全文获取类型
收费全文 | 65849篇 |
免费 | 15796篇 |
国内免费 | 5018篇 |
专业分类
化学 | 53788篇 |
晶体学 | 603篇 |
力学 | 1742篇 |
综合类 | 299篇 |
数学 | 4054篇 |
物理学 | 9589篇 |
无线电 | 16588篇 |
出版年
2024年 | 90篇 |
2023年 | 681篇 |
2022年 | 845篇 |
2021年 | 1253篇 |
2020年 | 2915篇 |
2019年 | 4041篇 |
2018年 | 2301篇 |
2017年 | 1931篇 |
2016年 | 5032篇 |
2015年 | 5367篇 |
2014年 | 5568篇 |
2013年 | 6425篇 |
2012年 | 5535篇 |
2011年 | 4817篇 |
2010年 | 4840篇 |
2009年 | 4816篇 |
2008年 | 4333篇 |
2007年 | 3559篇 |
2006年 | 3075篇 |
2005年 | 3111篇 |
2004年 | 2594篇 |
2003年 | 2291篇 |
2002年 | 3060篇 |
2001年 | 2234篇 |
2000年 | 1953篇 |
1999年 | 903篇 |
1998年 | 472篇 |
1997年 | 375篇 |
1996年 | 365篇 |
1995年 | 326篇 |
1994年 | 246篇 |
1993年 | 225篇 |
1992年 | 189篇 |
1991年 | 182篇 |
1990年 | 138篇 |
1989年 | 111篇 |
1988年 | 94篇 |
1987年 | 58篇 |
1986年 | 48篇 |
1985年 | 40篇 |
1984年 | 33篇 |
1983年 | 34篇 |
1982年 | 27篇 |
1981年 | 24篇 |
1980年 | 15篇 |
1979年 | 18篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1974年 | 11篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 250 毫秒
941.
Jean‐Louis Schmitt Adrian‐Mihail Stadler Nathalie Kyritsakas Jean‐Marie Lehn 《Helvetica chimica acta》2003,86(5):1598-1624
Control over the folding of molecular strands may be achieved by appropriate choice of the constituting subunits, in particular for chains of specific heterocycles such as sequences of directly connected pyridine (py) and pyrimidine (pym) rings, which are known to fold into extended helical structures. Since the hydrazone (hyz) group represents an isomorphic analogue of a py site, the condensation of hydrazine and carboxaldehyde derivatives of pym offers a very efficient approach to strands incorporating hyz instead of py units and constituted by sequences of alternating hyz and pym groups. A series of such strands of different lengths, up to ten hyz units, i.e., 1 – 7 , were synthesized. Their spectral properties indicate that they fold indeed into helical shapes. Extensive characterization was performed in solution by 1HNMR spectroscopy and in the solid state by determination of the crystal structures of eight such strands. They all display the expected helical geometry with up to 3 1/3 turns and direct stacking contacts. The efficiency and flexibility of the synthetic approach as well as its wide potential for generation of diversity through lateral decoration make the (hyz? pym) subunit a particularly attractive helicity codon. 相似文献
942.
Qing‐Xiang Liu Feng‐Bo Xu Qing‐Shan Li Xian‐Shun Zeng Xue‐Bing Leng Zheng‐Zhi Zhang 《中国化学》2002,20(9):878-883
Dinuclear silver (I) six‐membered ring complex [Ag2 (bta)2 ‐(hmbta)2] (ClO4)2 (3) has been synthesized by the reaction of benzotriazole (bta) (1) and 1‐hydroxymethyl benzotriazole (hmbta) (2) with Ag (CH3CN)4ClO4. The structures of compound 2 and Complex 3 have been studied by single crystal X‐ray diffraction analysis. The change of luminescent intensity of 1, 2 and 3 was reported. Compound 2 crystallizes in the monoclinic system with space group P2 (1)/c, a = 0.7655 (10) nm, b = 1.0126 (14) nm, c =0.9502 (13) nm, β = 95.07 (2)°, V = 0.7337 (17) nm3 and Z = 4. Complex 3 crystallizes in the triclinic system with space group P1, a = 0.73611 (18) nm, b = 0.9152 (2) nm, c = 1.2277 (3) nm, β = 87.170 (5)°, V = 0.8221 (3) nm3 and Z = 1. The main structural feature of complex 3 is a symmetric dinuclear six‐membered ring formed by two silver (I) atoms and four N‐atoms from two benzotriazoles. The second structural feature of complex 3 is the τ‐τ stacking interaction between two adjacent molecular planes, which forms the two‐dimentional layer structure. Besides, compared with 2, the luminescent intensity of complex 3 shows a remarkable enhancement. 相似文献
943.
An oligosaccharide homologue named SnS-2 was isolated from the root of Scrophularia ningpoensis Hemsl.SnS-2 was purified by means of gel-permeation chromatography and ion-exchange chromatography. Its physicochemical properties, including carbohydrate content and molecular weight were determined. The structure of SnS-2 was elucidated by chemical methods along with ^1H and ^13C NMR spectroscopy, including two-dimensional DQCOSY and H-detected ^1H, ^13C HMQC experiments. These results show that SnS-2 possesses a backbone consisting of terminal α-Galp-(1→, α-Galp-(1→6), α-Glcp-(1→6) and nonreducing end β-Fruf-(2→. The bioactive assay showed that it could inhibit the growth of Lewis pulmonary carcinoma implanted in mice. 相似文献
944.
945.
四(2,4—二叔戊基苯氧基)酞菁铜(Ⅱ)的合成及其LB膜 总被引:5,自引:3,他引:5
合成了标题酞菁铜衍生物,并通过元素分析,高压液相色谱,紫外光谱,红外光谱,核磁共振谱,电镜,顺磁共振谱及质谱加以确认。该化合物在稀氯仿溶液和LB膜中各以单,双分子缔合的形式存在。Z型沉积形成的单层LB膜对氨气有很高的灵敏度和选择性。 相似文献
946.
947.
新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征 总被引:1,自引:0,他引:1
金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1~6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域. 相似文献
948.
The photolytic release of substrates from caged substrates has proven to be an excellent method to generate concentration jumps for kinetic measurements in the microsecond time scale. In this report we use time-resolved FTIR in the step-scan mode to probe the photolysis mechanism of one such caged compound, namely gamma-(alpha-carboxy-2-nitrobenzyl)glutamate, and to obtain a direct measure of the rate of photorelease of the substrate glutamate. The time-resolved difference FTIR spectra exhibit specific signals that can be assigned to the reactant caged glutamate, photolytically released product glutamate, as well as to the aci-nitro intermediate, the key intermediate of the photolysis reaction. Therefore these signals allow the characterization of the kinetics of formation and decay of the intermediate and products. This is the first such report that provides a direct determination of the rate of formation of the photolysis product from a caged compound in the microsecond time scale. Furthermore, the results presented provide a good basis for further time-resolved FTIR studies of molecular reaction mechanisms, such as ligand protein interactions, in the microsecond time scale through the photolytic release of substrates from caged compounds. 相似文献
949.
Andrea Cornia Antonio Costantino Fabretti Roberta Sessoli Lorenzo Sorace Dante Gatteschi Anne‐Laure Barra Carole Daiguebonne Thierry Roisnel 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m371-m373
The structure of hexadeca‐μ‐acetato‐tetraaquadodeca‐μ3‐oxo‐dodecamanganese bis(acetic acid) tetrahydrate, [Mn12O12(CH3COO)16(H2O)4]·2CH3COOH·4H2O, known as Mn12–acetate, has been determined at 83 (2) K by X‐ray diffraction methods. The fourfold (S4) molecular symmetry is disrupted by a strong hydrogen‐bonding interaction with the disordered acetic acid molecule of solvation, which displaces one of the acetate ligands in the cluster. Up to six Mn12 isomers are potentially present in the crystal lattice, which differ in the number and arrangement of hydrogen‐bonded acetic acid molecules. These results considerably improve the structural information available on this molecular nanomagnet, which was first synthesized and characterized by Lis [Acta Cryst. (1980), B 36 , 2042–2046]. 相似文献
950.
JianGouHUANG ManCaiXU HaiTaoLI ZuoQingSHI 《中国化学快报》2003,14(9):914-916
Two polymeric adsorbents, poly(methyl p-vinylbenzvl ether) and oolv(ohenvl p-vinylbenzyl ether), were synthesized from chloromethylated polystyrene, Their adsorptionproperty for phenol in hexane solution was investigated. The results showed that the twoadsorbents adsorb phenol from hexane solution through hydrogen-bonding and π-π stacking interaction. 相似文献