A Self‐Reporting Photocatalyst for Online Fluorescence Monitoring of High Throughput RAFT Polymerization

Translating controlled/living radical polymerization (CLRP) from batch to the high throughput production of polymer libraries presents several challenges in terms of both polymer synthesis and characterization. Although recently there have been significant advances in the field of low volume, high throughput CLRP, techniques able to simultaneously monitor multiple polymerizations in an “online” manner have not yet been developed. Here, we report our discovery that 5,10,15,20‐tetraphenyl‐21H,23H‐porphine zinc (ZnTPP) is a self‐reporting photocatalyst that can mediate PET‐RAFT polymerization as well as report on monomer conversion via changes in its fluorescence properties. This enables the use of a microplate reader to conduct high throughput “online” monitoring of PET‐RAFT polymerizations performed directly in 384‐well, low volume microtiter plates.     

Extraction and Spectrophotometric Determination of Antimony in the Environment:

A new sensitive method for the extraction and spectrophotometric determination of antimony in the environment is described. The antimony forms a greenish yellow coloured complex with N-phenylbenzohydroxamic acid (PBHA) at 4 M HCl which is extracted from chloroform.

The Sb-PBHA complex is back extracted in 0.01 M NH₄OH and then antimony is estimated with rhodamine B in 6 M HCl media. This bluish violet coloured complex is extractable in benzene. The maximum absorbance of the antimony rhodamine B complex is observed at 565 nm. The effects of acidity, reagent concentration and diverse ions are discussed. The method is applied to the trace determination of antimony in industrial effluents and natural resources.     

Design of Monodisperse and Well‐Defined Polypeptide‐Based Polyvalent Inhibitors of Anthrax Toxin

The design of polyvalent molecules, presenting multiple copies of a specific ligand, represents a promising strategy to inhibit pathogens and toxins. The ability to control independently the valency and the spacing between ligands would be valuable for elucidating structure–activity relationships and for designing potent polyvalent molecules. To that end, we designed monodisperse polypeptide‐based polyvalent inhibitors of anthrax toxin in which multiple copies of an inhibitory toxin‐binding peptide were separated by flexible peptide linkers. By tuning the valency and linker length, we designed polyvalent inhibitors that were over four orders of magnitude more potent than the corresponding monovalent ligands. This strategy for the rational design of monodisperse polyvalent molecules may not only be broadly applicable for the inhibition of toxins and pathogens, but also for controlling the nanoscale organization of cellular receptors to regulate signaling and the fate of stem cells.     

Supramolecular Peptide Nanostructures Regulate Catalytic Efficiency and Selectivity

We report three constitutionally isomeric tetrapeptides, each comprising one glutamic acid (E) residue, one histidine (H) residue, and two lysine (K_S) residues functionalized with side-chain hydrophobic S-aroylthiooxime (SATO) groups. Depending on the order of amino acids, these amphiphilic peptides self-assembled in aqueous solution into different nanostructures:nanoribbons, a mixture of nanotoroids and nanoribbons, or nanocoils. Each nanostructure catalyzed hydrolysis of a model substrate, with the nanocoils exhibiting the greatest rate enhancement and the highest enzymatic efficiency. Coarse-grained molecular dynamics simulations, analyzed with unsupervised machine learning, revealed clusters of H residues in hydrophobic pockets along the outer edge of the nanocoils, providing insight for the observed catalytic rate enhancement. Finally, all three supramolecular nanostructures catalyzed hydrolysis of the l -substrate only when a pair of enantiomeric Boc-l /d -Phe-ONp substrates were tested. This study highlights how subtle molecular-level changes can influence supramolecular nanostructures, and ultimately affect catalytic efficiency.     

A brief review on miniaturized electrochemiluminescence devices: From fabrication to applications

Miniaturized electrochemiluminescence (ECL) systems are widely recognized as a highly detection, user-friendly, and turnkey strategy to develop point-of-care-testing devices. The ECL sensing approach provides numerous advantages over other methods, including high signal-to-noise ratio and measurement with minimal or no background signal. The ECL signal can be easily controlled by a small external potential while providing high sensitivity and decreased electrode fouling, resulting in the use of ECL-based miniaturized systems for detection and monitoring of different analytes, including DNA and bacteria. In this work, different types of miniaturized ECL systems with various fabrication techniques are reviewed and their application in point-of-care-testing is thoroughly discussed. Furthermore, such ECL platforms have been summarized based on the type of the ECL mechanism, electrodes, range of detection, and limit of detection. Finally, some of the upcoming technological interventions to make such a miniaturized ECL platform amenable for portable and on-field analysis have been discussed.     

Experimental studies on droplet characteristics in a microfluidic flow focusing droplet generator: effect of continuous phase on droplet encapsulation

The European Physical Journal E - Interaction of cytoskeletal filaments, motor proteins, and crosslinking proteins drives important cellular processes such as cell division and cell movement....     

Chemistry of enediynyl azides: activation through a novel pathway

The spontaneous activation of a nonaromatic enediynyl azide under ambient conditions has been demonstrated. The aromatic enediyne followed the expected cycloaddition with the alkene in the neighbouring arm to form a stable bridged bicyclic enediyne.     

Synthesis of C2-symmetric bis-indolyl sulfones

A new class of C₂-symmetric bis-indole derivatives with 2,2′-linkage has been synthesized from bis-propargyl sulfones. The method involves treatment of the sulfones with catalytic amount of triethylamine to form the indole derivatives presumably via the intramolecular Michael addition to the intermediate bis-allenic sulfones. Interestingly, the expected Garratt-Braverman pathway was not followed.     

Quantitative imaging of single, unstained viruses with coherent x rays

We report the recording and reconstruction of x-ray diffraction patterns from single, unstained viruses, for the first time. By separating the diffraction pattern of the virus particles from that of their surroundings, we performed quantitative and high-contrast imaging of a single virion. The structure of the viral capsid inside a virion was visualized. This work opens the door for quantitative x-ray imaging of a broad range of specimens from protein machineries and viruses to cellular organelles. Moreover, our experiment is directly transferable to the use of x-ray free electron lasers, and represents an experimental milestone towards the x-ray imaging of large protein complexes.     

Continuous-Flow Photocatalysis for the Direct C-H Trifluoromethylation of Heterocycles with an Organic Photoredox Catalyst

Photocatalysis for direct C−H trifluoromethylation represents an ideal way to synthesize trifluoromethyl-containing chemical compounds, but the conventional batch processes are inefficient with limited light penetration and indispensably irradiated for a long while. Herein, we report a continuous-flow protocol for photocatalytic direct C−H trifluoromethylation of heterocycles in the presence of an organic photoredox catalyst: 2,4,6-tris(diphenylamino)-3,5-difluorobenzonitrile (3DPA2FBN). In this approach, benefiting from the merger of organic photoredox catalysis and continuous-flow techniques, a variety of trifluoromethylated heterocycles were rapidly synthesized up to 85 % yield with 80 min residence time under metal- and oxidant-free reaction conditions.