全文获取类型
收费全文 | 1345篇 |
免费 | 11篇 |
国内免费 | 7篇 |
专业分类
化学 | 616篇 |
晶体学 | 13篇 |
力学 | 91篇 |
数学 | 197篇 |
物理学 | 446篇 |
出版年
2022年 | 16篇 |
2021年 | 16篇 |
2020年 | 29篇 |
2019年 | 24篇 |
2018年 | 28篇 |
2017年 | 36篇 |
2016年 | 46篇 |
2015年 | 13篇 |
2014年 | 36篇 |
2013年 | 39篇 |
2012年 | 51篇 |
2011年 | 68篇 |
2010年 | 56篇 |
2009年 | 42篇 |
2008年 | 54篇 |
2007年 | 51篇 |
2006年 | 45篇 |
2005年 | 36篇 |
2004年 | 45篇 |
2003年 | 30篇 |
2002年 | 20篇 |
2001年 | 39篇 |
2000年 | 26篇 |
1999年 | 13篇 |
1998年 | 13篇 |
1997年 | 25篇 |
1996年 | 16篇 |
1994年 | 19篇 |
1993年 | 12篇 |
1992年 | 12篇 |
1991年 | 19篇 |
1990年 | 15篇 |
1989年 | 24篇 |
1988年 | 15篇 |
1987年 | 21篇 |
1986年 | 14篇 |
1985年 | 26篇 |
1984年 | 13篇 |
1983年 | 11篇 |
1982年 | 15篇 |
1981年 | 15篇 |
1979年 | 12篇 |
1978年 | 16篇 |
1976年 | 21篇 |
1975年 | 16篇 |
1974年 | 11篇 |
1973年 | 11篇 |
1972年 | 11篇 |
1969年 | 14篇 |
1968年 | 17篇 |
排序方式: 共有1363条查询结果,搜索用时 31 毫秒
31.
K. N. Makarov T. N. Abroskina Yu. A. Cheburkov I. L. Knunyants 《Russian Chemical Bulletin》1976,25(4):922-924
1. | The cesium chloride adducts with perfluoroacetone, 1-methyl-2-oxaperfluoroenanthyl fluoride, and perfluoroisobutylene react smoothly with symmetrical dichlorodimethyl ether, replacing both chlorine atoms, with the formation of the corresponding ethers. |
2. | The interaction of,-dihydroperfluoroamyl alcoholate with symmetrical dichlorodimethyl ether leads to the replacement of both chlorine atoms, with the formation of the corresponding ether. |
3. | The reaction of perfluoro-t-butylanion with tris(chloromethyl)amine leads to tris-(1,1-dihydro-perfluoroneopentyl) amine. |
4. | Perfluoro-t-butylanion replaces only one chlorine atom in the molecule of unsymmetrical di-chlorodimethyl ether, forming-chloro- -perfluoro-t-butyldimethyl ether. |
32.
R. M. Kamalov G. M. Makarov D. Kh. Yarmukhametova M. A. Pudovik R. A. Cherkasov A. N. Pudovik 《Russian Chemical Bulletin》1989,38(11):2382-2388
Condensation of phenothiazine with phenyl isocyanide dichloride has given 10(N-phenylchloroformimidoyl)phenothiazine, exchange reactions of which with salts of diakylthio- and dithiophosphoric acids result in rearrangement of the initially formed 10-[N-phenyldialkoxy(thio)phosphorylthioformimidoyl]phenothiazines to 10-{N-phenyl-N-[dialkoxy(thio)phosphoryl]thiocarbamoyl}phenothiazines, while reaction with diisopropyl dithiophosphoric acid affords diisopropyl chlorothiophosphate, phenyl isothiocyanate, and phenothiazine. 10-(N-Phenylethoxyformimidoyl)phenothiazine alkylates dithiophosphoric acid to give 10-(N-phenylcarbamoyl)phenothiazine, while N2-phenyl-N1,N1-diethyl-(10-phenothiazinyl)formamidine reacts with diisopropyl dithiophosphoric acid, affording the salt N2-phenyl-N1,N1-diethyl-(10-phenothiazinyl)formamidinium O,O-diisopropyl dithiophosphate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2596–2601, November, 1989. 相似文献
33.
Multiphoton IR dissociation of SF6 (in a mixture with CH4) under nonequilibrium conditions of a compression shock formed by an intense, gas dynamically cooled, pulsed molecular beam impacting a solid surface was studied using the HF* luminescence detection ( 2.5 m) technique. The dependences of the HF* luminescence intensity on the distance x between the region in which molecules were excited and the surface and on the laser radiation frequency at different values of x were obtained. It was shown that, as the distance x decreased from 4 to 1.5 mm, the HF* luminescence intensity increased by more than an order of magnitude as compared to the case of excitation of molecules in an undisturbed flow, whereas the frequency dependences of luminescence intensity (SF6 dissociation yield) were broadened only insignificantly. 相似文献
34.
Single-molecule experiments in which proteins are unfolded by applying mechanical stretching forces generally force unfolding to proceed along a reaction coordinate that is different from that in chemical or thermal denaturation. Here we simulate the mechanical unfolding and refolding of a minimalist off-lattice model of the protein ubiquitin to explore in detail the slice of the multidimensional free-energy landscape that is accessible via mechanical pulling experiments. We find that while the free-energy profile along typical "chemical" reaction coordinates may exhibit two minima, corresponding to the native and denatured states, the free energy G(z) is typically a monotonic function of the mechanical coordinate z equal to the protein extension. Application of a stretching force along z tilts the free-energy landscape resulting in a bistable (or multistable) free energy G(z)-fz probed in mechanical unfolding experiments. We construct a two-dimensional free-energy surface as a function of both chemical and mechanical reaction coordinates and examine the coupling between the two. We further study the refolding trajectories after the protein has been prestretched by a large force, as well as the mechanical unfolding trajectories in the presence of a large stretching force. We demonstrate that the stretching forces required to destabilize the native state thermodynamically are larger than those expected on the basis of previous experimental estimates of G(z). This finding is consistent with the recent experimental studies, indicating that proteins may refold even in the presence of a substantial stretching force. Finally, we show that for certain temperatures the free energy of a polyprotein chain consisting of multiple domains is a linear function of the chain extension. We propose that the recently observed "slow phase" in the refolding of proteins under mechanical tension may be viewed as downhill diffusion in such a linear potential. 相似文献
35.
Potential dependences of the angle of contact between perfluorodecaline C10F18 and copper, copper(I) sulfide, and copper telluride Cu4Te3 in 0.1 M CH3COONa are measured. The data are in good agreement with the metal hardness measured in 1 M KOH. The uncharged-surface potentials (USP) for copper, copper(I) sulfide, and copper telluride equal 0.05–0.07, –0.02 to –0.04, and 0.05–0.07 V (NHE) in 0.1 M CH3COONa. Studying the effect of Br– ions shows that USP for copper and Cu2S shift in, respectively, the negative and positive directions with an increase in [Br–]. For copper telluride, USP shifts in the positive direction at low Br– concentrations, and at NaBr concentrations in excess of 0.04 M, in the negative direction. 相似文献
36.
37.
Yu. A. Simonov É. V. Ganin V. E. Zavodnik V. F. Makarov 《Chemistry of Heterocyclic Compounds》1987,23(10):1056-1059
It was demonstrated by x-ray diffraction investigation of the product of the reaction of 1,2-diaminoethane with phthalic acid dichloride that the resulting compound has the 1,2-diisophthalimidoethane structure. An improved method for its synthesis is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1320–1323, October, 1987. 相似文献
38.
V. I. Makarov G. I. Skubnevskaya N. M. Bazhin 《Reaction Kinetics and Catalysis Letters》1978,9(2):217-220
The spectrum of an intermediate, ascribed to nitrosopentane, has been detected in the photolysis of SO2-pentane-NO mixtures. This may be explained by a radical photolysis mechanism involving an initial H-atom abstraction from the pentane molecule by SO2.
SO2--NO , . , H .相似文献
39.
F. A. Shmidt N. M. Ryntina V. V. Saraev V. A. Gruznykh V. A. Makarov 《Reaction Kinetics and Catalysis Letters》1976,5(2):101-106
The reaction of tributylphosphine with the catalytic system (C5H5)2 TiCl2–LiC4H9 prepared in an atmosphere of H2 has been investigated in toluene solution. By using the ESR technique, a hydride complex Cp2Ti(H) (PBu3) has been detected. The proportionality between the rate of cyclohexene hydrogenation and the complex concentration has been established. The kinetics of cyclohexene hydrogenation has been investigated and a reaction mechanism is proposed.
Cp2TiCl2–LiC4H9 (Cp–C5H5), H2, Cp2Ti(H) (PBu3). Ti (III). .相似文献
40.
Exact difference scheme operators are used to construct a difference scheme for a second-order elliptical equation with discontinuous coefficients. The solution of the scheme converges to the solution of the original problem at a rate O(h1/2) in the grid norm W2
1().Translated from Vychislitel'naya i Prikladnaya Matematika, No. 56, pp. 3–7, 1985 相似文献