全文获取类型
收费全文 | 12478篇 |
免费 | 1451篇 |
国内免费 | 441篇 |
专业分类
化学 | 5108篇 |
晶体学 | 29篇 |
力学 | 1494篇 |
综合类 | 33篇 |
数学 | 5686篇 |
物理学 | 2020篇 |
出版年
2023年 | 168篇 |
2022年 | 122篇 |
2021年 | 233篇 |
2020年 | 438篇 |
2019年 | 334篇 |
2018年 | 304篇 |
2017年 | 286篇 |
2016年 | 492篇 |
2015年 | 492篇 |
2014年 | 630篇 |
2013年 | 1070篇 |
2012年 | 710篇 |
2011年 | 738篇 |
2010年 | 512篇 |
2009年 | 793篇 |
2008年 | 727篇 |
2007年 | 758篇 |
2006年 | 660篇 |
2005年 | 507篇 |
2004年 | 486篇 |
2003年 | 454篇 |
2002年 | 396篇 |
2001年 | 378篇 |
2000年 | 352篇 |
1999年 | 299篇 |
1998年 | 312篇 |
1997年 | 240篇 |
1996年 | 239篇 |
1995年 | 163篇 |
1994年 | 125篇 |
1993年 | 118篇 |
1992年 | 81篇 |
1991年 | 76篇 |
1990年 | 64篇 |
1989年 | 54篇 |
1988年 | 57篇 |
1987年 | 42篇 |
1986年 | 52篇 |
1985年 | 40篇 |
1984年 | 53篇 |
1983年 | 20篇 |
1982年 | 30篇 |
1981年 | 30篇 |
1980年 | 22篇 |
1979年 | 25篇 |
1978年 | 41篇 |
1977年 | 41篇 |
1976年 | 40篇 |
1975年 | 15篇 |
1974年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
191.
纳米ZrO2的合成对负载Ni催化剂的CH4/CO2重整反应的影响 总被引:1,自引:1,他引:1
采用共沉淀法、醇热合成法和干法分别合成了纳米ZrO2(ZrO2 CP、ZrO2 ET和ZrO2 S),用XRD、 BET、SEM等对其结构和表面性质进行表征,以CH4/CO2重整为探针反应研究了不同方法合成的纳米ZrO2负载Ni催化剂的催化性能,并与载体的物化性质进行了关联。实验结果表明,以干法合成的纳米介孔ZrO2 S具有较大的比表面积(133m2/g)和较好的孔径分布(4.9nm),Ni/ZrO2 S催化剂在CH4/CO2重整反应中表现出较好的催化性能。 相似文献
192.
Eric J.L. McInnes Grigore A. Timco Richard E.P. Winpenny 《Coordination chemistry reviews》2005,249(23):2577-2590
Studies of two distinct classes of chromium(III) cage complexes are discussed. The first are compact oxo- and carboxylate cages, made by heating precursors to high temperature under a flow of nitrogen. One of these cages, [Cr12O9(OH)3(O2CCMe3)15], has an S = 6 spin ground state which proves a very interesting subject for study by EPR and MCD spectroscopy. Use of other carboxylates leads to other octa- and dodeca-nuclear complexes. The second class of compounds are homo- and hetero-metallic wheels and chains bridged by fluoride and carboxylates. These include the first heterometallic anti-ferromagnetically coupled ring systems and are being widely studied in areas as diverse as magnetic cooling and quantum information processing. The mechanism by which these unusual cyclic and acyclic structures form is discussed. 相似文献
193.
T. de Beer G. Ph. Hoornweg G. J. Grootendorst N. H. Velthorst C. Gooijer 《Analytica chimica acta》1996,330(2-3):189-197
An explorative study on the compatibility of liquid separation systems, such as (micro) liquid chromatography (LC) and capillary electrophoresis (CE), and forward-scattering degenerate four-wave mixing (F-D4WM) as a detection method is presented. F-D4WM is a laser-based technique showing some analogy with holographic spectroscopy: a signal on a theoretical dark background is observed as a result of light absorption by an analyte. Parameters considered are solvent composition focussing on acetonitrile, methanol and water; mobile phases in LC and CE), detector cell construction, and influences of laser beam powers. A specially designed detector cell has been developed to meet the Brewster condition, both at the air-quartz and the quartz-liquid boundaries. For practical reasons, the tested cell has an optical pathlength of 1 mm; reduction to 100 μm is required to apply the cell in microseparations. The F-D4WM technique has been involved for detection in a conventional-size, reversed-phase LC separation of 1- and 2-aminoanthraquinones. The detection limit obtained (for the 1 mm cell) is 2 × 10−5 absorbance units. The experiments indicate that further reduction of background deserves explicit attention. 相似文献
194.
P.A. Fantin P.L. Barbieri A. Canal Neto F.E. Jorge 《Journal of Molecular Structure》2007,810(1-3):103-111
195.
The mathematical evaluation of the activation
energy, E, of non-isothermal degradation
reactions is usually made using the Ozawa/Flynn–Wall isoconversion principle
and involves the numerical resolution of a set of integrals without closed
form solution, which are solved by polynomial approximation or by numeric
integration. In the present work, the isoconversion principle, originally
described and maintained until now as an algebraic problem, was written as
a set of ordinary differential equations (ODEs). The individual ODEs obtained
are integrated by numeric methods and are used to estimate the activation
energy of simulated examples. A least square error (LSE) objective function
using the introduced ODEs was written to deal with multiple heating rate CaCO3
thermal decomposition TG experiments. 相似文献
196.
Daniel William Tholen 《Accreditation and quality assurance》1998,3(9):362-366
There are three stages to evaluating a laboratory's results in an interlaboratory proficiency test: establishing the correct
result for the test item, determining an evaluation statistic for the particular result, and establishing an acceptable range.
There are a wide variety of procedures for accomplishing these three stages and a correspondingly wide variety of statistical
techniques in use. Currently in North America the largest number of laboratory proficiency test programs are in the clinical
laboratory field, followed by programs for environmental laboratories that test drinking water and waste water. Proficiency
testing in both of these fields is under the jurisdiction of the federal government and other regulatory and accreditation
agencies. Many of the statistical procedures are specified in the regulations, to assure comparability of different programs
and a fair evaluation of performance. In this article statistical procedures recommended in International Organization for
Standardization Guide 43, Part 1, are discussed and compared with current practices in North America.
Received: 22 April 1998 · Accepted: 12 May 1998 相似文献
197.
The analytical methods mass spectrometry, UV/Vis, IR, Raman, Fluorometry, XRD, Mössbauer, and NMR used to elucidate chemical structure are evaluated regarding their capabilities to be used as primary analytical techniques in quantitative measurements, considering the criteria in the CCQM definition of primary methods. This includes a review of the respective measurement equations, the evaluation of the measurement uncertainty, and a discussion of evidence for the “highest metrological level”, as obtained from intercomparisons in contest with other methods. It is shown that only few methods fulfill the CCQM criteria. Quantitative NMR spectroscopy is one of them and may be considered as a potential primary method as recommended by CCQM because of being free of empirical factors in the uncertainty budget. 相似文献
198.
Heinz Günter Viehe Robert Mernyi Lucien Stella Zdenek Janousek 《Angewandte Chemie (International ed. in English)》1979,18(12):917-932
The 100 yers old Wurster's salts have long been recognized as compounds with redical cations. Their unusual stabilization derives partly form capto-dative (cd) substitution. This principle is now discussed as one factor of radical stabilization and it is applied to simple methine derivatives. cd-Substitution has synthetically useful applications: cd-substituents on a carbon atom allow its selective dehydrodimerization. Olefines with geminal and thus cross-conjugated cd-substituents are “radicophilic” and permit twofold carbon radical addition. cd-Substituted olefines are useful antioxidants, polymerization inhibitors and are promising agents in the control of biological radical reactions. Generally, many reactions of cd-substituted molecules appear to involve radicals. 相似文献
199.
Development and validation of methods for the trace determination of phthalates in sludge and vegetables 总被引:1,自引:0,他引:1
Sablayrolles C Montréjaud-Vignoles M Benanou D Patria L Treilhou M 《Journal of chromatography. A》2005,1072(2):233-242
A routine method which is simple, quick and precise has been set up and validated for phthalate analysis in environmental samples (tomato plants and sewage sludges). Six phthalates have been studied simultaneously: dimethylphthalate, diethylphthalate, di-n-butylphthalate, n-butylbenzylphthalate, di-2-ethyl-hexyl phthalate (DEHP) and di-n-octylphthalate. Optimization of sample, solvent extraction uses a Soxtec apparatus and extract purification with an a solid-phase extraction cartridge allows between 90 and 110% recovery of phthalates. Precise, sensitive and selective identification and quantifying of analytes is by GC-MS in the single ion monitoring mode. This protocol allows analytes with concentrations as low as 10 microg/kg dry matter (DM) to be determined from small (1-2 g DM) samples. This analytical method has been applied to the phthalate transfer study for agricultural recycling of sludges, where phthalate bioavailability has been studied in aquiculture using two types of experiments. Tomatoes have been grown in containers where the trace organics have been directly introduced as pure substances, and in a second experiment under the same growth conditions, sewage sludge has replaced the pure substances. Transfer of these trace organics has been followed into the various parts of the tomato plant and in general only the DEHP is worthy of note although its percentage transfer remains very low even in an experiment designed to maximize this. 相似文献
200.
分别用MNDO,AM1和PM3三种半经验方法对C59HN所有1-2,1-4和1-6氢加成物C59H3N的异构体进行几何构型全优化,结合频率分析及HF/6-31G单点能计算,确定了各异构体的基态结构及其相对稳定性,计算结果表明,C59HN氢加成物的立体选择性规律与C60和C60H2的不同,最稳定异构体不是1-2加成物,而是1-4加成的6,18-或12,15-异构体,次稳定异构体为1-2加成物,三种半经验方法计算得到的两者能量差为13~15kJ/mol,N原子取代碳笼骨架C原子后,改变了碳笼氢加成物的立体选择性规律. 相似文献