Conducting-Polymer Nanocomposites as Synergistic Supports That Accelerate Electro-Catalysis: PEDOT/Nano Co3O4/rGO as a Photo Catalyst of Oxygen Production from Water

This work describes how conducting polymer nanocomposites can be employed as synergistic supports that significantly accelerate the rate of electro-catalysis. The nanocomposite PEDOT/nano-Co3O4/rGO is discussed as an example in this respect, which is specific for photo electro-catalytic oxygen (O2) generation from water using light (PEDOT = poly (3,4-ethylenedioxythiophene; rGO = reduced graphene oxide). We show that the conducting polymer PEDOT and the conductive additive rGO may be used to notably amplify the rate of O2-generation from water by the nano catalyst, Co3O4. A composite film containing the precise molar ratio 7.18 (C; PEDOT):1 (Co):5.18 (C; rGO) exhibited high photocatalytic activity (pH 12) for the oxygen evolution reaction (OER) at 0.80 V (vs Ag/AgCl), with a current density of 1000 ± 50 μA/cm2 (including a photocurrent of 500 μA/cm2), achieved after >42 h of operation under illumination with a light of intensity 0.25 sun. By comparison, the best industrial catalyst, Pt, yielded a much lower 150 μA/cm2 under the same conditions. Oxygen gas was the sole product of the reaction.

The Synthesis of Biarylmonophosphonates via Palladium-Catalyzed Phosphonation, Iridium-Catalyzed C-H Borylation, Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling

The iridium-catalyzed C-H borylation of diethyl phenylphosphonate results in nonselective mono and bisborylation to afford a near statistical mixture of 3-, 3,5- and 4-boryl substituted aryl phosphonates whereas 3-substituted aryl phosphonates undergo highly regioselective C-H borylation to afford the corresponding meta-phosphonate substituted arylboronic esters as the sole product; the resulting boronic esters were used as nucleophilic reagents in a subsequent palladium-catalyzed Suzuki–Miyaura cross-coupling to generate a range of biarylmonophosphonates. Gratifyingly, the Suzuki–Miyaura cross-coupling can be conducted without purifying the boronic ester which greatly simplifies the synthetic procedure. Graphical Abstract

Total Synthesis of the Natural Carbazoles O-Demethylmurrayanine and Murrastanine A, and of a C4,C4′ Symmetric Murrastanine A Dimer from N-Phenyl-4,5-dimethylene-1,3-oxazolidin-2-one

The synthesis of natural carbazoles O-demethylmurrayanine and murrastanine A starting from the title exo-heterocyclic diene­ is described. In the synthesis of murrastanine A, its symmetric C4,C4′ dimer can be obtained as the sole product under rather mild conditions. In all cases, the key intermediate is the same diarylamine. The carbazole nucleus is obtained through a Pd-promoted cyclization of the appropriate diarylamine. For the synthesis of O-demethylmurrayanine, the cyclization takes place on a silylated derivative. The crystal structures of murrayanine, two diarylamines, and two non-natural carbazole intermediates are also presented.

Efficient Production of Pyruvate Using Metabolically Engineered Lactococcus lactis

Microbial production of commodity chemicals has gained increasing attention and most of the focus has been on reducing the production cost. Selecting a suitable microorganism, which can grow rapidly on cheap feedstocks, is of key importance when developing an economically feasible bioprocess. We chose Lactococcus lactis, a well-characterized lactic acid bacterium, as our microbial host to produce pyruvate, which is a commodity chemical with various important applications. Here we report the engineering of Lactococcus lactis into becoming an efficient microbial platform for producing pyruvate. The strain obtained, FS1076 (MG1363 Δ3ldh Δpta ΔadhE Δals), was able to produce pyruvate as the sole product. Since all the competitive pathways had been knocked out, we achieved growth-coupled production of pyruvate with high yield. More than 80 percent of the carbon flux was directed toward pyruvate, and a final titer of 54.6 g/L was obtained using a fed-batch fermentation setup. By introducing lactose catabolism into FS1076, we obtained the strain FS1080, which was able to generate pyruvate from lactose. We then demonstrated the potential of FS1080 for valorizing lactose contained in dairy side-streams, by achieving a high titer (40.1 g/L) and high yield (78.6%) of pyruvate using residual whey permeate (RWP) as substrate. The results obtained, show that the L. lactis platform is well-suited for transforming lactose in dairy waste into food-grade pyruvate, and the yields obtained are the highest reported in the literature. These results demonstrate that it is possible to achieve sustainable bioconversion of waste products from the dairy industry (RWP) to valuable products.

Editor's Introduction

New Sociology was created by and for graduate students; it is the sole product of our critical insights, creative impulses, radical political energies, and overall willingness to push the boundaries of knowledge. We created New Sociology on our own terms, with the ideas, politics, and best interests of emergent scholars, activists, and artists in mind. We created New Sociology to make academia a bit more survivable for people like us. We created New Sociology to honour the pedagogical power inherent, not just in academic critique, but in art and storytelling. We created New Sociology to challenge the idea that only old dead white men have something to say about society. We created New Sociology to give graduate students the chance to participate in the creation and dissemination of academic knowledge. We created New Sociology to distribute academic publications to a wide and diverse audience. We created New Sociology to support other graduate students; to support our friends, our communities, and our ourselves. We created New Sociology.

4′-(N-(Propan-1,2-dienyl)pyrrol-2-yl)-2,2′:6′,2″-terpyridine

A new pyrrole-substituted terpyridine derivative that possesses an allene moiety was obtained as an “unexpected” sole product during an attempt to alkylate the N-atom of pyrrole with propargyl bromide in order to obtain an alkyne-functionalized terpyridine.

CobT and BzaC catalyze the regiospecific activation and methylation of the 5-hydroxybenzimidazole lower ligand in anaerobic cobamide biosynthesis

Vitamin B12 and other cobamides are essential cofactors required by many organisms and are synthesized by a subset of prokaryotes via distinct aerobic and anaerobic routes. The anaerobic biosynthesis of 5,6-dimethylbenzimidazole (DMB), the lower ligand of vitamin B12, involves five reactions catalyzed by the bza operon gene products, namely the hydroxybenzimidazole synthase BzaAB/BzaF, phosphoribosyltransferase CobT, and three methyltransferases, BzaC, BzaD, and BzaE, that conduct three distinct methylation steps. Of these, the methyltransferases that contribute to benzimidazole lower ligand diversity in cobamides remain to be characterized, and the precise role of the bza operon protein CobT is unclear. In this study, we used the bza operon from the anaerobic bacterium Moorella thermoacetica (comprising bzaA-bzaB-cobT-bzaC) to examine the role of CobT and investigate the activity of the first methyltransferase, BzaC. We studied the phosphoribosylation catalyzed by MtCobT and found that it regiospecifically activates 5-hydroxybenzimidazole (5-OHBza) to form the 5-OHBza-ribotide (5-OHBza-RP) isomer as the sole product. Next, we characterized the domains of MtBzaC and reconstituted its methyltransferase activity with the predicted substrate 5-OHBza and with two alternative substrates, the MtCobT product 5-OHBza-RP and its riboside derivative 5-OHBza-R. Unexpectedly, we found that 5-OHBza-R is the most favored MtBzaC substrate. Our results collectively explain the long-standing observation that the attachment of the lower ligand in anaerobic cobamide biosynthesis is regiospecific. In conclusion, we validate MtBzaC as a SAM:hydroxybenzimidazole-riboside methyltransferase (HBIR-OMT). Finally, we propose a new pathway for the synthesis and activation of the benzimidazolyl lower ligand in anaerobic cobamide biosynthesis.

Lux Radio Theatre

Lux Radio Theatre was a radio program that remained on the air in the United States of America for more than twenty years (1934-1955). It aired radio plays which were adaptations of hit movies. Dozens of Hollywood movie stars were involved in the program, which was created by an advertiser and its agency, at the service of a sole product: Lux toilet soap. This chapter provides a discussion about the complex and costly, in terms of production, mode of advertising that were these radio plays, a unique encounter between Hollywood and advertising.

Acid-catalyzed rearrangements in arenes: interconversions in the quaterphenyl series

Arenes undergo rearrangement of phenyl, alkyl, halogen and other groups through the intermediacy of ipso arenium ions in which a proton is attached at the same carbon as the migrating substituent. Interconversions among the six quaterphenyl isomers have been studied here as a model for rearrangements of linear polyphenyls. All reactions were carried out in 1 M CF3SO3H (TfOH) in dichloroethane at 150 °C in a microwave reactor for 30–60 min, with product formation assessed by high field NMR analysis. Under these reaction conditions, m,p'-quaterphenyl is the equilibrium product. This isomer is unchanged by the reaction conditions and all other quaterphenyl isomers rearrange to m,p' as the dominant or sole product. DFT computations with inclusion of implicit solvation support a complex network of phenyl and biphenyl shifts, with barriers to rearrangement in the range of 10–21 kcal/mol. Consistent with experiments, the lowest energy arenium ion located on this surface is due to protonation of m,p'-quaterphenyl. This supports thermodynamic control based on carbocation energies.