全文获取类型
收费全文 | 2868篇 |
免费 | 106篇 |
国内免费 | 117篇 |
专业分类
化学 | 1638篇 |
晶体学 | 27篇 |
力学 | 96篇 |
综合类 | 12篇 |
数学 | 377篇 |
物理学 | 941篇 |
出版年
2022年 | 45篇 |
2021年 | 46篇 |
2020年 | 48篇 |
2019年 | 44篇 |
2018年 | 27篇 |
2017年 | 48篇 |
2016年 | 68篇 |
2015年 | 50篇 |
2014年 | 67篇 |
2013年 | 147篇 |
2012年 | 155篇 |
2011年 | 172篇 |
2010年 | 104篇 |
2009年 | 86篇 |
2008年 | 136篇 |
2007年 | 142篇 |
2006年 | 124篇 |
2005年 | 141篇 |
2004年 | 96篇 |
2003年 | 90篇 |
2002年 | 82篇 |
2001年 | 78篇 |
2000年 | 65篇 |
1999年 | 44篇 |
1998年 | 25篇 |
1997年 | 40篇 |
1996年 | 37篇 |
1995年 | 56篇 |
1994年 | 46篇 |
1993年 | 45篇 |
1992年 | 43篇 |
1991年 | 33篇 |
1990年 | 35篇 |
1989年 | 22篇 |
1988年 | 23篇 |
1987年 | 23篇 |
1985年 | 34篇 |
1984年 | 26篇 |
1983年 | 18篇 |
1982年 | 26篇 |
1981年 | 33篇 |
1980年 | 21篇 |
1979年 | 35篇 |
1978年 | 28篇 |
1977年 | 31篇 |
1976年 | 35篇 |
1975年 | 31篇 |
1974年 | 26篇 |
1973年 | 37篇 |
1972年 | 26篇 |
排序方式: 共有3091条查询结果,搜索用时 0 毫秒
21.
It is shown unequivocally by chemical correlations (cf. Schemes 1--3) and Raman optical activity spectra (cf. Fig. 1 and 2) that the (R)-configuration has to be attributed to (+)-1-methylindane ((+)- 1 ). This is in contradiction to an earlier assignment of the (R)-configuration to (?)- 1 [2] which was based on the (R)-configuration of (+)-indane-1-carboxylic acid ( 3 ) [11]. 相似文献
22.
The isothermal and temperature scanning calorimeters manufactured by Calorimetry Sciences Corporation are briefly described. Applications of calorimetry to determine thermodynamics and kinetics of reactions of interest in biotechnology are described with illustrative examples. 相似文献
23.
The rapid determination of chloride and inorganic phosphate in blood serum based on continuous flow spectrophotometry was adapted to Flow Injection Analysis by applying dialysis as well as differential dilution of the injected samples. In addition to the manual injection procedure, an automated microsampling unit was developed and used. By continuous dialysis, chloride could be determined reproducibly at a sampling rate of 125 samples per hour at sample volumes of 60 μl or less. A similar sampling rate and high precision were obtained for the determination of inorganic phosphate by using differential dilution. 相似文献
24.
The basic principles of Flow Injection Analysis are outlined. The parameters governing the dispersion of the injected sample zone in the system are discussed, and it is demonstrated how these parameters can be manipulated in order to suit the requirements of an individual analytical procedure. A number of examples illustrating the practical application of f.i.a. are described, comprising the use of automated, stopped-flow, merging-zones, extraction techniques as well as f.i.a. scanning and methods based on intermittent pumping. Updated lists on f.i.a. procedures published and species that can be determined by f.i.a. are included. 相似文献
25.
Hansen MR Madsen GK Jakobsen HJ Skibsted J 《The journal of physical chemistry. A》2005,109(9):1989-1997
The refinement of borate structures using DFT calculations combined with experimental (11)B quadrupole coupling parameters from solid-state NMR spectroscopy is presented. The (11)B electric field gradient (EFG) tensors, calculated using the WIEN2k software for trigonal and tetrahedral boron sites in a series of model compounds, exhibit a convincing linear correlation with the quadrupole coupling tensor elements, determined from (11)B MAS NMR spectra of the central or satellite transitions. The model compounds include Li(2)B(4)O(7), Mg(2)B(2)O(5), Mg(3)B(2)O(6), NH(4)B(C(6)H(5))(4), and colemanite (CaB(3)O(4)(OH)(3).H(2)O). The (11)B quadrupole moment, Q = 0.0409 +/- 0.0002 barn, derived from the linear correlation, is in excellent agreement with the accepted value for Q((11)B). This demonstrates that DFT (WIEN2k) calculations can provide precise (11)B quadrupole coupling parameters on an absolute scale. On the other hand, DFT calculations based on the reported crystal structures for datolite (CaBSiO(4)(OH)) and danburite (CaB(2)Si(2)O(8)) cannot reproduce the experimental (11)B quadrupole coupling parameters to the same high precision. However, optimization of these structures by minimization of the forces between the atoms (obtained by DFT) results in a significant improvement between the calculated and experimental (11)B quadrupole coupling parameters, which indicates that reliable refinements of the borate structures are obtained by this method. Finally, the DFT calculations also provide important structural information about the sign and orientation of the EFG tensor elements in the crystal frame, a kind of information that cannot be achieved from (11)B NMR experiments on powdered samples. 相似文献
26.
The Cyclopropa[c]chromenes 14 , trans-and cis- 15 , trans-and cis- 16 and 17 rearrange on heating > 200° in N, N-diethylaniline to give 2-alkyl-2H-chromenes 7, 8, 21, 22. The rate determining step of this rearrangement is the ‘homoelectrocyclic’ ring opening of the cyclopro-pa[c]chromenes to give ω-allyl-quinomethanes of type 4. These intermediates show fast [1,5s] and [1,7a] H-shifts, followed by electrocyclic ring closure. Deuterium labelling experiments are in agreement with this mechanism. The remarkable dependence of the rates of rearrangement with respect to the stereochemistry of the cyclopropa[c]chromenes (cf. table 2) suggests that in the first step only one of the two possible disrotatory modes of ring opening is involved. 相似文献
27.
Some 804 papers on flow injection analysis published to the end of May 1985 are summarized. Past trends are discussed and new developments are briefly outlined.The paper entitled “Flow Injection Analysis. Part 1. A New Concept of Fast Continuous Flow Analysis” [1], which appeared in August 1975, was the first of some 804 papers [1/2-804] published on flow injection analysis (f.i.a.) during the past ten years. In the present contribution, all these papers are collected to record the status quo of the general method and to reveal the present trends in applications of f.i.a. and in the geographical distribution of the research activities. Important concepts and technological innovations are reviewed and the future development of f.i.a. is briefly outlined. 相似文献
28.
M. Tinggaard P. Hansen P. K. Mogensen O. Simonsen J. Becher 《Journal of heterocyclic chemistry》1989,26(2):439-444
2-Acyl-3-methylthiofurans 3 are obtained in fair yields from 3-methylthio-2-pentene-1,5-dione enolates 1 by reaction with iodine. In a similar reaction 1-phenyl-3-methylthio-4-nitro-2-buten-1-one gave 3-methylthio-2-nitro-5-phenylfuran 11. In the crystalline state the 2-benzoyl-3-methylthio-5-phenylfuran 3b showed a non-bonded sulfur-oxygen interaction as inferred from an X-ray diffraction determination, with a S····O distance of 2.871(5)Å. 相似文献
29.
(?)-(S)- and (+)-(R)-3-methylcyclopentene (1) has been prepared in a stereochemically unambiguous synthesis. The (S)-configuration for (?)-1 was confirmed by correlation with (?)-(S)-1-methylindane. 相似文献
30.
The Flow Injection technique is shown to provide fast, reliable and sensitive methods for the determination of calcium in various aqueous as well as serum samples; spectrophotometric or potentiometric detection can be used. At sampling rates of 100–110 samples per hour, with 30-μl sample injections, high reproducibility of measurement and low reagent consumption are achieved in both methods. In the spectrophotometric method, the analytical readout is available within 12 s after sample injection at a total reagent consumption of 0.75 ml per analysis. The potentiometric measurement of the calcium activity in serum is placed on a reliable basis by alternating measurements of serum samples and aqueous standards without incurring any non-reproducible changes in potential between aqueous and serum solutions. This permits the simultaneous determination of pH and pCa, the analytical readout being available within XXX s of sample injection. The good agreement between the results obtained with the Flow Injection method and those attained by atomic absorption and EDTA titrations as well as pCa stat-measurements show that the new methods are potentially suitable for routine analysis. 相似文献