Natural products derived from marine microorganisms have been received great attention as a potential source of new compound entities for drug discovery.The unique marine environment brings us a large group of halogen...Natural products derived from marine microorganisms have been received great attention as a potential source of new compound entities for drug discovery.The unique marine environment brings us a large group of halogen-containing natural products with abundant biological functionality and good drugability.Meanwhile,biosynthetically halogenated reactions are known as a significant strategy used to increase the pharmacological activities and pharmacokinetic properties of compounds.Given that a tremendous increase in the number of new halogenated compounds from marine microorganisms in the last five years,it is necessary to summarize these compounds with their diverse structures and promising bioactivities.In this review,we have summarized the chemistry,biosynthesis(related halogenases),and biological activity of a total of 316 naturally halogenated compounds from marine microorganisms covering the period of 2015 to May 2021.Those reviewed chlorinated and brominated compounds with the ratio of 9:1 were predominantly originated from 36 genera of fungi(62%)and 9 bacterial strains(38%)with cytotoxic,antibacterial,and enzyme inhibitory activities,structural types of which are polyketides(38%),alkaloids(27%),phenols(11%),and others.This review would provide a plenty variety of promising lead halogenated compounds for drug discovery and inspire the development of new pharmaceutical agents.展开更多
Halogens are common in industrial thermal processes and can induce formation of toxic organic pollutants.Currently,the specific effects of coexisting halogens on toxic pollutant formation are unclear.In this study,we ...Halogens are common in industrial thermal processes and can induce formation of toxic organic pollutants.Currently,the specific effects of coexisting halogens on toxic pollutant formation are unclear.In this study,we found the boosting effects of halogens on organic pollutants formation during thermal processes.In situ electron paramagnetic resonance spectroscopy was used to distinguish the organic free radical intermediates of organic pollutants during thermal processes.The pure chlorine-containing reaction system dominantly induce the formation of highly chlorinated phenoxy radicals,whereas the pure bromine-containing reaction system induce the formation of semiquinone radicals.The results provide clear evidence for the molecular mechanisms by which halogen coexistence boosts pollutants formation.Coexisting halogens made the reactions much more complex.Bromine atom radicals(Br·)can enhance the level of active chlorine atoms radicals(Cl·),then(1)facilitating highly chlorinated organic radicals and toxic pollutants formation,(2)activating polycyclic aromatic hydrocarbons molecules for subsequent ring growth and(3)accelerating oxidation reactions.Combining the identification of organic free radical intermediates and characteristics of products,detailed mechanisms of halogens on the formations of organic pollutants during thermal-related processes were clarified,which can be helpful for their efficient control in the widespread bromines and chlorines co-existence reaction system.展开更多
The relentless drive toward miniaturization in the semiconductor industry demands photoresists capable of patterning sub-20 nm features for next-generation extreme ultraviolet(EUV)lithography.Metal-oxo clusters,with s...The relentless drive toward miniaturization in the semiconductor industry demands photoresists capable of patterning sub-20 nm features for next-generation extreme ultraviolet(EUV)lithography.Metal-oxo clusters,with sub-5 nm molecular dimensions,structural tunability,and high EUV absorption via metal centers,have emerged as promising EUV photoresist candidates.Advancing next-generation photoresist materials necessitates resolving the inherent trade-offs between sensitivity,resolution,and line-edge roughness.In this work,we report a series of halogenated metal-organic clusters based EUVL photoresists,aiming to modulate the sensitivity,resolution,and line-edge roughness.Here,we report the synthesis of halogenated metal-organic clusters as EUVL photoresists,designed to modulate the resolution-line edge roughness-sensitivity trade-off.Sub-20 nm critical dimensions and line edge roughness below 2 nm were achieved with the clusters by EUVL.The results demonstrated that halogen elements influenced the sensitivity of the clusters.To unravel the EUV-driven reaction pathways,we analyzed the chemical transformations in these clusters after exposure using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy.These findings pave the way for the rational design of high-performance EUV photoresists.展开更多
Zero-valent iron(ZVI),an ideal reductant treating persistent pollutants,is hampered by issues like corrosion,passivation,and suboptimal utilization.Recent advancements in nonmetallic modified ZVI(NM-ZVI)show promising...Zero-valent iron(ZVI),an ideal reductant treating persistent pollutants,is hampered by issues like corrosion,passivation,and suboptimal utilization.Recent advancements in nonmetallic modified ZVI(NM-ZVI)show promising potential in circumventing these challenges by modifying ZVI's surface and internal physicochemical properties.Despite its promise,a thorough synthesis of research advancements in this domain remains elusive.Here we review the innovative methodologies,regulatory principles,and reduction-centric mechanisms underpinning NM-ZVI's effectiveness against two prevalent persistent pollutants:halogenated organic compounds and heavy metals.We start by evaluating different nonmetallic modification techniques,such as liquid-phase reduction,mechanical ball milling,and pyrolysis,and their respective advantages.The discussion progresses towards a critical analysis of current strategies and mechanisms used for NM-ZVI to enhance its reactivity,electron selectivity,and electron utilization efficiency.This is achieved by optimizing the elemental compositions,content ratios,lattice constants,hydrophobicity,and conductivity.Furthermore,we propose novel approaches for augmenting NM-ZVI's capability to address complex pollution challenges.This review highlights NM-ZVI's potential as an alternative to remediate water environments contaminated with halogenated organic compounds or heavy metals,contributing to the broader discourse on green remediation technologies.展开更多
基金financially supported by the Natural Science Foundation of Guangxi Province(Nos.2020GXNSFGA297002,2021GXNSFDA075010,2020GXNSFBA159001)the Special Fund for Bagui Scholars of Guangxi Province(Y.Liu),the National Natural Science Foundation of China(Nos.22007019,U20A20101)+1 种基金the Specific Research Project of Guangxi for Research Bases and Talents(AD20297003)the Open Project of CAS Key Laboratory of Tropical Marine Bio-resources and Ecology(LMB20211005).
文摘Natural products derived from marine microorganisms have been received great attention as a potential source of new compound entities for drug discovery.The unique marine environment brings us a large group of halogen-containing natural products with abundant biological functionality and good drugability.Meanwhile,biosynthetically halogenated reactions are known as a significant strategy used to increase the pharmacological activities and pharmacokinetic properties of compounds.Given that a tremendous increase in the number of new halogenated compounds from marine microorganisms in the last five years,it is necessary to summarize these compounds with their diverse structures and promising bioactivities.In this review,we have summarized the chemistry,biosynthesis(related halogenases),and biological activity of a total of 316 naturally halogenated compounds from marine microorganisms covering the period of 2015 to May 2021.Those reviewed chlorinated and brominated compounds with the ratio of 9:1 were predominantly originated from 36 genera of fungi(62%)and 9 bacterial strains(38%)with cytotoxic,antibacterial,and enzyme inhibitory activities,structural types of which are polyketides(38%),alkaloids(27%),phenols(11%),and others.This review would provide a plenty variety of promising lead halogenated compounds for drug discovery and inspire the development of new pharmaceutical agents.
基金supported by the National Key Research and Development Program of China(No.2023YFC3707004)the National Natural Science Foundation of China(Nos.22376204,22076201 and 92143201)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Nos.XDB0750400,XDB0750100 and XDB0750000)the Second Tibetan Plateau Scientific Expedition and Research Program(STEP)(No.2019 QZKK0605).
文摘Halogens are common in industrial thermal processes and can induce formation of toxic organic pollutants.Currently,the specific effects of coexisting halogens on toxic pollutant formation are unclear.In this study,we found the boosting effects of halogens on organic pollutants formation during thermal processes.In situ electron paramagnetic resonance spectroscopy was used to distinguish the organic free radical intermediates of organic pollutants during thermal processes.The pure chlorine-containing reaction system dominantly induce the formation of highly chlorinated phenoxy radicals,whereas the pure bromine-containing reaction system induce the formation of semiquinone radicals.The results provide clear evidence for the molecular mechanisms by which halogen coexistence boosts pollutants formation.Coexisting halogens made the reactions much more complex.Bromine atom radicals(Br·)can enhance the level of active chlorine atoms radicals(Cl·),then(1)facilitating highly chlorinated organic radicals and toxic pollutants formation,(2)activating polycyclic aromatic hydrocarbons molecules for subsequent ring growth and(3)accelerating oxidation reactions.Combining the identification of organic free radical intermediates and characteristics of products,detailed mechanisms of halogens on the formations of organic pollutants during thermal-related processes were clarified,which can be helpful for their efficient control in the widespread bromines and chlorines co-existence reaction system.
基金supported by the National Science and Technology Major Project from the Ministry of Science and Technology of China(No.2018AAA0103100)the National Key Research and Development Program of China(No.2021YFB3200800)the National Natural Science Foundation of China(Nos.22201289,62305365)for financial support。
文摘The relentless drive toward miniaturization in the semiconductor industry demands photoresists capable of patterning sub-20 nm features for next-generation extreme ultraviolet(EUV)lithography.Metal-oxo clusters,with sub-5 nm molecular dimensions,structural tunability,and high EUV absorption via metal centers,have emerged as promising EUV photoresist candidates.Advancing next-generation photoresist materials necessitates resolving the inherent trade-offs between sensitivity,resolution,and line-edge roughness.In this work,we report a series of halogenated metal-organic clusters based EUVL photoresists,aiming to modulate the sensitivity,resolution,and line-edge roughness.Here,we report the synthesis of halogenated metal-organic clusters as EUVL photoresists,designed to modulate the resolution-line edge roughness-sensitivity trade-off.Sub-20 nm critical dimensions and line edge roughness below 2 nm were achieved with the clusters by EUVL.The results demonstrated that halogen elements influenced the sensitivity of the clusters.To unravel the EUV-driven reaction pathways,we analyzed the chemical transformations in these clusters after exposure using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy.These findings pave the way for the rational design of high-performance EUV photoresists.
基金supported by the NSFC-JSPS joint research program(No.51961145202)the National Natural Science Foundation of China(No.52370163,52321005,and 52293443)the State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(No.2022TS42).
文摘Zero-valent iron(ZVI),an ideal reductant treating persistent pollutants,is hampered by issues like corrosion,passivation,and suboptimal utilization.Recent advancements in nonmetallic modified ZVI(NM-ZVI)show promising potential in circumventing these challenges by modifying ZVI's surface and internal physicochemical properties.Despite its promise,a thorough synthesis of research advancements in this domain remains elusive.Here we review the innovative methodologies,regulatory principles,and reduction-centric mechanisms underpinning NM-ZVI's effectiveness against two prevalent persistent pollutants:halogenated organic compounds and heavy metals.We start by evaluating different nonmetallic modification techniques,such as liquid-phase reduction,mechanical ball milling,and pyrolysis,and their respective advantages.The discussion progresses towards a critical analysis of current strategies and mechanisms used for NM-ZVI to enhance its reactivity,electron selectivity,and electron utilization efficiency.This is achieved by optimizing the elemental compositions,content ratios,lattice constants,hydrophobicity,and conductivity.Furthermore,we propose novel approaches for augmenting NM-ZVI's capability to address complex pollution challenges.This review highlights NM-ZVI's potential as an alternative to remediate water environments contaminated with halogenated organic compounds or heavy metals,contributing to the broader discourse on green remediation technologies.
