Stress-induced self-assembly of hierarchically twisted stripe arrays.

Hierarchical organization is prevalent in nature, yet the artificial construction of hierarchical materials featuring asymmetric structures remains a big challenge. Herein, we report a stress-induced self-assembly strategy for the synthesis of hierarchically twisted stripe arrays (HTSAs) with mesoporous structures. A soft and thin mesostructured film assembled by micelles and TiO oligomers is the prerequisite.

Chemodivergent, enantio- and regioselective couplings of alkynes, aldehydes and silanes enabled by nickel/N-heterocyclic carbene catalysis.

Divergent synthesis of valuable molecules through common starting materials and metal catalysis represents a longstanding challenge and a significant research goal. We here describe chemodivergent, highly enantio- and regioselective nickel-catalyzed reductive and dehydrogenative coupling reactions of alkynes, aldehydes, and silanes. A single chiral Ni-based catalyst is leveraged to directly prepare three distinct enantioenriched products (silyl-protected trisubstituted chiral allylic alcohols, oxasilacyclopentenes, and silicon-stereogenic oxasilacyclopentenes) in a single chemical operation.

Synthesis of BODIPYs using organoindium reagents and survey of their cytotoxicity and cell uptake on nervous system cells.

In this study, a series of BODIPY dyes were synthesized, containing various substituents at meso position. Further functionalization of the BODIPY framework at C2 and C2-C6 position(s) by palladium-catalysed cross-coupling reactions using organoindium reagents (RIn) was efficiently assessed, starting from C2(6)-halogenated BODIPYs, and their optical properties were measured. The cytotoxicity of BODIPY dyes on SH-SY5Y neuronal cells by MTT assay showed that those compounds bearing thien-2-yl and benzonitrile moieties at meso position, exhibited great efficiency in maintaining cell viability under all tested conditions (up to 50 µM for 24 h and 48 h).

Transformation mechanism, kinetics and ecotoxicity of kaempferol and quercetin in the gaseous and aqueous phases: A theoretical combined experimental study.

The transformation and risk assessment of flavonoids triggered by free radicals deserve extensive attention. In this work, the degradation mechanisms, kinetics, and ecotoxicity of kaempferol and quercetin mediated by ∙OH, ∙OCH, ∙OOH, and O in gaseous and aqueous environments were investigated using cell experiments and quantum chemical calculations. Three radical scavenging mechanisms, including hydrogen atom transfer (HAT), radical adduct formation (RAF) and single electron transfer (SET) were discussed.

Structural design and evolution of one-dimensional Cu hydrogen-bonded organic framework for catalyzing the rapid decomposition of ammonium perchlorate.

Enhancing the decomposition rate of ammonium perchlorate (AP), the most common oxidizer in solid propellants, is important for improving propellant performance. Metal organic frameworks (MOFs) have been developed as key materials for catalyzing AP decomposition, as they can achieve good dispersion of active sites through in-situ decomposition. Despite having considerable potential, the structural transformation process and catalytic performance of MOFs in AP decomposition are still unclear, which seriously hinders their application in the field of AP decomposition.

Progress on One-dimensional Vanadium Pentoxide-based Nanomaterials for Advanced Energy Storage ANSTEEL Research Institute of Vanadium & Titanium (Iron & Steel), China.

One-dimensional (1D) vanadium-based nanostructures have advantageous properties and are showing emerging critical applications in the fields of catalysis, smart devices, and electrochemical energy storage. We herein timely gave an overview of the 1D vanadium pentoxide (VO)-based nanomaterials for these promising applications, especially regarding the merits of different synthetic methods, structures and properties combined with recent research frontiers in advanced energy storage, including batteries, supercapacitors and like. The high capacity, high rate and flexibility of 1D VO-based nanomaterials endow them with great potential in high-energy-density, high-power energy devices and specific/harsh environments.

Sorghum grain as a bio-template: emerging, cost-effective, and metal-free synthesis of C-doped g-CN for photo-degradation of antibiotic, bisphenol A (BPA), and phenol under solar light irradiation.

Due to the industry's rapid growth, the presence of organic pollutants, especially antibiotics, in water and wastewater resources is the main concern for wildlife and human health. Therefore, these days, a significant challenge is developing an efficient, sustainable, and eco-friendly photocatalyst. Natural biological models have numerous advantages compared to artificial model materials.

Anisotropic Plasmon Resonance in TiCT MXene Enables Site-Selective Plasmonic Catalysis.

The ever-growing interest in MXenes has been driven by their distinct electrical, thermal, mechanical, and optical properties. In this context, further revealing their physicochemical attributes remains the key frontier of MXene materials. Herein, we report the anisotropic localized surface plasmon resonance (LSPR) features in TiCT MXene as well as site-selective photocatalysis enabled by the photophysical anisotropy.

Advances and Challenges in Speciation Measurement and Microkinetic Modeling for Gas-Solid Heterogeneous Catalysis.

Microkinetic modeling of heterogeneous catalysis serves as an efficient tool bridging atom-scale first-principles calculations and macroscale industrial reactor simulations. Fundamental understanding of the microkinetic mechanism relies on a combination of experimental and theoretical studies. This Perspective presents an overview of the latest progress of experimental and microkinetic modeling approaches applied to gas-solid catalytic kinetics.

Coordination Equilibrium-Assisted Coprecipitation Synthesis of Atomically Dispersed 3d Metal Catalysts.

As a frontier of heterogeneous catalysis, single-atom catalysts (SACs) have been extensively studied fundamentally. One obstacle that limits the industrial application of SACs is the lack of a synthetic method that can prepare the catalysts on a large scale. Wet-chemistry methods that are conventionally used to prepare nanoparticle-based industrial catalysts might be a solution.

CO2-driven Oxygen Vacancy Diffusion and Healing on TiO2(110) at Ambient Pressure.

Understanding how TiO2 interacts with CO2 at the molecular level is crucial in the CO2 reduction toward value-added energy sources. Here, we report in-situ observations of the CO2 activation process on the reduced TiO2(110) surface at room temperature using ambient pressure scanning tunneling microscopy. We found that oxygen vacancies (Vo) diffuse dynamically along the bridging oxygen (Obr) rows of the TiO2(110) surface under ambient CO2(g) environments.

Synthesis of tertiary alkyl amines via photoinduced copper-catalysed nucleophilic substitution.

In view of the high propensity of tertiary alkyl amines to be bioactive, the development of new methods for their synthesis is an important challenge. Transition-metal catalysis has the potential to greatly expand the scope of nucleophilic substitution reactions of alkyl electrophiles; unfortunately, in the case of alkyl amines as nucleophiles, only one success has been described so far: the selective mono-alkylation of primary amines to form secondary amines. Here, using photoinduced copper catalysis, we report the synthesis of tertiary alkyl amines from secondary amines and unactivated alkyl electrophiles, two readily available coupling partners.

Silver nanoparticles immobilized on crosslinked vinyl polymer for catalytic reduction of nitrophenol: experimental and computational studies.

The removal of toxic nitrophenols from the industrial wastewater is urgently needed from health, environmental and economic aspects. The present study deals with the synthesis of crosslinked vinyl polymer Poly(divinylbenzene) (poly(DVB)) through free radical polymerization technique using AIBN as initiator and acetonitrile as solvent. The prepared polymer was used as a support for silver nanoparticles via chemical reduction of silver nitrate on the polymer network.

Multiscale X-ray scattering elucidates activation and deactivation of oxide-derived copper electrocatalysts for CO reduction.

Electrochemical reduction of carbon dioxide (CO) into sustainable fuels and base chemicals requires precise control over and understanding of activity, selectivity and stability descriptors of the electrocatalyst under operation. Identification of the active phase under working conditions, but also deactivation factors after prolonged operation, are of the utmost importance to further improve electrocatalysts for electrochemical CO conversion. Here, we present a multiscale in situ investigation of activation and deactivation pathways of oxide-derived copper electrocatalysts under CO reduction conditions.

Unconventional hexagonal open Prussian blue analog structures.

Prussian blue analogs (PBAs), as a classical kind of microporous materials, have attracted substantial interests considering their well-defined framework structures, unique physicochemical properties and low cost. However, PBAs typically adopt cubic structure that features small pore size and low specific surface area, which greatly limits their practical applications in various fields ranging from gas adsorption/separation to energy conversion/storage and biomedical treatments. Here we report the facile and general synthesis of unconventional hexagonal open PBA structures.

Isolated Neutral Organic Radical Unveiled Solvent-Radical Interaction in Highly Reducing Photocatalysis.

Diffusion-limited kinetics is a key mechanistic debate when consecutive photoelectron transfer (conPET) is discussed in photoredox catalysis. In-situ generated organic photoactive radicals can access catalytic systems as reducing as alkaline metals that can activate remarkably stable bonds. However, in many cases, the extremely short-lived transient nature of these doublet state open-shell species has led to debatable mechanistic studies, hindering adoption and development.

Carbon-Centered Reactivity in Carbodiphosphorane-Based Ligands Allowing for Redox-Non-Innocent Ligand/Ligand Dual Bond-Activation.

A pronounced nucleophilicity in combination with a distinct redox non-innocence is a unique feature of a coordinated ligand, which in the current case, leads to unprecedented carbon-centered reactivity patterns: A carbodiphosphorane-based (CDP) pincer-type rhodium complex allows to cleave two C-Cl-bonds of geminal dichlorides via two consecutive SN2-type oxidative additions resulting in the formation of a stabilized carbene fragment. In the presence of a suitable reductant the carbene fragment can even be converted into olefines or hydrodehalogenation products in a catalytic reaction. The developed method can also be used to convert chlorofluorocarbons (CFCs) such as CH2ClF to fluoromethane and methane.

The adsorption behavior and mechanism of Cu(Ⅱ), Fe(Ⅱ) and Co(Ⅱ) on straw biochar and their Fenton-like performance for ciprofloxacin decontamination.

In this study, the adsorption of aqueous Cu(Ⅱ), Fe(Ⅱ), and Co(Ⅱ) on biochars at diverse synthesized temperatures was evaluated. The optimal sample BC-800 achieved superior adsorption performance of Cu(Ⅱ), Fe(Ⅱ), and Co(Ⅱ) at 10-50 mg L initial concentration. Due to the larger surface area (349.

Microwave-assisted Lewis acid catalysis for one-step preparation of high-performance buckwheat peptide-based films: Efficacy, mechanism, and applications.

This study presents a novel method for the efficient preparation of peptide-based films through microwave-assisted Lewis acid catalysis (MALC) of buckwheat globulin (BG). The MALC process efficiently degraded BG into small molecular peptides (1.6-1.

Mechanistic Investigation of the Ce(III) Chloride Photoredox Catalysis System: Understanding the Role of Alcohols as Additives.

Photocatalytic C-H activation is an emerging area of research. While cerium chloride photocatalysts have been extensively studied, the role of alcohol additives in these systems remains a subject of ongoing discussion. It was demonstrated that the photocatalyst [NEt][CeCl] () produces •Cl and added alcohols exhibit zero-order kinetics.

Biomathematical enzyme kinetics model of prebiotic autocatalytic RNA networks: degenerating parasite-specific hyperparasite catalysts confer parasite resistance and herald the birth of molecular immunity.

Catalysis and specifically autocatalysis are the quintessential building blocks of life. Yet, although autocatalytic networks are necessary, they are not sufficient for the emergence of life-like properties, such as replication and adaptation. The ultimate and potentially fatal threat faced by molecular replicators is parasitism; if the polymerase error rate exceeds a critical threshold, even the fittest molecular species will disappear.

Photochemical Deracemization of 4,7-Diaza-1-isoindolinones by Unidirectional Hydrogen Atom Shuttling.

By coupling a photochemical and a thermal step, a single chiral catalyst can establish a photostationary state in which the enantiopure form of a chiral compound is favored over its racemate. Following this strategy, 3-substituted 4,7-diaza-1-isoindolones were successfully deracemized (74-98% yield, 86-99% ) employing 2.5 mol % of a photocatalyst.

Expanded Negative Electrostatic Network-Assisted Seawater Oxidation and High-Salinity Seawater Reutilization.

Coastal/offshore renewable energy sources combined with seawater splitting offer an attractive means for large-scale H electrosynthesis in the future. However, designing anodes proves rather challenging, as surface chlorine chemistry must be blocked, particularly at high current densities (). Additionally, waste seawater with increased salinity produced after long-term electrolysis would impair the whole process sustainability.

The intriguing role of L-cysteine in the modulation of chiroplasmonic properties of chiral gold nano-arrows.

Developing chiral plasmonic nanostructures represents a significant scientific challenge due to their multidisciplinary potential. Observations have revealed that the dichroic behavior of metal plasmons changes when chiral molecules are present in the system, offering promising applications in various fields such as nano-optics, asymmetric catalysis, polarization-sensitive photochemistry and molecular detection. In this study, we explored the synthesis of plasmonic gold nanoparticles and the role of cysteine in their chiroplasmonic properties.