摘要：
The contamination of drinking water by microbes is a critical health concern, underscoring the need for safe, reliable, and efficient methods to treat pathogenic microorganisms. While most sterilization materials are available in powder form, this presents safety risks and challenges in recycling. Herein, this study reports the preparation of an innovative copper oxide supported silver monolithic nanoarray mesh with abundant oxygen vacancies (Ag/CuO-V(O)) by laser ablation. The instantaneous high temperature caused by laser ablation preserves the material's original structure while generating oxygen vacancies on the CuO surface. The Ag/CuO-V(O) mesh demonstrated a remarkable ability to inactivate over 99% of Escherichia coli (E. Coli) within 20min. The oxygen vacancies in the Ag/CuO-V(O) enhance interactions between oxygen species and the Ag/CuO-V(O), leading to the accumulation of large amounts of reactive oxygen species (ROS). The generated ROS effectively disrupt both layers of the bacterial cell wall - the peptidoglycan and the phospholipid - as confirmed by Fourier Transform Infrared (FTIR) spectroscopy, culminating in cell death. This research presents a monolithic material capable of inactivating pathogenic microorganisms efficiently, offering a significant advancement in water sterilization technology.
摘要：
Spinel cobalt oxide (Co3O4), consisting of tetrahedral Co2+ (CoTd) and octahedral Co3+ (CoOh), is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction (CER). Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER. Herein, combining density functional theory calculations and experiment results assisted with operando analysis, we found that the CoOh site acts as the main active site for CER in spinel Co3O4, which shows better Cl- adsorption and more moderate intermediate adsorption toward CER than CoTd site, and does not undergo redox transition under CER condition at applied potentials. Guided by above findings, the oxygen vacancies were further introduced into the Co3O4 to precisely manipulate the electronic configuration of CoOh to boost Cl- adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly. Our work figures out the importance of geometric configuration dependent CER activity, shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level. (c) 2023 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press
摘要：
Water molecules are actively involved in many catalytic oxidation processes, which require the construction of highly active sites for their activation to accelerate the reaction rate, especially over non-noble metal catalysts. Herein, K species is embeded into the natural 2*2 channel of alpha-MnO2 by a hydrothermal coupled molten salt method, which would make these K species behave in an electron-rich state and provide more electrons for the activation of water molecules. Compared with surface K modification (namely, the electron-deficient K species), channel K confinement can lower the activation energy barrier of H2O dissociation on alpha-MnO2 to generate hydroxyl species with more nucleophilic oxygen atoms, contributing to the superior HCHO catalytic oxidation activity with a fourfold enhancement. The internal relationship among the confined channel, K species, and catalytic performance is systematically elucidated at the molecular level. This work offers a new ion confinement method and opens up new avenues to construct electron-rich metal sites with channel structures for the activation of water molecules.
摘要：
A visible‐light‐driven four‐component radical relay aminocarbonylation reaction of unactivated alkenes using 4CzIPN as an organic photocatalyst is developed, providing robust access to β‐fluoroalkyl amides with good yields and selectivity under metal‐free conditions. Importantly, this strategy also shows good compatibility with tertiary carbon radicals. Comprehensive Summary Catalytic four‐component radical carbonylation of unactivated alkenes has recently been recognized as a robust protocol for rapid construction of various structurally diverse carbonyl compounds. Given the significance of fluorine‐containing groups, this reaction class has been extensively applied to assembly of a variety of perfluoroalkyl carboxylic acid derivatives by transition metal catalysis. Herein, we report a visible‐light‐driven radical relay 1,2‐perfluoroalkylation aminocarbonylation of unactivated alkenes using CO gas as carbonyl source and 4CzIPN as organic photocatalyst. A wide range of alkenes and amines were well tolerated, providing the valuable β‐perfluoroalkylated amides with generally good yields and high chemoselectivity.
期刊：
JOURNAL OF ORGANIC CHEMISTRY,2024年89(6):3941-3953 ISSN：0022-3263
作者机构：
[Wang, Jun-Gang; Ma, Lin-Lin] School of Chemical Engineering, Guizhou Minzu University, Guiyang, Guizhou 550025, P. R. China;[Wang, Zheng-Hao; Tang, Yong-Xing; Zhou, You; Chen, Ting; Wu, An-Xin; Wu, Yan-Dong] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
摘要：
An efficient synthetic method for constructing 2,3- and 2,4-disubstituted pyrimidio[1,2-b]indazole skeletons through I(2)-DMSO-mediated and substrate-controlled regioselective [4 + 2] cyclization is reported. The reaction conditions are mild, its operation is simple, and the substrate scope is wide. More than 60 pyrimidio[1,2-b]indazole derivatives have been synthesized, providing a new methodology for constructing related molecules and potentially enriching bioactive-molecule libraries.
期刊：
CHEMISTRY-A EUROPEAN JOURNAL,2024年:e202303742 ISSN：0947-6539
通讯作者：
Li, HB
作者机构：
[Chen, Chunxiu; Li, Guang; Xu, Weiwei; Cai, Meng; Li, Haibing; Ma, Cuiguang; Li, HB; Zhang, Haifan; Noruzi, Ehsan Bahojb; Qu, Haonan] Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Li, Haibing; Li, HB] Guangxi Univ, State Key Lab Featured MetaMat & Life Cycle Safety, Nanning 530004, Peoples R China.;[Wang, Miao] Xiamen Univ, Coll Mat, Xiamen 361005, Peoples R China.;[Hou, Xu] Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China.
通讯机构：
[Li, HB ] C;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Guangxi Univ, State Key Lab Featured MetaMat & Life Cycle Safety, Nanning 530004, Peoples R China.
关键词：
Fluoride ion, Pillar[5]arene polymer, Nanochannel membrane, Green agriculture
摘要：
Excess fluoride ions in groundwater accumulate through the roots of crops, affecting photosynthesis and inhibiting their growth. Long-term bioaccumulation also threatens human health because it is poorly degradable and toxic. Currently, one of the biggest challenges is developing a unique material that can efficiently remove fluoride ions from the environment. The excellent properties of functionalized pillar[5]arene polymer-filled nanochannel membranes were explored to address this challenge. Constructing a multistage porous nanochannel membrane, consisting of microscale etched nanochannels and nanoscale pillar[5]arene cross-linked polymer voids. A fluoride removal rate of 0.0088 mmol & sdot; L-1 & sdot; min-1 was achieved. Notably, this rate surpassed the rates observed with other control ions by a factor of 6 to 8.8. Our research provides a new direction for developing water fluoride ion removal materials. Fluoride contamination of groundwater has become one of the most serious problems in the world. Currently, excessive absorption of fluoride can be toxic to humans and crops. To address the challenge, we explored the excellent properties of functionalized pillar[5]arene polymer framework. By constructing a multistage porous nanochannel membrane, the pillar[5]arene polymer-filled nanochannel membrane achieves a fluoride removal. image
摘要：
CsPbBr(3) has received more and more attention in the field of optoelectronic devices due to its excellent stability. To address the cost and environmental concerns associated with the use of toxic methanol, water has been explored as a substitute solvent for CsBr in the preparation of CsPbBr(3) perovskite solar cells (PSCs). In this study, we utilized methanol as an anti-solvent of the CsBr/H(2)O solution to regulate the detrimental effects of water on the CsPbBr(3) film and control the crystallization process. From results of the experiment, it was found that methanol anti-solvent treatment greatly improved the crystallization of the CsPbBr(3) film, increased the grain size, and reduced the defect density. After the introduction of methanol anti-solvent treatment, the power conversion efficiency (PCE) increased from 6.09% to 7.91%, while the open-circuit voltage (V(oc)) increased from 1.18 V to 1.39 V. Furthermore, we incorporated 2-hydroxyethylurea into the CsPbBr(3) PSCs to improve the wettability of PbBr(2) towards the CsBr/H(2)O solution and ensure the formation of pure-phase CsPbBr(3) films. The introduction of 2-hydroxyethylurea resulted in an additional increase in V(oc) from 1.19 V to 1.42 V. The PCE further improved from 6.56% to 8.62% after methanol anti-solvent treatment. These results demonstrate that methanol treatment effectively addresses the low V(oc) issue observed in CsPbBr(3) PSCs prepared with water as a solvent. Importantly, this approach significantly reduces the reliance on methanol compared to conventional fabrication methods for CsPbBr(3) PSCs. Overall, this work presents a promising pathway for achieving high V(oc) and efficiency in CsPbBr(3) PSCs by utilizing water as a solvent.
摘要：
Poly(ionic liquid)s (PILs) bearing high ionic densities are promising candidates for carbon dioxide (CO(2)) fixation. However, efficient and metal-free methods for boosting the catalytic efficiencies of PILs are still challenging. In this study, a novel family of poly(ionic liquid)-coated carbon nanotube nanoarchitectures (CNTs@PIL) were facilely prepared via a noncovalent and in-situ polymerization method. The effects of different carbon nanotubes (CNTs) and PILs on the structure, properties, and catalytic performance of the composite catalysts were systematically investigated. Characterizations and experimental results showed that hybridization of PIL with hydroxyl- or carboxyl-functionalized CNTs (CNT-OH, CNT-COOH) endows the composite catalyst with increased porosity, CO(2) capture capacity, swelling ability and diffusion rate with respect to individual PIL, and allows the CNTs@PIL to provide H-bond donors for the synergistic activation of epoxides at the interfacial layer. Benefiting from these merits, the optimal composite catalyst (CNT-OH@PIL) delivered a super catalytic efficiency in the cycloaddition of CO(2) to propylene oxide, which was over 4.5 times that of control PIL under metal- and co-catalyst free conditions. Additionally, CNT-OH@PIL showed high carbon dioxide/nitrogen (CO(2)/N(2)) adsorptive selectivity and could smoothly catalyze the cycloaddition reaction with a simulated flue gas (15% CO(2) and 85% N(2)). Furthermore, the CNT-OH@PIL exhibited broad substrate tolerance and could be readily recycled and efficiently reused at least 12 times. Hybridization of PIL with functionalized CNTs provides a feasible approach for boosting the catalytic performance of PIL-based solid catalysts for CO(2) fixation.
摘要：
Nanozymes with peroxidase (POD)-like activity have garnered significant attention due to their exceptional performance in colorimetric assays. However, nanozymes often possess oxidase (OD) and POD-like activity simultaneously, which affects the accuracy and sensitivity of the detection results. To address this issue, inspired by the catalytic pocket of natural POD, a single-atom nanozyme with FeN(5) configuration is designed, exhibiting enhanced POD-like activity in comparison with a single-atom nanozyme with FeN(4) configuration. The axial N atom in FeN(5) highly mimics the amino acid residues in natural POD to optimize the electronic structure of the metal active center Fe, realizing the efficient activation of H(2)O(2). In addition, in the presence of both H(2)O(2) and O(2), FeN(5) enhances the activation of H(2)O(2), effectively avoiding the interference of dissolved oxygen in colorimetric sensing. As a proof-of-concept application, a colorimetric detection platform for uranyl ions (UO(2)(2+)) in seawater is successfully constructed, demonstrating satisfactory sensitivity and specificity.
期刊：
Sensors and Actuators B-Chemical,2024年405 ISSN：0925-4005
通讯作者：
Xu, Miao;Gu, WL;Ye, HR
作者机构：
[Xu, Weiqing; Chen, Yifeng; Zhu, Chengzhou; Xu, Miao; Sha, Meng; Zou, Chufan; Gu, Wenling; Chen, Guo] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Ye, Huarong; Ye, HR] China Resources & Wisco Gen Hosp, Wuhan 430080, Peoples R China.;[Zhu, Chengzhou] Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 311121, Peoples R China.;[Gu, Wenling] Hubei Univ, Sch Life Sci, State Key Lab Biocatalysis & Enzyme Engn, Wuhan 430062, Peoples R China.
通讯机构：
[Xu, M; Gu, WL ; Ye, HR ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;China Resources & Wisco Gen Hosp, Wuhan 430080, Peoples R China.;Hubei Univ, Sch Life Sci, State Key Lab Biocatalysis & Enzyme Engn, Wuhan 430062, Peoples R China.
摘要：
The fragility inherent in enzymes can be overcome by immobilizing them within nano-carriers, which offer designability and controllability and serve as a promising strategy for overcoming the inherent fragility of enzymes. While enzyme immobilization enhances enzyme stability and reusability, it can potentially hinder their bioactivity and catalytic efficiency. In this study, we present an enzyme-directed biomimetic mineralization approach for the in situ encapsulation of horseradish peroxidase (HRP) within hydrogen-bonded organic frameworks (HOFs) to obtain HOF@HRP nanocomposites. Remarkably, the HOF@HRP nanocomposites exhibit an ultrahigh protein content and demonstrate comparable catalytic activity to that of the free enzyme. Moreover, the HOFs act as protective shields, safeguarding the internal enzymes against various environmental disturbances. Leveraging the unique properties of HOF@HRP, we propose a dual-modal enzyme-linked immunosorbent assay for the sensitive detection of prostate-specific antigen in human serum. The resultant biosensor exhibits a good linear range, excellent sensitivity, and selectivity, showcasing its promising potential and clinical application in the field of diagnostic medicine.
作者机构：
[Zhu, Chengzhou; Gu, Wenling; Li, Jingshuai; Xi, Mengzhen] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Hu, Liuyong] Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.;[Sun, Hongcheng] Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 311121, Peoples R China.;[Gu, Wenling] Key Lab Opt Elect Sensing & Analyt Chem Life Sci, MOE, Qingdao 266042, Peoples R China.
通讯机构：
[Gu, WL ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Key Lab Opt Elect Sensing & Analyt Chem Life Sci, MOE, Qingdao 266042, Peoples R China.
摘要：
Improving the sensitivity in electrochemiluminescence (ECL) detection systems necessitates the integration of robust ECL luminophores and efficient signal transduction. In this study, we report a novel ECL nanoprobe (Zr-MOF) that exhibits strong and stable emission by incorporating aggregation-induced emission ligands into Zr-based metal-organic frameworks (MOFs). Meanwhile, we designed a high-performance signal modulator through the implementation of a well-designed controlled release system with a self-on/off function. ZnS quantum dots (QDs) encapsulated within the cavities of aminated mesoporous silica nanoparticles (NH(2)-SiO(2)) serve as the ECL quenchers, while adenosine triphosphate (ATP) aptamers adsorbed on the surface of NH(2)-SiO(2) through electrostatic interaction act as "gatekeepers." Based on the target-triggered ECL resonance energy transfer between Zr-MOF and ZnS QDs, we establish a coreactant-free ECL aptasensor for the sensitive detection of ATP, achieving an impressive low detection limit of 0.033 nM. This study not only demonstrates the successful combination of ECL with controlled release strategies but also opens new avenues for developing highly efficient MOFs-based ECL systems.
摘要：
Picolinamide fungicides, structurally related to UK-2A and antimycin-A, bind into the Qi-site in the bc(1) complex. However, the detailed binding mode of picolinamide fungicides remains unknown. In the present study, antimycin-A and UK-2A were selected to study the binding mode of picolinamide inhibitors with four protonation states in the Qi-site by integrating molecular dynamics simulation, molecular docking, and molecular mechanics Generalized Born surface area (MM/GBSA) calculations. Subsequently, a series of new picolinamide derivatives were designed and synthesized to further understand the effects of substituents on the tail phenyl ring. The computational results indicated that the substituted aromatic rings in antimycin-A and UK-2A were the pharmacophore fragments and made the primary contribution when bound to a protein. Compound 9g-hydrolysis formed H-bonds with Hie201 and Ash228 and showed an IC(50) value of 6.05 ± 0.24 μM against the porcine bc(1) complex. Compound 9c, with a simpler chemical structure, showed higher control effects than florylpicoxamid against cucumber downy mildew and expanded the fungicidal spectrum of picolinamide fungicides. The structural and mechanistic insights obtained from the present study will provide a valuable clue for the future designing of new promising Qi-site inhibitors.
摘要：
Highly efficient three‐component coupling of organic halides, sodium cyanate and amines or alcohols was achieved with a nickel/photoredox dual catalysis system. Significant N‐containing functional compounds, ureas and carbamates, were produced under green and sustainable conditions. Comprehensive Summary Ureas are widely used in drugs, materials and catalysts because of their diamide structure, which can form strong hydrogen bonds. Therefore, it is of great scientific significance to develop efficient and green methods for the synthesis of urea compounds, especially unsymmetrical ureas. Here, we have disclosed novel and highly efficient three‐component coupling reactions of organic halides, sodium cyanate and amines enabled by nickel/photoredox dual catalysis for the preparation of unsymmetrical ureas. The reaction features simple and safe operations, broad substrate scopes, and product diversities. It allows the facile synthesis of N‐aryl/vinyl ureas from readily available, user‐friendly feedstocks under mild conditions (27 examples, 36%—98% yields). In addition, this method is further derived to alcohols as nucleophiles to synthesize a series of carbamates (15 examples, 40%—95% yields). The mechanism experiment shows that the isocyanate produced by the coupling of halide and sodium cyanate may be the key intermediate in this reaction.
通讯机构：
[Li, DF ] C;Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.
摘要：
The research on electron transfer coupled spin transition regulating the valence state and spin state transition of metal ions is promising and challenging. Herein, we report a cyano-bridged {(Fe2Fe2II)-Fe-III} molecular square complex, {[Fe(Tp)(CN)(3)](2) [Fe(bnbpen)](2)}(ClO4)(2)<middle dot>8CH(3)OH (1<middle dot>8CH(3)OH, bnbpen = N,N '-bis-(2-naphthylmethyl)-N,N '-bis(2-picolayl)-ethylenediamine), and its free of solvents form (1). Combined single-crystal X-ray diffraction, temperature-dependent infrared (IR) spectra, magnetic measurements, and M & ouml;ssbauer spectra reveal that 1<middle dot>8CH(3)OH and 1 exhibit reversible one-step and two-step electron transfer coupled spin transition (ETCST) with temperature change, between the low-temperature state {Fe-II,Fe-LS(mu-CN)Fe-III,Fe-LS}(2) (LS = low spin, HS = high spin) and the high-temperature state {Fe-III,Fe-LS(mu-CN)Fe-II,Fe-HS}(2), respectively.
摘要：
Viruses are ubiquitous in human life. Some viruses can be used as vectors of genetic engineering and specific pesticides. Other viruses trigger a variety of diseases in humans, animals and plants, resulting in high infection rates and mortality. Therefore, convenient, accurate and rapid detection of viruses is of great significance for the diagnosis and treatment of subsequent diseases. In contrast to traditional methods of detection, which rely on time-consuming and complex techniques such as polymerase chain reaction (PCR), fluorescent probes and imaging methods generate real-time results, with high specificity, and have been widely used in viral detection. In this review, the application of viral fluorescent probes in analyzing the molecular structure, detection and biological imaging is discussed. In particular, we catego-rized the probes based on their specificity for human and plant viruses, reviewing the latest findings and analyzing their limitations. The potential of fluorescent molecular probes in the treatment of viral dis-ease and environmental analysis, and their possible combinations with protein and immune technology are discussed.(c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
摘要：
Cancer, a leading cause of death worldwide, still needs surgery as essential curation in over 80% population. However, complete resection of cancerous tissues remains a great challenge due to the difficulty in tumor margin identification. Fluorescent probe based imaged-guided surgery (IGS) for in-situ local disease focus imaging is thought to be an ideal method for intraoperation tumor identification due to its high spatiotemporal resolution and real-time manner. By targeting tumor microenvironments (TME) or tumor-associated biomolecules, fluorescent probes could "light-up" tumor tissues and navigate surgical operation. Among which, biosensors targeting aminopeptidase N (APN) have attracted intense attention due to its high relevance with progression of tumor. However, most of the probes adopting its natural substrate (L-Alaine) as the recognition unit may be vulnerable toward other widely distributed aminopeptidase such as leukotriene A4 hydrolase (LTA4H) and leucine aminopeptidase (LAP). In order to acquire high specific APN targeted probe for accurate detection of APN activity in biological samples and fulfill high contrast tumor imaging, herein a non-natural amino acid (P-ChloroL-Phenylalanine, PCPA) based fluorescent probe was firstly reported for APN targeted bioimaging. The acquired named as TMN-PCPA showed high affinity (Km = 3.27 +/- 0.23 mu M) and dramatically improved selectivity toward APN than previously reported APN probe. TMN-PCPA was successfully applicated into discrimination tumor biosamples from normal bio-samples in both cellular and ex vivo level with significantly increased tumor to normal (T/N) ratio, thus showed great potential in intraoperation application such imaged-guided surgery and providing structural basis to high specific APN targeted biosensor construction.
作者机构：
[Hao, Ge-Fei; Li, Xiao-Hong; Gao, Yang-Yang] Guizhou Univ, Ctr Res & Dev Fine Chem, Natl Key Lab Green Pesticide, Key Lab Green Pesticide & Agr Bioengn,Minist Educ, Guiyang, Peoples R China.;[Li, Jing-Yi; Liu, Chun-Rong; Hao, Ge-Fei; Li, Meng-Zhao; Li, JY] Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan, Peoples R China.
通讯机构：
[Liu, CR; Li, JY] C;[Hao, GF ] G;Guizhou Univ, Ctr Res & Dev Fine Chem, Natl Key Lab Green Pesticide, Key Lab Green Pesticide & Agr Bioengn,Minist Educ, Guiyang, Peoples R China.;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan, Peoples R China.
关键词：
wearable sensors;in-situ and continuous;monitoring;plant health information;precision agriculture
摘要：
Plant health is intricately linked to crop quality, food security and agricultural productivity. Obtaining accurate plant health information is of paramount importance in the realm of precision agriculture. Wearable sensors offer an exceptional avenue for investigating plant health status and fundamental plant science, as they enable real-time and continuous in-situ monitoring of physiological biomarkers. However, a comprehensive overview that integrates and critically assesses wearable plant sensors across various facets, including their fundamental elements, classification, design, sensing mechanism, fabrication, characterization and application, remains elusive. In this study, we provide a meticulous description and systematic synthesis of recent research progress in wearable sensor properties, technology and their application in monitoring plant health information. This work endeavours to serve as a guiding resource for the utilization of wearable plant sensors, empowering the advancement of plant health within the precision agriculture paradigm.
通讯机构：
[Zhang, ZH; Lei, HH ] C;Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.;Wuhan Inst Photochem & Technol, Wuhan 430083, Hubei, Peoples R China.
摘要：
Regioselective C-H amination of simple arenes is highly desirable, but accessing meta-sites of ubiquitous arenes has proven challenging due to the lack of both electronic and spatial preference. This study demonstrates the successful use of various privileged nitrogen-containing functionalities found in pharmaceutical compounds to direct meta-C-H amination of arenes, overcoming the long-standing requirement for a redundant directing group. The remarkable advancements in functional group accommodation for precise regiochemical control were achieved through the discovery of an unprecedented organo-initiator and the strategic utilization of non-covalent interactions. This protocol has been successfully applied in the concise synthesis and late-stage derivatization of drug molecules, which would have been otherwise challenging to achieve.
通讯机构：
[Peng, X ] C;[Quan, FJ ] W;Wuhan Polytech Univ, Sch Chem & Environm Engn, Wuhan 430023, Peoples R China.;Cent China Normal Univ, Inst Environm & Appl Chem, Minist Educ, Key Lab Pesticide & Chem Biol, Wuhan 430079, Peoples R China.
摘要：
Recently, researchers have been paying much attention to zero-valent iron (ZVI) in the field of pollution remediation. However, the depressed electron transport from the iron reservoir to the iron oxide shell limited the wide application of ZVI. This study was aimed at promoting the performance of microscale ZVI (mZVI) for hexavalent chromium (Cr(vi)) removal by accelerating iron cycle with the addition of boron powder. It was found that the addition of boron powder enhanced the Cr(vi) removal rate by 2.1 times, and the proportion of Cr(iii) generation after Cr(vi) removal process also increased, suggesting that boron could promote the reduction pathway of Cr(vi) to Cr(iii). By further comparing the Cr(vi) removal percentage of Fe(iii) with or without the boron powder, we found that boron powder could promote the percentage removal of Cr(vi) with Fe(iii) from 10.1% to 33.6%. Moreover, the presence of boron powder could decrease the potential gap values (ΔE(p)) between Fe(iii) reduction and Fe(ii) oxidation from 0.668 V to 0.556 V, further indicating that the added boron powder could act as an electron sacrificial agent to promote the reduction process of Fe(iii) to Fe(ii), and thus enhancing the reduction of Cr(vi) with Fe(ii). This study shed light on the promoted mechanism of Cr(vi) removal with boron powder and provided an environmentally friendly and efficient approach to enhance the reactivity of the mZVI powder, which would benefit the wide application of mZVI technology in the environmental remediation field.
