全文获取类型
收费全文 | 1933篇 |
免费 | 330篇 |
国内免费 | 152篇 |
专业分类
化学 | 700篇 |
晶体学 | 26篇 |
力学 | 261篇 |
综合类 | 21篇 |
数学 | 275篇 |
物理学 | 1132篇 |
出版年
2024年 | 2篇 |
2023年 | 15篇 |
2022年 | 33篇 |
2021年 | 53篇 |
2020年 | 44篇 |
2019年 | 40篇 |
2018年 | 52篇 |
2017年 | 71篇 |
2016年 | 50篇 |
2015年 | 59篇 |
2014年 | 80篇 |
2013年 | 156篇 |
2012年 | 84篇 |
2011年 | 127篇 |
2010年 | 122篇 |
2009年 | 129篇 |
2008年 | 123篇 |
2007年 | 125篇 |
2006年 | 126篇 |
2005年 | 98篇 |
2004年 | 97篇 |
2003年 | 107篇 |
2002年 | 87篇 |
2001年 | 57篇 |
2000年 | 60篇 |
1999年 | 70篇 |
1998年 | 52篇 |
1997年 | 46篇 |
1996年 | 44篇 |
1995年 | 38篇 |
1994年 | 25篇 |
1993年 | 25篇 |
1992年 | 21篇 |
1991年 | 14篇 |
1990年 | 8篇 |
1989年 | 18篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 6篇 |
1981年 | 6篇 |
1980年 | 2篇 |
1977年 | 1篇 |
1976年 | 6篇 |
1974年 | 1篇 |
1971年 | 2篇 |
1959年 | 1篇 |
排序方式: 共有2415条查询结果,搜索用时 31 毫秒
51.
Steven R. Woodcock 《Tetrahedron letters》2005,46(42):7213-7215
Ether tethers allow Heck cyclizations to proceed in high yields. Ester tethers lead to low yields. Styrene trapping experiments indicate that ester reactions form viable organopalladium intermediates that cannot cyclize efficiently. 相似文献
52.
Cataldo L Dutan C Misra SK Loss S Grützmacher H Geoffroy M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(11):3463-3468
The EPR spectrum of the novel radical Mes*(CH3)P--PMes* (Mes*=2,4,6-(tBu)3C6H2) was measured in the temperature range 100-300 K, and was found to be drastically temperature dependent as a result of the large anisotropy of the 31P hyperfine tensors. Below 180 K, a spectrum of the liquid solution is accurately simulated by calculating the spectral modifications due to slow tumbling of the radical. To achieve this simulation, an algorithm was developed by extending the well-known nitroxide slow-motion simulation technique for the coupling of one electron spin to two nuclear spins. An additional dynamic process responsible for the observed line broadening was found to occur between 180 K and room temperature; this broadening is consistent with an exchange between two conformations. The differences between the isotropic 31P couplings associated with the two conformers are shown to be probably due to an internal rotation about the P--P bond. 相似文献
53.
Enantio-uracil dinucleotide 5, which consists of two l-uridylic acids and one pyrophosphate, was synthesized for the first time in our laboratory. Benzolyated l-uridine was prepared by a stereoselective glycosylation of silylated uracil with l-1-O-acetyl-2,3,5-tri-O-benzoylribose (l-ABR 7). After deprotection, l-uridine 9 was converted to P1,P4-di(l-uridine 5′-) tetraphosphate tetrasodium salt (l-UP4U 5) by treatment of l-UMP morpholidate 10c with triethylammonium pyrophosphate (TEA-PPi 11b). Spectral data of synthesized l-UP4U 5 are given in the references. All spectral data were identical with those of UP4U 3 except the specific rotation, which showed a positive value compared to UP4U 3 having a negative value. Furthermore, the separation by chiral column chromatography was investigated. 相似文献
54.
Petrovic AG Polavarapu PL Drabowicz J Zhang Y McConnell OJ Duddeck H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(14):4257-4262
The enantiomers of 3,3,3',3'-tetramethyl-1,1'-spirobi[3 H,2,1]benzoxaselenole have been separated on a chiral preparative chromatographic column. The experimental vibrational circular dichroism (VCD) spectra have been obtained for both enantiomers in CH(2)Cl(2). The theoretical VCD spectra have been obtained by means of density functional theoretical calculations with the B3 LYP density functional. From a comparison of experimental and theoretical VCD spectra, the absolute configuration of an enantiomer with positive specific rotation in CH(2)Cl(2) at 589 nm is determined to be R. This conclusion has been verified by comparing results of experimental optical rotatory dispersion (ORD) and electronic circular dichroism (ECD) to predictions of the same properties using the B3 LYP functional for the title compound. 相似文献
55.
Otto Vogl Jan Bartus Joseph R. Murdoch 《Monatshefte für Chemie / Chemical Monthly》1990,121(4):311-316
Summary We report techniques for measuring optical rotation of suspended solids, including dissymmetric molecular crystals (e.g. sodium chlorate and bromate), synthetic polymers, polypeptides and biopolymers. Examples include poly(triphenylmethyl methacrylate), poly-S-lactide, poly-L-hydroxyproline, hemocyanine, cellulose acetate andRNA. The results indicate that optical rotation measurements are sensitive to differences in secondary structure and can serve as a probe for structural differences between solid-state and solution.
Messung der optischen Rotation von Makromolekülen im Festzustand unter Verwendung von Pulversuspensionen
Zusammenfassung Es wird über eine Methode zur Messung der optischen Rotation von Festkörpern in Suspensionen berichtet, wobei dissymetrische Kristalle (z. B. Natriumchlorat und -bromat), synthetische Polymere, Polypeptide und Biopolymere behandelt werden. Die Beispiele umfassen Poly(triphenylmethylmethacrylat), Poly-S-lactid, Poly-L-hydroxyprolin, Hemocyanin, Celluloseacetat undRNA. Die Ergebnisse zeigen, daß die optischen Rotationen bezüglich Unterschiede in der Sekundärstruktur empfindlich sind und daß diese Messungen als ein Maß für Strukturunterschiede zwischen Festzustand und Lösung herangezogen werden können.相似文献
56.
An efficient angular momentum method is presented and used to derive analytic expressions for the vibration-rotational kinetic energy operator of polyatomic molecules.The vibration-rotational kinetic energy operator is expressed in terms of the total angular momentum operator J,the angular momentum operator J and the momentum operator p conjugate to Z in the molecule-fixed frame Not only the method of derivation is simpler than that in the previous work,but also the expressions ot the kinetic energy operators arc more compact.Particularly,the operator is easily applied to different vibrational or rovibrational problems of the polyatomic molecules by variations of matrix elements Gn of a mass-dependent constant symmetric matrix 相似文献
57.
58.
The stability constants and the partial molal volume and isentropic partial molal compressibility changes of complex formation between cations and crown ethers in water at 25°C are presented. The cations involved are Na+, K+, Rb+, Cs+, Ca2+, and Ba2+, and the crown ethers are 12-crown-4, 15-crown-5, and 18-crown-6. Values of V of complex formation have been discussed in terms of two simple models, one based on the scaled particle theory, and the others on the Drude-Nernst continuum model. The results indicate that the charge of the potassium cation in 18-crown-6 is especially well screened from the water. On this basis hydration numbers of complexed cations have been calculated. This shows that the size of the cation compared to the crown ether hole is important for the contacts between complexed cations and water. 相似文献
59.
60.
Antonio Fernández-Ramos Benjamin A. Ellingson Rubén Meana-Pañeda Jorge M. C. Marques Donald G. Truhlar 《Theoretical chemistry accounts》2007,118(4):813-826
This article shows how to evaluate rotational symmetry numbers for different molecular configurations and how to apply them
to transition state theory. In general, the symmetry number is given by the ratio of the reactant and transition state rotational
symmetry numbers. However, special care is advised in the evaluation of symmetry numbers in the following situations: (i)
if the reaction is symmetric, (ii) if reactants and/or transition states are chiral, (iii) if the reaction has multiple conformers
for reactants and/or transition states and, (iv) if there is an internal rotation of part of the molecular system. All these
four situations are treated systematically and analyzed in detail in the present article. We also include a large number of
examples to clarify some complicated situations, and in the last section we discuss an example involving an achiral diasteroisomer. 相似文献