全文获取类型
收费全文 | 64919篇 |
免费 | 14686篇 |
国内免费 | 5598篇 |
专业分类
化学 | 61378篇 |
晶体学 | 745篇 |
力学 | 2211篇 |
综合类 | 308篇 |
数学 | 6181篇 |
物理学 | 14380篇 |
出版年
2024年 | 100篇 |
2023年 | 707篇 |
2022年 | 1061篇 |
2021年 | 1350篇 |
2020年 | 2582篇 |
2019年 | 3804篇 |
2018年 | 2120篇 |
2017年 | 1799篇 |
2016年 | 4767篇 |
2015年 | 4986篇 |
2014年 | 5191篇 |
2013年 | 6301篇 |
2012年 | 5684篇 |
2011年 | 5003篇 |
2010年 | 4852篇 |
2009年 | 4676篇 |
2008年 | 4373篇 |
2007年 | 3581篇 |
2006年 | 3075篇 |
2005年 | 2898篇 |
2004年 | 2500篇 |
2003年 | 2153篇 |
2002年 | 2954篇 |
2001年 | 2129篇 |
2000年 | 1894篇 |
1999年 | 979篇 |
1998年 | 532篇 |
1997年 | 453篇 |
1996年 | 465篇 |
1995年 | 407篇 |
1994年 | 334篇 |
1993年 | 243篇 |
1992年 | 234篇 |
1991年 | 221篇 |
1990年 | 173篇 |
1989年 | 124篇 |
1988年 | 90篇 |
1987年 | 80篇 |
1986年 | 92篇 |
1985年 | 78篇 |
1984年 | 44篇 |
1983年 | 38篇 |
1982年 | 20篇 |
1981年 | 18篇 |
1980年 | 7篇 |
1975年 | 3篇 |
1974年 | 5篇 |
1959年 | 3篇 |
1957年 | 5篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 546 毫秒
941.
Macrocyclic Schiff‐base ligand, bisacetylaceton‐ethylenediimine (BAE) and its transition metal complexes M(BAE) (M = Cu2+, Ni2+) were synthesized. The complexes having characteristics of aromatic systems and well‐defined one‐dimensional structures, reacted with p‐phthaloyl chloride, to obtain polymer complexes. The complexes were characterized by elemental analysis, inductively coupled plasma (ICP), FT‐IR, and thermal analysis and show good thermal stability. ESR spectra analysis discovered that there are free radicals in the chain of polymers, indicating that a weak magnetic spin‐exchange interaction operates between the metal ions and free radicals. It is found that, as the bridging p‐phthaloyl group is able to propagate the magnetic exchange interaction, the polymer complexes show paramagnetic properties by measurement of temperature dependence of the magnetic property, and obey Curie–Weiss law. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
942.
The paper reported the synthetic procedure and character of Copper(Ⅱ) binuclear coordination compound of 1,4-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,4-butanedione. The non-isothermal kinetic of the thermal decomposition of the complex has been studied from the TG-DTG curves by means of the Achar et al and Coats-Redfern methods. The electrochemical characterization of the complex were studied by means of powder microelectrodes technique. 相似文献
943.
钴(Ⅱ)-5-取代邻菲罗啉-α-氨基酸三元配合物的稳定性研究 总被引:5,自引:1,他引:5
本文在25.0±0.1℃,I=0.1mol·dm-3KNO3存在下,采用pH法测得了5-取代邻菲罗啉的质子化常数以及钴(Ⅱ)与5-取代邻菲罗啉、α-氨基酸的二元、三元配合物的稳定常数。结果表明三元配合物的稳定性与5-取代邻菲罗啉的质子化常数、取代基常数均存在直线自由能关系。并用三元配合物稳定性的表征值logKM、△logK,讨论了三元配合物的稳定性,发现钴(Ⅱ)与配体5-取代邻菲罗啉之间也存在着d-p反馈π键。该π健的强度对三元配合物稳定性有着显著影响。 相似文献
944.
We introduce generalized bond orders defined in terms of weighted Kekule valence structures. The weights were determined by the contributions of linearly independent and minimal conjugated circuits in individual Kekule valence structure. When special values for the contributions of conjugated circuits of different size are assumed, one obtains quantities that show considerable similarity to the Pauling and the Clar's bond orders. Pauling bond orders are obtained when one assumes that all conjugated circuits make equal contribution to bond orders. © 1994 John Wiley & Sons, Inc. 相似文献
945.
Ya‐Ping Du Ya‐Wen Zhang Prof. Dr. Zheng‐Guang Yan Dr. Ling‐Dong Sun Prof. Dr. Song Gao Prof. Dr. Chun‐Hua Yan Prof. Dr. 《化学:亚洲杂志》2007,2(8):965-974
We report the synthesis of single‐crystalline and near‐monodispersed NaMF3 (M=Mn, Co, Ni, Mg), LiMAlF6 (M=Ca, Sr), and NaMgF3:Yb,Er nanocrystals (quasisquare nanoplates, nanorods, and nanopolygons) by the cothermolysis of multiple trifluoroacetates in hot combined organic solvents (oleic acid, oleylamine, and 1‐octadecene). The nanocrystals were characterized by XRD, TEM, superconductive quantum interference device (SQUID), and upconversion luminescence spectroscopy. By regulating the polarity of the dispersant, the NaMF3 (M=Mn, Co, Ni) nanoplates were partially aligned to form nanoarrays on copper TEM grids. The sizes of the NaMF3 nanocrystals were easily tuned by the use of proper synthetic conditions such as reaction temperature and time and solvent composition. On the basis of a series of experiments in which the reaction conditions were varied, together with GC–MS and FTIR analysis, the reaction pathways for the formation of these nanocrystals from trifluoroacetate precursors were proposed. The magnetic measurements showed that the differently sized NaMnF3 square plates displayed interesting weak ferromagnetic behavior on the nanometer scale. The strong red upconversion luminescence emitted from the NaMgF3:Yb,Er nanorods under 980‐nm near‐IR laser excitation suggests that NaMgF3 may be a good candidate host material for red upconversion luminescence. 相似文献
946.
In this study, we developed an analytical method for the enantioseparation of ofloxacin, using capillary electrophoresis with fluorescence detection. The optimum background electrolyte was obtained to be 60 mM hydroxylpropyl‐β‐cyclodextrin (HP‐β‐CD) in 50 mM phosphate buffer at pH 2.30. Under these conditions, the (+) and (‐) ofloxacin were completely separated, with the detection limit of 10 nM when the sample was prepared in deionized water. The linear ranges of levofloxacin in deionized water and untreated urine were 10?7 to 5 × 10?3 M with R2 = 0.9989 and 5 × 10?6to 5 × 10?3 M with R2 = 0.9943, respectively. We also applied this method to investigate the purity of a commercial drug. The results revealed that the ratio between (+)‐ofloxacin and (‐)‐ofloxacin (levofloxacin) was 99.9:0.1, and there is about 93 mg levofloxacin per tablet (200 mg). The concentration of levofloxacin in patient's urine was founded to be 7.9 × 10?4M, and the ratio between the two optical isomers was 99.3:0.7. 相似文献
947.
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
948.
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
949.
950.
A GPI-anchored dipeptide of sperm CD52 antigen was prepared through a convergent synthesis. First, the dipeptide with its C-terminus free and the GPI with its nonreducing end phosphoethanolamine bearing a free amino group were synthesized separately. Then, the two building blocks were coupled with use of EDC/HOBt as the condensation reagent. Finally, the GPI-anchored peptide was deprotected to give the target molecule 1. 相似文献