全文获取类型
收费全文 | 49014篇 |
免费 | 5080篇 |
国内免费 | 3154篇 |
专业分类
化学 | 28056篇 |
晶体学 | 310篇 |
力学 | 936篇 |
综合类 | 667篇 |
数学 | 7110篇 |
物理学 | 20169篇 |
出版年
2023年 | 361篇 |
2022年 | 783篇 |
2021年 | 1943篇 |
2020年 | 1385篇 |
2019年 | 1394篇 |
2018年 | 1002篇 |
2017年 | 1265篇 |
2016年 | 1550篇 |
2015年 | 1527篇 |
2014年 | 2131篇 |
2013年 | 3124篇 |
2012年 | 2209篇 |
2011年 | 2685篇 |
2010年 | 2298篇 |
2009年 | 2918篇 |
2008年 | 2910篇 |
2007年 | 3211篇 |
2006年 | 2555篇 |
2005年 | 1637篇 |
2004年 | 1537篇 |
2003年 | 1495篇 |
2002年 | 3878篇 |
2001年 | 1568篇 |
2000年 | 1120篇 |
1999年 | 868篇 |
1998年 | 917篇 |
1997年 | 636篇 |
1996年 | 624篇 |
1995年 | 558篇 |
1994年 | 542篇 |
1993年 | 581篇 |
1992年 | 575篇 |
1991年 | 389篇 |
1990年 | 317篇 |
1989年 | 261篇 |
1988年 | 278篇 |
1987年 | 229篇 |
1986年 | 225篇 |
1985年 | 335篇 |
1984年 | 251篇 |
1983年 | 145篇 |
1982年 | 301篇 |
1981年 | 473篇 |
1980年 | 436篇 |
1979年 | 469篇 |
1978年 | 370篇 |
1977年 | 281篇 |
1976年 | 238篇 |
1974年 | 77篇 |
1973年 | 161篇 |
排序方式: 共有10000条查询结果,搜索用时 468 毫秒
971.
前驱体水解对纳米铂形状控制合成的影响 总被引:5,自引:1,他引:5
以聚丙烯酸钠(NaPA: M_w ≈ 2100)为保护剂,对比研究了H_2还原K_2PtCl_4 和K_2PtCl_6水溶液制备纳米铂晶粒的形状选择性,揭示了前驱体的水解对纳米铂 晶粒的形状控制合成具有显著影响。文献中通常采用的合成立方形状纳米铂的 K_2PtCl_4前驱体在水溶液中不稳定,避光静置一周会析出黑色沉淀。这种不稳定 性导致了以K_2PtCl_4为Pt前驱体的合成结果难以重复。相比而言,避光静墨的 K_2PtCl_6水溶液很稳定,以它为前驱体合成的纳米铂通常为削角八面体。 K_2PtCl_6水溶液暴露于室内光线中会出现[PtCl_6]~(-2)的光致水解。当[PtCl_6] ~(2-)的紫外特征吸收峰(260nm)由于光致水解完全消失后,以聚丙烯酸钠为保护剂 ,通过H_2还原可以有选择性地(约80%)合成由{100}晶面包裹的立方体形状的纳米 铂。 相似文献
972.
Walter Weissensteiner 《Monatshefte für Chemie / Chemical Monthly》1992,123(8-9):785-800
Summary The conformational possibilities of 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cycloheptene (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2), and 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (3) are analysed using empirical force field methods. Minimum energy conformations, interconversion pathways, interconversion graphs and interconversion energies are examined in view of the analysis of conformer equilibria of1,2, or3 in solution. In addition, some basic requirements of the analysis of fast interconverting conformers using the lanthanide induced shift method are discussed.
Konformation und interne Beweglichkeit von 5H-Dibenzo[a,d]cyclohepten Derivaten in Lösung. Konformationsanalyse hochflexibler Strukturen, Teil 2
Zusammenfassung Die konformativen Möglichkeiten von 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cyclohepten (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (2) und 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (3) wurden mit Hilfe empirischer Kraftfeldmethoden analysiert. Jene Konformationen, die einem energetischen Minimum entsprechen, sowie Interkonversionswege, Interkonversionsgraphen und Interkonversionsenergien wurden in Hinblick auf die Analyse der Konformerengleichgewichte von1,2 oder3 in Lösung untersucht. Weiters werden noch einige grundlegende Voraussetzungen für die Analyse von sich schnell ineinander umwandelnden Konformeren mittels der Lanthaniden-induzierten Verschiebungsmethode besprochen.相似文献
973.
The first thermodynamic dissociation constants of o-phthalic acid were determined at five temperatures from 278.15 to 318.15 K in 10, 14.93 and 20 wt% isopropanol-water solvent mixtures, by precise e. m. f. measurements of hydrogen-silver chlorld electrodes in cells without liquid junction. On the basis of Pitzer's theory, the method of polynomial approximation was used to determine the dissociation constants of H_2P and the results obtained were compared with traditional extrapolation according to the extended Debye-Huckel equation Results obtained from both methods agree within experimental error. The dependence of the first thermodynamic dissociation constant on temperature was given as a function of the thermodynamic temperature T by the empirical equation: pK_1=A_0+A_1/T+A_2/T. The thermodynamic quantities of dissociation in the mixed solvents have been calculated, and the results have been discussed. 相似文献
974.
The performance of a PTV injector operated in the solvent venting mode with Tenax in the glass insert was evaluated with synthetic mixtures containing 5 to 50 ng of n-alkanes, ethyl esters, n-alcohols, and carboxylic acids. The influence of the sampled amount, the injected volume, and the nature of the solvent on accuracy and precision were studied. Coefficients of variation of relative (normalized) peak areas and absolute peak area ratios of each compound to the standard are of the order of 5 %. 相似文献
975.
976.
Multiple zigzag chains of length n and width m constitute an important class of regular graphene flakes of rectangular shape. The physical and chemical properties of these basic pericondensed benzenoids can be related to their various topological invariants, conveniently encoded as the coefficients of a combinatorial polynomial, usually referred to as the ZZ polynomial of multiple zigzag chains . The current study reports a novel method for determination of these ZZ polynomials based on a hypothesized extension to John–Sachs theorem, used previously to enumerate Kekulé structures of various benzenoid hydrocarbons. We show that the ZZ polynomial of the multiple zigzag chain can be conveniently expressed as a determinant of a Toeplitz (or almost Toeplitz) matrix of size consisting of simple hypergeometric polynomials. The presented analysis can be extended to generalized multiple zigzag chains , i.e., derivatives of with a single attached polyacene chain of length k. All presented formulas are accompanied by formal proofs. The developed theoretical machinery is applied for predicting aromaticity distribution patterns in large and infinite multiple zigzag chains and for computing the distribution of spin densities in biradical states of finite multiple zigzag chains . 相似文献
977.
(Z)-γ-Cyano-β-perfluoroalkyl-β,γ-unsaturated esters have been synthesized by the reaction of perfluoroacylated phosphonates with organozinc reagent in 50-71% (three steps) yields. 相似文献
978.
The present short review deals with electroanalytical aspects of electrochemical response of ascorbic acid (Vitamin C) at conducting and electrogenerated polymer modified electrodes. Two main topics are considered: (i) electrocatalytic oxidation of ascorbate at conducting polymer modified electrodes, leading to electroanalytical techniques for ascorbate assay, and (ii) retardation of ascorbate penetration through a layer of electrogenerated polymers, leading to permselective coatings and their diverse uses, especially for biosensing devices. 相似文献
979.
通过对离子轰击下固体表面电离过程重新考虑认为,在固体表面覆氧或氧离子轰击下除表面原子的直接电离外,激发态双原子间电子交换和断键亦起重要作用。在此基础上修正了局部热力学平衡模型,得到了一个包含各类离子内配分函数、电离能、金属-氧原子键断键能以及表面金属原子与氧原子结合份数等参数决定的新电离几率分析表达式。应用该分析表达式解释了金属表面覆氧、氧离子轰击金属、化合物半导体表面二次离子发射中氧增强效应、充氧量对二次离子发射的影响及其基体效应等实验现象。并由此得到了元素相对灵敏度因子的分析表达式,对化合物半导体及一些陶瓷材料表面二次离子质谱分析中元素灵敏度因子随元素电离能变化曲线给予了相应的物理解释。 相似文献
980.
Determination of selenium, zinc and cadmium in antidandruff shampoos by atomic spectrometry after microwave assisted sample digestion 总被引:1,自引:0,他引:1
Microwave assisted pre-treatments for atomic spectrometric determination (inductive coupled plasma-optical emission spectrometry, ICP-OES or flame atomic absorption spectrometry, FAAS) of metallic elements, usually present in antidandruff shampoos, are proposed. They are based on the digestion of the sample with HNO3 into a closed reactor, which is irradiated at 800 W for a few minutes. Selenium was determined by ICP-OES. The limit of detection was 0.11 mg l−1; the relative standard deviation (R.S.D.) for the selenium content in the samples was in the 0.6–3.6% range. The results obtained were in agreement with the label contents and the recovery of the proposed method was in the 100–106% range. Zinc and cadmium were determined by FAAS. The limit of detection for zinc determination was 0.078 mg l−1; the R.S.D. for zinc contents was in the 0.8–8.6% range. A limit of detection of 0.09 mg l−1 was obtained for cadmium determination; the R.S.D. for cadmium contents was in the 0.7–2.7% range. The determinations were performed after two different sample mineralization pre-treatments — dry ashing (in an electric furnace) and wet mineralization (in a microwave oven). Both methodologies provided comparable results for zinc and cadmium determination in shampoos. The proposed microwave assisted digestion procedures allow a precise and accurate determination of selenium, zinc and cadmium in commercial antidandruff shampoos, and the sample pre-treatment is less time-consuming than the classic methods. 相似文献