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排序方式: 共有241条查询结果,搜索用时 140 毫秒
101.
102.
Suisui He Siyu Lu Sha Liu Tianrong Li Jieling Li Shihao Sun Meilin Liu Kun Liang Xu Fu Fengjuan Chen Genping Meng Lang Zhang Jun Hai Baodui Wang 《Chemical science》2020,11(33):8817
Carrying out the in vivo syntheses of drugs toxic to tumors based on the specific features of the tumor microenvironment is critical for ensuring specific antitumor efficacy. However, achieving in situ high-yield synthetic toxic drugs from non-toxic agents and reducing their drug resistance in hypoxic tumors remain challenges. Herein we created a tumor-microenvironment-responsive porous Pt/Pt(iv) methylene blue coordination polymer nanoshuttle (Pt/PtMBCPNS) photosensitizer with spatiotemporally controlled O2 and singlet oxygen (1O2) self-sufficient for the in vivo high-yield synthesis of drugs and efficient hypoxic tumor therapy. After being endocytosed, the nanophotosensitizer as a cascade catalyst was observed to effectively catalyze the conversion of endogenous H2O2 to O2, and was hence found to play a dual role in the enhanced tumor therapy. PtMBCPNSs, upon being irradiated with red light, efficiently converted O2 into 1O2. Subsequently, 1O2 oxidized non-toxic 1,5-dihydroxynaphthalene to form the anticancer agent juglone with a high yield. In addition, O2 was found to be able to improve the hypoxic microenvironment without light irradiation, thus enhancing the antitumor efficacy of the produced drugs and reducing drug resistance. As a result, by enhancing the synergistic effect of the treatment, this nanophotosensitizer significantly inhibited the growth of tumors and avoided damage to normal tissues/organs. Collectively, this work highlights a robust nanoplatform with the spatiotemporally controlled in vivo high-yield synthesis of drugs and generation of O2 to help overcome the current limitations of chemical-based therapies against hypoxic tumors.A porous photosensitizer displaying catalase-like activity and drug synthesis ability was synthesized for the synergistic chemo-photodynamic therapy, opening new promising ways for carrying out the precise cooperative treatment of hypoxic tumors. 相似文献
103.
1989年,Kresge等人发现溶液中苯炔醇的酸性比苯烯醇高7pK_α,这引起理论和实验化学家的兴趣.Smith等人曾对一对典型炔醇(CHCOH)和烯醇(CH_2CHOH)的生成反应的热效应进行理论研究,本文进一步从理论上研究了这一对反应(反应(1)、(2))的反应机理。 相似文献
104.
采用较新的半经验分子轨道方法Austin Model 1(简称AM1方法),辅以Berny梯度优化方法,对单线态氧(~1O_2)与咪唑的1,2-环加成反应,进行了理论研究。计算获得实验尚未检测到的4,5-二氧环丁烷(4,5-dioxetane)的结构,并在反应势能面上找到单重态双自由基中间体及通过该中间体的两步反应的过渡态。通过对过渡态的结构特征、虚振动方向以及对反应过程的电荷分布情况、轨道相互作用等的分析,说明该反应是经由单重态双自由基中间体的分步反应。两步反应的活化势垒分别为39.2kJ·mol~(-1)和150.5kJ·mol~(-1)。 相似文献
105.
106.
Zhongyu Du Siyu Duan Mingfang Ma Xiangyu Xu Zhenquan Li Lingdong Kong Jun Liu 《国际化学动力学杂志》2019,51(4):258-265
The rate constants of two redox reactions and in the critical solution of 2-butoxyethanol and water have been measured by using the UV spectrophotometry at the initial reaction stage. It was found that the rate constants at various temperatures for two reactions were well described by the Arrhenius equation in the noncritical region. The critical slowing down effect was detected in the critical region. The critical slowing down exponents were determined to be 0.044 ± 0.004 and 0.046 ± 0.005 for reactions and , respectively. The values of the critical slowing down exponents showed that only dynamic critical slowing down effect, and no thermodynamic singularity could be observed for the two reactions. 相似文献
107.
Dr. Lin Ai Dr. Ziqi Song Dr. Mingjun Nie Dr. Jingkun Yu Dr. Fukang Liu Dr. Haoqiang Song Prof. Biao Zhang Prof. Geoffrey I. N. Waterhouse Prof. Siyu Lu 《Angewandte Chemie (International ed. in English)》2023,62(12):e202217822
Carbon dots (CDs) find widespread attention due to their remarkable fluorescent and electronic properties. However, aggregation-caused quenching currently limits the application of CDs in colored displays. The construction of CDs with color-tunable solid-state fluorescence (SSF) is rarely reported, since the preparation of SSF CDs is technically challenging. Herein, through surface ligand modulation, SSF CDs with an emission-color span of almost 300 nm (from blue to deep red) were obtained. In-depth structure-property studies reveal that intra- and inter-molecular hydrogen-bonding inside SSF CDs provokes the emission properties in the aggregated state. Photodynamic characterizations demonstrate emission wavelengths can be switched smoothly by deliberately altering conjugation ability between substituent ligands and CDs core. Three-dimensional printing patterning is used to create a range of emissive objects, demonstrating the commercial potential for use in optical lamps. 相似文献
108.
Runjia Lin Liqun Kang Karolina Lisowska Weiying He Siyu Zhao Shusaku Hayama Graham J. Hutchings Dan J. L. Brett Furio Corà Ivan P. Parkin Guanjie He 《Angewandte Chemie (International ed. in English)》2023,62(21):e202301433
Electrocatalytic oxygen reduction reaction (ORR) has been intensively studied for environmentally benign applications. However, insufficient understanding of ORR 2 e−-pathway mechanism at the atomic level inhibits rational design of catalysts with both high activity and selectivity, causing concerns including catalyst degradation due to Fenton reaction or poor efficiency of H2O2 electrosynthesis. Herein we show that the generally accepted ORR electrocatalyst design based on a Sabatier volcano plot argument optimises activity but is unable to account for the 2 e−-pathway selectivity. Through electrochemical and operando spectroscopic studies on a series of CoNx/carbon nanotube hybrids, a construction-driven approach based on an extended “dynamic active site saturation” model that aims to create the maximum number of 2 e− ORR sites by directing the secondary ORR electron transfer towards the 2 e− intermediate is proven to be attainable by manipulating O2 hydrogenation kinetics. 相似文献
109.
Wei Zhang Dr. Xuan Zhang Dr. Dandan Feng Dr. Yajing Liang Dr. Zhenying Wu Siyu Du Yu Zhou Dr. Ce Geng Dr. Ping Men Prof. Chunxiang Fu Prof. Xuenian Huang Prof. Xuefeng Lu 《Angewandte Chemie (International ed. in English)》2023,62(12):e202215529
Flavonoids are important plant natural products with variable structures and bioactivities. All known plant flavonoids are generated under the catalysis of a type III polyketide synthase (PKS) followed by a chalcone isomerase (CHI) and a flavone synthase (FNS). In this study, the biosynthetic gene cluster of chlorflavonin, a fungal flavonoid with acetolactate synthase inhibitory activity, was discovered using a self-resistance-gene-directed strategy. A novel flavonoid biosynthetic pathway in fungi was revealed. A core nonribosomal peptide synthetase-polyketide synthase (NRPS-PKS) is responsible for the generation of the key precursor chalcone. Then, a new type of CHI catalyzes the conversion of a chalcone into a flavanone by a histidine-mediated oxa-Michael addition mechanism. Finally, the desaturation of flavanone to flavone is catalyzed by a new type of FNS, a flavin mononucleotide (FMN)-dependent oxidoreductase. 相似文献
110.
Yunfeng Luo Xiaoli Ma Yufan Qiu Yun Lu Siyu Shen Yang Li Haiyun Gao Kang Chen Jiawei Zhou Tianyuan Hu Lichan Tu Huan Zhao Dan Li Faqiang Leng Wei Gao Tao Jiang Changli Liu Luqi Huang Ruibo Wu Yuru Tong 《Angewandte Chemie (International ed. in English)》2023,62(48):e202313429
The oxidosqualene cyclase (OSC) catalyzed cyclization of the linear substrate (3S)-2,3-oxidosqualene to form diverse pentacyclic triterpenoid (PT) skeletons is one of the most complex reactions in nature. Friedelin has a unique PT skeleton involving a fascinating nine-step cation shuttle run (CSR) cascade rearrangement reaction, in which the carbocation formed at C2 moves to the other side of the skeleton, runs back to C3 to yield a friedelin cation, which is finally deprotonated. However, as crystal structure data of plant OSCs are lacking, it remains unknown why the CSR cascade reactions occur in friedelin biosynthesis, as does the exact catalytic mechanism of the CSR. In this study, we determined the first cryogenic electron microscopy structure of a plant OSC, friedelin synthase, from Tripterygium wilfordii Hook. f (TwOSC). We also performed quantum mechanics/molecular mechanics simulations to reveal the energy profile for the CSR cascade reaction and identify key residues crucial for PT skeleton formation. Furthermore, we semirationally designed two TwOSC mutants, which significantly improved the yields of friedelin and β-amyrin, respectively. 相似文献