全文获取类型
收费全文 | 4808篇 |
免费 | 703篇 |
国内免费 | 435篇 |
专业分类
化学 | 3492篇 |
晶体学 | 56篇 |
力学 | 250篇 |
综合类 | 25篇 |
数学 | 554篇 |
物理学 | 1569篇 |
出版年
2024年 | 13篇 |
2023年 | 124篇 |
2022年 | 194篇 |
2021年 | 210篇 |
2020年 | 184篇 |
2019年 | 170篇 |
2018年 | 162篇 |
2017年 | 118篇 |
2016年 | 222篇 |
2015年 | 218篇 |
2014年 | 262篇 |
2013年 | 298篇 |
2012年 | 369篇 |
2011年 | 406篇 |
2010年 | 242篇 |
2009年 | 240篇 |
2008年 | 292篇 |
2007年 | 276篇 |
2006年 | 245篇 |
2005年 | 204篇 |
2004年 | 176篇 |
2003年 | 159篇 |
2002年 | 130篇 |
2001年 | 105篇 |
2000年 | 93篇 |
1999年 | 123篇 |
1998年 | 104篇 |
1997年 | 93篇 |
1996年 | 96篇 |
1995年 | 82篇 |
1994年 | 59篇 |
1993年 | 36篇 |
1992年 | 41篇 |
1991年 | 33篇 |
1990年 | 26篇 |
1989年 | 17篇 |
1988年 | 22篇 |
1987年 | 20篇 |
1986年 | 13篇 |
1985年 | 9篇 |
1984年 | 15篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 9篇 |
1978年 | 2篇 |
1976年 | 7篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1972年 | 2篇 |
排序方式: 共有5946条查询结果,搜索用时 15 毫秒
221.
Kinetic Resolution of Racemic Mandelic Acid Esters by N,N′‐Dioxide–Scandium‐Complex‐Catalyzed Enantiomer‐Selective Acylation 下载免费PDF全文
Yuheng Zhang Prof. Dr. Xiaohua Liu Lin Zhou Wangbin Wu Tianyu Huang Yuting Liao Lili Lin Prof. Dr. Xiaoming Feng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(48):15884-15890
A simple and efficient acylative kinetic resolution of racemic mandelic acid esters was accomplished with a chiral N,N’‐dioxide–scandium(III) complex under mild and base‐free reaction conditions. A variety of mandelic acid esters performed well in the reaction, obtaining both acylated products (up to 49% yield, 97% ee) and recovered substrates (up to 49% yield, 95% ee) in high enantioselectivities with perfect selectivity factors (up to 247). The enantioselective recognition and catalytic models were also proposed for the catalytic KR reaction. 相似文献
222.
Silver‐Catalyzed Cross‐Coupling of Propargylic Alcohols with Isocyanides: An Atom‐Economical Synthesis of 2,3‐Allenamides 下载免费PDF全文
Jianquan Liu Zhenhua Liu Nannan Wu Dr. Peiqiu Liao Prof. Xihe Bi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2154-2158
Cross‐coupling reactions between propargylic alcohols and isocyanides, by means of silver catalysis, have been described. This new reaction is both atom and step efficient and is applicable to a broad scope of substrates, allowing the synthesis of a range of synthetically valuable 2,3‐allenamides in moderate to excellent yields. 相似文献
223.
Hetero‐tri‐spin [2p‐3d‐4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo‐Ligands: Synthesis,Structure, and Magnetic Properties 下载免费PDF全文
Mei Zhu Peng Hu Yungai Li Xiufeng Wang Prof. Licun Li Prof. Daizheng Liao V. M. L. Durga Prasad Goli Prof. S. Ramasesha Dr. Jean‐Pascal Sutter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13356-13365
Employing nitronyl nitroxide lanthanide(III) complexes as metallo‐ligands allowed the efficient and highly selective preparation of three series of unprecedented hetero‐tri‐spin (Cu?Ln‐radical) one‐dimensional compounds. These 2p–3d–4f spin systems, namely [Ln3Cu(hfac)11(NitPhOAll)4] (LnIII=Gd 1Gd , Tb 1Tb , Dy 1Dy ; NitPhOAll=2‐(4′‐allyloxyphenyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide), [Ln3Cu(hfac)11(NitPhOPr)4] (LnIII=Gd 2Gd , Tb 2Tb , Dy 2Dy , Ho 2Ho , Yb 2Yb ; NitPhOPr=2‐(4′‐propoxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) and [Ln3Cu(hfac)11(NitPhOBz)4] (LnIII=Gd 3Gd , Tb 3Tb , Dy 3Dy ; NitPhOBz=2‐(4′‐benzyloxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) involve O‐bound nitronyl nitroxide radicals as bridging ligands in chain structures with a [Cu‐Nit‐Ln‐Nit‐Ln‐Nit‐Ln‐Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal–radical interactions take place in these hetero‐tri‐spin chain complexes, these and the next‐neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single‐chain magnet behavior. 相似文献
224.
Phosphate Monoester Hydrolysis by Trinuclear Alkaline Phosphatase; DFT Study of Transition States and Reaction Mechanism 下载免费PDF全文
Alkaline phosphatase (AP) is a trinuclear metalloenzyme that catalyzes the hydrolysis of a broad range of phosphate monoesters to form inorganic phosphate and alcohol (or phenol). In this paper, by using density functional theory with a model based on a crystal structure, the AP‐catalyzed hydrolysis of phosphate monoesters is investigated by calculating two substrates, that is, methyl and p‐nitrophenyl phosphates, which represent alkyl and aryl phosphates, respectively. The calculations confirm that the AP reaction employs a “ping‐pong” mechanism involving two chemical displacement steps, that is, the displacement of the substrate leaving group by a Ser102 alkoxide and the hydrolysis of the phosphoseryl intermediate by a Zn2‐bound hydroxide. Both displacement steps proceed via a concerted associative pathway no matter which substrate is used. Other mechanistic aspects are also studied. Comparison of our calculations with linear free energy relationships experiments shows good agreement. 相似文献
225.
采用全原子分子动力学模拟方法研究了纤连蛋白(FN)在金红石表面、23%石墨烯覆盖率的金红石表面、92%石墨烯覆盖率的金红石表面、石墨表面的吸附行为.模拟结果表明:FN在金红石表面吸附不稳定.通过石墨烯修饰二氧化钛表面可降低金红石表面的亲水性;当表面含有石墨烯层时,FN都将稳定地吸附在表面上.在23%石墨烯覆盖率的金红石表面上,FN的特异性识别位点朝向溶液而有利于整合素识别.DSSP分析结果显示在40 ns的分子动力学模拟过程中,FN的七个β-折叠结构在所有体系中均没有发生太大变化.由于有石墨烯层存在,表面附近水分子层密度减小.FN的表面吸附能随着表面石墨烯覆盖率的增加而增大.石墨烯修饰能加强二氧化钛表面对蛋白质的吸附.本工作可以为移植体修饰生物材料设计与开发提供参考. 相似文献
226.
Dunhua Hong Taisong Pan Dayu Feng Zhenlong Huang Feiyi Liao XiaoMei Li Yin Zhang Min Gao 《Journal of Sol-Gel Science and Technology》2014,71(3):464-469
(LaBa)Co2O5+δ (LBCO) thin films were successfully fabricated on Si (001) substrates by polymer-assisted deposition method. Microstructures were examined by X-ray diffraction technique, which confirmed the films were a single phase, pseudo cubic structure. The electrical transport properties of the films were investigated by the temperature dependence of films resistance, which suggested that LBCO films have typical semiconductor properties. After circle tests, the oxygen–hydrogen response rate did not show obvious variation in the specific temperature environment of 580 °C. This demonstrates that the LBCO thin films have a superior stability in both oxygen and hydrogen (6 % H2, 94 % N2) environment. Simultaneously, the drastic changes of films resistance (from ~106 to ~102 Ω) with the switch of redox (O2–H2) environment within such a short time (~2.2 s) indicated that LBCO films have an excellent oxygen sensitive property and extraordinary fast surface exchange rate. 相似文献
227.
Zheng Li Lingcong Jiao Yunhai Sun Zeying He Dr. Zhonglin Wei Prof. Wei-Wei Liao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(18):7333-7337
An unprecedented electrochemical trifluoromethylation/SO2 insertion/cyclization process has been achieved in an undivided cell in an atom-economic fashion. The protocol relies on tandem cyclization of N-cyanamide alkenes by using Langlois’ reagent as a source of both CF3 and SO2 under direct anodically oxidative conditions, in which two C−C bonds, two C−X bonds (N−S and S−C), and two rings were formed in a single operation. This transformation enabled efficient construction of various trifluoromethylated cyclic N-sulfonylimines from readily accessible materials. 相似文献
228.
Rational Design of Cyclometalated Iridium(III) Complexes for Three-Photon Phosphorescence Bioimaging
Dr. Chengzhi Jin Fengyin Liang Dr. Jinquan Wang Dr. Lili Wang Dr. Jiangping Liu Xinxing Liao Dr. Thomas W. Rees Bo Yuan Prof. Dr. Hui Wang Prof. Dr. Yong Shen Prof. Dr. Zhong Pei Prof. Dr. Liangnian Ji Prof. Dr. Hui Chao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16121-16125
Compared to 2PE (two-photon excitation) microscopy, 3PE microscopy has superior spatial resolution, deeper tissue penetration, and less defocused interference. The design of suitable agents with a large Stokes shift, good three-photon absorption (3PA), subcellular targeting, and fluorescence lifetime imaging (FLIM) properties, is challenging. Now, two IrIII complexes (3PAIr1 and 3PAIr2) were developed as efficient three-photon phosphorescence (3PP) agents. Calculations reveal that the introduction of a new group to the molecular scaffold confers a quadruple promotion in three-photon transition probability. Confocal and lifetime imaging of mitochondria using IrIII complexes as 3PP agents is shown. The complexes exhibit low working concentration (50 nm ), fast uptake (5 min), and low threshold for three-photon excitation power (0.5 mW at 980 nm). The impressive tissue penetration depth (ca. 450 μm) allowed the 3D imaging and reconstruction of brain vasculature from a living specimen. 相似文献
229.
Jiann-Jyh Huang Yu-Hsiang Lin Chun-Liang Lai Sheng-Chuan Yang Shu Fu Lin Ju-Ying Yang Hung-Jyun Huang Chiawei Liu Win-Yin Wei Shih-Hsien Chuang Chao-Cheng Chiang Ying-Shuen E. Lee Chu-Bin Liao Ching Yuh Chern 《中国化学会会志》2020,67(3):422-429
In this study, we reported the inhibition profiles of 4′-acylpyrrole–5-fluoroindolin-2-one 3 with a C-3′ side chain for VEGFR2, PDGFR-β, and FGFR-1 protein kinases. The pyrrole-fused cyclohexanone moiety provided 3 with the best potency to inhibit the three kinases, and the C-3′ side chains contributed to the different inhibition profiles of 3 . Compound 3b with a C-3′ 2-carboxylethyl side chain showed good potency for the three kinase (IC50: 25–260 nM), and compound 3g with a N,N-dialkyl-2-carbamoylethyl side chain was more active for VEGFR2 (IC50: 59 nM) and PDGFR-β (IC50: 16 nM) than FGFR-1 (IC50: 1.7 μM). The C-3′ 3-(dialkylamino)propyl side chain accomplished 3h – j as selective PDGFR-β inhibitors (IC50: 7.8–13 nM). Compound 3b was further investigated and found potent to inhibit VEGF- and FGF-dependent cell proliferation with moderate in vivo anticancer activity. Results from docking simulations revealed that the interactions of 3b with VEGFR2 and FGFR-1 which could account for the different inhibition profiles of 3 . 相似文献
230.
We report two anion-templated Ag40 clusters, [Ag40(E)4(SO4){S2P(OEt)2}24](PF6)6 (E = S, 1 ; Se, 2 ). The anionic templates were generated in situ from the decomposition of dithiophosphate (dtp) ligands. The extrusion of sulfur undergoes disproportionation reactions to generate sulfide and sulfate anions, which provide the source of templates in the subsequent cluster assembly reactions. Two Ag40 clusters display high similarity in their structures. The sulfide (selenide) anions and the central sulfate anion reveal a six-coordinate and a rare dodecametallic dodecaconnective pattern, respectively. Four near-equivalent [Ag10(E){S2P(OEt)2}6]2+ motifs were assembled via the connection of central sulfate anion to construct Ag40 clusters. The cluster cation, [Ag40(E)4(SO4){S2P(OEt)2}24]6+, displayed in T symmetry, is unprecedented in anion-templated silver clusters. 相似文献