Self-Supporting g-C3N4 Nanosheets/Ag Nanoparticles Embedded onto Polyester Fabric as “Dip-Catalyst” for Synergic 4-Nitrophenol Hydrogenation

Herein, we report the design of a cost-effective catalyst with excellent recyclability, simple recuperation and facile recovery, and the examination between the reaction cycles via the development of self-supporting g-C3N4 nanosheets/Ag NPs polyester fabric (PES) using a simple, facile and efficient approach. PES fabrics were coated via a sono-coating method with carbon nitride nanosheets (GCNN) along with an in situ setting of Ag nanoparticles on PES coated GCNN surface producing PES-GCNN/Ag0. The elaborated textile-based materials were fully characterized using FTIR, 13C NMR, XRD, TGA, SEM, EDX, etc. Catalytic performance of the designed “Dip-Catalyst” demonstrated that the as-prepared PES-GCCN/Ag0 has effectively catalyzed the hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of NaBH4. The 3 × 3 cm2 PES-GCNN/Ag0 showed the best catalytic activity, displaying an apparent rate constant (Kapp) equal to 0.43 min−1 and more than 10 reusability cycles, suggesting that the prepared catalyst-based PES fabric can be a strong nominee for sustainable chemical catalysis. Moreover, the coated fabrics exhibited appreciable antibacterial capacity against Staphylococcus epidermidis (S. epidermidis) and Escherichia coli (E. coli). The present study opens up new opportunities for the future design of a low cost and large-scale process of functional fabrics.

Reactivity of Iridium Complexes of a Triphosphorus-Pincer Ligand Based on a Secondary Phosphine. Catalytic Alkane Dehydrogenation and the Origin of Extremely High Activity

The selective functionalization of alkanes and alkyl groups is a major goal of chemical catalysis. Toward this end, a bulky triphosphine with a central secondary phosphino group, bis(2 di-t-butyl-phosphinophenyl)phosphine (tBuPHPP), has been synthesized. When complexed to iridium it adopts a meridional (“pincer”) configuration. The secondary phosphino H atom can undergo migration to iridium to give an anionic phosphido-based-pincer (tBuPPP) complex. We describe novel metal-ligand cooperativity of the iridium-phosphido unit. Stoichiometric reactions of the (tBuPPP)Ir complexes reflect a distribution of steric bulk around the iridium center in which the coordination site trans to the phosphido group is quite crowded, one coordination site cis to the phosphido is even more crowded, while the remaining site is particularly open. The (tBuPPP)Ir precursors are the most active catalysts reported to date for dehydrogenation of n-alkanes, by about two orders of magnitude. The electronic properties of the iridium center are very similar to that of well-known analogous (RPCP)Ir catalysts. Accordingly, DFT calculations predict that (tBuPPP)Ir and (tBuPCP)Ir are, intrinsically, comparably active for alkane dehydrogenation. While dehydrogenation by (RPCP)Ir proceeds through an intermediate trans-(PCP)IrH2(alkene), (tBuPPP)Ir follows a pathway proceeding via cis-(PPP)IrH2(alkene), thereby circumventing unfavorable placement of the alkene at the bulky site trans to phosphorus. (tBuPPP)Ir and (tBuPCP)Ir, however, have analogous resting states: square planar (pincer)Ir(alkene). Alkene coordination at the crowded trans site is therefore unavoidable in the resting states. Thus the resting state of the (tBuPPP)Ir catalyst is destabilized by the unusual architecture of the ligand, and this is largely responsible for its unusually high catalytic activity.

The Spatiotemporal Evolution of Temperature During Transient Heating of Nanoparticle Arrays

Nanoparticle (NP) are promising agents to absorb external energy excitation and generate heat. Cluster of NPs or NP array heating have found essential roles for biomedical applications, diagnostic techniques and chemical catalysis. Various studies have shed light on the heat transfer of nanostructures and greatly advanced our understanding of NP array heating. However, there is a lack of analytical tools and dimensionless parameters to describe the transient heating of NP arrays. Here we demonstrate a comprehensive analysis of the transient NP array heating. Firstly, we developed analytical solution for the NP array heating and provide a useful mathematical description of the spatial-temporal evolution of temperature for 2D, 3D and spherical NP array heating. Based on this, we proposed the idea of thermal resolution that quantifies the relationship between minimal heating time, NP array size, energy intensity and target temperature. Lastly, we define a dimensionless parameter that characterize the transition from confined heating to delocalized heating. This study advances the understanding of nanomaterials heating and provides guidance for rationally designing innovative approaches for NP array heating.

A first principles investigation on the structural, mechanical, electronic, and catalytic properties of biphenylene

Recently, a new two-dimensional allotrope of carbon (biphenylene) was experimentally synthesized. Using first-principles calculations, we systematically investigated the structural, mechanical, electronic, and HER properties of biphenylene. A large cohesive energy, absence of imaginary phonon frequencies, and an ultrahigh melting point up to 4500 K demonstrate its high stability. Biphenylene exhibits a maximum Young’s modulus of 259.7 N/m, manifesting its robust mechanical performance. Furthermore, biphenylene was found to be metallic with a n-type Dirac cone, and it exhibited improved HER performance over that of graphene. Our findings suggest that biphenylene is a promising material with potential applications in many important fields, such as chemical catalysis.

Heterogeneous Strategies For Selective Conversion of Lignocellulosic Polysaccharides

Lignocellulosic biomass is the most abundant renewable carbon resource on earth, for which many efforts have been made to convert it using various chemocatalytic processes. Heterogeneously chemocatalytic conversion conducted based on reusable solid catalysts is the process with the greatest potential studied presently. This review provides insights into the representative achievements in the research area of heterogeneous chemical catalysis technologies for the production of value-added chemicals from lignocellulosic polysaccharides (cellulose and hemicellulose). Popular approaches for the conversion of lignocellulosic polysaccharides into chemicals, including hydrolyzation (glucose, xylose and arabinose), dehydration (5-hydroxymethylfurfuran, furfural and levulinic acid), hydrogenation/hydrogenolysis (sorbitol, mannitol, xylitol, 1,2-propylene glycol, ethlyene glycol and ethanol), selective oxidation (gluconic acid and lactic acid), have been comprehensively reviewed. However, technological barriers still exist, which have to be overcome to further integrate hydrolysis with the refinery processes based on multifunctional solid catalysts, and convert ligncellulosic polysaccharides into value-added fine chemicals. In general, the approaches and technologies are discussed and critically evaluated in terms of the possibilities and potential for further industrial implementation.

Chemoenzymatic access to enantiopure N-containing furfuryl alcohol from chitin-derived N-acetyl-D-glucosamine

Background Chiral furfuryl alcohols are important precursors for the synthesis of valuable functionalized pyranones such as the rare sugar L-rednose. However, the synthesis of enantiopure chiral biobased furfuryl alcohols remains scarce. In this work, we present a chemoenzymatic route toward enantiopure nitrogen-containing (R)- and (S)-3-acetamido-5-(1-hydroxylethyl)furan (3A5HEF) from chitin-derived N-acetyl-D-glucosamine (NAG). Findings 3-Acetamido-5-acetylfuran (3A5AF) was obtained from NAG via ionic liquid/boric acid-catalyzed dehydration, in an isolated yield of approximately 31%. Carbonyl reductases from Streptomyces coelicolor (ScCR) and Bacillus sp. ECU0013 (YueD) were found to be good catalysts for asymmetric reduction of 3A5AF. Enantiocomplementary synthesis of (R)- and (S)-3A5HEF was implemented with the yields of up to > 99% and the enantiomeric excess (ee) values of > 99%. Besides, biocatalytic synthesis of (R)-3A5HEF was demonstrated on a preparative scale, with an isolated yield of 65%. Conclusions A two-step process toward the chiral furfuryl alcohol was successfully developed by integrating chemical catalysis with enzyme catalysis, with excellent enantioselectivities. This work demonstrates the power of the combination of chemo- and biocatalysis for selective valorization of biobased furans. Graphic abstract

Expression of soluble methane monooxygenase in Escherichia coli enables methane conversion

Natural gas and biogas provide an opportunity to harness methane as an industrial feedstock. Bioconversion is a promising alternative to chemical catalysis, which requires extreme operating conditions and exhibits poor specificities. Though methanotrophs natively utilize methane, efforts have been focused on engineering platform organisms like Escherichia coli for synthetic methanotrophy. Here, a synthetic E. coli methanotroph was developed by engineering functional expression of the Methylococcus capsulatus soluble methane monooxygenase in vivo via expression of its cognate GroESL chaperone. Additional overexpression of E. coli GroESL further improved activity. Incorporation of an acetone formation pathway then enabled the conversion of methane to acetone in vivo, as validated via 13C tracing. This work provides the first reported demonstration of methane bioconversion to liquid chemicals in a synthetic methanotroph.

Probing Biosensing Interfaces With Single Molecule Localization Microscopy (SMLM)

Far field single molecule localization microscopy (SMLM) has been established as a powerful tool to study biological structures with resolution far below the diffraction limit of conventional light microscopy. In recent years, the applications of SMLM have reached beyond traditional cellular imaging. Nanostructured interfaces are enriched with information that determines their function, playing key roles in applications such as chemical catalysis and biological sensing. SMLM enables detailed study of interfaces at an individual molecular level, allowing measurements of reaction kinetics, and detection of rare events not accessible to ensemble measurements. This paper provides an update to the progress made to the use of SMLM in characterizing nanostructured biointerfaces, focusing on practical aspects, recent advances, and emerging opportunities from an analytical chemistry perspective.

Purification of Biodiesel Produced by Lipase Catalysed Transesterification by Two-Phase Systems Based on Deep Eutectic Solvents in a Microextractor: Selection of Solvents and Process Optimization

The most important and the most used process of biodiesel synthesis is transesterification. The main byproduct formed in the biodiesel synthesis by transesterification is glycerol. Biodiesel produced by transesterification is not suitable for application in engines since it contains soap (if biodiesel is produced by chemical catalysis), traces of the catalyst, methanol, metals, water, oil, and glycerides. All those impurities must be removed in order to reach the standards (ASTM D6751 and EN 14214). The most dominant industrial method for biodiesel purification is wet washing, which generates up to 10 L of wastewater per 1 L of purified biodiesel. Therefore, cheaper and more efficient solutions for biodiesel purification should be found. Deep eutectic solvents (DESs) have been already demonstrated as viable options in biodiesel purification. DESs, a mixture of two or more components with a lower melting point than each individual component, are considered less toxic to the environment, non-volatile, biodegradable, and more stable; in other words, they are economically and environmentally friendly in comparison with organic solvents. In this study, purification of biodiesel produced by lipase catalysed transesterification by DESs was performed by two-phase liquid extraction in a microextractor. A total of 13 different DESs were synthesized and used for biodiesel purification in order to find the one that provides the best glycerol extraction efficiency. After initial screening, three DESs were selected and used for the optimization of process conditions for extraction performed in a microsystem. A three-level-four-factor Box–Behnken experimental design was employed to define the optimal process conditions (biodiesel–DES mass ratio, temperature, residence time). At optimal process conditions, the glycerol content in biodiesel was reduced below 0.02% (w/w), which is the value specified by standards (ASTM D6751 and EN 14214).