全文获取类型
收费全文 | 16048篇 |
免费 | 2563篇 |
国内免费 | 3279篇 |
专业分类
化学 | 12763篇 |
晶体学 | 217篇 |
力学 | 960篇 |
综合类 | 279篇 |
数学 | 2007篇 |
物理学 | 5664篇 |
出版年
2024年 | 51篇 |
2023年 | 375篇 |
2022年 | 628篇 |
2021年 | 686篇 |
2020年 | 764篇 |
2019年 | 757篇 |
2018年 | 590篇 |
2017年 | 665篇 |
2016年 | 880篇 |
2015年 | 886篇 |
2014年 | 977篇 |
2013年 | 1313篇 |
2012年 | 1285篇 |
2011年 | 1419篇 |
2010年 | 1003篇 |
2009年 | 1001篇 |
2008年 | 1091篇 |
2007年 | 900篇 |
2006年 | 847篇 |
2005年 | 787篇 |
2004年 | 626篇 |
2003年 | 579篇 |
2002年 | 665篇 |
2001年 | 537篇 |
2000年 | 430篇 |
1999年 | 362篇 |
1998年 | 244篇 |
1997年 | 170篇 |
1996年 | 206篇 |
1995年 | 169篇 |
1994年 | 187篇 |
1993年 | 144篇 |
1992年 | 97篇 |
1991年 | 110篇 |
1990年 | 116篇 |
1989年 | 57篇 |
1988年 | 49篇 |
1987年 | 45篇 |
1986年 | 53篇 |
1985年 | 42篇 |
1984年 | 20篇 |
1983年 | 25篇 |
1982年 | 12篇 |
1981年 | 10篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1971年 | 1篇 |
1959年 | 4篇 |
1957年 | 7篇 |
1936年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
191.
Zhen‐Yu Li Ping Chen Hong‐Gui Xu Shu‐Ying Peng Yi‐Ming Yang Zhong‐Zhen Zhao Yue‐Wei Guo 《Helvetica chimica acta》2007,90(7):1353-1359
Five new polycyclic Daphniphyllum alkaloids, macropodumines F ( 1 ) and G ( 2 ), 17‐oxoyuzurimine ( 3 ), and macropodumines H ( 4 ) and I ( 5 ), were isolated from the leaves of D. macropodum Miq ., collected in Sichuan Province, China. The structures and relative configurations of the new compounds – as well as of four known, related alkaloids – were elucidated on the basis of in‐depth spectroscopic and mass‐spectrometric analyses, by chemical derivatization, and by comparison of spectroscopic data with those of known compounds. 相似文献
192.
YANG Fa-fu JI Yan-qing GUO Hong-yu LIN Jian-rong PENG Qi 《高等学校化学研究》2006,22(6):808-810
IntroductionCalixarenes are one of the most important supra-molecular building blocks, which can be modified byintroducing different functional and/or structural groupsto create a specific interaction between the host and thetarget molecules, such as meta… 相似文献
193.
Synthesis of mesoporous titania networks consisting of anatase nanowires by templating of bacterial cellulose membranes 总被引:5,自引:0,他引:5
Mesoporous titania networks consisting of interconnected anatase nanowires have been synthesized by using unique bacterial cellulose membranes as natural biotemplates; the titania networks exhibit enhanced photocatalytic activity compared with titania microfiber networks. 相似文献
194.
The first kinetic study of a substrate (CN(-)) binding to the isolated active site (extracted FeMo-cofactor) of nitrogenase is described. The kinetics of the reactions between CN(-) and various derivatives of extracted FeMo-cofactor [FeMoco-L; where L is bound to Mo, and is NMF, Bu(t)NC, or imidazole (ImH)] have been followed using a stopped-flow, sequential-mix method in which the course of the reaction is followed indirectly, by monitoring the change in the rate of the reaction of the cofactor with PhS(-). The kinetic results, together with DFT calculations, indicate that the initial site of CN(-) binding to FeMoco-L is controlled by a combination of the electron-richness of the cluster core and lability of the Mo-L bond. Ultimately, the reactions between FeMoco-L and CN(-) involve displacement of L and binding of CN(-) to Mo. These reactions occur with a variety of rates and rate laws dependent on the nature of L. For FeMoco-NMF, the reaction with CN(-) is complete within the dead-time of the apparatus (ca. 4 ms), while with FeMoco-CNBu(t) the reaction is much slower and exhibits first order dependences on the concentrations of both FeMoco-CNBu(t) and CN(-) (k = 2.5 +/- 0.5 x 10(4) dm(3) mol(-1) s(-1)). The reaction of FeMoco-ImH with CN(-) occurs at a rate which exhibits a first order dependence on FeMoco-ImH but is independent of the concentration of CN(-) (k = 50 +/- 10 s(-1)). The results are interpreted in terms of CN(-) binding directly to the Mo site for FeMoco-NMF and FeMoco-ImH, but with FeMoco-CNBu(t) initial binding at an Fe site is followed by movement of CN(-) to Mo. Complementary DFT calculations are consistent with this interpretation, indicating that, in FeMoco-L, the Mo-L bond is stronger for L = ImH than for L = CNBu(t) and the binding of CN(-) to Mo is stronger than to any Fe atom in the cofactor. 相似文献
195.
研究了羟丙基纤维素和羟丙基醋酸纤维素的合成。制备羟丙基纤维素的较佳反应温度为40℃左右和2小时或稍长,羟丙基含量随环氧丙烷浓度的增加而增加。在制备羟丙基醋酸纤维素时,随羟丙基含量的增加,所需醋化和水解的时间减少。以甘油-正丙醇或磷酸为添加剂,丙酮为溶剂经30~60s蒸发后制得了羟丙基醋酸纤维素反渗透膜。后者在20kg/cm~2下对氯化钠脱盐率可达95~98%,水通量1.0~2.1mL/cm~2·h,其使用温度上限比醋酸纤维素反渗透膜提高10℃以上。 相似文献
196.
Guangdong Zhou Zhanlin Xu Xiaohong Guo Hong Zhuang Yanan Li Xueju Lü Tiexin Cheng Wenxing Li Kaiji Zhen 《Reaction Kinetics and Catalysis Letters》2005,85(1):57-64
Summary The oxidation of hexanol in the presence of the Keggin-type heteropoly compounds (HPCs) H3PMonW12-nO40 (denoted as PMonW12-n, n=0,1) and Na5PW11ZO39 (denoted as PW11Z, Z = Mn, Fe, Co, Ni, Cu and Zn) was carried out to produce hexanal and hexanoic acid. The reaction was conducted in tert-butanol (t-BuOH), using cetylpyridinium bromide (CPB) salts of HPA and 15% aqueous H2O2 as oxidant under mild condition. The PMoW11 catalyst showed higher hexanol conversion of 25%, the lowest selectivity to hexanal of 64.4% and an efficient utilization of H2O2 of 34%. Over the transition metal substituted PW11Z catalysts decomposition of H2O2 was rapid. For these PW11Z catalysts, the efficient utilization of H2O2 decreased to 9% or even lower. By means of IR, UV-visible and GC-MS techniques the catalysts were characterized. 相似文献
197.
Yi‐Zhen Tang Hao Sun Ya‐Ru Pan Xiu‐Mei Pan Rong‐Shun Wang 《International journal of quantum chemistry》2007,107(6):1495-1501
The mechanisms for the reaction of CH3S with NO2 are investigated at the QCISD(T)/6‐311++G(d,p)//B3LYP/6‐311++G(d,p) on both single and triple potential energy surfaces (PESs). The geometries, vibrational frequencies, and zero‐point energy (ZPE) correction of all stationary points involved in the title reaction are calculated at the B3LYP/6‐311++G(d,p) level. More accurate energies are obtained at the QCISD(T)/6‐311++G(d,p). The results show that 5 intermediates and 14 transition states are found. The reaction is more predominant on the single PES, while it is negligible on the triple PES. Without any barrier height for the whole process, the main channel of the reaction is to form CH3SONO and then dissociate to CH3SO+NO. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
198.
Jun Zhou Jie Yang Li Qi Xuan Shen Dunru Zhu Yan Xu You Song 《Transition Metal Chemistry》2007,32(6):711-715
A novel dinuclear nickel(II) complex, [Ni2(MOBPT)2Cl2(H2O)2]Cl2 · 7H2O (MOBPT = 4-(p-methoxyphenyl) −3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, IR and single crystal X-ray
diffraction methods. The crystal structure determination shows that the dinuclear Ni2N8 unit is almost planer in which each NiII ion is coordinated by four nitrogen atoms from MOBPT equatorially and a water molecule and a chloride ion axially in a distorted
octahedral geometry. Magnetic measurements reveal a relatively weak antiferromagnetic exchange in the complex. 相似文献
199.
Yi‐Jun Huang Guo‐Rong Qi Yu‐Hua Wang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1142-1150
A double metal‐cyanide catalyst based on Zn3[Co(CN)6]2 was prepared. This catalyst is very effective for the ring‐opening polymerization of propylene oxide. Polyether polyols of moderate molecular weight having low unsaturation (<0.015 meq/g) can be prepared under mild conditions. The molecular weight of polymer is entirely controlled by a reacted monomer‐to‐initiator ratio. The polymers prepared with stepwise addition of monomer exhibit a narrower molecular weight distribution as compared with those prepared with one‐step addition of monomer. Various compounds containing active hydrogen, except basic compounds and low‐carbon carboxylic acid, may be used as initiators. The reaction rate increases with increasing catalyst amount and decreases with rising initiator concentration. Polymerization involves a rapid exchange reaction between the active species and the dormant species. It was also proven that, to a certain extent, the chain termination of this catalytic system is reversible or temporary. 13C NMR analysis showed that the polymer has a random distribution of the configurational sequences and head‐to‐tail regiosequence. It is assumed that the polymerization proceeds via a cationic coordination mechanism. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1142–1150, 2002 相似文献
200.
Qi‐Wei Zhang Yi‐Hang Wen Yun‐Long Feng 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(6):m255-m257
The title compound, [Zn2(C5H6O4)2(C13H14N2)]n or [Zn2(glu)2(bpp)]n, is a novel zinc polymer based on mixed flexible glutarate (glu) and 1,3‐di‐4‐pyridylpropane (bpp) ligands. The ZnII center has a distorted tetrahedral geometry and the central atom of the bpp ligand is located at a special site with a C2 axis passing through it. A layer is formed by Zn–glu bonding. Such layers are pillared by bpp ligands, forming a three‐dimensional framework with large channels. The inverted interpenetration of two three‐dimensional frameworks completes the molecular structure. 相似文献