Potent Inducers of Paraptosis through Electronic Tuning of Hemicyanine Electrophiles.

Paraptosis is a distinct form of programmed cell death characterized by cytoplasmic vacuolization, mitochondrial swelling, and endoplasmic reticulum (ER) dilation, offering an alternative to apoptosis for therapeutic applications. In this study, we identified a hemicyanine derivative that is a potent paraptosis inducer in two cancer cell lines. This compound triggers hallmark paraptotic features, including ER swelling, mitochondrial morphological changes, increased superoxide production, and caspase-independent cell death.

Cation Dehydration by Surface-Grafted Phenyl Groups for Enhanced C Production in Cu-Catalyzed Electrochemical CO Reduction.

The challenge to produce multicarbon (C) products in high current densities in the electrochemical reduction of carbon dioxide (CORR) has motivated intense research. However, the ability of solvated cations to tune and activate water for C production in the CORR has been overlooked. In this study, we report the incorporation of a covalently grown layer of functionalized phenyl groups on the Cu surface that leads to a 7-fold increase in ethylene production (to -530 mA cm) and a 6-fold increase in C products (to -760 mA cm).

Synthesis of a MXene/Metal-Organic Framework Composite for Efficient Supercapacitor and Electrocatalytic CO Reduction.

Metal-organic frameworks (MOFs) are remarkable electroactive materials for energy storage and electrochemical CO reduction (CORR) due to their high surface area and tunable pore structures. However, challenges such as stability, conductivity, and product selectivity at high current densities must be addressed to realize their full potential. We crossbreed a zeolite imidazolate framework-8 (ZIF-8)-based MOF with MXene using a simple layer-by-layer deposition technique and investigate the supercapacitive and CORR performances.

Flame-Made Surface-Substituted Copper-Ceria as an Excellent Reverse Water-Gas Shift Reaction Catalyst via Three Reaction Pathways.

The limited mechanistic understanding and ambiguous structure-performance relationships have hindered the optimization of Cu-based catalysts for the reverse water-gas shift (rWGS) reaction. Here, we report a flame spray pyrolysis (FSP)-derived Cu-CeO catalyst featuring highly dispersed, surface-substituted Cu species (CuCeO) anchored on a defect-rich ceria matrix. This catalyst demonstrates excellent stability and outstanding rWGS activity at 600 °C, achieving a CO production rate of 8094 mmol/g/h, surpassing the conventional Cu-CeO catalyst and other reported rWGS catalysts.

A Ship-in-a-Bottle Strategy: Crosslinking Amines and Epoxides inside MOF Pores for Enhanced CO Capture Performance.

This study introduces a "ship-in-a-bottle" technique to impregnate porous supports with amines via a straightforward in situ polymerization process. Specifically, alkylamines-tris(2-aminoethyl)amine (TAEA) and tetraethylene pentamine (TEPA)-are crosslinked with epoxides-trimethylolpropane triglycidyl ether (TMPTE) and 1,3-butadiene diepoxide (BDE)-within the pores of the metal-organic framework (MOF) Cr-BDC (also MIL-101(Cr), where BDC = 1,4-benzenedicarboxylate), producing four distinct MOF-polymer composites. These composites are subsequently evaluated for their efficacy in postcombustion carbon capture, examining metrics such as CO capacity, CO/N selectivity, isosteric heat of CO adsorption, kinetic breakthrough times, and cyclability.

Comparative analysis of search approaches to discover donor molecules for organic solar cells.

Identifying organic molecules with desirable properties from the extensive chemical space can be challenging, particularly when property evaluation methods are time-consuming and resource-intensive. In this study, we illustrate this challenge by exploring the chemical space of large oligomers, constructed from monomeric building blocks, for potential use in organic photovoltaics (OPV). For this purpose, we developed a python package to search the chemical space using a building block approach: .

SPRING, an effective and reliable framework for image reconstruction in single-particle Coherent Diffraction Imaging.

Coherent Diffraction Imaging (CDI) is an experimental technique to image isolated structures by recording the scattered light. The sample density can be recovered from the scattered field through a Fourier Transform operation. However, the phase of the field is lost during the measurement and has to be algorithmically retrieved.

Wacker Oxidation of Trisubstituted Alkenes: Pd(II)-Catalyzed Oxidative Ring Expansion of Exocyclic α,β-Unsaturated Carbonyl to 2-Fluoro-1,3-Dicarbonyl Compounds.

The Wacker oxidation is a powerful synthetic method widely employed for the transformation of monosubstituted alkenes into methyl ketones. Its substrate scope has progressively expanded to include internal disubstituted and, more recently, gem-disubstituted alkenes. Herein, we report the first examples of Wacker-type oxidation of trisubstituted alkenes under Pd(II)/Pd(IV) catalysis.

Recent Advances in Photocatalytic CO Reduction into Valuable Products Using Nickel-Based Metal-Organic Frameworks.

The conversion of carbon dioxide into valuable chemicals through photochemical processes has been considered to be a potential technique to address environmental challenges. A good number of MOFs-based nickel (Ni-MOFs) compounds have garnered significant interest in the photocatalytic reduction of CO due to their abundant active sites, tunable structure, the good affinity between CO, Ni elements, and other properties. This mini-review summarizes the different works on using Ni-MOFs as catalysts for the photocatalytic reduction of CO by focusing on applying pristine, monometallic, and multimetallic Ni-MOFs.

Unexpected Pathway in Organic Semiconductor Nanoparticle Formation.

Organic semiconductor (OSC) nanoparticles (NPs) are promising for numerous applications including greener organic photovoltaics and heterogeneous photocatalysts for solar H production. Single component or mixed bulk-heterojunction (BHJ) OSC NPs are commonly prepared from conventional polymer OSCs via the miniemulsion-evaporation method using ultrasonication. However, realizing the expected NP size control with this approach remains elusive, limiting optimization.

Single junction CsPbBr solar cell coupled with electrolyzer for solar water splitting.

Artificial photosynthesis system to realize Solar overall water splitting has been regarded as sustainable and renewable solution for energy and environmental issues. While artificial photosynthesis system (efficiency of 12.4%) greatly exceeds efficiency of natural photosynthesis, yet such high efficiency needs multiple, 2 or more light absorbers to achieve, total photovoltage above 1440 mV.

Spiro-Phenothiazine Hole-Transporting Materials: Unlocking Stability and Scalability in Perovskite Solar Cells.

Improving both the efficiency and long-term stability of perovskite solar cells (PSCs) is critical for their commercial deployment. Despite the widespread use of spiro-OMeTAD as a hole-transporting material (HTM), its inhomogeneous doping behavior and susceptibility to moisture and heat have hindered its large-scale industrial implementation. Here, a family of spiro-phenothiazine-based HTMs (PTZ) is reported to address these drawbacks.

Nanoscale size effects in α-FAPbI evinced by large-scale ab initio simulations.

Formamidinium-lead-iodide (FAPbI) has a rich phase diagram, and long-range correlation between the organic cations and lattice dipoles can influence phase transitions and optoelectronic properties. System size effects are crucial for an appropriate theoretical description of FAPbI. We perform a systematic ab initio study on the structural and electronic properties of the photoactive phase of FAPbI as a function of system size.

Best practices for multi-fidelity Bayesian optimization in materials and molecular research.

Multi-fidelity Bayesian optimization (MFBO) is a promising framework to speed up materials and molecular discovery as sources of information of different accuracies are at hand at increasing cost. Despite its potential use in chemical tasks, there is a lack of systematic evaluation of the many parameters playing a role in MFBO. Here we provide guidelines and recommendations to decide when to use MFBO in experimental settings.

Chiral Phosphoric Acid-Catalyzed Enantioselective Higher-Order Cycloadditions: Temperature-Dependent Periselectivity.

Higher-order cycloadditions (HOCs) are powerful tools for constructing complex cyclic structures, but their synthetic utility is often limited by poor periselectivity and challenges in achieving high diastereo- and enantioselectivity. Herein, we report a chiral phosphoric acid-catalyzed reaction between tropones and trifluoroacetamido-1,3-dienes that proceeds efficiently at room temperature, delivering bicyclo[4.4.

Building Blocks for the Screening of Histone Deacetylase Inhibitors Using μSPOT.

Histone deacetylase (HDAC) inhibitors are approved as cancer chemotherapy and studied for the treatment of various diseases. However, there is a lack of isozyme-selective compounds to determine the biological role of each of the 11 HDACs, and to develop drugs applicable to a wider range of disorders. Here, we describe the synthesis of hydroxamic acid and trifluoromethyl ketone-containing building blocks and their use to synthesize libraries of HDAC-binding peptides.

Large Macrocyclic Libraries via Thioether Cyclization.

Macrocyclic peptides, known for their high specificity, binding affinity, and potential membrane permeability, represent a promising modality in drug discovery, particularly for intracellular targets deemed undruggable by conventional small molecules. Traditional methods for macrocycle synthesis often involve labor-intensive purification steps, limiting throughput and scalability. This protocol presents a streamlined approach for the synthesis of large macrocyclic peptide libraries, utilizing solid-phase peptide synthesis (SPPS) followed by purification-free cyclization of linear dithiol peptides in high-throughput array formats.

Molecular recording of cellular protein kinase activity with chemical labeling.

Protein kinases control most cellular processes and aberrant kinase activity is involved in numerous diseases. Here we introduce molecular recorders of kinase activities for later analysis to investigate the link between specific kinase activities and cellular phenotypes in heterogeneous cell populations and in vivo. Based on split-HaloTag and a phosphorylation-dependent molecular switch, our recorders become rapidly labeled in the presence of a specific kinase activity and a fluorescent HaloTag substrate.

Active Sites under Electronic Effect Are More Sensitive to Microenvironment in CO Electroreduction.

Tailoring the structure of the active sites and engineering the microenvironment to tune catalytic performance are both at the forefront of catalysis. Yet, design principles bridging the two remain missing. Here, we synthesize a platform consisting of well-defined cubic Cu nanocrystals with an oxide coating of tunable porosity, here alumina.

Facile N-C bond cleavage and arene reduction by a transient uranium(ii) complex.

Complexes of uranium(ii) remain extremely rare and their reactivity is practically unexplored. Here we report that the reduction of the heteroleptic bis-aryloxide U(iii) complex [U( -{( ArO)Me-cyclam})I], A, yields a rare and highly reactive U(ii) intermediate that enables a rare example of intramolecular uranium mediated N-C cleavage and effects arene reduction resulting in the isolation of the U(iv) complex [U{ -(( BuArO)Me-cyclam)}{ -( BuArOCH)}] (2) and of the inverse-sandwich complex [{U( -{( ArO)Me-cyclam})}( : -benzene)] (3) respectively. Moreover, the U(ii) solvent-dependent reactivity results in the formation of a putative U-N complex in diethyl ether.

Turning a micromixer into a separation column: The role of minimal surfaces and transversal transport in enhancing the performance of micro/nano Liquid Chromatography.

Microchannels hosting spatially-periodic supports for the stationary phase have drawn intense attention in Liquid Cromatography (LC) research in the last two decades, with second-generation μPACs (micro-pillar array columns) setting the current limit of separation efficiency both in terms of plate height and flow resistance. Inspired by recent theoretical and experimental results, suggesting that an increased rate of transversal mixing in the mobile phase can significantly reduce the dispersion bandwidth of the analytes, we investigate and numerically predict the separation performance of a capillary LC column hosting a periodic alternate sequence of helicoidal baffles arranged in a Kenics Mixer (KM) configuration. The comparison of the KM-LC column performance with that of packed, random-monolithic, and μPAC columns, carried out by matching the capillary diameter of the KM to the size of the flow-through pores of the other geometries, shows a potential further enhancement of LC efficiency, with a minimal plate height reduced by a factor 3 for an unretained solute, and by a factor 2 for a solute with retention factor k=2 with respect to the best performing columns reported so far.

Polycondensation as a Universal Method for Preparing High-Density Single-Atom Catalyst Libraries.

Single-atom catalysts (SACs) present a promising subclass of classic heterogeneous catalysts by maximizing metal dispersion and enhancing efficiency. Although high-density SACs (HD-SACs) are reported, their synthesis is typically constrained to specific metal-support combinations and high-temperature annealing, limiting their translation to wider applications. Herein, a universal bottom-up approach for the preparation of mono- and bimetallic HD-SACs based on the polycondensation of 1,2,4,5-benzenetetramine with a wide range of metal monomers containing 1,10-phenanthroline-5,6-dione ligands is introduced.

Valence and Site Engineering Enable Efficient Broadband Near-Infrared Emission at 960 nm in Cr-Activated Forsterite.

Near-infrared (NIR) light sources hold great potential for applications in night vision illumination, bio-imaging, and non-destructive testing. However, radiationless de-activation and low absorption restrict the development of high-efficiency blue light excitable NIR phosphors, especially for emissions beyond 900 nm. Herein we report a high-performance Cr-activated forsterite (MgSiO:1.

SNAP-tag2 for faster and brighter protein labeling.

SNAP-tag is a powerful tool for labeling proteins with synthetic fluorophores in bioimaging. However, its utility in live-cell applications can be constrained by its relatively slow labeling kinetics and the limited cell permeability of its substrates. Here, we introduce improved labeling substrates and an engineered SNAP-tag for faster labeling in vitro and in live cells.

Remote Iron dynamics of NiFe (oxy)hydroxides toward robust active sites in water oxidation.

Ni(Fe) (oxy)hydroxides have long been recognized as benchmark electrocatalysts for water oxidation in alkaline media. Maximizing their activity and longevity will be vital for facilitating scalable water electrolysis. However, progress is hindered by insufficient understandings of surface Fe dynamics and by the absence of effective regulatory approach.