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1NEW GUAIANOLIDES FROM Centipeda minima显示文摘Ⅰ. NEW GUAIANOLIDES FROM CENTIPEDA MINIMA The Chinese medical herb Centipeda minima (L.) A. Br. et Ascher (Compositae) has been used for treatment of rhinitis, sinusitis and nasopharynger tumor. Previous chemical investigations only gave steroids and triterpenes and cis-chrysanthenyl acetate. A reinvestigation of the dried drug (whole plant) afforded in addition to the triterpenes and steroids 10-isobutyryloxy-8, 9-epoxithymol-isobutyrate 6, the derivatives 1 and 2, three pseudoguaianolides, arnicolide 7, brevilin8 and helenalin 9, as well as three guaianolides, the 2-O-esters of florilenalin 3—5.FERDINAND BOHLMANN 陈仲良 1984Chinese Science Bulletin1984,29,7:11
2Antibacterial photodynamic therapy:overview of a promising approach to fight antibiotic-resistant bacterial infections显示文摘Antibacterial photodynamic therapy(APDT)has drawn increasing attention from the scientific society for its potential to effectively kill multidrug-resistant pathogenic bacteria and for its low tendency to induce drug resistance that bacteria can rapidly develop against traditional antibiotic therapy.The review summarizes the mechanism of action of APDT,the photosensitizers,the barriers to PS localization,the targets,the in vitro-,in vivo-,and clinical evidence,the current developments in terms of treating Gram-positive and Gram-negative bacteria,the limitations,as well as future perspectives.Relevance for patients:A structured overview of all important aspects of APDT is provided in the context of resistant bacterial species.The information presented is relevant and accessible for scientists as well as clinicians,whose joint effort is required to ensure that this technology benefits patients in the post-antibiotic era.Yao Liu Rong Qin Sebastian A.J.Zaat Eefjan Breukink Michal Heger 2015Journal of Clinical & Translational Research2015,1,3:8
3Preparation and photoactivity of thermosensitive polymer supported metallophthalocyanine显示文摘A novel reactive metallophthalocyanine derivative,zinc tetra(2,4-dichloro-1,3,5-triazine)aminophthalo-cyanine(Zn-TDTAPc),was prepared and immobilized on poly(N-isopropylacrylamide)(PNIPAAm) by covalent bonding to obtain a thermosensitive polymer(Zn-TDTAPc-g-PNIPAAm).Compared with zinc tetraaminophthalocyanine(Zn-TAPc),Zn-TDTAPc-g-PNIPAAm exhibits excellent solubility in water and in most organic solvents.Furthermore,it has a special thermosensitive property in water and the lower critical solution temperature(LCST) is 34.1℃.It was found that both dissolved and precipitated Zn-TDTAPc-g-PNIPAAm present high photoactivity evidenced by the experiment of photocatalytic degra-dation of 1,3-diphenylisobenzofuran(DPBF) in the presence of Zn-TDTAPc-g-PNIPAAm.These proper-ties suggest that it can be used potentially in photodynamic therapy(PDT).CHEN WenXing LIU Fan LU WangYang SHEN XiaoYuan YAO YuYuan XU MinHong 2008Science China Chemistry2008,51,6:5
4Photogeneration of the free radicals and singlet oxygen by chrysophanol from rheum显示文摘In the current work, chryosphanol (MHAQ) was isolated and purified from rheum, and the photosensitization activities were studied. In nitrogen-saturated DMSO solution, irradia- tion of chryosphanol (MHAQ) with visible light (>430 nm) produced the semiquinone radical anions (MHAQ??), which was intensified significantly by an electron donor NADH, suggesting electron transfer between the excited and ground state photosensitizer molecules. In an air-saturated DMSO solution, superoxide radical anions (O2 ), trapped by DMPO, were detected. ?? It was proved that O2 was not originated from the singlet oxygen (1O2) but dependent on DMPO, ?? chrysophanol, oxygen and the irradiation time. The singlet oxygen and OH could also be pro- ? duced by the photosensitization of the photosensitizer. These suggest that chrysophanol pos- sesses the photosensitization activity via Type I mechanism and Type II mechanism. To evaluate the photosensitization activities of MHAQ, emodin and mixed anthraquinone derivatives ex- tracted from rheum, the relative productivities of O2 were estimated to be 1.8, 1.1 and 1.0 re- ?? spectively and the quantum yields for singlet oxygen to be 0.36, 0.53 and 0.14 respectively. Therefore, these low-cost pigments may be potentially used as phototherapeutic medicine for some kind of vascular diseases or photo-activated pesticides.RAO Jing1,2, XIE Jie1, ZHAO Jingquan1 & ZHU Teng2 1. Key Laboratory of Photochemistry, Center for Molecular Science, Institute of Chemistry, The Chinese Academy of Sciences, Beijing 100080, China 2. University of Science and Technology Beijing, Beijing 10083, China 2004Science China Chemistry2004,47,5:3
5Ag7(MBISA)6 Nanoclusters Conjugated with Quinacrine for FRET-Enhanced Photodynamic Activity under Visible Light Irradiation显示文摘Singlet oxygen(1 O2) plays an important role in various applications, such as in the photodynamic therapy(PDT) of cancers,photodynamic inactivation of microorganisms, photo-degradation of toxic compounds, and photo-oxidation in synthetic chemistry. Recently,water-soluble metal nanoclusters(NCs) have been utilized as photosensitizers for the generation of highly reactive 1 O2 because of their high water solubility, low toxicity, and surface functionalizability for targeted substances. In the case of metal NC-based photosensitizers, the photo-physical properties depend on the core size of the NCs and the core/ligand interfacial structures. A wide range of atomically precise gold NCs have been reported; however, reports on the synthesis of atomically precise silver NCs are limited due to the high reactivity and low photostability(i.e., easy oxidation) of Ag NCs. In addition, there have been few reports on what kinds of metal NCs can generate large amounts of 1 O2. In this study, we developed a new one-pot synthesis method of water-soluble Ag7(MBISA)6(MBISA= 2-mercapto-5-benzimidazolesulfonic acid sodium salt) NCs with highly efficient 1 O2 generation ability under the irradiation of white light emitting diodes(LEDs). The molecular formula and purity were determined by electrospray ionization mass spectrometry and gel electrophoresis. To the best of our knowledge, this is the first report on atomically precise thiolate silver clusters(Agn(SR)m) for efficient 1 O2 generation under visible light irradiation. The 1 O2 generation efficiency of Ag7(MBISA)6 NCs was higher than those of the following known water-soluble metal NCs: bovine serum albumin(BSA)-Au25 NCs,BSA-Ag8 NCs, BSA-Ag14 NCs,Ag25(dihydrolipoic acid)14 NCs,Ag35(glutathione)18 NCs,and Ag75(glutathione)40 NCs. The metal NCs examined in this study showed the following order of 1 O2 generation efficiency under white light irradiation: Ag7(MBISA)6 > BSA-Ag14 > Ag75(SG)40 > Ag35(SG)18 >BSA-Au25 >>BSA-Ags(not detected) and Ag2 s(DHLA)14(not detected). For further improving the 1 O2 generation of Ag7(MBISA)6 NCs, we developed a novel fluorescence resonance energy transfer(FRET) system by conjugating Ag7(MBISA)6 NCs with quinacrine(QC)(molar ratio of Ag NCs to QC is 1 : 0.5). We observed the FRET process,from QC to Ag7(MBISA)6 NCs,occurring in the conjugate. That is,the QC works as a donor chromophore,while the Ag NCs work as an acceptor chromophore in the FRET process. The FRET-mediated process caused a 2.3-fold increase in 1 O2 generation compared to that obtained with Ag7(MBISA)6 NCs alone. This study establishes a general and simple strategy for improving the PDT activity of metal NC-based photosensitizers.TOMINAGA Chiaki HIKOSOU Dailo OSAKA Issey KAWASAK Hideya 2018物理化学学报2018,34,7:2
6NEW HETEROCYCLIC SYSTEM SYNTHESIS H THE REACTION OF 2,3-DIHYDRO-1,5-BENZOTHIAZEPINES WITH DICHLOROCARBENE显示文摘The reaction of two series of 2,3-dihydro-1,5-henzothiazepines Ⅰ with dichloro-carbene,gave azirino[2,1-d][1,5]benzothiazepines Ⅷ,azirino[2,1-e][1,6]benzothiazocines Ⅸ,pyrrolo[2,1-b][1,3]benzothiazoles Ⅹ,substituted-cyclopropanes Ⅺ and 2H-1,4-benzothiazin-2-onesⅫ.The structures of these products were confirmed by the analytical and spectral data.CompoundⅧ and Ⅸ are two new ring systems.Ruo Xi LAN Sheng JIN Department of Chemistry,Peking University,Beijing 100871Zheng Ming LI Elemento-Organic Chemistry Laboratory,Nankai University,Tianjing 300071 1992Chinese Chemical Letters1992,3,1:2
7Photogenerated singlet oxygen over zeolite-confined carbon dots for shape selective catalysis显示文摘Singlet oxygen as an activated oxygen species played an important role in organic synthesis. Suitable catalyst for converting ubiquitous oxygen molecule to singlet oxygen under mild conditions has attracted a wide range of attention. Herein, carbon dots have been confined into mesopores of silicalite-1 nanocrystals framework and acted as active sites for generation of singlet oxygen. The high oxygen-adsorption capacity of zeolite nanocrystals facilitated the photocatalytic generation rate of singlet oxygen, outpacing the free-standing carbon dots for 14-fold. The integrated carbon dot-zeolite nanocrystal hybrid also exhibited a special size-dependent selectivity for organic synthesis by using the in situ formed and confined singlet oxygen as active oxygen species.Qiu-Ying Yu Guang-Yao Zhai Tian-Lu Cui Hui Su Zhong-Hua Xue Jun-Jun Zhang Peter J.Pauzauskie Shin-ichi Hirano Xin-Hao Li Jie-Sheng Chen 2019Science China Chemistry2019,62,4:2
8THE OPTICAL PROPERTIES OF PHEOPHORBIDE A显示文摘Photochemical therapy has become a new area in treating malignant tumour with photosensitive medicines. In recent years, a new photosensitive medicine phcophorbide A (PhA) is developed, with curative effect ten times as high as that of Hematoporphyrin. In this note, the method of preparing PhA from pteridophyte is reported, the electronic spectra of PhA is qualitatively analyzed by HMO figure theory and the mechanism of photochemically treating cancer is discussed.孟继武 侯尚公 黄世华 徐叙瑢 1990Chinese Science Bulletin1990,35,22:1
9THE CHEMICAL STRUCTURES OF SPIRAMINEN AND SPIRAMINOL显示文摘Two new Components, spiramine N (1) and spiraminol (2) were isolated fromSpiraea japonica var. aecuminata Franch. Their structureswere elucidated bychemical and spectxalmeans.Xiao Jiang HAO Jun ZHOU Kaoru FUJI Manabu NODE Laberatiry of Phytochemistry, Kunming Institute of Botany, Acedemia Sinica, Kunming, 650204 Institute of Chemical Research, Kyoto University, Kyoto 611, Japan 1992Chinese Chemical Letters1992,3,6:1
10NEW EREMOPHILANOLIDES FROM LIGULARIA VEITCHIANA显示文摘The structures of three new eremophilanolides isolated from the roots of LigulariaVeitchiana were shown,by the spectral and chemical evidences,to be 1β,10β-epoxy-6β-hydrox-y-8β-methoxy-eremophil-7(11)-en-12,8α-olide(3),1β,10β-epoxy-6β-(2’ hydroxymethylacryloyloxy)-8β-methoxy-eremophil-7(11)-en-12,8α-olide(4)and 1β,10β-epoxy-6β-(2’-methoxymethylacryloyloxy)-8β-hydroxy-eremophil-7(11)-en-12,8α-olide(5).Yu ZHAO Zhong Jian JIA Ren Xiang TAN Institute of Organic Chemistry,State Key Laboratory of Applied Organic Chemistry at Lanzhou University,Lanzhou 730000, 1992Chinese Chemical Letters1992,3,1:1
11Photochemistry of hypocrellin derivatives under aerobic conditions显示文摘Hypocrellins are a novel type of photosensitizers. A series of new hypocrellin B (HB) derivatives have been synthesized to overcome their limitations, i.e. to improve their red absorption and amphiphilicity. The generation of reactive oxygen species (including superoxide anion radical, hydroxyl radical and singlet oxygen) is investigated in the presence of oxygen. The chemical structures of HB derivatives affect not only the generation efficiencies of superoxide and hydroxyl radicals, but also quantum yields of singlet oxygen.Yuying He Jingyi An Lijin Jiang 2000Chinese Science Bulletin2000,45,12:1
12Photodynamic action of hypocrellin A in liposomes显示文摘Hypocrellin A (HA), a perylenequinone derivative, is an efficient phototherapeutic agent. When HA is incorporated into small unilamellar liposomes of egg phosphatidylcholine, it generates 1O2 as demonstrated by 9,10-diphenylanthracene (9,10-DPA) photobleaching and detection of nitroxide radicals with ESR. The 1O2 quantum yield measured is 0.80±0.02. On irradiation of oxygen-saturated solution of HA-liposomes, hydroxyl radical OH is detected using DMPO as the ESR spin trapping agent. Hydroxyl radical is derived from superoxide radical anion O2-. The electron transfer reaction is also studied in deaerated solution. The results suggest that the photodynamic action of HA in lipid membranes proceeds via both Type I and Type II reactions.邹伟 安静仪 李滨 蒋丽金 1996Science China Chemistry1996,39,5:1
13Magnetic field effects on photochemical reaction——III. Mechanistic study of the photodecarboxylation of arylmethyl esters in micellar solutions显示文摘Photolysis of benzyl phenylacetate (ACO2A), benzyl p-methylphenylacetate (BCO2A) and1-naphthyl phenylacetate (ACO2Np) in homogeneous and micellar solutions results in products typicalof radical coupling reactions and loss of carbon dioxide. The cage effects upon direct photolysis ofthese esters in acetonitrile are significantly greater than zero and those in SDS or HDTBr micellarsolutions are even greater. In the triplet sensitization reaction of ACO2 Np in micellar solutions thecage effects are smaller than those obtained upon direct irradiation. However, the application of a0.05 or 0.2 T external magnetic field in the photolysis in micellar solutions decreases the cage effectsdramatically. All these results suggest that the photoextrusions of carbon dioxide from these estersproceed via radical intermediates, and upon direct photolysis the reactive states for the cleavage re-action involve both singlet and triplet excited states.TONG, Zhen-He TUNG, Chen-Ho* YUAN, Long-Hua, Institute of Photographic Chemistry, The Chinese Academy of Sciences, Beijing 100101 1991Chinese Journal of Chemistry1991,9,6:1
14Finding predictive models for singlet fission by machine learning显示文摘Singlet fission(SF),the conversion of one singlet exciton into two triplet excitons,could significantly enhance solar cell efficiency.Molecular crystals that undergo SF are scarce.Computational exploration may accelerate the discovery of SF materials.However,many-body perturbation theory(MBPT)calculations of the excitonic properties of molecular crystals are impractical for large-scale materials screening.We use the sure-independence-screening-and-sparsifying-operator(SISSO)machine-learning algorithm to generate computationally efficient models that can predict the MBPT thermodynamic driving force for SF for a dataset of 101 polycyclic aromatic hydrocarbons(PAH101).SISSO generates models by iteratively combining physical primary features.The best models are selected by linear regression with cross-validation.The SISSO models successfully predict the SF driving force with errors below 0.2 eV.Based on the cost,accuracy,and classification performance of SISSO models,we propose a hierarchical materials screening workflow.Three potential SF candidates are found in the PAH101 set.Xingyu Liu Xiaopeng Wang Siyu Gao Vincent Chang Rithwik Tom Maituo Yu Luca M.Ghiringhelli Noa Marom 2022npj Computational Materials2022,,1:1
15The effects of detergents DDM and β-OG on the singlet excited state lifetime of the chlorophyll a in cytochrome b_6f complex from spinach chloroplasts显示文摘The singlet excited state lifetime of the chlorophyll a (Chl a) in cytochrome b6f (Cyt b6f) complex was reported to be shorter than that of free Chl a in methanol, but the value was different for Cyt b6f com-plexes from different sources (~200 and ~600 ps are the two measured results). The present study demonstrated that the singlet excited state lifetime is associated with the detergents n-dodecyl-β-D- maltoside (DDM) and n-octyl-β-D-glucopyranoside (β-OG), but has nothing to do with the different sources of Cyt b6f complexes. Compared with the Cyt b6f dissolved in β-OG, the Cyt b6f in DDM had a lower fluorescence yield, a lower photodegradation rate of Chl a, and a shorter lifetime of Chl a excited state. In short, the singlet excited state lifetime, ~200 ps, of the Chl a in Cyt b6f complex in DDM is closer to the true in vivo.CHEN XiaoBo1,3, ZHAO XiaoHui2, ZHANG JianPing2, LI LiangBi1& KUANG TingYun1 1 Key Laboratory of Photosynthesis and Environmental Molecular Physiology, Institute of Botany, Chinese Academy of Sciences, Beijing 100093, China 2 State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sci- ences, Beijing 100080, China 3 Graduate University of Chinese Academy of Sciences, Beijing 100039, China 2007Science China(Life Sciences)2007,50,4:1
16THE SYNTHESIS AND STRUCTURAL INVESTIGATIONS OF SOME ORGANOMETALLIC COMPLEXES WITH TIN TO RARE EARTH BOND显示文摘Organometallic complexes having metal-metal bonds constitute a new series of compounds with specific characters in structure, bonding, and spectroscopic properties. Moreover, there has also been a growing interest in the reactivity patterns associated with these compounds. Since the seventies there have been many reports on the investigation of the synthesis and structure of complexes with tin-to-transition metal bonds,王序昆 周晓欣 张经坤 夏元复 刘荣川 王述新 1985Chinese Science Bulletin1985,30,12:1
17Phase Transition of Spin-Peierls Systems with Impurities显示文摘The quasi-one-dimensional spin-Peierls(SP)systems with impurities are studied in their bosonized form.The spins of the dimerized state are bounded into singlets with an SP gap,while the impurities of doped systems will induce fluctuations of the coupling strength between the spins at different sites and break some pairs of spin singlets.The doping suppresses the dimerized SP state and induces a Kosterlitz-Thouless phase transition from the dimerized state into the undimerized one.许伯威 丁国辉 叶飞 2000Chinese Physics Letters2000,17,8:0
18Study on the Total Synthesis of Hainanolide (V)-Oxidation of the Tricyclic Alkenes with Singlet Oxygen显示文摘Six tricyclic compounds containing C3, C4 double bonds were oxidized with singlet oxygen. Different regio-selectivity was found with regard to steric hinderence.Xiao Ming YU Lu Yan ZHANG Shi Zhi CHEN Liang HUANG (Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050) 1999Chinese Chemical Letters1999,10,8:0
19Quantum Phases of SrCu2(BO3)2 from High-Pressure Thermodynamics显示文摘In recent years,theoretical proposals for exotic states in quantum magnets are developing very rapidly,but many of these intriguing quantum phases and transitions have been difficult to realize experimentally.One class of such states is the valence bond solid,in which spins entangle locally and form symmetry-breaking singlet patterns.Signatures of a state with four-spin singlets were recently detected in the two-dimensional(2D)quantum magnet SrCu2(BO3)2 under high pressure.SUN Liling Anders Sandvik 2020Bulletin of the Chinese Academy of Sciences2020,34,2:0
20Enhanced Peroxymonosulfate Activation by NixCo1-xOOH for Efficient Catalytic Oxidation of Organic Pollutants显示文摘Peroxymonosulfate(PMS) has received increasing attention as viable technology for recalcitrant organics removal from polluted waters. Although promising, alternative heterogeneous catalysts with stable structure, strong hydrophilicity, environmental friendliness and excellent catalytic performance are highly desirable to facilitate the wide industrialization of PMS. In this work, Ni doped CoOOH catalyst was employed as PMS activator. Ni dopant had a significant influence on the morphology, structure and catalytic performance of CoOOH. NiojCoo.gOOH exhibited the best catalytic performance. Reaction rate ofNio.2Coo.8OOH was 2, 4, and 4.4 times that of CoOOH, CoFe2O4 and CO3O4, respectively. Moreover, Ni。2C00.8OOH/PMS system had potential application to organic pollutants and displayed a great catalytic activity over a broader pH value(e.g., 4-10). More importantly, Ni doping accelerated the transfonnation of Co(Ⅲ) and Co(Ⅱ) and formed active species CoOH^+ and NiOH^+ which were responsible to the enhancement of PMS activation.OH, SO4^-:O2^- and 1^O2 were detected, indicating both non-radical and radical processes in the Nio.2Coo.8OOH/PMS system. These findings provide a promising alternative to mixed-metal oxyhydroxides catalysts for PMS activation, demonstrating a great potential in environmental remediation and wastewater treatment.LYU Cong LI Yicheng FANG Chen FENG Wei SUN Wentian ZHANG Qihui 2019Chemical Research in Chinese Universities2019,35,3:0
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