全文获取类型
收费全文 | 1102篇 |
免费 | 128篇 |
国内免费 | 103篇 |
专业分类
化学 | 745篇 |
晶体学 | 8篇 |
力学 | 62篇 |
综合类 | 7篇 |
数学 | 174篇 |
物理学 | 337篇 |
出版年
2024年 | 3篇 |
2023年 | 22篇 |
2022年 | 32篇 |
2021年 | 26篇 |
2020年 | 28篇 |
2019年 | 38篇 |
2018年 | 26篇 |
2017年 | 22篇 |
2016年 | 49篇 |
2015年 | 42篇 |
2014年 | 45篇 |
2013年 | 65篇 |
2012年 | 83篇 |
2011年 | 97篇 |
2010年 | 64篇 |
2009年 | 76篇 |
2008年 | 74篇 |
2007年 | 65篇 |
2006年 | 73篇 |
2005年 | 44篇 |
2004年 | 46篇 |
2003年 | 41篇 |
2002年 | 23篇 |
2001年 | 18篇 |
2000年 | 31篇 |
1999年 | 36篇 |
1998年 | 19篇 |
1997年 | 24篇 |
1996年 | 15篇 |
1995年 | 9篇 |
1994年 | 17篇 |
1993年 | 16篇 |
1992年 | 13篇 |
1991年 | 11篇 |
1990年 | 7篇 |
1989年 | 8篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 5篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1973年 | 3篇 |
排序方式: 共有1333条查询结果,搜索用时 15 毫秒
161.
Weiwei Liu Song Ou Xiang He Hongwen Hu Qiangjin Wu Zixiang Huang 《Journal of chemical crystallography》2003,33(10):795-798
1-Methyl-2-phenylindolizine-3-acetonitrile was unexpectedly obtained in the reaction of 1-methyl-2-phenylindolizine-3-thioaldehyde with cyanide ions. Its structure was determined by IR, 1H NMR, MS, elemental analyses, and X-ray crystallography. Colorless regular prism shaped crystals of C17H14N2 crystallize in the space group C2/c with cell dimensions a = 12.956(3) Å, b =10.516(2) Å, c = 20.429(4) Å, and = 90°, = 104.98(3)°, = 90°, V =2688.7(9) Å3, D
calc =1.217 Mg/m3, and Z = 8. 相似文献
162.
Electrochemical Reduction of Carbon Dioxide to Methanol on Hierarchical Pd/SnO2 Nanosheets with Abundant Pd–O–Sn Interfaces
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Wuyong Zhang Qing Qin Dr. Lei Dai Ruixuan Qin Dr. Xiaojing Zhao Xumao Chen Daohui Ou Dr. Jie Chen Dr. Tracy T Chuong Prof. Binghui Wu Prof. Nanfeng Zheng 《Angewandte Chemie (International ed. in English)》2018,57(30):9475-9479
Electrochemical conversion of CO2 into fuels using electricity generated from renewable sources helps to create an artificial carbon cycle. However, the low efficiency and poor stability hinder the practical use of most conventional electrocatalysts. In this work, a 2D hierarchical Pd/SnO2 structure, ultrathin Pd nanosheets partially capped by SnO2 nanoparticles, is designed to enable multi‐electron transfer for selective electroreduction of CO2 into CH3OH. Such a structure design not only enhances the adsorption of CO2 on SnO2, but also weakens the binding strength of CO on Pd due to the as‐built Pd–O–Sn interfaces, which is demonstrated to be critical to improve the electrocatalytic selectivity and stability of Pd catalysts. This work provides a new strategy to improve electrochemical performance of metal‐based catalysts by creating metal oxide interfaces for selective electroreduction of CO2. 相似文献
163.
Ming-Li Sun Feng Zhang Yan Qian Chang-Jin Ou Bin Liu Ling-Hai Xie Ying Wei Bao-Yi Ren Wei Huang 《Tetrahedron》2018,74(16):2063-2067
A green protocol with catalyst-free photo-induced cyclization for the synthesis of a spiro-fused organic semiconductor molecule based on spiro[fluorene-9,9′-xanthene] (SFX) was developed. The photophysical and electrochemical properties of the spiro-fused compound (DPCzSFX) have been characterized. The results showed that the molecular stability and the property of the charge injecting/transporting were improved due to the cyclization. And the broadening of the emission spectrum in film makes the sipro-fused compound possible for the application as a host in the white phosphorescent organic light-emitting diodes. However, the same reaction for the spirobifluorene-based dipenylamine derivative did not occur under the same condition, which also highlights the importance of the oxygen heteroatom in the ring to the reaction of cyclization. 相似文献
164.
165.
Shu Ying Wu Xiao Min Zhang Hai Ou Tang Long Chen Bo Xuan Li 《Journal of solid state chemistry》2008,181(9):2171-2177
Ag/carbon hybrids were fabricated by the redox of glucose and silver nitrate (AgNO3) in the presence of imidazolium ionic liquid ([C14mim]BF4) under hydrothermal condition. Monodisperse carbon hollow sub-microspheres encapsulating Ag nanoparticles and Ag/carbon cables were selectively prepared by varying the concentration of ionic liquid. Other reaction parameters, such as reaction temperature, reaction time and the mole ratio of silver nitrate to glucose, play important roles in controlling the structures of the products. The products were characterized by XRD, TEM (HRTEM), SEM, energy-dispersive X-ray spectroscopy (EDX), FTIR spectroscopy and a Raman spectrometer. The possible formation mechanism was proposed. The catalytic property of the hybrid in the oxidation of 1-butanol by H2O2 was also investigated. 相似文献
166.
Lithium iron phosphate (LiFePO4) doped with magnesium was hydrothermally synthesized from commercial LiOH, FeSO4, H3PO4 and MgSO4 with glucose as carbon precursor in aqueous solution. The samples were characterized by X-ray powder diffraction, scanning electron microscopy and constant charge-discharge cycling. The results show that the synthesized powders have been in situ coated with carbon precursor produced from caramel reaction of glucose. At ambient temperature (28±2℃), the electrochemical performances of LiFePO4 prepared exhibit the high discharge capacity of 135 mAh g^-1 at 5C and good capacity retention of 98% over 90 cycles. The excellent electrochemical performances should be correlated with the intimate contact between carbon and LiFePO4 primary and secondary particles, resulting from the in situ formation of carbon precursor/carbon, leading to the increase in conductivity of LiFePO4. 相似文献
167.
168.
Docosanoic (C22), tetracosanoic (C24) and hexacosanoic (C26) acids are saturated very-long-chain fatty acids (VLCFA) present at trace levels in biosamples. VLCFA can be used as potential biomarkers for the diagnosis of hereditary diseases such as X-linked adrenoleukodystrophy. Because the analytes to be detected are at trace levels, a sensitive fluorimetric liquid chromatographic method was developed to analyze VLCFA in plasma. The method is simple based on extracting VLCFA from plasma with toluene, and the obtained toluene extract was subject to the derivatization of VLCFA with a fluorescent reagent 2-(2-naphthoxy)ethyl-2-(piperidino)ethanesulfonate (NOEPES) without solvent evaporation/replacement. The resulting fluorescent derivatives were monitored by fluorimetric detection (excitation at 225 nm and emission at 360 nm), giving a high sensitivity with the limit of detection about 5.0 nM (S/N = 3, 10 μL injected) of the analytes. Application of the method to the analysis of VLCFA in the plasma of patients with adrenoleukodystrophy proved practical and effective. 相似文献
169.
The reactions of a racemic four-coordinated nickel(II) complex [Ni(alpha-rac-L)](ClO4)2 (containing equal amount of SS and RR enantiomers) with l- and d-phenylalanine in acetonitrile/water gave two less-soluble six-coordinated enantiomers of {[Ni( f-SS-L)(l-Phe)](ClO4)}n (Delta-1) and {[Ni(f- RR-L)(d-Phe)](ClO4)}n (Lambda-1), respectively. Evaporation the remaining solutions gave two six-coordinated diastereomers of {[Ni 3(f- RR-L)3(l-Phe)2(H 2O)](ClO4)4}n (a-2) and {[Ni3(f- SS-L)3(d-Phe)2(H2O)](ClO4)4}n (b-2), respectively (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, Phe(-) = phenylalanine anion). The reaction of [Ni(alpha-rac-L)](ClO4)2 with dl-Phe(-) gave a conglomerate of c-1; in which, the SS and RR enantiomers preferentially coordinate to l- and d-Phe(-) respectively to give a racemic mixture of Delta-1 and Lambda-1, and the spontaneous resolution occurs during the reaction, in which each crystal crystallizes to become enantiopure. Removing Phe(-) from Delta-1 and Lambda-1 using perchloric acid gave two enantiomers of [Ni(alpha-SS-L)](ClO4)2 (S-3) and [Ni(alpha-RR-L)](ClO4)2 (R-3). Dissolving S-3 and R-3 in acetonitrile gave two six-coordinated enantiomers of [Ni( f-SS-L)(CH3CN)2](ClO4)2 (S-4) and [Ni( f- RR-L)(CH3CN)2](ClO4)2 (R-4), while dissolving [Ni(alpha-rac-L)](ClO4)2 in acetonitrile gave a racemic twining complex [Ni(f-rac-L)(CH3CN)2](ClO4)2 (rac-4). Delta-1 and Lambda-1 belong to supramolecular stereoisomers, which are constructed via hydrogen bond linking of [Ni( f-SS-L)(l-Phe)](+) and [Ni(f-RR-L)(d-Phe)](+) monomers to form 1D homochiral right-handed and left-handed helical chains, respectively. The reaction of S-3 with d-Phe(-) gave {[Ni(f-SS-L)(d-Phe)](ClO4)}n (5), which shows a motif of a 1D hydrogen bonded zigzag chain instead of a 1D helical chain. Compound a-2/ b-2 contains dimers of [{Ni(f-RR-L)}2(l-Phe)(H2O)](3+)/[{Ni( f- SS-L)}2(d-Phe)(H2O)](3+) and 1D zigzag chains of {[Ni(f-RR-L)(l-Phe)](+)}n /{[Ni(f-SS-L)(d-Phe)](+) n . The homochiral nature of Delta-1/Lambda-1, a-2/b-2, S-3/R-3, and S-4/R-4 are confirmed by the results of circular dichroism (CD) spectra measurements. 相似文献
170.
Zhi-Kun Rao Jing Long Cong Li Sui-Shuan Zhang Mei He Ling-Cheng Ou Yong-Tang Zheng Yan-Ping He 《Monatshefte für Chemie / Chemical Monthly》2008,139(8):967-974
Several 2-heteroaryl-, 2-heteroarylcarbonylmethyl-, 2-arylcarbonylmethyl, and 2-arylethyl derivatives of S-dihydro(alkyloxy)benzyloxypyrimidines have been synthesized and the anti-HIV activities of these compounds were tested in
C8166 cell and against RT enzyme. It was found that some of these compounds showed good activity against HIV-1 (EC
50 = 0.014–0.8 μM) with low toxicity (CC
50 value of 222–564 μM) and high selectivity (SI value of 278–37743). The structure-activity relationships (SAR) of these compounds have also been discussed.
First two authors contributed equally to this work
Correspondence: Yan-Ping He, Key Laboratory of Medicinal Chemistry for Natural Resource Ministry of Education, School of Chemical
Science and Technology, Yunnan University, Kunming 650091, People’s Republic of China; Yong-Tang Zheng, Laboratory of Molecular
Immunopharmacology, Key Laboratory of Animal Models and Human Disease Mechanisms, Chinese Academy of Sciences, Kunming Institute
of Zoology, Kunming, Yunnan 650223, People’s Republic of China. 相似文献