Precision Chemistry最新文献

Hydrogen sulfide (H₂S) is a signaling molecule with a plethora of biological functions, yet precision tools for modulating its intracellular flux remain scarce. Conventional small-molecule donors and enzymatic systems often suffer from off-target reactivity, uncontrolled release kinetics, and redox crosstalk, confounding mechanistic studies. Here, we establish a Salmonella typhimurium d-cysteine desulfhydrase (stDCyD)-derived chemogenetic tool for controlled H₂S manipulation in living cells. stDCyD catalyzes the α,β-elimination of d-cysteine to selectively yield bioavailable H₂S. We term this tool H₂SWITCH. Our approach exhibits pronounced enantioselectivity for d-cysteine, robust catalytic efficiency at physiological temperatures, and temporal tunability through substrate dosing. This chemogenetic tool provides a chemically defined and interference-free method to unravel the physiological and pathological roles of H₂S with unprecedented precision in complex biological systems.

Carbon nanotubes (CNTs) exhibit remarkable properties that have spurred extensive exploration across domains such as integrated circuits, aerospace, and energy storage. With application scenarios becoming increasingly specialized, the structure-controllable synthesis of CNTs faces escalating challenges. This review summarizes chemical vapor deposition (CVD) techniques for controlled CNT synthesis and examines the structural-control mechanisms during growth, emphasizing the critical factors influencing CNT diameter, electronic properties, and chirality. Conventional trial-and-error approaches have become inadequate in addressing the demands for precise structural manipulation during synthesis and complex variable optimization in scaled production. Recently, artificial intelligence (AI) has substantially advanced scientific research and technological innovation. In the concluding perspective, we highlight emerging paradigms that incorporate AI into CNT synthesis, where the synergy between data-driven experimentation and physics-informed constraints may enable the development of accurate and efficient digital twins of CNT growth systems. Such approaches offer promise for the inverse design of synthesis routes and deeper insight into structure-control mechanisms. We conclude by identifying promising directions for AI-enhanced CNT synthesis, including multiscale computational simulations, catalyst design, automated experimental platforms, and pilot-scale production, which may collectively advance the Frontier of precision nanomanufacturing.

Macrolactones are structurally important motifs that are found in a variety of natural products. While conventional approaches to their synthesis involve the use of seco acids with condensing agents or activators, methods based on hydroxyaldehydes as substrates remain relatively unexplored. Furthermore, the development of macrolactonization reactions that proceed via radical processes is still in its infancy, and to date, examples that use hydroxyaldehydes have not yet been reported. In this study, a photochemical macrolactonization of hydroxyaldehydes via in-situ-generated acyl bromide intermediates has been developed. Lactones with ring sizes ranging from 7-21 were successfully obtained in a good yield. The present photochemical radical macrolactonization therefore represents a promising tool for the synthesis of natural products.

Herein, we introduce a straightforward synthesis approach for highly active dendritic multimetallic high-entropy alloy (DMHEA@PtIrPdAgRu) nanoparticles with sufficient entropic mixing, featuring uniform distribution of five noble group metals (Pt, Ir, Pd, Ag, and Ru) via a block copolymer-mediated one-pot solvothermal reduction method for oxygen evolution reaction (OER). In this synthesis, N,N-dimethylformamide (DMF) is used as a reductant as well as solvent and core-shell-corona-type (poly-(styrene)-block-poly-(vinylpyridine)-block-poly-(ethylene oxide)) (PS-PVP-PEO) block copolymer as a structure directing agent. The cooperative effect between the copolymer architecture and the reducing environment of DMF promoted a confined nucleation mechanism for forming a single-phase dendritic structure HEA with high compositional uniformity, thereby mitigating phase segregation, a common challenge in the synthesis of multimetallic nanoparticles. This prepared DMHEA@PtIrPdAgRu catalyst exhibits a low overpotential of 490 mV to attain a high current density of 100 mA cm^-2 with a Tafel slope of 442 mV dec^-1 for oxygen evolution. The superior OER performance is attributed to the synergistic cooperation among its active and coordinated metal centers as well as the incorporation of corrosion-resistant metal like platinum.

Synthesis and application of polysubstituted 2-pyrones have attracted a great deal of attention over the past several decades. Recently, transition metal-catalyzed transformations of propargylamines have emerged as a powerful strategy for accessing diverse heterocyclic frameworks. Here, we report an efficient protocol for the synthesis of structurally diverse 4,6-disubstituted 2-pyrones from readily available propargylamines and malonates. Mechanistic investigations reveal that this formal [1 + 2 + 3] annulation reaction proceeds via a sequential copper-catalyzed oxidative cross-dehydrogenative coupling, 1,3-amino migration, and acid-promoted deaminative cyclization in a one-pot operation. The method exhibits broad functional group tolerance, providing a versatile and robust platform for the rapid assembly of heterocyclic libraries. Furthermore, the synthetic utility of this methodology is demonstrated through further transformations of the obtained products, highlighting its practical value in organic synthesis.

The widespread use of polymeric materials has brought unparalleled convenience and utility, but their environmental persistence presents a critical and growing challenge. As demand increases for sustainable solutions to polymer waste, depolymerization continues to be a promising strategy for achieving true circularity. In this Perspective, we examine depolymerization from a fundamental standpoint, aiming to rationalize the advantages, limitations, and future directions of state-of-the-art technologies. We advocate for standardized reporting practices to enable meaningful comparisons across studies and, in alignment with this goal, we provide key metrics and contextual information throughout the article to support consistent evaluation of different depolymerization strategies. Ultimately, we hope to inspire readers to explore innovative and scalable solutions that advance the transformative potential of depolymerization toward the realization of a circular polymer economy.

Photocatalytic hydrogen (H₂) evolution integrated with selective oxidation offers a prominent pathway for sustainable energy production and high-value chemical production. Metal sulfide-based photocatalysts (named MSP) have gained attention due to their appropriate band alignments, strong light absorption, and adjustable surface characteristics. This review systematically summarizes recent advances in MSP design for coupled H₂ production and selective oxidation of representative organic molecules, including benzyl alcohol (BA), furfural alcohol (FFA), 5-hydroxymethylfurfural (HMF), benzylamine (BAm), and lactic acid (LA). Particularly, we highlight their photocatalytic performance and charge transfer mechanisms. Finally, this review presents current challenges and future strategies for designing efficient and industrially feasible photocatalytic systems.