全文获取类型
收费全文 | 1238篇 |
免费 | 21篇 |
国内免费 | 4篇 |
专业分类
化学 | 900篇 |
晶体学 | 3篇 |
力学 | 23篇 |
数学 | 196篇 |
物理学 | 141篇 |
出版年
2020年 | 9篇 |
2019年 | 10篇 |
2017年 | 11篇 |
2016年 | 17篇 |
2015年 | 12篇 |
2014年 | 18篇 |
2013年 | 59篇 |
2012年 | 47篇 |
2011年 | 32篇 |
2010年 | 35篇 |
2009年 | 27篇 |
2008年 | 54篇 |
2007年 | 54篇 |
2006年 | 42篇 |
2005年 | 47篇 |
2004年 | 53篇 |
2003年 | 43篇 |
2002年 | 32篇 |
2001年 | 15篇 |
2000年 | 14篇 |
1999年 | 14篇 |
1998年 | 15篇 |
1997年 | 20篇 |
1996年 | 13篇 |
1995年 | 15篇 |
1994年 | 11篇 |
1993年 | 11篇 |
1992年 | 15篇 |
1988年 | 8篇 |
1987年 | 11篇 |
1985年 | 25篇 |
1984年 | 23篇 |
1983年 | 15篇 |
1982年 | 21篇 |
1981年 | 25篇 |
1980年 | 19篇 |
1979年 | 23篇 |
1978年 | 30篇 |
1977年 | 15篇 |
1976年 | 24篇 |
1975年 | 26篇 |
1974年 | 25篇 |
1973年 | 23篇 |
1972年 | 10篇 |
1970年 | 12篇 |
1969年 | 10篇 |
1968年 | 11篇 |
1960年 | 8篇 |
1959年 | 9篇 |
1954年 | 8篇 |
排序方式: 共有1263条查询结果,搜索用时 0 毫秒
11.
A new C19 hydroxylated enyne 15, as potential A-ring building block of vitamin D analogues, was synthesized in enantiomerically pure form in nine steps from (−)-(S)-limonene. This short synthesis involved ozonolyzis of 1,2-limonene oxide followed by a Criegee rearrangement, epoxide trans diaxial ring opening by lithium acetylide, elimination, epoxidation and syn β-elimination of the resulting homopropargylic oxirane. 相似文献
12.
Taw FL Mueller AH Bergman RG Brookhart M 《Journal of the American Chemical Society》2003,125(32):9808-9813
Cationic Rh(III) complex [Cp(PMe(3))Rh(SiPh(3))(CH(2)Cl(2))]BAr(4)' (1) activates the carbon-carbon bond of aryl and alkyl cyanides (R-CN, where R = Ph, (4-(CF(3))C(6)H(4)), (4-(OMe)C(6)H(4)), Me, (i)Pr, (t)Bu) to produce complexes of the general formula [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. With the exception of the (t)BuCN case, every reaction proceeds at room temperature (t(1/2) < 1 h for aryl cyanides, t(1/2) < 14 h for alkyl cyanides). A general mechanism is presented on the basis of (1) an X-ray crystal structure determination of an intermediate isolated from the reaction involving 4-methoxybenzonitrile and (2) kinetic studies performed on the C-C bond cleavage of para-substituted aryl cyanides. Initial formation of an eta(1)-nitrile species is observed, followed by conversion to an eta(2)-iminoacyl intermediate, which was observed to undergo migration of R (aryl or alkyl) to rhodium to form the product [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. 相似文献
13.
The system BaF2/AlF3 is investigated by X-ray and D.T.A., and the liquid-solid phase diagram is established. Five ternary fluorides are disclosed: trimorphic BaAlF5, Ba3Al2F12, Ba5AlF19, polymorphic Ba3AlF9 and Ba5AlF13. Neutron thermodiffractometry experiments are performed to specify some parts of the diagram. The cell parameters of the fluorides are given and the results are discussed and compared with those of the previous works. 相似文献
14.
The examination of 19F chemical shifts for ca. 650 F-alkylated compounds of general formula CF3(CF2)nCF2X led to the following conclusions: the CF2 groups α to X are very sensitive to the nature of X, and are spread over a range of 85 ppm. The effect of the length of the F-alkyl chain decreases rapidly, so that δCF2(α) can already be considered as characteristic of X for n = 1 or 2 for most practical purposes. Solvent effects (in 9 different solvents having ε = 1.8 to 52.1) were found to be rather small except for the F-alkyl iodides. A chart which indicates the domain in which the CF2(α) resonance signal is to be expected is given for 42 different series of F-alkylated compounds; it is expected to provide the synthetic chemist with a useful tool for the identification and characterization of such compounds. 相似文献
15.
Continuing the recent work of the second author, we prove that the diophantine equation
for has exactly 12 solutions except when , when it has 16 solutions. If denotes one of the zeros of , then for we also find all with .
16.
Russell SC Czerwieniec G Lebrilla C Tobias H Fergenson DP Steele P Pitesky M Horn J Srivastava A Frank M Gard EE 《Journal of the American Society for Mass Spectrometry》2004,15(6):900-909
The appearance of informative signals in the mass spectra of laser-ablated bio-aerosol particles depends on the effective ionization probabilities (EIP) of individual components during the laser ionization process. This study investigates how bio-aerosol chemical composition governs the EIP values of specific components and the overall features of the spectra from the bio-aerosol mass spectrometry (BAMS). EIP values were determined for a series of amino acid, dipicolinic acid, and peptide aerosol particles to determine what chemical features aid in ionization. The spectra of individual amino acids and dipicolinic acid, as well as mixtures, were examined for extent of fragmentation and the presence of molecular ion dimers, which are indicative of ionization conditions. Standard mixtures yielded information with respect to the significance of secondary ion plume reactions on observed spectra. A greater understanding of how these parameters affect EIP and spectra characteristics of bio-aerosols will aid in the intelligent selection of viable future biomarkers for the identification of bio-terrorism agents. 相似文献
17.
Improved L.C.A.O. method primitively built for conjugated molecules holding only atoms of second row in the periodic classification is extended to molecules holding atoms of the third row. The application is done for thiophen, thioketones, SO2 and SO3. d orbitals are not introduced in this study. Discussion about results shows that d orbitals must be introduced when the sulphur atom is strongly positively charged like in sulphur oxides. 相似文献
18.
The cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)-cyclopentane-[PdCl(eta3-C3H5)]2 system catalyses the coupling of aryl halides with alkynes with very high ratios of substrates-catalyst in good yields; a turnover number of 2600000 can be obtained for the reaction of 4-trifluoromethylbromobenzene with phenylacetylene in the presence of this catalyst. 相似文献
19.
20.
John Yamanis Maurice Adelman 《Journal of polymer science. Part A, Polymer chemistry》1976,14(8):1945-1959
Experimental investigations dealing with and mathematical models proposed for the kinetics of the transesterification of dimethyl terephthalate with ethylene glycol were critically reviewed. The models were found to be inadequate, while the investigations were found to be entirely lacking in information about the significance of oligomerization reactions. The significance of these reactions was deduced to be negligible by carrying out an analysis of the kinetics of possible ester interchange and transesterification reactions by use of data on methanol reported in the reviewed literature. This analysis was made possible by the application of numerical quadrature routines in testing the assumed models by the integral method. 相似文献