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For the synthesis of 2-oxo-3-butynoates and 2-oxo-3-butynoamides, a Cu(I)-catalyzed cross-coupling reaction of terminal alkynes and monooxalyl chloride was developed. Important classes of organic compounds are discussed.

The rhodium(I)-species-catalyzed cycloisomerization reaction of a wide spectrum of 1 ,6-enynes with an unusual intramolecular halogen shift was investigated. This Rh-catalyzed enyne cyclization reaction represents a new process for the synthesis of stereodefined α-halomethylene-γ-butyrolactones, lactams, tetrahydrofurans, pyrrolidines, and cyclopentanes. Coordinatively unsaturated rhodium species ([Rh(COD)- Cl]2 + dppb + AgSbF6) only catalyzes the reaction with enyne substrates bearing a Z-form double bond, while neutral rhodium species (RhCl(PPh3)3) could catalyze enyne substrates bearing a Z- or E-form double bond to form the desired products and has a wider substrate scopes. The mechanism of the reaction was studied by the employment of control experiments with different enyne isomers, and a π-allyl rhodium intermediate was suggested to explain the formation of the cyclic products with an intramolecular halogen shift. [ABSTRACT FROM AUTHOR]

Biosynthesis offers opportunities for cost-effective and sustainable production of semiconductor quantum dots (QDs), but is currently restricted by poor controllability on the synthesis process, resulting from limited knowledge on the assembly mechanisms and the lack of effective control strategies. In this work, we provide molecular-level insights into the formation mechanism of biogenic QDs (Bio-QDs) and its connection with the cellular substrate metabolism in Escherichia coli. Strengthening the substrate metabolism for producing more reducing power was found to stimulate the production of several reduced thiol-containing proteins (including glutaredoxin and thioredoxin) that play key roles in Bio-QDs assembly. This effectively diverted the transformation route of the selenium (Se) and cadmium (Cd) metabolic from Cd 3 (PO 4 ) 2 formation to CdS x Se 1- x QDs assembly, yielding fine-sized (2.0 ± 0.4 nm), high-quality Bio-QDs with quantum yield (5.2%) and fluorescence lifetime (99.19 ns) far exceeding the existing counterparts. The underlying mechanisms of Bio-QDs crystallization and development were elucidated by density functional theory calculations and molecular dynamics simulation. The resulting Bio-QDs were successfully used for bioimaging of cancer cells and tumor tissue of mice without extra modification. Our work provides fundamental knowledge on the Bio-QDs assembly mechanisms and proposes an effective, facile regulation strategy, which may inspire advances in controlled synthesis and practical applications of Bio-QDs as well as other bionanomaterials.

A bioelectrochemical system (BES) allows direct electricity production from wastes, but its low-power density, which is mainly associated with its poor anodic performance, limits its practical applications. Here, the anodic performance of a BES can be significantly improved by electrodepositing vitamin B 2 (VB 2 ) onto a graphene [reduced graphene oxide (rGO)]-modified glassy carbon electrode (VB 2 /rGO/GC) with Geobacter sulfurreducens as the model microorganisms. The VB 2 /rGO/GC electrode results in 200% higher electrochemical activity than a bare GC anode. Additionally, in microbial electrolysis cells, the current density of this composite electrode peaks at ∼210 μA cm -2 after 118 h and is maintained for 113 h. An electrochemical analysis coupled with molecular simulations reveals that using VB 2 as a linker between the electrochemically active protein of this model strain and the rGO surface accelerates the electron transfer, which further improves the bioelectricity generation and favors the long-term stability of the BES. The VB 2 bound with a flexible ribityl group as the organic molecular bridge efficiently mediates energy conversion in microbial metabolism and artificial electronics. This work provides a straightforward and effective route to significantly enhance the bioenergy generation in a BES.

Azo dyes are a class of recalcitrant organic pollutants causing severe environmental pollution. For their biodecolorization, the azo reductase system was considered as the major molecular basis in bacteria. However, the intracellular localization of azo reductase limits their function for efficient azo dye decolorization. This limitation may be circumvented by electrochemically active bacteria (EAB) which is capable of extracellular respiration. To verify the essential role of extracellular respiration in azo dye decolorization, Geobacter sulfurreducens PCA, a model EAB, was used for the bioreduction of methyl orange (MO), a typical azo dye. G. sulfurreducens PCA efficiently reduced MO into amines. Kinetic results showed that G. sulfurreducens PCA had the highest decolorization efficiency among the currently known MO reducing bacteria. Electrons from acetate oxidization by this strain were transferred by the respiratory chain to MO. The mass and electron balances, fluorescent probing and proteinase K treatment experimental results indicate that the biodecolorization of MO by G. sulfurreducens PCA is an exclusive extracellular process. OmcB, OmcC and OmcE were identified as the key outer-membrane proteins for the extracellular MO reduction. This work deepens our understanding of EAB physiology and is useful for the decontamination of environments polluted with azo dyes. The contribution of extracellular respiration to pollutants reduction will broaden the environmental applications of EAB.

Phenazines, as a type of electron shuttle, are involved in various biological processes to facilitate microbial energy metabolism and electron transfer. They constitute a large group of nitrogen-containing heterocyclic compounds, which can be produced by a diverse range of bacteria or by artificial synthesis. They vary significantly in their properties, depending mainly on the nature and position of substitutent group. Thus, it is of great interest to find out the most favorable substituent type and molecular structure of phenazines for electron transfer routes. Here, the impacts of the substituent group on the reduction potentials of phenazine-type redox mediators in aqueous solution were investigated by quantum chemical calculations, and the calculation results were further validated with experimental data. The results show that the reaction free energy was substantially affected by the location of substituent groups on the phenazine molecule and the protonated water clusters. For the main proton addition process, the phenazines substituted with electron-donating groups and those with electron-withdrawing groups interacted with different protonated water clusters, attributed to the proximity effect of water molecules on proton transfer. Thus, high energy conversion efficiency could be achieved by controlling electron flow route with appropriate substituted phenazines to reduce the biological energy acquisition. This study provides useful information for designing efficient redox mediators to promote electron transfer between microbes and terminal acceptors, which are essential to bioenergy recovery from wastes and environmental bioremediation.

A palldium(0)-catalyzed tandem cyclization/Suzuki coupling reaction of various 1,6-enyne substrates was developed. This Pd-catalyzed enyne cyclization reaction represents a new process for the synthesis of stereodefined alpha-arylmethylene-gamma-butyrolactones, lactams, multifunctional tetrahydrofurans, pyrrolidines, and cyclopentanes. The mechanism of the reaction was studied by the employment of different enyne isomers and boronic acids; a pi-allyl palladium intermediate was suggested to explain the formation of the cyclic products. The stereochemistry of this reaction can be well explained by a chairlike transition state.

The synthesis and resolution of a bulky and electron-rich derivative of SEGPhos and its application in Ru-catalyzed asymmetric hydrogenation reaction of beta-ketoesters are reported. Up to 99.5% ee was achieved. Under solvent-free reaction conditions, acetoacetates could be reduced with good enantioselectivity and high efficiency; a TON of 20 000 was obtained within 3.5 h. The results obtained were comparable to those when SEGPhos was applied.