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Green Chemical Engineering 2024年第4期5卷 409-417页

作者： Yu Chen Zhiwu Yu MOE Key Laboratory of Bioorganic Phosphorous chemistry and Chemical Biology Department of ChemistryTsinghua University

Green solvents such as water and ionic liquids(ILs) are pillars of the great mansion of green chemistry and green processing. Initially proposed as a new family of ILs,deep eutectic solvents(dESs) have received fast development in the past two decades. In this contribution,dESs are reviewed critically and the concept is extended to lowmelting mixture solvents(Lo MMSs),which cover all kinds of materials including ionic compounds,molecular compounds,and metals. Six classes of Lo MMSs are proposed as the new classification system and examples are given. Finally,several thermodynamic issues concerning Lo MMSs are discussed. Two new concepts,robustness of Lo MMSs and high-entropy Lo MMSs,are proposed.

关键词： Green solvents deep eutectic solvents Low transition temperature mixture solvents Phase diagram EGaIn

Increase of chiral sensing ability in host-guest chemistry by magnetic anisotropy

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Science China chemistry 2024年第8期67卷 2775-2782页

作者： Jia-Liang Chen Bin Li Feng Yang Tiesheng Shi Xun-Cheng Su State Key Laboratory of Elemento-organic chemistry Tianjin Key Laboratory of Biosensing and Molecular RecognitionCollege of ChemistryNankai UniversityTianjin 300071China College of chemistry Chemical Engineering and Materials ScienceZaozhuang UniversityZaozhuang 277160China

Enantiomeric molecules generally play distinct functions in chemistry,biology,and *** physical and chemical properties of chiral analytes lay difficulty in discrimination and quantification of the *** report herein an efficient approach of increasing the chiral sensing ability ofβ-cyclodextrin(β-Cd),a widely used host molecule,in the hostguest chemistry by magnetic anisotropy.A rigid and chiral lanthanide binding tag was attached to theβ-Cd to amplify the changes of nuclear magnetic resonance(NMR)signals in the host-guest recognition *** installation of the paramagnetic lanthanide ion inβ-Cd greatly enhances the enantiomeric discrimination up to 30-fold in comparison with the diamagneticβ-Cd *** addition,the magnitude of the paramagnetic effects is tunable according to the diverse range of paramagnetic strength of the lanthanide *** reported method significantly increases the chiral sensing ability ofβ-Cd,which can be applied to other host *** transferred paramagnetic effects,pseudocontact shifts(PCSs)and paramagnetic relaxation enhancements(PREs),from the host to the guest molecules,are valuable structural restraints to determine the absolute stereochemistry of the chiral *** strategy does not need modification of the analytes and is complementary to the reported analytical methods that rely on the functionalization of the chiral analytes.

关键词： chiral recognition nuclear magnetic resonance host-guest chemistry magnetic anisotropy lanthanide ions

Fabrication of sub-20 nm MoS_(2) horizontal nanowire on silicon substrates by inclusion of precursors into polystyrene-bpolyethylene oxide nanopatterns: detailed structural investigation

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Nano Research 2024年第3期17卷 2145-2153页

作者： Tandra Ghoshal Michael A.Morris School of chemistry AMBER and CRANNTrinity College DublinDublinIrelandD02 AK60

Herein,we demonstrate the fabrication of sub-20 nm MoS_(2) horizontal nanowire arrays on silicon substrates using a self-assembled block copolymer assisted in situ inclusion *** separated long-range ordered polystyrene-b-polyethylene oxide(PS-b-PEO)block copolymer(BCP)line-space nanopatterns were achieved through thermo-solvent *** patterns produced had long-range order and domain sizes>1μ*** BCP structures were lightly etched and modified by anhydrous ethanol to facilitate insertion of molybdenum precursor within the film maintaining the parent BCP *** ordered molybdenum oxide nanowire arrays were then fabricated by ultraviolet(UV)/ozone treatment at room *** oxides were converted to sulphides by thermal evaporation at different temperatures in Ar/H_(2) environment.X-ray photoelectron spectroscopy revealed the composition and phases of the molybdenum oxide and sulphide *** mapping was performed to investigate the interfaces between the oxide and sulphide nanowires with the substrate *** formation and stability of the sulphide nanowires were studied at different *** photoluminescence and Raman properties were studied at different formation temperatures to investigate defects and estimate the number of layers.

关键词： MoS_(2) block copolymer nanowires inclusion X-ray photoelectron spectroscopy(XPS) mapping photoluminescence

Layered oxide cathodes for sodium-ion batteries:microstructure design,local chemistry and structural unit

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Science China chemistry 2024年第1期67卷 191-213页

作者： Ling-Yi Kong Han-Xiao Liu Yan-Fang Zhu Jia-Yang Li Yu Su Hong-Wei Li Hai-Yan Hu Yi-Feng Liu Ming-Jing Yang Zhuang-Chun Jian Xin-Bei Jia Shu-Lei Chou Yao Xiao Institute for Carbon Neutralization College of Chemistry and Materials EngineeringWenzhou UniversityWenzhou 325035China

Because of the low price and abundant reserves of sodium compared with lithium,the research of sodium-ion batteries(SIBs)in the field of large-scale energy storage has returned to the research *** oxides distinguish themselves from the mains cathode materials of SIBs owing to their advantages such as high specific capacity,simple synthesis route,and environmental ***,the commercial development of the layered oxides is limited by sluggish kinetics,complex phase transition and poor air *** on the research ideas from macro-to micro-scale,this review systematically summarizes the current optimization strategies of sodium-ion layered oxide cathodes(SLOC)from different dimensions:microstructure design,local chemistry regulation and structural unit *** the dimension of microstructure design,the various structures such as the microspheres,nanoplates,nanowires and exposed active facets are prepared to improve the slow kinetics and electrochemical ***,from the view of local chemistry regulation by chemical element substitution,the intrinsic electron/ion properties of SLOC have been enhanced to strengthen the structural ***,the optimization idea of endeavors to regulate the physical and chemical properties of cathode materials essentially is put forward from the dimension of structural unit *** opinions and strategies proposed in this review will provide some inspirations for the design of new SLOC in the future.

关键词： sodium-ion batteries layered oxide cathodes microstructure design local chemistry structural unit

Who is Who in the Carbene chemistry of N-Sulfonyl Hydrazones

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Chinese Journal of chemistry 2024年第17期42卷 2071-2108页

作者： Paramasivam Sivaguru Yongzhen Pan Nan Wang Xihe Bi departmentof chemistry Northeast Normal UniversityChangchunJilin130024China

Over the past few decades,N-sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis,allowing for diverse innovative and original chemical transformations that were otherwise difficult to *** critical review summarizes the major advancements in the carbene chemistry of N-sulfonyl *** contents of this review are organized based on research conducted by leading scientists who have made significant contributions to this *** individual carbene transfer reactions and their mechanisms,as well as the potential applications in the synthesis of natural products and complex bioactive molecules,are thoroughly discussed.

关键词： N-Sulfonyl hydrazones Carbene chemistry Cross-coupling Cycloaddition Asymmetric reactions

Energy and blast performance of beryllium in a model thermobaric composition in comparison with aluminum and magnesium

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defence Technology（防务技术） 2024年第6期36卷 13-19页

作者： Thomas M.Klapotke Stanisław Cudziło Waldemar A.Trzcinski Jozef Paszula Energetic Materials Research Department of ChemistryUniversity of Munich(LMU)Butenandtstrasse 5-13(D)81377MunichGermany Military University of Technology Faculty of Advanced Technologies and ChemistrySylwester Kaliski Str.200-908WarsawPoland

A direct comparison is made between the effectiveness of Al,Mg,and Be powders as additional fuels in model thermobaric compositions containing 20%fuel,20%ammonium perchlorate,and 60%RdX(1,3,5-Trinitro-1,3,5-triazacyclohexane)passivated with *** determined calorimetric measurements of the heat of detonation,along with the overpressure histories in an explosion chamber filled with nitrogen,were used to determine the quasi-static pressure(QSP)under anaerobic *** measurements were also performed in a semi-closed bunker,and all blast wave parameters generated after the detonation of 500 g charges of the tested explosives were *** calorimetry results,QSP values,and blast wave parameters(pressure amplitude,specific and total impulses)clearly indicate that Be is much more effective as an additional fuel than either Al or Mg in both anaerobic post-detonation reactions as well as the subsequent aerobic *** heat of detonation of the RdXwax/AP/Be explosive mixture is over 40%and 50%higher than that of the mixture containing aluminum and magnesium instead of beryllium,***,the TNT equivalent of the Be-containing composition due to the overpressure in the nitrogen-filled explosion chamber is 1.66,while the equivalent calculated using an air shock wave-specific impulse at a distance of 2.5 m is equal to *** high values of these parameters confirm the high reactivity of beryllium in both the anaerobic and aerobic stages of the thermobaric explosion.

关键词： Thermobaric explosives Beryllium Heat of detonation Quasi-static overpressure Blast wave parameters

Self-separation ionic liquid catalyst for the highly effective conversion of H2S by α,β-unsaturated carboxylate esters under mild conditions

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Green Energy & Environment 2024年第9期9卷 1440-1448页

作者： Wenjie Xiong Xiaomin Zhang Xingbang Hu Youting Wu Key Laboratory of Mesoscopic chemistry of MOE School of Chemistry and Chemical Engineering Nanjing University The Institute of Green chemistry and Engineering School of Chemistry and Chemical Engineering Nanjing University

The deep-processing utility of pure hydrogen sulfide （H2S） is a significant direction in natural gas chemical ***,a brand-new strategy of H2S conversion by a,β-unsaturated carboxylate esters into thiols or thioethers using task-specific carboxylate ionic liquids （ILs） as catalyst has been developed,firstly accomplishing the phase separation of product and catalyst without introducing the third *** can be considered as a cascade reaction in which the product selectivity can be controlled by adjusting the molar ratio of H2S to a,β-unsaturated carboxylate ***,the effects of ILs with different anions and cations,intermittent feeding operations,as well as pressure-time kinetic behaviors on cascade reaction were ***,the proposed interaction mechanism of H2S conversion using butyl acrylate catalyzed by[Emim][Ac]was revealed by dFT-based theoretical *** approach enables the self-phase separation promotion of catalyst and product and achieves 99%quantitative conversion under mild conditions in the absence of solvent,making the entire process ecologically ***-efficiency reaction activity can still be maintained after ten cycles of the ***,the good results,combined with its simplicity of operation and the high recyclability of the catalyst,make this green method environmentally friendly and *** is anticipated that this self-separation method mediated by task-specific ILs will provide a feasible strategy for H2S utilization,which will guide its application on an industrial scale.

关键词： Ionic liquid Cascade reaction Self-separation H 2 S conversion Catalysis

Synthesis and characterization of a 1,3-dibutylimidazolium azide([BBIm][N_(3)]) : A promising green energetic ionic liquid

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defence Technology（防务技术） 2024年第8期38卷 1-15页

作者： Nawel Matmat Amir Abdelaziz djalal Trache Achour Sabrina Ahmed Fouzi Tarchoun Hani Boukeciat Sourbh Thakur Weiqiang Pang Thomas M.Klapotke Energetic Materials Laboratory(EMLab) Teaching and Research Unit of Energetic ProcessesEcole Militaire PolytechniqueBP 17 Bordj El-BahriAlgiers 16046Algeria department of Organic chemistry Bioorganic Chemistry and BiotechnologySilesian University of TechnologyB.Krzywoustego 444-100 GliwicePoland Xi'an Modern chemistry Research Institute Xi'an 710065China Energetic Materials Research Department of ChemistryLudwig-Maximilian UniversityMunich Butenandtstrasse 5-13(D)D-81377 MunichGermany

In the pursuit of advancing imidazolium-based energetic ionic liquids (EILs),the current study is devoted to the synthesis and characterization of 1,3-dibutyl-imidazolium azide ([BBIm][N_(3)]),as a novel member in this ionic liquids *** chemical structure of this EIL was rigorously characterized and confirmed using FTIR spectroscopy,1d,and 2d-NMR *** thermal behavior assessment was conducted through dSC and TGA *** analysis revealed an endothermic glass transition at T_(g)=-61℃,followed by an exothermic degradation event at T_(onset)=311℃.Similarly,TGA thermograms exhibited a one-stage decomposition process resulting in 100% mass loss of the ***,the short-term thermal stability of the azide EIL was investigated by combining the non-isothermal TGA data with the TAS,it-KAS,and VYA/CE isoconversional kinetic ***,the Arrhenius parameters(E_(a)=154 kJ·mol^(-1),Log(A/s^(-1))=11.8) and the most probable reaction model g(a) were *** observed high decomposition temperatures and the significantly elevated activation energy affirm the enhanced thermal stability of the modified *** findings revealed that[BBIm][N_(3)]EIL can be a promising candidate for advanced energetic material application.

关键词： 1,3-dibutyl-imidazolium azide[BBIm][N_(3)] Energetic imidazolium-base ionic liquids 1d-/2d-NMR analyses Short-term thermal stability Isoconversional approaches

The 4^(th)CCL Organic chemistry Forum held in Zhangye

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Chinese Chemical Letters 2024年第8期35卷 3-6页

作者： Yingxiao Zong Yangfei Wei Xiaoqing Liu Junke Wang Huanfang Guo Junli Wang Zhuangzhi Shi Tao Tu Cheng Yang Chongyang Wang Leyong Wang Key Laboratory of Hexi Corridor Resources Utilization of Gansu School of Chemistry and Chemical EngineeringHexi UniversityZhangye 734000China Institute of Materia Medica Chinese Academy of Medical SciencesBeijing 100050China School of chemistry and Chemical Engineering Nanjing UniversityNanjing 210023China department of chemistry Fudan UniversityShanghai 200438China College of chemistry Sichuan UniversityChengdu 610064China Institute of chemistry Chinese Academy of SciencesBeijing 100190China

The first Chinese Chemical Letters(CCL)Organic chemistry Forum was held in Xiamen of Fujian in Jan.2018,followed by the successful events in Zhengzhou of Henan in dec.2019 and Linzhi of Tibet in July *** series of forums aim to build a high-level organic chemistry academic exchange platform for(Chinese)youthful organic chemists,fully showcase their latest fron-tier achievements,and enhance the international level of organic chemistry in *** the same time,the convening of the series of forums has also played a positive role in promoting the devel-opment of China’s scientific journal publishing,accelerating the re-alization of the strategic goal of building a world-class journal.

关键词： journal Forum Xiamen

Elucidating solvent effects on the stability of phenoxyl radicals in monohydric alcohols via electron paramagnetic resonance

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Green Chemical Engineering 2024年第4期5卷 483-488页

作者： Xinyu Wang Wenjing Sun Yongtao Wang Haoran Li department of chemistry Zhejiang University Center of chemistry for Frontier Technologies ZJU-NHU United R&D Center Zhejiang University State Key Laboratory of Chemical Engineering College of Chemical and Biological Engineering Zhejiang University

Research on solvent effects is an important and long-standing topic, but there still is some room, especially for the special solvent effect of fluoroalcohols. In this work, we investigated the stability of phenoxyl radical in monohydric alcohol solvents through in-situ electron paramagnetic resonance detections. The decay behavior of phenoxyl radical showed a reasonable relationship with the mesoscopic structure of alcohols, characterized by smalland wide-angle X-ray scattering. Moreover, the distinct solvent effects of fluoroalcohols were emphasized, and the significant influence of van der Waals distance in the solvents was suggested. Overall, the stability of phenoxyl radical in alcohols was quantified and correlated with the solvent structures. We believe that the established method for stability study on radicals will encourage solvent effect studies on various organic reactions, and the proposed solvent effects in fluoroalcohols may inspire the development of green solvents in both industrial conversions and organic synthesis.

关键词： Solvent effect Fluoroalcohol Phenoxyl radical Stability Electron paramagnetic resonance