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苝二酰亚胺共价有机框架超级还原剂用于高效光催化芳基卤化物还原反应
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作者 金昱丞 刘小琳 +9 位作者 曲琛 李长骏 王海龙 詹晓宁 曹昕怡 李晓锋 于宝秋 张琪 齐冬冬 姜建壮 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第2期171-183,共13页
自由基离子型分子光催化剂被证实是具有很强还原能力的可见光超级还原剂,它们在促进惰性的有机反应(例如将芳基卤化物还原为芳基自由基)方面具有突出的催化能力.然而,由于分子聚集严重地降低其催化活性,因而针对非均相超级还原剂的研究... 自由基离子型分子光催化剂被证实是具有很强还原能力的可见光超级还原剂,它们在促进惰性的有机反应(例如将芳基卤化物还原为芳基自由基)方面具有突出的催化能力.然而,由于分子聚集严重地降低其催化活性,因而针对非均相超级还原剂的研究较少.本文提出了一种新的方法来解决上述问题,通过溶剂热反应将具有连续光诱导电子转移机制的苝二亚胺超级还原剂(PDI)异质化为二维给体-受体(D-A)共价有机框架(COFs).即以N,N'-双(3-戊基)-2,5,8,11-四(4-甲酰基苯基)苝二酰亚胺(TFPDI)与1,3,6,8-四(4-氨基苯基)芘\(Py-TA)或2,3,6,7-四(4-氨基基苯基)四硫富瓦烯(TTF-TA)为原料,通过溶剂热反应分别制备了两种高晶态二维D-A型COF结构:USTB-21和USTB-22,并用于芳基氯化物、芳基溴化物和芳基碘化物的光催化还原反应.X射线衍射和理论模拟结果表明,USTB-21和USTB-22具有二维共价键连接的层状结构,分别呈现AA和AB的堆积方式.在各自最佳反应条件下,COFs显示出与均相催化剂相媲美的可见光催化性能,可高效地还原一系列芳基氯化物、芳基溴化物和芳基碘化物.其中,USTB-22在可见光驱动不同的芳香卤化物还原时,3 h内的转化率高达99%.瞬态吸收光谱结果表明,相比于均相催化剂(N,N'-双(2,6-二异丙基苯基)苝二酰亚胺),自由基阴离子激发态寿命是150 ps,USTB-21和USTB-22具有更长的激发态寿命,分别为210和260 ps.顺磁共振波谱测试结果证明,自由基阴离子光催化剂异质化成晶态D-A型COFs能够有效地促进电荷分离效率和延长激发态寿命.上述结果说明,USTB-22具有良好的光催化性能主要是因为其激发态寿命较长以及电荷分离效率较好.理论模拟结果表明,所制备的材料具有D-A型的电子结构.对COF的模型片段进行理论计算,揭示了各步反应路径中吉布斯自由能的变化,从而进一步阐明了光催化机理.在催化反应过程中,芳基卤化物还原途径可分为两个阶段:第一阶段为双光子能量输入和光驱电子转移,包括光子捕获和(TTF-PDI•−)^(*)产生以及光驱动电子转移到4-溴苯乙酮底物;第二阶段为能量输出,用于还原4-溴苯乙酮底物生成苯乙酮.综上所述,本文通过溶剂热反应将具有连续光诱导电子转移机制的苝二亚胺超级还原剂异质化为二维D-A型COFs结构.该结构在芳基氯化物、芳基溴化物和芳基碘化物等的光催化还原反应中,可很好地促进电子从光催化剂转移到反应物,进而显著提高光催化反应的活性和选择性;本研究对于未来设计新型自由基离子型高效光催化剂提供了新的思路. 展开更多
关键词 苝酰亚胺 共价有机骨架 光催化剂 均相 芳基卤化物的还原
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金融时间序列系统风险度量:动态二元Dvine模型
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作者 陈昱 曹心怡 +1 位作者 金姝玥 徐涛 《中国科学技术大学学报》 CAS CSCD 北大核心 2023年第11期1-11,I0001,I0007,共13页
在金融市场中,对金融资产的尾部风险的精准度量一直是研究者关注的焦点。本文提出了一个新的二元时间序列模型,用来计算和预测金融资产的在险价值(VaR)和条件在险价值(CoVaR)。该模型可以同时捕捉二元时间序列中存在的序列相关性和横截... 在金融市场中,对金融资产的尾部风险的精准度量一直是研究者关注的焦点。本文提出了一个新的二元时间序列模型,用来计算和预测金融资产的在险价值(VaR)和条件在险价值(CoVaR)。该模型可以同时捕捉二元时间序列中存在的序列相关性和横截面相关性,从而提高估计和预测的精度。本文在模型推导中给出了该二元时间序列模型的参数估计值,并且基于plug-in方法给出了VaR和CoVaR的估计值。还建立了Dvine模型估计量的渐近性质。对金融股价的实证分析表明我们的模型在风险度量和预测方面表现良好。 展开更多
关键词 序列相关性 横截面相关性 时变COPULA 金融风险管理 条件分位数
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A tetraaldehyde-derived porous organic cage and covalent organic frameworks:Syntheses,structures,and iodine vapor capture 被引量:1
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作者 xinyi cao Yucheng Jin +5 位作者 Hailong Wang Xu Ding Xiaolin Liu Baoqiu Yu Xiaoning Zhan Jianzhuang Jiang 《Chinese Chemical Letters》 SCIE CAS CSCD 2024年第9期426-431,共6页
Dynamic covalent imine reactions between 2,3-dimethoxy-[1,1:4,1-terphenyl]-3,3,5,5-tetracarbaldehyde(DMTT)and cyclohexanediamine,p-phenylenediamine,and benzidine,respectively,generate a porous organic cage(DMPOC)and t... Dynamic covalent imine reactions between 2,3-dimethoxy-[1,1:4,1-terphenyl]-3,3,5,5-tetracarbaldehyde(DMTT)and cyclohexanediamine,p-phenylenediamine,and benzidine,respectively,generate a porous organic cage(DMPOC)and two covalent organic frameworks(COFs),USTB-29,and USTB-30.DMPOC shows a[3+6]topological cage-like structure according to single crystal X-ray diffraction result.In contrast,both microcrystalline USTB-29 and USTB-30 exhibit two-dimensional monoporous structures in an eclipsed AA stacking style based on powder X-ray diffraction and theoretical simulations.In addition,DMPOC is capable of efficiently absorbing the iodine vapor with an outstanding uptake of 5.10 g/g,much higher than that of USTB-29(3.07 g/g)and USTB-30(3.16 g/g).Cage to COFs transformations have been realized from DMPOC to USTB-29 and USTB-30 via the imine bond exchange with slightly increased iodine vapor uptake.Mechanism investigations uncover that both nitrogen and oxygen atoms of POC and COFs contribute to iodine vapor capture due to the formation of charge transfer matter,and loose interaction introducing adaptive expanding voids of DMPOC is suggested to capture more iodine vapor than that of COFs with strongπ-πinteractions. 展开更多
关键词 Porous organic cage Crystal structure Covalent organic framework Transformation Iodine vapor adsorption
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Absolute pose estimation of UAV based on large-scale satellite image
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作者 Hanyu WANG Qiang SHEN +2 位作者 Zilong DENG xinyi cao Xiaokang Wang 《Chinese Journal of Aeronautics》 SCIE EI CAS CSCD 2024年第6期219-231,共13页
Obtaining absolute pose based on pre-loaded satellite images is one of the important means of autonomous navigation for small Unmanned Aerial Vehicles(UAVs)in Global Navigation Satellite System(GNSS)denied environment... Obtaining absolute pose based on pre-loaded satellite images is one of the important means of autonomous navigation for small Unmanned Aerial Vehicles(UAVs)in Global Navigation Satellite System(GNSS)denied environments.Most of the previous works have tended to build Convolutional Neural Networks(CNNs)to extract features and then directly regress the pose,which will fail when solving the challenges caused by the huge viewpoint and size differences between“UAV-satellite”image pairs in real-world scenarios.Therefore,this paper proposes a probability distribution/regression integrated deep model with the attention-guided triple fusion mechanism,which estimates discrete distributions in pose space and three-dimensional vectors in translation space.In order to overcome the shortage of the relevant dataset,this paper simulates image datasets captured by UAVs with forward-facing cameras during target searching and autonomous attacking.The effectiveness,superiority,and robustness of the proposed method are verified by simulated datasets and flight tests. 展开更多
关键词 Satellite imagery Unmanned Aerial Vehicle(UAV) Deep neural networks Vision navigation von Mises-Fisher distribution
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EMC10 governs male fertility via maintaining sperm ion balance 被引量:2
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作者 Yuchuan Zhou Fei Wu +13 位作者 Man Zhang Zuquan Xiong Qianqian Yin Yanfei Ru Huijuan Shi Jinsong Li Shanhua Mao Yanliang Li xinyi cao Renming Hu Chong Wee Liew Qiang Ding Xuanchun Wang Yonglian Zhang 《Journal of Molecular Cell Biology》 SCIE CAS CSCD 2018年第6期503-514,共12页
Infertility is a severe public health problem worldwide that prevails up to 15% in reproductive-age couples,and male infertility accounts for half of total infertility.Studies on genetically modified animal models hav... Infertility is a severe public health problem worldwide that prevails up to 15% in reproductive-age couples,and male infertility accounts for half of total infertility.Studies on genetically modified animal models have identifed lots of genes involved in the pathogenesis of male infertility.The underlying causes,however,remain largely unclear.In this study,we provide evidence that EMCIO,one subunit of endoplasmic reticulum (ER)membrane protein complex (EMC),is required for male fertility.EMC10 is significantly decreased in spermatozoa from patients with asthenozoospermia and positively associated with human sperm motility. Male mice lacking Emc10 gene are completely sterile.Emc10-null spermatozoa exhibit multiple defects including abnormal morphology,decreased motility,impaired capacitation,and impotency of acrosome reaction,thereby which are incapable of fertilizing intact or ZP-free oocytes.However,intracytoplasmic sperm injection could rescue this defect caused by EMC10 deletion. Mechanistically,EMC10 deficiency leads to inactivation of Na/K-ATPase,in turn giving rise to an increased level of intraceltutar Na^+ in spermatozoa,which contributes to decreased sperm motility and abnormal morphology.Other mechanistic investigations demonstrate that the absence of EMC10 results in a reduction of HCO3^- entry and subsequent decreases of both cAMP-dependent protein kinase A substrate phosphorylation and protein tyrosine phosphorytation.These data demonstrate that EMC10 is indispensable to mate fertility via maintaining sperm ion balance of Na^+ and HCO3^-,and also suggest that EMC10 is a promising biomarker for male fertility and a potential pharmaceutical target to treat male infertility. 展开更多
关键词 Emc10 KNOCKOUT SPERM MATURATION male INFERTILITY ion IMBALANCE Na/K-ATPase
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Plasmonic nanostructure characterized by deep-neuralnetwork-assisted spectroscopy[Invited] 被引量:2
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作者 董奇奥 王文琦 +5 位作者 曹欣怡 肖依博 郭笑涵 马敬轩 汪联辉 高丽 《Chinese Optics Letters》 SCIE EI CAS CSCD 2023年第1期17-24,共8页
The lateral geometry and material property of plasmonic nanostructures are critical parameters for tailoring their optical resonance for sensing applications.While lateral geometry can be easily observed by a scanning... The lateral geometry and material property of plasmonic nanostructures are critical parameters for tailoring their optical resonance for sensing applications.While lateral geometry can be easily observed by a scanning electron microscope or an atomic force microscope,characterizing materials properties of plasmonic devices is not straightforward and requires delicate examination of material composition,cross-sectional thickness,and refractive index.In this study,a deep neural network is adopted to characterize these parameters of unknown plasmonic nanostructures through simple transmission spectra.The network architecture is established based on simulated data to achieve accurate identification of both geometric and material parameters.We then demonstrate that the network training by a mixture of simulated and experimental data can result in correct material property recognition.Our work may indicate a simple and intelligent characterization approach to plasmonic nanostructures by spectroscopic techniques. 展开更多
关键词 PLASMONICS soft nanoimprint lithography deep neural network nanostructure characterization
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Nascent Proteome and Glycoproteome Reveal the Inhibition Role of ALG1 in Hepatocellular Carcinoma Cell Migration 被引量:3
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作者 xinyi cao Yuyin Shao +8 位作者 Peiyi Meng Zhao cao Guoquan Yan Jun Yao Xinwen Zhou Chao Liu Lei Zhang Hong Shu Haojie Lu 《Phenomics》 2022年第4期230-241,共12页
Asparagine-linked glycosylation protein 1 homolog(ALG1)participates in the initial stage of protein N-glycosylation and N-glycosylation has been implicated in the process of hepatocellular carcinoma(HCC)progression.Ho... Asparagine-linked glycosylation protein 1 homolog(ALG1)participates in the initial stage of protein N-glycosylation and N-glycosylation has been implicated in the process of hepatocellular carcinoma(HCC)progression.However,whether ALG1 plays a role in human HCC remains unknown.In this study,the expression profile of ALG1 in tumorous and corresponding adjacent non-tumor tissues was analyzed.The relationship of ALG1 expression with clinical features and prognosis of HCC patients was also evaluated using immuno-histochemical method.Here we found ALG1 decreased in HCC tissues compared with adjacent normal liver tissues,which predicted an unfavorable prognosis.Combined with RNA interference,nascent proteome and glycoproteome were determined systematically in Huh7 cell line.Bioinformatics analysis indicated that the differentially expressed proteins participating in the response of ALG1 knockdown were most significantly associated with cell-cell adhesion.Functional studies confirmed that knockdown of ALG1 reduced cell adhesion capacity,and promoted cell migration.Furthermore,down-regulation of H8N2(on N-glycosite N651)and H5N4S2F1(on N-glycosite N692)from N-cadherin was identified as a feature of ALG1 knockdown.Our findings revealed that ALG1 controlled the expression of glycosylated N-cadherin and played a role in HCC migration,with implications for prognosis. 展开更多
关键词 Nascent proteome ALG1 GLYCOSYLATION N-CADHERIN Hepatocellular carcinoma
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Water and fluorinated alcohol mediated/promoted tandem insertion/aerobic oxidation/bisindolylation under metal-free conditions:Easy access to bis(indolyl)methanes
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作者 Yong Wang xinyi cao +4 位作者 Jingfei Ji Xiuling Cui Chao Pi Leyao Zhao Yangjie Wu 《Chinese Chemical Letters》 SCIE CAS CSCD 2021年第5期1696-1700,共5页
A green tandem reaction,including insertion/aerobic oxidation/bisindolylation,starting from indoles and diazo compounds has been developed.The combination of water and fluorinated alcohol plays dual roles as solvent a... A green tandem reaction,including insertion/aerobic oxidation/bisindolylation,starting from indoles and diazo compounds has been developed.The combination of water and fluorinated alcohol plays dual roles as solvent and promoter in this chemical transformation.Molecular oxygen in the air acts as an oxidant.3,3’-Bis(indolyl)methanes with quaternary carbon were produced under metal-free conditions.No any catalyst and additive were required.N2 and water were released as sole by-products.Absence of water and fluorinated alcohol resulted in Wolff rearrangement product. 展开更多
关键词 Bis(indolyl)mcthanes DIAZO Fluorinated alcohol INDOLE WATER
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