全文获取类型
收费全文 | 2126篇 |
免费 | 98篇 |
国内免费 | 18篇 |
专业分类
化学 | 1426篇 |
晶体学 | 13篇 |
力学 | 75篇 |
综合类 | 3篇 |
数学 | 234篇 |
物理学 | 491篇 |
出版年
2023年 | 14篇 |
2022年 | 24篇 |
2021年 | 44篇 |
2020年 | 47篇 |
2019年 | 21篇 |
2018年 | 32篇 |
2017年 | 17篇 |
2016年 | 53篇 |
2015年 | 57篇 |
2014年 | 67篇 |
2013年 | 110篇 |
2012年 | 150篇 |
2011年 | 151篇 |
2010年 | 90篇 |
2009年 | 93篇 |
2008年 | 145篇 |
2007年 | 140篇 |
2006年 | 120篇 |
2005年 | 107篇 |
2004年 | 79篇 |
2003年 | 83篇 |
2002年 | 90篇 |
2001年 | 34篇 |
2000年 | 49篇 |
1999年 | 25篇 |
1998年 | 23篇 |
1997年 | 26篇 |
1996年 | 34篇 |
1995年 | 16篇 |
1994年 | 13篇 |
1993年 | 21篇 |
1992年 | 23篇 |
1991年 | 15篇 |
1990年 | 19篇 |
1989年 | 19篇 |
1988年 | 9篇 |
1986年 | 13篇 |
1985年 | 15篇 |
1984年 | 12篇 |
1983年 | 11篇 |
1982年 | 9篇 |
1981年 | 11篇 |
1980年 | 6篇 |
1979年 | 14篇 |
1978年 | 7篇 |
1977年 | 13篇 |
1976年 | 10篇 |
1974年 | 11篇 |
1973年 | 6篇 |
1972年 | 7篇 |
排序方式: 共有2242条查询结果,搜索用时 15 毫秒
121.
Aysu Yarman Christopher Schulz Cristoph Sygmund Roland Ludwig Lo Gorton Ulla Wollenberger Frieder W. Scheller 《Electroanalysis》2014,26(9):2043-2048
For the first time the direct electron transfer of an enzyme ‐ cellobiose dehydrogenase, CDH ‐ has been coupled with the hexokinase catalyzed competition for glucose in a sensor for ATP. To enhance the signal output for ATP, pyruvate kinase was coimmobilized to recycle ADP by the phosphoenolpyruvate driven reaction. The new sensor overcomes the limit of 1 : 1 stoichiometry of the sequential or competitive conversion of ATP by effective enzymatic recycling of the analyte. The anodic oxidation of the glucose converting CDH proceeds at electrode potentials below 0 mV vs. Ag|AgCl thus potentially interfering substances like ascorbic acid or catecholamines do not influence the measuring signal. The combination of direct electron transfer of CDH with the enzymatic recycling results in an interference‐free and oxygen‐independent measurement of ATP in the lower µmolar concentration range with a lower limit of detection of 63.3 nM (S/N=3). 相似文献
122.
Elevated Catalytic Activity of Ruthenium(II)–Porphyrin‐Catalyzed Carbene/Nitrene Transfer and Insertion Reactions with N‐Heterocyclic Carbene Ligands 下载免费PDF全文
Ka‐Ho Chan Dr. Xiangguo Guan Dr. Vanessa Kar‐Yan Lo Prof. Dr. Chi‐Ming Che 《Angewandte Chemie (International ed. in English)》2014,53(11):2982-2987
Bis(NHC)ruthenium(II)–porphyrin complexes were designed, synthesized, and characterized. Owing to the strong donor strength of axial NHC ligands in stabilizing the trans M?CRR′/M?NR moiety, these complexes showed unprecedently high catalytic activity towards alkene cyclopropanation, carbene C? H, N? H, S? H, and O? H insertion, alkene aziridination, and nitrene C? H insertion with turnover frequencies up to 1950 min?1. The use of chiral [Ru(D4‐Por)(BIMe)2] ( 1 g ) as a catalyst led to highly enantioselective carbene/nitrene transfer and insertion reactions with up to 98 % ee. Carbene modification of the N terminus of peptides at 37 °C was possible. DFT calculations revealed that the trans axial NHC ligand facilitates the decomposition of diazo compounds by stabilizing the metal–carbene reaction intermediate. 相似文献
123.
124.
Dr. Hong‐Jay Lo M. Sc. Chin‐Yin Lin Dr. Mei‐Chun Tseng Prof. Rong‐Jie Chein 《Angewandte Chemie (International ed. in English)》2014,53(34):9026-9029
A hydroxy‐directed alkylation of an N,N‐diethylarylamide using CIPE‐assisted α‐silyl carbanions (CIPE=complex‐induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus–Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3‐kinase (PI3K) inhibitor LY294002, are reported. 相似文献
125.
Florent Jasinski Emeline Lobry Abraham Chemtob Céline Croutxe-Barghorn Loïc Vidal Ludovic Josien Jocelyne Brendlé Adrien Criqui 《Colloid and polymer science》2014,292(12):3095-3102
When finally processed to provide the function for which the latex was selected―binding, protecting, finishing―components such as surfactant, costabilizer or initiator become generally useless, not to say detrimental. In this study, we show that miniemulsion photopolymerization provides a suitable method to create latex without the apparent addition of these three compounds. Indeed, UV-driven monomer self-initiation can create initiating radicals without the aid of initiator, the fast in situ photogenerated polymer can hinder Ostwald ripening with the assistance of external costabilizer, and finally, UV-transparent clay can replace conventional surfactant to ensure colloidal stabilization. Each strategy has been developed individually before being combined together to end up with a unique miniemulsion procedure free of initiator, costabilizer and surfactant. Such approach paves the way to a simplified and environmentally improved pathway towards aqueous polymer dispersions. 相似文献
126.
Kang-Chieh Lo Chiao-Yin Sun Yu-Ju Ding Jen-Ning Tsai Kai-Ping Chang Yi-En Wen Wan-Ling Chang Shin C. Chang Ming-Fu Chang Yun-Hsin Wang Yau-Hung Chen 《Research on Chemical Intermediates》2014,40(6):2177-2185
Benzo(a)pyrene is a chemical produced during the process of making fried, roasted, and smoked foods. It remains unclear whether benzo(a)pyrene affects the early development of human organs. In this study, we used the transgenic zebrafish line Tg(wt1b:GFP) as a model to assess benzo(a)pyrene-induced kidney malformation. By soaking zebrafish embryos in benzo(a)pyrene at various doses (2, 20, and 200 ppb), only a minor effect on the survival rate was detected (0 ppb: 97.8 ± 1.9 %; 2–200 ppb: 89.1 ± 5.8–91.5 ± 8.3 %). However, benzo(a)pyrene significantly affected the development of the kidney (malformation rates ranges from 50.0 ± 3.5 to 77.4 ± 5.3 %). Various abnormalities, such as unusual curving of pronephric tubes, swollen glomerulus, and incomplete development of pronephric ducts, were observed. This study provides a rapid and effective protocol for the evaluation of the notable effects of benzo(a)pyrene on embryonic kidney development. 相似文献
127.
Dr. Weihui Ou Dr. Binbin Zhou Junda Shen Dr. Tsz Wing Lo Prof. Dangyuan Lei Dr. Shengliang Li Jing Zhong Prof. Yang Yang Li Prof. Jian Lu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(17):6856-6859
Hot carriers (HCs) and thermal effects, stemming from plasmon decays, are crucial for most plasmonic applications. However, quantifying these two effects remains extremely challenging due to the experimental difficulty in accurately measuring the temperature at reaction sites. Herein, we provide a novel strategy to disentangle HCs from photothermal effects based on the different traits of heat dissipation (long range) and HCs transport (short range), and quantitatively uncover the dominant and potential-dependent role of photothermal effect by investigating the rapid- and slow-response currents in plasmon-mediated electrochemistry at nanostructured Ag electrode. Furthermore, the plasmoelectric surface potential is found to contribute to the rapid-response currents, which is absent in the previous studies. 相似文献
128.
Dr. Yongxin Li Pan Sun Luyang Zhao Prof. Xuehai Yan Prof. Dennis K. P. Ng Prof. Pui-Chi Lo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(51):23428-23438
A facile approach to assemble catalase-like photosensitizing nanozymes with a self-oxygen-supplying ability was developed. The process involved Fe3+-driven self-assembly of fluorenylmethyloxycarbonyl (Fmoc)-protected amino acids. By adding a zinc(II) phthalocyanine-based photosensitizer (ZnPc) and the hypoxia-inducible factor 1 (HIF-1) inhibitor acriflavine (ACF) during the Fe3+-promoted self-assembly of Fmoc-protected cysteine (Fmoc-Cys), the nanovesicles Fmoc-Cys/Fe@Pc and Fmoc-Cys/Fe@Pc/ACF were prepared, which could be disassembled intracellularly. The released Fe3+ could catalyze the transformation of H2O2 enriched in cancer cells to oxygen efficiently, thereby ameliorating the hypoxic condition and promoting the photosensitizing activity of the released ZnPc. With an additional therapeutic component, Fmoc-Cys/Fe@Pc/ACF exhibited higher in vitro and in vivo photodynamic activities than Fmoc-Cys/Fe@Pc, demonstrating the synergistic effect of ZnPc and ACF. 相似文献
129.
Di- and tri-organotin(IV) derivatives of N -acetyltriglycine and N -benzoyltriglycine (HA) were obtained by refluxing equimolar mixtures of the ligand and the organotin(IV) oxide or hydroxide in methanol or acetone. According to the spectroscopic data, triorganotin(IV) derivatives adopt a trigonal-bipyramidal structure in which the planar R3SnIV unit is bonded by a monodentate carboxylate group and a donor group, presumably the amide CO. The reaction of HA with the appropriate diorganotin(IV) compounds gave both dicarboxylates R2SnA2, with six-coordinated tin, and dimeric tetraorganodistannoxanes {[R2SnA]2O}2, in which the tin atoms are essentially five-coordinated. 相似文献
130.
Mark Brouar Helen Chadwick Sean D. S. Gordon Cornelia G. Hei Balazs Hornung Bethan Nichols Jacek K?os Pablo G. Jambrin F. Javier Aoiz 《化学物理学报》2020,33(2):217-233
本文对NO(X)-Xe碰撞系统在碰撞能量为519 cm-1,测量了完全?-双峰分解的微分截面和碰撞引起的旋转准直力矩. 同时结合初始量子态选择,使用六极杆的非均质电场,借助量子态分辨的测量,利用(1+1'')共振增强的多光子电离和速度离子成像. 结果显示,微分截面以及偏振相关的微分截面均显示与从头算势能面上进行的量子力学散射计算[J. K?os etal. J. Chem. Phys. 137, 014312 (2012)]一致. 通过与准经典轨迹、硬壳势能的量子力学散射以及运动近端模型的比较,评估了势能对所测微分截面和碰撞引起的旋转准直力矩的影响. 相似文献