Photoinduced Charge Transfer between Metal Halide Perovskite and Ru-Polypyridyl Complexes Toward Biocatalytic Reactions.

Vacancy-ordered Bi-based perovskites, such as CsBiBr (CBB), exhibit relatively high Lewis acidity due to Bi⁺ centers, providing favorable acidic sites for organic transformations. Coupled with their tuneable optoelectronic properties, these features render CBB an efficient photocatalyst for various acid-catalyzed reactions. In this study, CBB is conjugated with a classical Ru(II)-polypyridyl photosensitizer (RuPS) to form a hybrid material, CBB/RuPS, capable of facilitating thermodynamically favourable inner-sphere electron transfer.

Dispersion-Dominated S-H···Se H-Bonds in the Dimethyl Selenide-HS Complex Identified in a Nitrogen Matrix: Cooperative Strengthening by Molecular Nitrogen.

The S-H···Se H-bonded complex formation between dimethyl selenide (MeSe) and HS was studied using Fourier transform infrared (FTIR) spectroscopy in a cold and solid nitrogen (N) matrix. Concentration variation and annealing experiments confirmed the formation of the binary MeSe-HS complex along with larger (1:2 and 2:1) clusters. The S-H···Se H-bonded binary complex exhibited a large red shift of 146.

Contact Dynamics of Cytoadhering -Infected Erythrocytes in Flow.

The virulence of the human malaria parasite is linked to the altered mechanical and adhesive properties of infected erythrocytes, which adhere to the microvascular endothelium to evade splenic clearance. The underlying biophysical mechanisms remain incompletely understood, particularly regarding the contact area and bond landscape, due in part to the rapid and transient nature of these interactions. In this study, we investigated the dynamic adhesion behavior of -infected erythrocytes on surfaces functionalized with intercellular adhesion molecule 1 (ICAM-1), cluster of differentiation 36 (CD36), or a combination of both.

Exploring the role of microbiota in mediating sexually dimorphic infection outcomes in mealworm beetles.

Sexually dimorphic responses to pathogenic infections in animals may stem from sex-specific differences in their life history and immune investment. Recent evidence highlights that such sex-specific variations in immune responses can also be critically regulated by the microbiota. However, direct experiments to test how the microbiota jointly impacts sex-specific immunity and vulnerability to pathogens are still limited.

Enigmatic roles of hemolysin/cytolysin in the bacterial pathogenesis and host-pathogen interactions.

cytolysin (VCC; also known as hemolysin) is a β-barrel pore-forming toxin (β-PFT) secreted by the cholera pathogen . VCC acts to disrupt the selective permeability barrier function of the target cell membranes. Monomeric VCC molecules bind to and form heptameric transmembrane water-filled pores or channels in the lipid bilayer of the membranes, thus resulting in colloid-osmotic lysis of the target cells.

Emerging frontiers in visual ecology.

Visual ecology, the study of how animals acquire and respond to visual information in nature, has grown rapidly over the past few decades. Research in this field has transformed our understanding of fundamental processes, such as the neurobiological basis of behavior and the diversification of species through sensory drive. The recent growth in the field has been accompanied by leaps in our understanding of the diversity of visual systems and in the development of novel technologies and techniques (for example, those allowing us to measure scenes and signals).

Enhanced condensate fluidity in modified patchy particle models.

Biomolecular condensates are formed via liquid-liquid phase separation of proteins, often together with nucleic acids, typically driven by interactions between low-affinity binding sites. The computational study of such condensates that accounts for both the droplet-scale fluid behavior and the internal structure of the condensate requires coarse-grained models. Recently, patchy particle models, representing proteins as spheres with a repulsive core and directional attractive patches, have emerged as a powerful tool.

Expanding the Scope of BICAAC Organocatalyst: Hydroboration of Carbonyl and Alkyne Substrates.

Bicyclic (alkyl)(amino)carbene (BICAAC) (I) has been used as a highly effective catalyst for hydroboration of aldehydes, ketones, and alkynes. The catalyst is effective across a broad range of substrates bearing both electron-donating and electron-withdrawing groups, indicating its robust functional group tolerance. Mechanistic investigations, supported by both experimental studies and computational analyses, suggest the initial step involves the reaction of BICAAC (I) with pinacolborane (HBpin), leading to the formation of boron-carbene complex (active catalyst II).

Experimental determination of tripartite quantum discord.

Quantum discord is a measure of nonclassical correlations in quantum systems. While the bipartite version of quantum discord is experimentally well-studied, the multipartite version has never been convincingly measured. In this study, we experimentally investigate tripartite quantum discord using an NMR quantum information processor.

A secreted virulence factor Rv1435c/hsr1 disrupts host snRNP biogenesis.

Transcriptional adaptation drives the host responses to () infection. However, alters host RNA splicing to quench host antibacterial responses, the mechanism for which remains unknown. Here, we report a mechanism whereby a secreted protein interferes with the biogenesis of key spliceosomal components.

Nitrogen-Rich Mn-Based Metal-Organic Frameworks for Small Molecule Adsorption and Activation through Polarization.

To address the far-reaching consequences of radioiodine contamination and CO emissions, heteroatom engineering in materials has emerged as a promising strategy. In this study, three thermally and chemically stable Mn-based metal-organic frameworks (MOFs), 1-3, are synthesized using (i) a dicarboxylate ligand with an oxadiazole core, and (ii) nitrogen-rich ligands with varying spacers between the bis(tridentate) ends. The incorporation of a heterocyclic core and nitrogen atoms enhances polarity, while Lewis acidity of Mn ion strengthens small molecule interactions.

Establishing Structure-Activity Relationships in Heterogeneous Catalysis of Three-Component Organic Coupling Reactions by Lewis Acidic Metal Sites and Polar Moieties.

The postpandemic surge in demand for antimicrobial drugs has accelerated the customization of suitable catalysts, fostering a synergy between their structure and activity in promoting the multicomponent organic coupling reactions. In this work, we have successfully constructed two new polar metal-organic frameworks, viz., and , where bpaipa = 5-(bis(pyridin-2-ylmethyl)amino)isophthalate, embedded with catalytically active Co/Ni Lewis acidic metal sites and polar moieties (such as O/N heteroatoms) for a critical evaluation of their role in the synthesis of an important category of antimicrobial drugs, oxazolidinones, from a three-component coupling reactions.

Operational Constraints in Quantum Otto Engines: Energy-Gap Modulation and Majorization.

The performance of a quantum Otto engine is analyzed with regard to the constraints on the modulation of energy gaps relative to the changes in probability distributions at the two given heat reservoirs. We performed a detailed analysis with a generic three-level system (3LS), which serves as a non-trivial working medium with two energy gaps. A three-level Otto engine becomes feasible if at least one energy gap shrinks during the first quantum adiabatic stage.

Liquid crystal-aqueous interface renders selective detection of distinct mycobacterial cell envelope responses.

Antibiotic-resistant latent tuberculosis mandates sensitive, label-free screening platforms that permit the detection of changes in bacterial membranes as a potential therapeutic target. Growth stage-induced alterations in the mycobacterial lipidome, which underlie drug tolerance, further intensify this goal. In this work, liquid crystal (LC)-based detection captured the selective, spatiotemporal modulation of lipid membranes induced by bacterial dormancy.

Transformation of a Pd trifacial barrel to a Pd tetrafacial barrel by C as guest and oxidative photolysis of alkenes using the C encapsulated barrel under red light.

Fabricating discrete molecular cages as fullerene receptors has been a compelling task. The main objective of confining fullerene molecules is to utilize their physico-chemical properties in commonly used media in which they are insoluble. Herein, a fluorenone-based large trigonal Pd molecular barrel (M1) was synthesized by coordination self-assembly to act as a potential fullerene trap.

Low-Valent Group 14 Species Supported by BICAAC: Isolation of a Germylone and a Digermanium Compound.

Herein, we have disclosed the successful isolation and spectroscopic characterization of a series of bicyclic (alkyl)(amino) carbene (BICAAC) complexes of GeCl and SnX; [BICAAC-GeCl (1); BICAAC-GeCl (2); BICAAC-SnX (X = Cl (3); X = Br, (4))]. The in-situ KC reduction of GeCl·dioxane in the presence of BICAAC led to the isolation of a zero-valent di-coordinated germylone [(BICAAC)Ge] (5), whereas the reduction of adduct 2 afforded a trans-bent digermanium complex, [BICAAC→Ge═Ge←BICAAC] (6), having a Ge═Ge (2.3652(5) Å) double bond.

Rh(III)-Catalyzed Fabrication of [4,3,1]-Bridged Azaheterocycles using Quinone Monoacetals.

A rhodium-catalyzed annulation strategy for the fabrication of cyclohexanone-bridged indazolones and other related diazole-ones and diazine-ones was established using quionone monoacetals under mild conditions. On the other hand, the use of 4-hydroxy-4-methylcyclohexa-2,5-dienone under the optimized Rh-conditions produced an C-arylated product in moderate reactivity. Mechanistic studies suggested that the coupling proceeded one-pot C-H activation-Michael/hetero-Michael additions into the enone moiety.

A Dimolybdenum Paddlewheel Embedded Covalent Organic Framework for Photocatalytic Hydrogen Peroxide Generation.

In the midst of the global energy crisis, the conversion of solar energy into chemical energy or high-value chemicals has become critical. Hydrogen peroxide (HO), a versatile oxidizing agent, plays an important role in chemical synthesis, medical disinfection, and clean energy generation via fuel cells. Recently, photocatalytic HO generation from water and oxygen using covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) has emerged as a sustainable approach.

Spatial organization of multiple species of active particles interacting with an interface.

We investigate the steady-state organization of active particles residing on an interface. Particle activity induces interface deformations, while the local shape of the interface guides particle movement. We consider multiple species of particles which can locally pull on the interface or push it.

Electronically Asynchronous Transition State Tuned from Remote Site for Oxygen Atom Transfer by Cu-Nitrite Complexes.

Nitrite (NO ) reduction to nitric oxide (NO) is of paramount interest in biology. In biology, Cu-nitrite reductase reduces NO  to NO, while alternatively NO  can be reduced to NO at copper center via oxygen atom transfer (OAT) to electron-rich substrate like PPh. This work demonstrates systematic tuning of lowest unoccupied molecular orbital (LUMO) energy by remote site modification, which leads to systematic change in electrochemical property and OAT activity of Cu-NO  involving electronically asynchronous transition state.

Modulation of heme peroxo nucleophilicities with axial ligands reveal key insights into the mechanistic landscape of nitric oxide synthase.

Mid-valent heme-oxygen intermediates are central to a medley of pivotal physiological transformations in humans, and such systems are increasingly becoming more relevant therapeutic targets for challenging disease conditions. Nonetheless, precise mechanistic details pertaining to mid-valent heme intermediates as well as key structure-activity relationships remain enigmatic. To this end, this study strives to describe the influence of heme proximal ligation on the nucleophilic reactivity patterns of heme peroxo intermediates.

Zn-Doped Cesium Bismuth Bromide Perovskites: Impact of Structural and Morphological Modifications on Linear and Non-Linear Optical Properties.

Cesium bismuth bromide (CBB) provides a compelling lead free, non-toxic alternative in perovskite optoelectronic applications. Doping with transition metal has been employed for the improvement of photophysical characteristics in perovskites. In this study, the incorporation of heterovalent Zn ions in CBB nanosheets and its effect on the structural, morphological, linear, and non-linear properties are investigated.

Phase separation in active binary mixtures with chemical reaction.

We study motility-induced phase separation (MIPS) in active AB binary mixtures undergoing the chemical reaction A ⇌ B. Starting from the evolution equations for the density fields (,) describing MIPS, we phenomenologically incorporate the effects of the reaction through the reaction rate into the equations. The steady-state domain morphologies depend on and the relative activity of the species, .