoir is uncontrolled. Here, a radiometric technique was developed to accurately measure drug solubility in silicone oil and measure release into culture media.

Pyrene-cored covalent organic polymers by thiophene-based isomers, their gas adsorption, and photophysical properties.

Two new pyrene-cored covalent organic polymers (COPs), and , were synthesized via the one-step polymerization of two thiophene-based isomers, 1,3,6,8-tetra(thiophene-2-yl) pyrene ( ) and 1,3,6,8-tetra(thiophene-3-yl) pyrene ( ). The resulting pyrene-cored COPs exhibit rather different surface areas of 54 m g and 615 mg for and , respectively. The CO uptake capacities of and also show different values of 2.

Chemically Selective Alternatives to Photoferroelectrics for Polarization-Enhanced Photocatalysis: The Untapped Potential of Hybrid Inorganic Nanotubes.

elucidates the interplay between wall-polarization, bands separation, charge-transfer excitation, and tunable electrostatics inside and outside the NT-cavity. The results suggest that integration of polarization-enhanced selective photocatalysis and chemical separation into one overall dipole-free material should be possible. Strategies are proposed to increase the NT polarization for maximally enhanced electron-hole separation.

A Click Chemistry-Based Proteomic Approach Reveals that 1,2,4-Trioxolane and Artemisinin Antimalarials Share a Common Protein Alkylation Profile.

In spite of the recent increase in endoperoxide antimalarials under development, it remains unclear if all these chemotypes share a common mechanism of action. This is important since it will influence cross-resistance risks between the different classes. Here we investigate this proposition using novel clickable 1,2,4-trioxolane activity based protein-profiling probes (ABPPs).

Selective trioxolane based bifunctional molecular linkers for covalent heme surface functionalisation.

A bifunctional molecular linker containing both aryl diazonium and trioxolane groups was synthesised and its ability to sequentially functionalise glassy carbon and covalently immobilise heme investigated. Functionalisation was demonstrated by electrochemical techniques.

Silynes (RC≡SiR') and Disilynes (RSi≡SiR'): Why Are Less Bonds Worth Energetically More?

Bond stabilization through bending! Valence bond analysis shows that the σ frames of 1-3 (1: E = Si, E' = C; 2: E = E' = Si; 3: E = E' = C) are stabilized by trans bending (B), while π bonding is weakened. In acetylene (3) π bonding overrides the σ frame and establishes a linear molecule (3 L). In contrast, the σ frames dominate in silyne (1) and disilyne (2) and lead to trans-bent structures (1 B and 2 B).