Carboxylation of alkenes and alkynes using CO2 as a reagent: an overview

: CO2 fixation reactions are of paramount interest both from economical and environmental perspectives. As an abundant, non-toxic, and renewable C1 feedstock, CO2 can be utilized for the synthesis of fuels and commodity chemicals under elevated reaction conditions. The major challenge in the CO2 utilization reactions is its chemical inertness due to high thermodynamic stability and kinetic barrier. The carboxylation of unsaturated hydrocarbons with CO2 is an important transformation as it forms high-value reaction products having industrial as well as medicinal importance. This mini-review is mainly focused on the recent developments in the homogeneously and heterogeneously catalyzed carboxylation of alkenes and alkynes by using carbon dioxide as a reagent. We have highlighted various types of carboxylation reactions of alkenes and alkynes involving different catalytic systems, which comprise mainly C-H bond activation, hydrocarboxylation, carbocarboxylation, heterocarboxylation, and ring-closing carboxylation, including visible-light assisted synthesis processes. The mechanistic pathways of these carboxylation reactions have been described. Moreover, challenges and future perspectives of these carboxylation reactions are discussed.

The Catalytic Role of D-block Elements and Their Compounds for Improving Sorption Kinetics of Hydride Materials: A Review

The goal of finding efficient and safe hydrogen storage material motivated researchers to develop several materials to fulfil the demand of the U.S. Department of Energy (DOE). In the past few years, several metal hydrides, complex hydrides such as borohydrides and alanates, have been researched and found efficient due to their high gravimetric and volumetric density. However, the development of these materials is still limited by their high thermodynamic stability and sluggish kinetics. One of the methods to improve the kinetics is to use catalysts. Among the known catalysts for this purpose, transition metals and their compounds are known as the leading contender. The present article reviews the d-block transition metals including Ni, Co, V, Ti, Fe and Nb as catalysts to boost up the kinetics of several hydride systems. Various binary and ternary metal oxides, halides and their combinations, porous structured hybrid designs and metal-based Mxenes have been discussed as catalysts to enhance the de/rehydrogenation kinetics and cycling performance of hydrogen storage systems.

Specific length and structure rather than high thermodynamic stability enable regulatory mRNA stem-loops to pause translation

SUMMARYTranslating ribosomes unwind mRNA secondary structures by three basepairs each elongation cycle. Despite the ribosome helicase, certain mRNA stem-loops stimulate programmed ribosomal frameshift by inhibiting translation elongation. Here, using mutagenesis, biochemical and single-molecule experiments, we examine whether high stability of three basepairs, which are unwound by the translating ribosome, is critical for inducing ribosome pauses. We find that encountering frameshift-inducing mRNA stem-loops from the E. coli dnaX mRNA and the gag-pol transcript of Human Immunodeficiency Virus (HIV) hinders A-site tRNA binding and slows down ribosome translocation by 15-20 folds. By contrast, unwinding of first three basepairs adjacent to the mRNA entry channel slows down the translating ribosome by only 2-3 folds. Rather than high thermodynamic stability, specific length and structure enable regulatory mRNA stem-loops to stall translation by forming inhibitory interactions with the ribosome. Our data provide the basis for rationalizing transcriptome-wide studies of translation and searching for novel regulatory mRNA stem-loops.

A comprehensive nano-interpenetrating semiconducting photoresist toward all-photolithography organic electronics

Owing to high resolution, reliability, and industrial compatibility, all-photolithography is a promising strategy for industrial manufacture of organic electronics. However, it receives limited success due to the absence of a semiconducting photoresist with high patterning resolution, mobility, and performance stability against photolithography solution processes. Here, we develop a comprehensive semiconducting photoresist with nano-interpenetrating structure. After photolithography, nanostructured cross-linking networks interpenetrate with continuous phases of semiconducting polymers, enabling submicrometer patterning accuracy and compact molecular stacking with high thermodynamic stability. The mobility reaches the highest values of photocrosslinkable organic semiconductors and maintains almost 100% after soaking in developer and stripper for 1000 min. Owing to the comprehensive performance, all-photolithography is achieved, which fabricates organic inverters and high-density transistor arrays with densities up to 1.1 × 105 units cm−2 and 1 to 4 orders larger than conventional printing processes, opening up a new approach toward manufacturing highly integrated organic circuits and systems.

Structure elucidation of the elusive Enzyme I monomer reveals the molecular mechanisms linking oligomerization and enzymatic activity

Enzyme I (EI) is a phosphotransferase enzyme responsible for converting phosphoenolpyruvate (PEP) into pyruvate. This reaction initiates a five-step phosphorylation cascade in the bacterial phosphotransferase (PTS) transduction pathway. Under physiological conditions, EI exists in an equilibrium between a functional dimer and an inactive monomer. The monomer–dimer equilibrium is a crucial factor regulating EI activity and the phosphorylation state of the overall PTS. Experimental studies of EI’s monomeric state have yet been hampered by the dimer’s high thermodynamic stability, which prevents its characterization by standard structural techniques. In this study, we modified the dimerization domain of EI (EIC) by mutating three amino acids involved in the formation of intersubunit salt bridges. The engineered variant forms an active dimer in solution that can bind and hydrolyze PEP. Using hydrostatic pressure as an additional perturbation, we were then able to study the complete dissociation of the variant from 1 bar to 2.5 kbar in the absence and the presence of EI natural ligands. Backbone residual dipolar couplings collected under high-pressure conditions allowed us to determine the conformational ensemble of the isolated EIC monomeric state in solution. Our calculations reveal that three catalytic loops near the dimerization interface become unstructured upon monomerization, preventing the monomeric enzyme from binding its natural substrate. This study provides an atomic-level characterization of EI’s monomeric state and highlights the role of the catalytic loops as allosteric connectors controlling both the activity and oligomerization of the enzyme.

Synthesis of Magnetic α-Fe2O3/Rutile TiO2 Hollow Spheres for Visible-Light Photocatalytic Activity

The high recombination rate of the electron-hole pair on the surface of rutile TiO2 (RT) reduces its photocatalytic performance, although it has high thermodynamic stability and few internal grain defects. Therefore, it is necessary for RT to develop effective methods to reduce electron-hole pair recombination. In this study, magnetic α-Fe2O3/Rutile TiO2 self-assembled hollow spheres were fabricated via a facile hydrothermal reaction and template-free method. Based on the experimental result, phosphate concentration was found to play a crucial role in controlling the shape of these hollow α-Fe2O3/RT nanospheres, and the optimal concentration is 0.025 mM. Due to a heterojunction between α-Fe2O3 and RT, the electron-hole pair recombination rate was reduced, the as-synthesized hollow α-Fe2O3/RT nanospheres exhibited excellent photocatalysis in rhodamine B (RhB) photodegradation compared to α-Fe2O3 and RT under visible-light irradiation, and the degradation rate was about 16% (RT), 60% (α-Fe2O3), and 93% (α-Fe2O3/RT) after 100 min. Moreover, α-Fe2O3/RT showed paramagnetism and can be recycled to avoid secondary environmental pollution.

Elucidating the Influence of Electric Fields toward CO2 Activation on YSZ (111)

Despite its high thermodynamic stability, the presence of a negative electric field is known to facilitate the activation of CO2 through electrostatic effects. To utilize electric fields for a reverse water gas shift reaction, it is critical to elucidate the role of an electric field on a catalyst surface toward activating a CO2 molecule. We conduct a first-principles study to gain an atomic and electronic description of adsorbed CO2 on YSZ (111) surfaces when external electric fields of +1 V/Å, 0 V/Å, and −1 V/Å are applied. We find that the application of an external electric field generally destabilizes oxide bonds, where the direction of the field affects the location of the most favorable oxygen vacancy. The direction of the field also drastically impacts how CO2 adsorbs on the surface. CO2 is bound by physisorption when a +1 V/Å field is applied, a similar interaction as to how it is adsorbed in the absence of a field. This interaction changes to chemisorption when the surface is exposed to a −1 V/Å field value, resulting in the formation of a CO3− complex. The strong interaction is reflected through a direct charge transfer and an orbital splitting within the Olatticep-states. While CO2 remains physisorbed when a +1 V/Å field value is applied, our total density of states analysis indicates that a positive field pulls the charge away from the adsorbate, resulting in a shift of its bonding and antibonding peaks to higher energies, allowing a stronger interaction with YSZ (111). Ultimately, the effect of an electric field toward CO2 adsorption is not negligible, and there is potential in utilizing electric fields to favor the thermodynamics of CO2 reduction on heterogeneous catalysts.

Preparation of iron(IV) nitridoferrate Ca4FeN4 through azide-mediated oxidation under high-pressure conditions

Transition metal nitrides are an important class of materials with applications as abrasives, semiconductors, superconductors, Li-ion conductors, and thermoelectrics. However, high oxidation states are difficult to attain as the oxidative potential of dinitrogen is limited by its high thermodynamic stability and chemical inertness. Here we present a versatile synthesis route using azide-mediated oxidation under pressure that is used to prepare the highly oxidised ternary nitride Ca4FeN4 containing Fe4+ ions. This nitridometallate features trigonal-planar [FeN3]5− anions with low-spin Fe4+ and antiferromagnetic ordering below a Neel temperature of 25 K, which are characterised by neutron diffraction, 57Fe-Mössbauer and magnetisation measurements. Azide-mediated high-pressure synthesis opens a way to the discovery of highly oxidised nitrides.