Photocatalyzed Azidofunctionalization of Alkenes via Radical-Polar Crossover.

The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range of alkenes, including vinyl arenes, enamides, enol ethers, vinyl sulfides, and dehydroamino esters, were regioselectively functionalized with an azide and nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric acids, oximes, and phenols. The method led to a more efficient synthesis of 1,2-azidofunctionalized pharmaceutical intermediates when compared to previous approaches, resulting in both reduction of step count and increase in overall yield.

Selective Recycling of Mixed Polyesters via Heterogeneous Photothermal Catalysis.

The selective recycling of mixed plastic wastes with similar structural units is challenging. While heterogeneous catalysis shows potential for selective recycling, challenges such as complex mass transfer at multiphase interfaces and unclear catalytic mechanisms have slowed progress. In this study, a breakthrough in recycling mixed polyester wastes is introduced using heterogeneous photothermal catalysis.

Understanding the Dynamic Evolution of Active Sites among Single Atoms, Clusters, and Nanoparticles.

Catalysis remains a cornerstone of chemical research, with the active sites of catalysts being crucial for their functionality. Identifying active sites, particularly during the reaction process, is crucial for elucidating the relationship between a catalyst's structure and its catalytic property. However, the dynamic evolution of active sites within heterogeneous metal catalysts presents a substantial challenge for accurately pinpointing the real active sites.

Advanced Catalysts for the Chemical Recycling of Plastic Waste.

Plastic products bring convenience to various aspects of the daily lives due to their lightweight, durability and versatility, but the massive accumulation of post-consumer plastic waste is posing significant environmental challenges. Catalytic methods can effectively convert plastic waste into value-added feedstocks, with catalysts playing an important role in regulating the yield and selectivity of products. This review explores the latest advancements in advanced catalysts applied in thermal catalysis, microwave-assisted catalysis, photocatalysis, electrocatalysis, and enzymatic catalysis reaction systems for the chemical recycling of plastic waste into valuable feedstocks.

Efficient Electrosynthesis of Hydrogen Peroxide Enabled by a Hierarchical Hollow RE-P-O (RE = Sm, La, Gd) Architecture with Open Channels.

The electrochemical two-electron oxygen reduction reaction (2e ORR) offers a sustainable pathway for the production of HO; however, the development of electrocatalysts with exceptional activity, selectivity, and long-term stability remains a challenging task. Herein, a novel approach is presented to addressing this challenge by synthesizing hierarchical hollow SmPO nanospheres with open channels via a two-step hydrothermal treatment. The produced compound demonstrates remarkable 2e selectivity, exceeding 93% across a wide potential range of 0.

Impact of Harsh Grinding on the Structure and Color of LiCoPO and LiNiPO Pigments.

LiCoPO and LiNiPO phosphate pigments have colorations very close to the primary colors of the subtractive system: magenta and yellow, respectively. These two pigments are therefore of great interest in a variety of applications, including e-reader devices. However, the need to reduce their crystallite size in order to formulate stable electrophoretic inks has revealed that aggressive milling results in significant color changes, particularly for cobalt-based pigments.

Unlocking Chiral Sulfinimidoyl Electrophiles: Asymmetric Synthesis of Sulfinamides Catalyzed by Anionic Stereogenic-at-Cobalt(III) Complexes.

Asymmetric catalysis involving a sulfoxide electrophile intermediate presents an efficient methodology for accessing stereogenic-at-sulfur compounds, such as sulfinate esters, sulfinamides, , which have garnered increasing attention in modern pharmaceutical sciences. However, as the aza-analog of sulfoxide electrophiles, the asymmetric issues about electrophilic sulfinimidoyl species remain largely unexplored and represent a significant challenge in sulfur stereochemistry. Herein, we exhibit an anionic stereogenic-at-cobalt(III) complex-catalyzed asymmetric synthesis of chiral sulfinamides via chiral sulfinimidoyl iodide intermediates.

Development of Antibacterial Hydrogels Based on Biopolymer Aloe Vera/Gelatin/Sodium Alginate Composited With SM-AgNPs Loaded Curcumin-Nanoliposomes.

To address the rising prevalence of bacterial infections and the need for innovative therapeutic solutions, this study has developed a novel antibacterial hydrogel composite composed of Aloe vera, gelatin, sodium alginate, and Sterculia monosperma-silver nanoparticles (SM-AgNPs) loaded curcumin-nanoliposomes (NLPs). The aloe vera/gelatin/sodium alginate hydrogels (AGS) are prepared using different weight ratios of Aloe vera, gelatin, and sodium alginate, aiming to optimize mechanical properties and biocompatibility for biomedical applications. The incorporation of SM-AgNPs and curcumin-loaded NLPs enhanced the hydrogels' antibacterial properties.

An Emerging Toolkit of Ho Sensitized Lanthanide Nanocrystals with NIR-II Excitation and Emission for Bioimaging.

Optical imaging in the second near-infrared window (NIR-II, 1000-1700 nm) holds great promise for biomedical detection due to reduced tissue scattering and autofluorescence. However, the rational design of NIR-II probes with superior excitation wavelengths to balance the effects of tissue scattering and water absorption remains a great challenge. To address this issue, here we developed a series of Ho-sensitized lanthanide (Ln) nanocrystals (NaYF: Ho, Ln@NaYF) excited at 1143 nm, featuring tunable emissions ranging from 1000 to 2200 nm for bioimaging.

Rare Earth Complex-Based Functional Materials: From Molecular Design and Performance Regulation to Unique Applications.

ConspectusRare earth (RE) elements, due to their unique electronic structures, exhibit excellent optical, electrical, and magnetic properties and thus have found widespread applications in the fields of electronics, optics, and biomedicine. A significant advancement in the use of RE elements is the formation of RE complexes. RE complexes, created by the coordination of RE ions with organic ligands, not only offer high molecular design flexibility but also incorporate features such as a broad absorption band and efficient energy transfer of organic ligands.

Ligand-Induced Activation of Single-Atom Palladium Heterogeneous Catalysts for Cross-Coupling Reactions.

Single-atom heterogeneous catalysts (SACs) are potential, recoverable alternatives to soluble organometallic complexes for cross-coupling reactions in fine-chemical synthesis. When developing SACs for these applications, it is often expected that the need for ligands, which are essential for organometallic catalysts, can be bypassed. Contrary to that, ligands remain almost always required for palladium atoms stabilized on commonly used functionalized carbon and carbon nitride supports, as the catalysts otherwise show limited activity.

Phthalocyanine aggregates as semiconductor-like photocatalysts for hypoxic-tumor photodynamic immunotherapy.

Photodynamic immunotherapy (PIT) has emerged as a promising approach for efficient eradication of primary tumors and inhibition of tumor metastasis. However, most of photosensitizers (PSs) for PIT exhibit notable oxygen dependence. Herein, a concept emphasizing on transition from molecular PSs into semiconductor-like photocatalysts is proposed, which converts the PSs from type II photoreaction to efficient type I photoreaction.

Nucleophilic addition of bulk chemicals with imines using N-functionalized hydroxylamine reagents as precursors.

C-C and C-X bond forming reactions are essential tools in organic synthesis, constantly revolutionizing human life. Among the key methods for constructing new chemical bonds are nucleophilic addition reactions involving imines. However, the inherent challenges in synthesizing and storing imines have stimulated interest in designing stable precursors, which generates imines in situ during the reaction.

LiZrF protective layer enabled high-voltage LiCoO positive electrode in sulfide all-solid-state batteries.

The application of high-voltage positive electrode materials in sulfide all-solid-state lithium batteries is hindered by the limited oxidation potential of sulfide-based solid-state electrolytes (SSEs). Consequently, surface coating on positive electrode materials is widely applied to alleviate detrimental interfacial reactions. However, most coating layers also react with sulfide-based SSEs, generating electronic conductors and causing gradual interface degradation and capacity fading.

Efficient direct formic acid electrocatalysis enabled by rare earth-doped platinum-tellurium heterostructures.

The lack of high-efficiency platinum (Pt)-based nanomaterials remains a formidable and exigent challenge in achieving high formic acid oxidation reaction (FAOR) and membrane electrode assembly (MEA) catalysis for direct formic acid fuel cell (DFAFC) technology. Herein, we report 16 Pt-based heterophase nanotrepang with rare earth (RE)-doped face-centered cubic Pt (fcc-Pt) and trigonal Pt-tellurium (t-PtTe) configurations ((RE-Pt)-PtTe HPNT). Yttrium (Y) is identified as the optimal dopant, existing as single sites and clusters on the surface.

Screening of Plant UDP-Glycosyltransferases for Betanin Production in Yeast.

To cover the rising demand for natural food dyes, new sources and production methods are needed. Microbial fermentation of nature-identical colours, such as the red pigment betanin, has the potential to be a cost-efficient alternative to plant extraction. The last step of betanin production is catalysed by a UDP-glycosyltransferase (UGT).

Sensitive and accurate photoluminescent-multiphonon resonant Raman scattering dual-mode detection of microRNA-21 via catalytic hairpin assembly amplification and magnetic assistance.

A novel dual-mode detection method for microRNA-21 was developed. Photoluminescent (PL) and multiphonon resonant Raman scattering (MRRS) techniques were combined by using ZnTe nanoparticles as signal probes for reliable detection. The catalytic hairpin assembly (CHA) strategy was integrated with superparamagnetic FeO nanoparticle clusters (NCs) to enhance sensitivity.

Evolutionary origins of archaeal and eukaryotic RNA-guided RNA modification in bacterial IS110 transposons.

Transposase genes are ubiquitous in all domains of life and provide a rich reservoir for the evolution of novel protein functions. Here we report deep evolutionary links between bacterial IS110-family transposases, which catalyse RNA-guided DNA recombination using bridge RNAs, and archaeal/eukaryotic Nop5-family proteins, which promote RNA-guided RNA 2'-O-methylation using C/D-box snoRNAs. On the basis of conservation of protein sequence, domain architecture, three-dimensional structure and non-coding RNA features, alongside phylogenetic analyses, we propose that programmable RNA modification emerged through the exaptation of components derived from IS110-like transposons.

Innovative cross-linked electrospun PVA/MOF nanocomposites for removal of cefixime antibiotic.

In this study, we synthesized two nanocomposites, cross-linked PVA/HKUST and PVA/ZIF-67, by integrating metal-organic frameworks (MOFs) into electrospun polyvinyl alcohol (PVA). Several characterization techniques including FTIR, XRD, ICP, SEM, TGA, UV-Vis, zeta potential, and N adsorption-desorption were employed. The adsorption performance of the composites for cefixime (CFX) removal was assessed under varying conditions such as MOF content, contact time, pH, initial CFX concentration, and temperature.

General synthesis of neighboring dual-atomic sites with a specific pre-designed distance via an interfacial-fixing strategy.

A potential non-precious metal catalyst for oxygen reduction reaction should contain metal-N moieties. However, most of the current strategies to regulate the distances between neighboring metal sites are not pre-designed but depend on the probability by tuning the metal loading or the support. Herein, we report a general method for the synthesis of neighboring metal-N moieties (metal = Fe, Cu, Co, Ni, Zn, and Mn) via an interfacial-fixing strategy.

Nano-island-encapsulated cobalt single-atom catalysts for breaking activity-stability trade-off in Fenton-like reactions.

Single-atom catalysts (SACs) have been increasingly acknowledged for their performance in sustainable Fenton-like catalysis. However, SACs face a trade-off between activity and stability in peroxymonosulfate (PMS)-based systems. Herein, we design a nano-island encapsulated single cobalt atom (Co-ZnO) catalyst to enhance the activity and stability of PMS activation for contaminant degradation via an "island-sea" synergistic effect.

Structural basis for catalysis and selectivity of phospholipid synthesis by eukaryotic choline-phosphotransferase.

Phospholipids are the most abundant component in lipid membranes and are essential for the structural and functional integrity of the cell. In eukaryotic cells, phospholipids are primarily synthesized de novo through the Kennedy pathway that involves multiple enzymatic processes. The terminal reaction is mediated by a group of cytidine-5'-diphosphate (CDP)-choline /CDP-ethanolamine-phosphotransferases (CPT/EPT) that use 1,2-diacylglycerol (DAG) and CDP-choline or CDP-ethanolamine to produce phosphatidylcholine (PC) or phosphatidylethanolamine (PE) that are the main phospholipids in eukaryotic cells.

Synergistic enhancement of electrochemical alcohol oxidation by combining NiV-layered double hydroxide with an aminoxyl radical.

Electrochemical alcohol oxidation (EAO) represents an effective method for the production of high-value carbonyl products. However, its industrial viability is hindered by suboptimal efficiency stemming from low reaction rates. Here, we present a synergistic electrocatalysis approach that integrates an active electrode and aminoxyl radical to enhance the performance of EAO.

Efficient biodiesel production from waste cooking oil using a bifunctional Ce/Mn/γ-Al₂O₃ catalysts.

As the demand for sustainable energy sources intensifies, biodiesel emerges as a compelling renewable alternative to petroleum-based fuels. Leveraging waste cooking oil (WCO) as a feedstock not only offers an environmentally friendly fuel source but also addresses waste disposal issues. However, biodiesel production from WCO faces challenges, particularly due to its high free fatty acid (FFA) content, which can hinder efficient conversion and lead to soap formation in traditional alkaline-catalysed processes.

A cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systems.

Hybrid density functionals, such as B3LYP and PBE0, have achieved remarkable success by substantially improving over their parent methods, namely Hartree-Fock and the generalized gradient approximation, and generally outperforming the second-order Møller-Plesset perturbation theory (MP2) that is more expensive. Here, we extend the linear scheme of hybrid multiconfiguration pair-density functional theory (HMC-PDFT) by incorporating a cross-entropy ingredient to balance the description of static and dynamic correlation effects, leading to a consistent improvement on both exchange and correlation energies. The B3LYP-like translated on-top functional (tB4LYP) developed along this line not only surpasses the accuracy of its parent methods, the complete active space self-consistent field (CASSCF) and the original MC-PDFT functionals (tBLYP and tB3LYP), but also outperforms the widely used complete active space second-order perturbation theory (CASPT2).