Presence of β-Turn Structure in Recombinant Spider Silk Dissolved in Formic Acid Revealed with NMR

Spider dragline silk is a biopolymer with excellent mechanical properties. The development of recombinant spider silk protein (RSP)-based materials with these properties is desirable. Formic acid (FA) is a spinning solvent for regenerated Bombyx mori silk fiber with excellent mechanical properties. To use FA as a spinning solvent for RSP with the sequence of major ampullate spider silk protein from Araneus diadematus, we determined the conformation of RSP in FA using solution NMR to determine the role of FA as a spinning solvent. We assigned 1H, 13C, and 15N chemical shifts to 32-residue repetitive sequences, including polyAla and Gly-rich regions of RSP. Chemical shift evaluation revealed that RSP is in mainly random coil conformation with partially type II β-turn structure in the Gly-Pro-Gly-X motifs of the Gly-rich region in FA, which was confirmed by the 15N NOE data. In addition, formylation at the Ser OH groups occurred in FA. Furthermore, we evaluated the conformation of the as-cast film of RSP dissolved in FA using solid-state NMR and found that β-sheet structure was predominantly formed.

A Smart Colorimetric Platform for Detection of Methanol, Ethanol and Formic Acid

Carbon dioxide (CO2) is a greenhouse gas in the atmosphere and scientists are working on converting it to useful products, thereby reducing its quantity in the atmosphere. For converting CO2, different approaches are used, and among them, electrochemistry is found to be the most common and more efficient technique. Current methods for detecting the products of electrochemical CO2 conversion are time-consuming and complex. To combat this, a simple, cost-effective colorimetric method has been developed to detect methanol, ethanol, and formic acid, which are formed electrochemically from CO2. In the present work, the highly efficient sensitive dyes were successfully established to detect these three compounds under optimized conditions. These dyes demonstrated excellent selectivity and showed no cross-reaction with other products generated in the CO2 conversion system. In the analysis using these three compounds, this strategy shows good specificity and limit of detection (LOD, ~0.03–0.06 ppm). A cost-effective and sensitive Internet of Things (IoT) colorimetric sensor prototype was developed to implement these dyes systems for practical and real-time application. Employing the dyes as sensing elements, the prototype exhibits unique red, green, and blue (RGB) values upon exposure to test solutions with a short response time of 2 s. Detection of these compounds via this new approach has been proven effective by comparing them with nuclear magnetic resonance (NMR). This novel approach can replace heavy-duty instruments such as high-pressure liquid chromatography (HPLC), gas chromatography (G.C.), and NMR due to its extraordinary selectivity and rapidity.

Hydrogen production in an aerobic environment by Escherichia coli K-12

Escherichia coli (E. coli) is a facultative anaerobe that can grow in a variety of environmental conditions. In the complete absence of O2, E. coli can perform a mixed-acid fermentation that contains within it an elaborate metabolism of formic acid. In this study, we use cavity-enhanced Raman spectroscopy (CERS), FTIR, liquid Raman spectroscopy, isotopic labelling, and molecular genetics to make advances in the understanding of bacterial formate and H2 metabolism. It is shown that, under anaerobic conditions, formic acid is generated endogenously, excreted briefly from the cell, and then taken up again to be disproportionated to H2 and CO2 by formate hydrogenlyase (FHL-1). However, exogenously added D-labelled formate behaves quite differently from the endogenous formate and is taken up immediately, independently, and possibly by a different mechanism, by the cell and converted to H2 and CO2. Our data support an anion-proton symport model for formic acid transport. In addition, when E. coli was grown in a microaerobic environment it was possible to analyse aspects of formate and O2 respiration occurring alongside anaerobic metabolism. While cells growing under microaerobic conditions generated endogenous formic acid, no H2 was produced. However, addition of exogenous formate at the outset of cell growth did induce FHL-1 biosynthesis and resulted in formate-dependent H2 production in the presence of O2.

Recent Progress in Homogeneous Catalytic Dehydrogenation of Formic Acid

Recently, there has been a strong demand for technologies that use hydrogen as an energy carrier, instead of fossil fuels. Hence, new and effective hydrogen storage technologies are attracting increasing attention. Formic acid (FA) is considered an effective liquid chemical for hydrogen storage because it is easier to handle than solid or gaseous materials. This review presents recent advances in research into the development of homogeneous catalysts, primarily focusing on hydrogen generation by FA dehydrogenation. Notably, this review will aid in the development of useful catalysts, thereby accelerating the transition to a hydrogen-based society.

How palladium inhibits CO poisoning during electrocatalytic formic acid oxidation and carbon dioxide reduction

Development of reversible and stable catalysts for the electrochemical reduction of CO2 is of great interest. Here, we elucidate the atomistic details of how a palladium electrocatalyst inhibits CO poisoning during both formic acid oxidation to carbon dioxide and carbon dioxide reduction to formic acid. We compare results obtained with a platinum single-crystal electrode modified with and without a single monolayer of palladium. We combine (high-scan-rate) cyclic voltammetry with density functional theory to explain the absence of CO poisoning on the palladium-modified electrode. We show how the high formate coverage on the palladium-modified electrode protects the surface from poisoning during formic acid oxidation, and how the adsorption of CO precursor dictates the delayed poisoning during CO2 reduction. The nature of the hydrogen adsorbed on the palladium-modified electrode is considerably different from platinum, supporting a model to explain the reversibility of this reaction. Our results help in designing catalysts for which CO poisoning needs to be avoided.