This study reports a simple and efficient photocatalytic radical cascade cyclization strategy for the one-step synthesis of allyl- and vinyl-sulfonyl fluorides bearing dibenzazepine or dioxodibenzothiazepine scaffolds. In contrast to the existing synthesis methods of allyl sulfonyl fluoride, this approach employs aryl-terminal alkynes as starting materials, thereby avoiding the reliance on preformed allylic frameworks. The reaction utilizes inexpensive and readily accessible -CH2SO2F and -SO2F precursors, exhibits a broad substrate scope, proceeds under mild conditions, and delivers high stereoselectivity. The synthetic utility of this methodology was further demonstrated through SuFEx-based ligation with other molecules.

Abstract This study reports a novel class of bench-stable, oxime ester-derived bifunctional fluorosulfamoyl reagents for photosensitized 1,n-fluorosulfonamidylimination of alkenes. Upon visible-light irradiation, these reagents undergo energy-transfer-mediated homolysis, simultaneously generating a transient fluorosulfonamide radical and a persistent iminyl radical. This dual-radical system enables efficient 1,2- and 1,4-fluorosulfonamidylimination of alkenes, thereby providing direct access to valuable amino-aliphatic sulfamoyl fluorides under mild conditions. The utility of this method is demonstrated by the late-stage modification of bioactive molecules and further diversification of products via SuFEx click chemistry and selective deprotection.

We report a photoredox strategy for radical-initiated ring-opening fluorosulfonamidation/fluorosulfonylmethylation of methylenecyclobutanols using NFSAP (N-fluorosulfamoylpyridinium salts) and BMSF (bromomethylsulfonyl fluoride) as the respective radical sources. This approach provides efficient access to FSO2CH2-/FSO2N-functionalized γ,δ-unsaturated carbonyl compounds─both FSO2CH2-/FSO2N and γ,δ-unsaturated carbonyl motifs are useful structural scaffolds─while offering good scalability and broad compatibility with postderivatization reactions.

Poly-beta-hydroxybutyrate (PHB) has emerged as a promising biodegradable polymer with extensive potential for diverse applications. When modified with chitosan (CS), PHB demonstrates enhanced metal-loading capabilities, significantly expanding its utility in environmental fields. In this study, a green heterobimetallic gold (Au) and palladium (Pd) catalyst (designated as Au/Pd@PHB-CS), was synthesized through a sequential coordination reduction process on the surface of the PHB-CS nanosphere. The resulting bimetallic nanoparticles on the nanosphere predominantly exhibit a particle size of approximately 4.0 +/- 0.9 nm and expose a substantial number of highly active crystal planes. Catalysts possess adsorption capacities for three pollutants: congo red (CR), methylene blue (MB) and 4-nitrophenol (4-NP). Besides, catalysts with low bimetallic loading of Au (0.11 wt%) and Pd (0.11 wt%) show significant removal efficiencies for the three pollutants. Notably, in the degradation of CR, the catalyst exhibits complete reduction of CR with exceptionally fast reaction kinetics. Furthermore, the catalyst maintains a high catalytic activity (95 %) after multiple cycles of utilization. Compared to monometallic Au or Pd catalysts, bimetallic catalysts exhibit significantly enhanced reaction activity due to the synergistic interaction between the two metal components. This improved catalytic performance underscores the potential of PHB-based materials as effective catalyst supports, broadening their research and application prospects in catalysis.

There are abundant wind and solar resources in Northwest China, but it is extremely difficult for the local power grid to accommodate them. Renewable power-to-methanol (RePtM) is a viable approach for utilizing surplus renewable energy. Due to its high energy density and low storage costs, methanol shows significant promise for large-scale and long-term energy storage. However, the large-scale and long-distance transportation of methanol remains a critical issue. This paper investigates how to boost the multi-product pipeline to transport methanol in Northwest China. First, a comprehensive RePtM model that incorporates the dynamic production, storage, and transportation of methanol is integrated into the coupled power–hydrogen–methanol–oil system. Second, a detailed single-source and multi-destination transportation model that takes into account the downstream demand for methanol is developed by fully utilizing the remaining capacity of existing multi-product pipelines. Third, a medium-to-long term coordinated scheduling model for the coupled power–hydrogen–methanol–oil system is presented and verified using a real-world test system in Northwest China. Case studies indicate that the pipeline transportation cost is only 14.7%–49.0% of the truck transportation cost, demonstrating the effectiveness and feasibility of the proposed model.

Gene therapy for cancer faces challenges like enzymatic degradation and low delivery efficiency. This study developed a multifunctional nanoplatform (AuNRs@apt-siRNA-GQs/PPIX) integrating gene, photodynamic, and photothermal therapies. Gold nanorods (AuNRs) served as the carrier, with AS1411 aptamer enabling targeting to nucleolin-overexpressing cells, and G-quadruplex (GQ, T30695) plus aptamer complex loading CHK1-siRNA and photosensitizer PPIX. The nanocomplex had high loading efficiencies (87.9% for apt-siRNA-GQs, 83.5% for PPIX), and its synthesis was confirmed by TEM/EDS and FTIR (Au-S bond at 615 cm−1). It showed good stability in nucleases, FBS, and different pH buffers. Under NIR irradiation, AuNRs’ photothermal effect enhanced PPIX-generated ROS, triggering CHK1-siRNA release. In vitro, it accumulated 4-fold more in HeLa cells than normal L-02 cells, induced ~40.18% apoptosis in HeLa cells (minimal toxicity to L-02 cells, survival >50%), and silenced CHK1 by 70% at mRNA level (qPCR/Western blot). This novel ROS-responsive co-delivery strategy combines aptamer targeting, GQ-based loading, and triple-modal synergy, providing a promising platform for combinatorial cancer therapy.

Nanozymes show great potential as alternatives to natural enzymes. Covalent organic frameworks (COFs) have attracted huge attention for the design of nanozymes due to their unique structures and intriguing properties. Incorporation of appropriate building blocks into COFs can endow them with specific properties, allowing the possibility to design highly efficient COF-based nanozymes. Herein, a heteroporous COF (COF-P5-OH-Fe) was designed and constructed by introducing pillar[5]arenes with polyphenol structures into the porphyrin-based COFs through post-modification strategies, and subsequently, Fe was further modified on the COFs through coordination. The obtained COF-P5-OH-Fe nanozyme showed outstanding peroxidase-like activity, the catalytic activity of which could be enhanced efficiently under light irradiation. The unique polyphenol motif of pillar[5]arenes endows COF-P5-OH-Fe with a narrow energy band gap and enhanced photocurrent and improves the circulation of Fe3+/Fe2+. As a result, the activity of COF-P5-OH-Fe nanozyme was enhanced to generate reactive oxygen species, enabling efficient antibacterial action. In particular, the absorption wavelength of the COF-P5-OH-Fe nanozyme, which was around 986 nm, enabled it to exhibit superior photo-enhanced bactericidal activity under near-infrared light irradiation. Furthermore, the antibacterial mechanism was also investigated by genome-wide transcriptome analysis using RNA sequencing.

Electron transport layers comprising colloidal ZnO nanocrystals are commonly utilized in PbS quantum dot solar cells. However, the presence of surface defects induced by oxygen vacancies and surface hydroxyls poses a significant obstacle to high-performance device. Consequently, there is an urge for realizing ZnO nanocrystals with reduced surface defects. Herein, we developed an in-situ passivation strategy for synthesizing ZnO nanocrystals, denoted as Cl/K-ZnO, with suppressed surface defects by Cl/K ions. The integration of the Cl/K-ZnO electron transport layer into the photovoltaics has led to a remarkable decrease in surface defects and reasonable energy band alignment for better carrier extraction. Accordingly, we achieved the efficient photovoltaics with a champion power conversion efficiency of 11.17 % and an impressive operational stability, retained 83 % of the initial power conversion efficiency after an operation period of 200 h under AM 1.5 G illumination in N2 glovebox.

Sulfonyl/sulfamoyl fluoride and tetrahydropyridazine cores represent pivotal structural units in chemical and medicinal science. We herein disclose a photocatalytic strategy for the fluorosulfonylation/fluorosulfonamidation of N-homoallyl aldehyde hydrazones using FABI (1-fluorosulfonyl-2-arylbenzoimidazolium triflate salts) and NFSAP (N-fluorosulfamoylpyridinium salts), enabling efficient access to sulfonyl-/sulfamoyl-substituted tetrahydropyridazines. This protocol demonstrates excellent synthetic scalability and facilitates diverse postderivatization reactions, including SuFEx click reactions and elimination processes. Preliminary mechanistic studies reveal that the transformation proceeds via a fluorosulfonyl/fluorosulfonamidyl radical-mediated cascade cyclization pathway.

Covalent organic frameworks (COFs) serve as suitable templates for constructing photocontrol nanozymes due to their highly tunable skeletons and controllable porous channels. Unfortunately, the development of high-performance COFs remains challenging because of their narrow absorption bandwidth, rapid electron-hole separation or recombination, and other limitations. Herein, a polyethylene glycol (PEG) engineering strategy is developed to construct high-efficiency photocontrol oxidase (OXD) mimics based on COFs. A series of COFs with PEG side chains were synthesized through the condensation of an N-containing aldehyde ligand (TPY) with PEGylated amine ligands, which were decorated with PEG chains of different lengths. By introducing PEG chains, the electron-hole recombination of COFs can be slowed down, while electron-hole separation is accelerated; meanwhile, the affinity between COFs and the substrate can be enhanced, thereby improving the photoactive OXD-like activity of COFs. The N atom in TPY induces a red shift in the band-edge absorption of COFs and reduces the band gap, further improving their light absorption performance. Notably, COF-TPY-4O exhibited greater activity than other COFs. As a proof of concept, COF-TPY-4O was used for the construction of biosensors and elimination of bacteria, demonstrating its potential as a photoactive nanozyme with good application prospects. This study highlights the construction of highly active photocontrol nanozymes through PEG engineering.

Hydrazine had important applications in medicine, the chemical industry, and agriculture, but hydrazine pollution was also very harmful to human beings. Chemists have reported many types of hydrazine fluorescent probes. However, it was still challenging to continuously improve the selectivity and sensitivity of hydrazine fluorescent probes. Here, we designed and synthesized a novel NH2NH2 fluorescent probe based on the neighboring group participation (NGP). We choose bromine and chlorine as the neighboring group respectively. The probe had good anti-interference ability. The detection limits to hydrazine were 0.027 mu M (probe A) and 0.054 mu M (probe B). The sensing mechanism was confirmed by 1H NMR, 13C NMR, and FT-IR. Theoretical calculation showed that the energy barrier could be reduced by NGP. In terms of application, the probe has the function of quantitative detection of hydrazine in actual water samples.

Screening carbonyl reductases with the ability to catalyze the reduction of complex carbonyl compounds is of great significance for the biosynthesis of R-tolvaptan(R-TVP). In this study, the target carbonyl reductase in the crude enzyme extract of rabbit liver was separated, purified, and identified by ammonium sulfate precipitation, gel-filtration chromatography, ion exchange chromatography, affinity chromatography, and protein mass spectrometry. With the rabbit liver genome as the template, the gene encoding the carbonyl reductase rlsr5 was amplified by PCR and the recombinant strain was successfully constructed. After RLSR5 was purified by affinity chromatography, its enzymatic properties were characterized. The results indicated that the gene sequence of rlsr5 was 972 bp, encoding a protein with a molecular weight of 40 kDa. RLSR5 was a dimeric protein, and each monomer was composed of a (α/β)8-barrel structure. RLSR5 could asymmetrically reduce 7-chloro-1-[2-methyl-4-[(2- methylbenzoyl)amino]benzoyl]-5-oxo-2,3,4,5-tetrahydro-1H-1-benzazepine (prochiral ketone, PK) to synthesize R-TVP. The specific activity of the enzyme was 36.64 U/mg, and the optical purity of the product was 99%. This enzyme showcased the optimal performance at pH 6.0 and 30 °C. It was independent of metal ions, with the activity enhanced by Mn2+. This study lays a foundation for the biosynthesis of tolvaptan of optical grade.

Multicolor detection and image transmission technologies across multiple wavelengths exhibit great application prospects in the fields of autonomous driving, security monitoring, biological imaging, and related fields. However, despite significant advances in perovskite-based multicolor detection, achieving high performance and stability in complex perovskite systems remains a considerable challenge. In this work, the first controlled synthesis of vertical-standing bandgap-tunable CsPb(Br1- xIx)3 (x = 0 to 1) triangular nanoplates is reported via a CVD method combined with elemental substitution. The synthesized CsPb(Br1- xIx)3 triangular nanoplates exhibit lateral dimensions up to several tens of micrometers and tunable photoluminescence ranging from green (530 nm, 2.34 eV) to red (709 nm, 1.75 eV). Furthermore, photodetectors based on the CsPb(Br1- xIx)3 perovskite demonstrate high-performance detection and image transmission at specific wavelengths (520, 590, and 660 nm). More importantly, by integrating customized perovskite devices with a neural network algorithm, a traffic light recognition system is developed with a recognition accuracy of 92.78%. The vertical-standing, bandgap-tunable perovskite materials represent a promising material platform for integrated photonics, with broad potential in multicolor detection, display technologies, and intelligent sensing applications.

An in vivo self-assembly strategy was developed to overcome the limitation of traditional enzyme immobilization methods. An engineered E. coli system was employed to immobilize carbonyl reductase (LcCR) onto intracellular polyhydroxyalkanoate (PHA) microspheres, which was realized by fusion expression of LcCR with covalent PhaC or non-covalent PhaP. The fusion of LcCR and PHA surface binding proteins (Phac, PhaP) was optimized by adjusting the fusion direction (C/N end) and replacing peptide linkers (GSA, (G4S)3, (G4S)4). The expression form for fusion of N-terminal of LcCR with three series connected PhaP, LcCR@PHA-3PhaP, showed the highest enzyme load and enzyme activity recovery rate of 36.8 % while maintaining the intact morphology of PHA particles. This immobilized enzyme was used for the catalytic reduction of the carbonyl compound 2-chloro-1-(3,4-difluorophenyl) ethanone (CFPO) to the corresponding chiral alcohol, (1S)-2-chloro-1-(3,4-difluorophenyl) ethanol ((S)-CFPL), achieving both high enantioselectivity (98.5 % e.e.) and specific operational stability (75.0 % activity retention after eight reuse cycles). These findings establish fundamental design principles for engineered self-assembled biocatalysts while providing a robust and economic platform for industrial biotransformation.

A size-controlled polyhydroxyalkanoate (PHA) nanosphere, loaded with the amphiphilic cationic peptide melittin (Mel), was synthesized using E. coli to enhance the stability and delivery efficiency of Mel. It demonstrated that Mel efficiently mediated the delivery of plasmid DNA into cancer cells at concentrations below 1 μmol/L. To enhance Mel's expression, it was genetically fused with the PHA granule-associated protein (PhaP) through recombinant engineering. The fusion gene was inserted into the pET-28a(+) and transformed into an E. coli capable of synthesizing PHA nanospheres. This engineered strain not only produced Mel-PHA nanospheres but also regulated their size to approximately 100 nm under the control of PhaP, with a Mel loading concentration of 9.9 μmol/L. The purified Mel-PHA nanospheres could adsorb CRISPR/Cas12a plasmids. Optimal adsorption conditions were achieved by incubating the nanospheres and plasmids at 37 °C in PBS with a pH of 5.35 for 1 h, yielding a mass ratio of 2:1. Under simulated in vitro physiological conditions, the Mel-PHA@CRISPR exhibited stability in a culture medium containing fetal bovine serum for 24 h. Furthermore, the Mel-PHA@CRISPR were effectively internalized by HEK 293 A cells. This study successfully developed a self-assembled and size-controlled nanocarrier within E. coli for the delivery of CRISPR plasmids.

This study reported a novel and unprecedented photoredox-catalyzed protocol for direct allylic C-H fluorosulfonylation of alkenes with FABI. This mild protocol exhibited excellent compatibility with various functional groups, broad substrate scope, and promising scalability, enabling convenient access to a wide range of allyl sulfonyl fluorides with exceptional regioselectivity. The synthetic robustness of this strategy was further demonstrated by the late-stage functionalization of natural products and their ligation with other drugs via SuFEx chemistry.

Amphiphilic cationic peptide (ACP) is a widely studied biofilm-active peptide that has great potential in cancer treatment. However, poor stability, a short half-life, and complex preparation pose significant challenges for practical therapeutic applications. In the current investigation, the amphiphilic peptide Melittin (Mel), recognized for its powerful anticancer properties, was chosen from natural and synthetic ACP, and integrated into a nanostructure by utilizing polyhydroxyalkanoate (PHA) microspheres as carriers to produce Mel-loaded PHA microspheres (Mel@PHA-PhaC). Mel@PHA-PhaC nanostructure was self-assembled in Escherichia coli, simplifying its preparation and making it more convenient and high-yield. Mel@PHA-PhaC were spherical, with a particle size of approximately 300 nm, as observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The concentration of Mel in Mel@PHA-PhaC was 4 μg/mg. Mel@PHA-PhaC still maintained good stability after being treated with pancreatic enzymes. Furthermore, in vitro experiments demonstrated that Mel@PHA-PhaC enhanced the inhibitory effect on cancer cells compared to free Mel. This study provides insights and guidelines for the development and utilization of peptide delivery systems using PHA microspheres to create stable and improved peptides for cancer therapy.

Recently, the radical fluorosulfonylation of alkenes is emerging as an appealing strategy for the rapid construction of diverse sulfonyl fluorides, which are in high demand across various scientific disciplines, particularly in chemical biology and drug discovery. However, most existing methodologies have primarily focused on the vicinal difunctionalization of C=C bonds, while the selective allylic C-H fluorosulfonylation of alkenes remains an underexplored and challenging transformation. This study reported a novel and unprecedented photoredox-catalyzed protocol for direct allylic C-H fluorosulfonylation of alkenes with FABI (1-fluorosulfonyl 2-aryl benzoimidazolium triflate salts). This mild protocol exhibited excellent compatibility with various functional groups, broad substrate scope, and promising scalability, enabling convenient access to a wide range of allyl sulfonyl fluorides with exceptional regioselectivity. The synthetic robustness of this strategy was further demonstrated by the late-stage functionalization of natural products and their further ligation with other drugs via SuFEx chemistry. Experimental and theoretical analyses indicated that this transformation proceeds through a photoredox mechanism, where the selective formation of allylic sulfonyl fluorides was governed by both the dynamics and thermodynamic processes.

In this report, we describe a copper-catalyzed cascade reaction involving oxygen radical-induced cyclization/SO2 insertion/fluorination of β,γ-unsaturated oximes with sulfur dioxide and Selectfluor under mild conditions for the synthesis of isoxazoline-functionalized aliphatic sulfonyl fluorides. The synthetic potential of these compounds has been evaluated through diverse SuFEx reactions.