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Chain Extender-induced Hydrogen Bonding Organization Determines the Morphology and Properties of Thermoplastic Polycarbonate Polyurethane

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Chinese Journal of Polymer Science 2024年第1期42卷 87-96,I0009页

作者： Yi-Lang Qin ping zhu Chen-Xi Ouyang Xia Dong Fuwai Hospital Chinese Academyof Medical Sciences&Peking Union Medical College/National Center for Cardiovascular DiseasesBejing 100037China CASKey Laboratoryof Engineering Plastics CAS Research/Education Centerfor Excellence in Molecular SciencesInstitute ofChemistryChinese Academy of SciencesBeijing 100190China University of Chinese Academy of Sciences Beijing 100049China

Thermoplastic polycarbonate polyurethanes(PCUs) are multiblock copolymers that have been applied for medical devices for long time. Aliphatic diols are common chain extenders(CE) involved in the composition of the hard segments of PCU. However, limited knowledge was discovered about how the chemical structure of CE affects the hydrogen bonding organization within PCUs and their mechanical properties.To investigate this problem, a group of PCUs were synthesized respectively by extending the polymer chain with 1,4-butanediol(BDO),aminoethanol(MEA), ethanediol(EO) as three kinds of chain extenders. Tiny differences in the CE chemical structure results in remarkable variations in phase separation, condensed morphologies, thermal and mechanical properties, which are characterized by Fourier transform infrared spectrometer, atomic force microscopy, small-angle X-ray scattering, differential scanning calorimetry, and tensile tests. The microstructural evolution during unilateral deformation and the different mechanism induced by the different CEs was probed and unveil by in situ wide-and small-angle X-ray diffraction. Symmetry of CE can improve the organization of the hydrogen bonding. The coherence strength of the urethane/urea group also plays a key role by comparing the two PCUs with ethanediol and aminoethanol.

关键词： Thermoplastic polycarbonate polyurethane Chain extender Hydrogen bonding Mechanical properties

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A Disulfide-Based Poly(ether-b-amide)Copolymer with Rapid Self-healing Ability under Moderate

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Chinese Journal of Chemistry 2024年第9期42卷 943-950页

作者： Weijan Lu ping zhu Ying Zhao Dujin Wang Xia Dong Institute of Chemistry Chinese Academy of SciencesBeijing 100190China Schoolof Chemical Sciences University of Chinese Academy of SciencesBejing 100049China

Comprehensive Summary A disulfide-based poly(ether-b-amide)copolymer with rapid self-healing capability under moderate conditions was synthesized from 4,4’-dithiodibutyric acid(DTDBA),isophorondiamine(IPDA)and poly(tetramethylene oxide)(PTMO)based on a two-step method.The incorporation of IPDA with asymmetric structure and substantial steric hindrance not only effectively decreased the number of regular H-bonds,but also inhibited the crystallization of polyamide segments,imparting the synthesized poly(ether-b-amide)copolymer with an amorphous structural feature.Based on the coordination of segmental diffusion and recombination of disulfide bonds and hydrogen bonds,the scratches and damaged mechanical properties of PEBADS-I611 could be completely self-healed after healing at 40°C for only 11 min and 3 h,respectively.

关键词： Poly(ether-b-amide)copolymer Disulfide bonds Hydrogen bonds Polycondensation Smart polymers Self-healing

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Estimating the optimal vegetation coverage for the dominant tree and shrub species over China's northwest drylands

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Science China Earth Sciences 2024年第5期67卷 1500-1517页

作者： Zhongdian ZHANG Xiaoxu JIA ping zhu Mingbin HUANG Lidong REN Ming’an SHAO School of Geographic Sciences Xinyang Normal UniversityXinyang 464000China Key Laboratory of Ecosystem Network Observation and Modeling Institute of Geographic Sciences and Natural Resources ResearchChinese Academy of SciencesBeijing 100101China College of Resources and Environment University of Chinese Academy of SciencesBeijing 100190China Yellow River Delta Modern Agricultural Engineering Laboratory Chinese Academy of SciencesBeijing 100101China State Key Laboratory of Soil Erosion and Dryland Farming on the Loess Plateau Institute of Soil and Water ConservationNorthwest A&F UniversityYangling 712100China

Anthropogenic revegetation is an effective way to control soil erosion and restore degraded ecosystems in China's northwest drylands(NWD).However,excessive vegetation cover expansion has long been known to increase evapotranspiration,leading to reduced local water availability,which can in turn threaten the health and services of restored ecosystems.Determining the optimal vegetation coverage(OVC)is critical for balancing the trade-off between plant growth and water consumption in water-stressed areas,yet quantitative assessments over the entire NWD are still lacking.In this study,a modified Biome BioGeochemical Cycles(Biome-BGC)model was used to simulate the long-term(1961–2020)dynamics of actual evapotranspiration(ET_(a)),net primary productivity(NPP),and leaf area index(LAI)for the dominant non-native tree(R.pseudoacacia and P.sylvestris)and shrub(C.korshinkii and H.rhamnoides)species at 246 meteorological sites over NWD.The modified model incorporated the Richards equation to simulate transient unsaturated water flow in a multilayer soil module,and both soil and eco-physiological parameters required by the model were validated using field-observed ETadata for each species.Spatial distributions of OVC(given by the mean maximum LAI,LAI_(max))for the dominant species were determined within three hydrogeomorphic sub-areas(i.e.,the loess hilly-gully sub-area,the windy and sandy sub-area,and the desert sub-area).The modified Biome-BGC model performed well in terms of simulating ET_(a) dynamics for the four plant species.Spatial distributions of mean ET_a,NPP,and LAI_(max)generally exhibited patterns similar to mean annual precipitation(MAP).In the loess hilly-gully sub-area(MAP:210 to 710 mm),the OVC respectively ranged from 1.7 to 2.9 and 0.8 to 2.9 for R.pseudoacacia and H.rhamnoides.In the windy and sandy sub-area(MAP:135 to 500 mm),the OVC ranged from 0.3 to 3.3,0.5 to 2.6 and 0.6 to 2.1for P.sylvestris,C.korshinkii and H.rhamnoides,respectively.In the desert sub-area(MAP:90 to 500 mm),the OVC ranged from 0.4 t

关键词： Optimal vegetation coverage Water balance Leaf area index Biome-BGC model Dryland

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A fungal CYP from Beauveria bassiana with promiscuous steroid hydroxylation capabilities

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Chinese Chemical Letters 2024年第5期35卷 218-222页

作者： Yu Peng Yue Wang Tian-Jiao Chen Jing-Jing Chen Jin-Ling Yang Ting Gong ping zhu State Key Laboratory of Bioactive Substance and Function of Natural Medicines NHC Key Laboratory of Biosynthesis of Natural ProductsCAMS Key Laboratory of Enzyme and Biocatalysis of Natural DrugsInstitute of Materia MedicaChinese Academy of Medical Sciences&Peking Union Medical CollegeBeijing 100050China

Hydroxylation of steroid core is critical to the synthesis of steroid drugs.Direct sp^(3) C-H hydroxylation is challenging through chemical catalysis,alternatively,fungal biotransformation offers a possible solution to this problem.However,mining and metabolic engineering of cytochrome P450 monooxygenases(CYPs)is usually regarded as a more eco-friendly and efficient strategy.Herein,we report the mining and identification of a new steroid CYP(CYP68BE1)from Beauveria bassiana by transcriptomics,heterologous expression,in vivo and in vitro functional characterization.The catalytic promiscuity of CYP68BE1 was explored,and CYP68BE1 showed promiscuously and catalytically versatile,which is qualified for monohydroxylation on C11α,C1α,C6βand dihydroxylation on C1β,11αand C6β,11αof six steroids,leading to the production of key steroid intermediates required in the industrial synthesis of some indispensable steroid drugs.Molecular dynamics simulations were performed,revealing the molecular basis of different binding orientations of CYP68BE1 with different substrates.The discovery of CYP68BE1 offers a promising biocatalyst for enriching the steroid structural and functional diversity,which also can be applied to biosynthesize valuable steroid drug intermediates.

关键词： Fungal CYPs Steroid hydroxylase Beauveria bassiana Promiscuous biocatalyst Molecular dynamics

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Reshaping the active pocket of an aldo-keto reductase to enhance its detoxification activity towards 3-keto-deoxynivalenol

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Food Science and Human Wellness 2024年

作者： Jiafeng Niu Bin Ma Hao zhu Huawei Liu Haizhen Zhao Xiaomei Bie Fengxia Lu ping zhu College of Food Science and Technology Nanjing Agricultural University State Key Laboratory of Desert and Oasis Ecology Xinjiang Institute of Ecology and Geography Chinese Academy of Sciences

Deoxynivalenol （DON）， the most common mycotoxin in the world， poses serious health hazards to both humans and animals and causes significant economic losses to the food and feed industry. An intriguing method for DON detoxification involves enzymatic cascade catalysis by dehydrogenase （DADH） and aldo-keto reductase （AKR13B3）. However， the poor catalytic activity of AKR13B3 has limited its usefulness. Here， structure-guided steric hindrance engineering， computer-assisted protein engineering， and combinatorial mutagenesis were carried out to increase the catalytic efficiency of AKR13B3. The best mutant in this project was M28S/S65V， which outperformed wild-type AKR13B3 in terms of catalytic efficiency (kcat/Km) and specific activity by factors of 45.08 and 43.11， respectively. Kinetic parameter determination revealed that the enhanced catalytic efficiency of M28S/S65V toward 3-keto-DON was attributed to the decreased Kmand increased kcatvalues. Moreover， the engineered enzyme was applied to degrade DON in contaminated corn steep liquor， for a 90.62% removal rate. Structure-based computational analysis provided insights into the enhanced catalytic efficiency of M28S/S65V， which was attributed to the enlarged substrate-binding pocket and reshaped pocket with a favorable hydrophilic attack distance. The results provide a reference for improving the catalytic activity of an enzyme toward non-native bulky substrates and pave the way for the development of enzymes as detoxification agents to mitigate DON in the food and feed industry.

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Generation and regulation of electromagnetic pulses generated by femtosecond lasers interacting with multitargets

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Nuclear Science and Techniques 2024年第1期35卷 96-107页

作者： Ya-Dong Xia De-Feng Kong Qiang-You He Zhen Guo Dong-Jun Zhang Tong Yang Hao Cheng Yu-Ze Li Yang Yan Xiao Liang ping zhu Xing-Long Xie Jian-Qiang zhu Ting-Shuai Li Chen Lin Wen-Jun Ma Xue-Qing Yan State Key Laboratory of Nuclear Physics and Technology and Key Laboratory of HEDP of the Ministry of EducationCAPTPeking UniversityBeijing 100871China Beijing Laser Acceleration Innovation Center Beijing 101407China Institute of Guangdong Laser Plasma Technology Guangzhou 510540China National Laboratory on High Power Laser and Physics Shanghai Institute of Optics and FineChinese Academy of SciencesShanghai 201800China School of Materials and Energy University of Electronic Science and Technology of ChinaChengdu 611731China

Ultrashort and powerful laser interactions with a target generate intense wideband electromagnetic pulses(EMPs).In this study,we report EMPs generated by the interactions between petawatt(30 fs,1.4×10^(20) W/cm^(2))femtosecond(fs)lasers with metal flat,plastic flat,and plastic nanowire-array(NWA)targets.Detailed analyses are conducted on the EMPs in terms of their spatial distribution,time and frequency domains,radiation energy,and protection.The results indicate that EMPs from metal targets exhibit larger amplitudes at varying angles than those generated by other types of targets and are enhanced significantly for NWA targets.Using a plastic target holder and increasing the laser focal spot can significantly decrease the radiation energy of the EMPs.Moreover,the composite shielding materials indicate an effective shielding effect against EMPs.The simulation results show that the NWA targets exert a collimating effect on thermal electrons,which directly affects the distribution of EMPs.This study provides guidance for regulating EMPs by controlling the laser focal spot,target parameters,and target rod material and is beneficial for electromagnetic-shielding design.

关键词： Electromagnetic pulses Laser plasma interaction Electromagnetic shielding Electron distribution

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Id2 epigenetically controls CD8^(+)T-cell exhaustion by disrupting the assembly of the Tcf3-LSD1 complex

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Cellular & Molecular Immunology 2024年第3期21卷 292-308页

作者： Yiming Li Mingwei Han Haolin Wei Wan Huang Zhinan Chen Tianjiao Zhang Meirui Qian Lin Jing Gang Nan Xiuxuan Sun Shuhui Dai Kun Wang Jianli Jiang ping zhu Liang Chen Department of Cell Biology of National Translational Science Center for Molecular Medicine and Department of Clinical Immunology of Xijing Hospital Fourth Military Medical UniversityXi’anShaanxi 710032China State Key Laboratory of New Targets Discovery and Drug Development for Major Diseases GanzhouJiangxi341000Xi’anShaanxi 710032China School of Medicine Shanghai UniversityShanghai 200444China

CD8^(+)T-cell exhaustion is a state of dysfunction that promotes tumor progression and is marked by the generation of Slamf6^(+)progenitor exhausted(Tex^(prog))and Tim-^(3+)terminally exhausted(Tex^(term))subpopulations.Inhibitor of DNA binding protein 2(Id2)has been shown to play important roles in T-cell development and CD8^(+)T-cell immunity.However,the role of Id2 in CD8^(+)T-cell exhaustion is unclear.Here,we found that Id2 transcriptionally and epigenetically regulates the generation of Texprog cells and their conversion to Texterm cells.Genetic deletion of Id2 dampens CD8^(+)T-cell-mediated immune responses and the maintenance of stem-like CD8^(+)T-cell subpopulations,suppresses PD-1 blockade and increases tumor susceptibility.Mechanistically,through its HLH domain,Id2 binds and disrupts the assembly of the Tcf3-Tal1 transcriptional regulatory complex,and thus modulates chromatin accessibility at the Slamf6 promoter by preventing the interaction of Tcf3 with the histone lysine demethylase LSD1.Therefore,Id2 increases the abundance of the permissive H3K4me2 mark on the Tcf3-occupied E-boxes in the Slamf6 promoter,modulates chromatin accessibility at the Slamf6 promoter and epigenetically regulates the generation of Slamf6+Texprog cells.An LSD1 inhibitor GSK2879552 can rescue the Id2 knockout phenotype in tumor-bearing mice.Inhibition of LSD1 increases the abundance of Slamf6^(+)Tim-3^(−)Tex^(prog) cells in tumors and the expression level of Tcf1 in Id2-deleted CD8+T cells.This study demonstrates that Id2-mediated transcriptional and epigenetic modification drives hierarchical CD8^(+)T-cell exhaustion,and the mechanistic insights gained may have implications for therapeutic intervention with tumor immune evasion.

关键词： Id2 T-cell exhaustion Epigenetic modification Immune evasion

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A case of solitary choroidal tuberculoma with highly positive tuberculin skin test and negative interferon gamma release assays

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International Journal of Ophthalmology(English edition) 2024年第5期17卷 969-972页

作者： Lin Zhou Bin Hu zhu-ping Xu Department of Ophthalmology Sichuan Provincial People’s HospitalUniversity of Electronic Science and Technology of ChinaChengdu 610072Sichuan ProvinceChina Department of Ophthalmology Chengdu Tianfu New District People’s HospitalChengdu 641400Sichuan ProvinceChina Department of Ophthalmology West China HospitalSichuan UniversityChengdu 610041Sichuan ProvinceChina

Dear Editor,Tuberculosis(TB)is an infectious disease which has been considered as a global public health emergency problem during the past 25y.The World Health Organization has estimated that approximately one-third of the world’s population are infected by TB.However,only 10%of patients with TB is symptomatic.TB can affect multiple organs throughout the body.Eighty percent of those infected are pulmonary TB.Ocular TB can occur with or without lung or other systemic TB.It is a rare extrapulmonary form of the disease and occupied about 3.5%–5%of all of the TB.It should not be disregarded as its potential influence on vision loss.The intraocular and/or extraocular structures could be impacted by ocular TB[1].Uvea was the most common affected structure[2].

关键词： organs ocular infected

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Poly(3-hexylthio) thiophene Field-effect Transistor Device Performance: Impact of the Content of Hexylthio Side Chain on Backbone

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Chinese Journal of Polymer Science 2024年第1期42卷 14-23,I0005页

作者： Hao-Yu Liu Lian-He Han Ling-Wei Kong Li-ping zhu Xiao-Lan Qiao Mei-Fang zhu State Key Laboratory for Modification of Chemical Fibers and Polymer Materials College of Materials Science and EngineeringDonghua UniversityShanghai 201620China School of Electronic Information and Electrical Engineering Shanghai Jiao Tong UniversityShanghai 200240China

Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT generally exhibits low charge mobility mostly due to poor solution processability attributed to dense arrangement of hexylthio side chain in polymer, which led to strong noncovalent interactions among sulfur atoms. To balance the nonvalent interaction and aggregation for P3HTT, herein, we systematically study the effect of hexylthio side chain content in polymer backbone on the structure and properties. A series of regioregular P3HTT-based homopolymers(P3HTT, P3HTT-50,P3HTT-33 and P3HTT-25) were prepared via Kumada catalyst transfer polycondensation method from a set of mono-, bi-, ter-and quarterthiophenes containing different contents of hexylthio side chain. The DFT calculation shows the planarity of polymers backbone could be improved through reducing the density of hexylthio side chain in polymer mainchain. And significant changes in their crystallinity, aggregation and optical properties were observed with the content of hexylthio side chain reducing. The P3HTT-33 displayed the highest field-effect transistor hole mobility of 2.83×10^(-2) cm^(2)·V^(-1)·s^(-1) resulting from a balance between the crystallinity and planarity. This study demonstrates modulating the content of hexylthio side chain in P3HTT is an effective strategy to optimize the opto-electronic properties of polymer obtaining excellent semiconductor device performance.

关键词： Conjugated polymer Polythiophene Noncovalent interaction Molecular aggregation Organic field-effect transistor

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An interview with Vladimir Tikhonchuk

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High Power Laser Science and Engineering 2023年第6期11卷 95-100页

作者： ping zhu Joint Laboratory on High Power Laser and Physics Shanghai Institute of Optics and Fine MechanicsChinese Academy of SciencesShanghaiChina

Vladimir Tikhonchuk,Professor Emeritus at Centre Lasers Intenses et Applications,University of Bordeaux,France,and senior researcher at the Extreme Light Infrastructure ERIC,ELI-Beamlines Facility,Czech Republic.His research is in the domain of high energy density physics and nonlinear optics,including inertial confinement fusion(ICF),dynamic processes in laboratory astrophysics,laser–plasma interactions,excitation of parametric instabilities,generation of magnetic and electric fields,acceleration of charged particles and energy transport.

关键词： interview optics excitation

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