全文获取类型
收费全文 | 635篇 |
免费 | 10篇 |
国内免费 | 4篇 |
专业分类
化学 | 447篇 |
晶体学 | 4篇 |
力学 | 5篇 |
数学 | 25篇 |
物理学 | 168篇 |
出版年
2021年 | 5篇 |
2020年 | 8篇 |
2019年 | 6篇 |
2016年 | 11篇 |
2015年 | 9篇 |
2014年 | 9篇 |
2013年 | 39篇 |
2012年 | 25篇 |
2011年 | 22篇 |
2010年 | 13篇 |
2009年 | 20篇 |
2008年 | 33篇 |
2007年 | 27篇 |
2006年 | 29篇 |
2005年 | 32篇 |
2004年 | 26篇 |
2003年 | 20篇 |
2002年 | 19篇 |
2001年 | 12篇 |
2000年 | 16篇 |
1999年 | 10篇 |
1998年 | 11篇 |
1997年 | 5篇 |
1996年 | 19篇 |
1995年 | 8篇 |
1994年 | 7篇 |
1993年 | 5篇 |
1992年 | 13篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 16篇 |
1984年 | 7篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 7篇 |
1980年 | 13篇 |
1979年 | 6篇 |
1978年 | 4篇 |
1977年 | 7篇 |
1976年 | 9篇 |
1975年 | 7篇 |
1974年 | 9篇 |
1972年 | 5篇 |
1970年 | 6篇 |
1969年 | 6篇 |
1968年 | 10篇 |
1967年 | 14篇 |
1966年 | 10篇 |
排序方式: 共有649条查询结果,搜索用时 296 毫秒
11.
Y. Ohsumi T. Higashimura S. Okamura 《Journal of polymer science. Part A, Polymer chemistry》1967,5(4):849-862
Methyl vinyl ether (MVE) was polymerized under various conditions by BF3·O(C2H5)2 and SnCl4·CCl3CO2H catalysts. The effect of polymerization conditions on the steric structure of poly(methyl vinyl ether) (PMVE) was studied by NMR spectra. It was found that the triad isotacticity of PMVE decreased and the syndiotacticity and heterotacticity increased with increasing polarity of the solvent and increasing polymerization temperature. This result coincided with the qualitative conclusion estimated from softening point and infrared spectra. However, the variation of tacticity by the change of the polarity of a solvent was not so large as expected. There was no large difference between the behavior of BF3·O(C2H5)2 and SnCl4·CCl3CO2H as catalysts. From the relation between the difference of free energy of monomer addition due to the steric structure of the polymer and the polymerization temperature, it was concluded that the penultimate effect really existed and was due to only the difference in enthalpy in the MVE–BF3. O(C2H5)2 or MVE–SnCl4·CCl3CO2H systems. The penultimate effect was not greatly changed by the polymerization conditions in these systems. 相似文献
12.
Bolm C Verrucci M Simic O Cozzi PG Raabe G Okamura H 《Chemical communications (Cambridge, England)》2003,(22):2826-2827
Quinoline-based C1-symmetric sulfoximines have been used as chiral ligands in copper-catalyzed asymmetric hetero Diels-Alder reactions leading to cycloadducts with up to 96% ee. 相似文献
13.
Okamura WH Zhu GD Hill DK Thomas RJ Ringe K Borchardt DB Norman AW Mueller LJ 《The Journal of organic chemistry》2002,67(5):1637-1650
Isotope-labeled drug molecules may be useful for probing by NMR spectroscopy the conformation of ligand associated with biological hosts such as membranes and proteins. Triple-labeled [7,9,19-(13)C(3)]-vitamin D(3) (56), its 25-hydroxylated and 1 alpha,25-dihydroxylated metabolites (58 and 68, respectively), and other labeled materials have been synthesized via coupling of [9-(13)C]-Grundmann's ketone 39 or its protected 25-hydroxy derivative 43 with labeled A ring enyne fragments 25 or 26. The labeled CD-ring fragment 39 was prepared by a sequence involving Grignard addition of [(13)C]-methylmagnesium iodide to Grundmann's enone 28, oxidative cleavage, functional group modifications leading to seco-iodide 38, and finally a kinetic enolate S(N)2 cycloalkylation. The C-7,19 double labeling of the A-ring enyne was achieved by the Corey-Fuchs/Wittig processes on keto aldehyde 11. By employing these labeled fragments in the Wilson-Mazur route, the C-7,9,19 triple-(13)C-labeled metabolites 56, 58, and 68 as well as other (13)C-labeled metabolites have been prepared. In an initial NMR investigation of one of the labeled metabolites prepared in this study, namely [7,9,19-(13)C(3)]-25-hydroxyvitamin D(3) (58), the three (13)C-labeled carbons of the otherwise water insoluble steroid could be clearly detected by (13)C NMR analysis at 0.1 mM in a mixture of CD(3)OD/D(2)O (60/40) or in aqueous dimethylcyclodextrin solution and at 2 mM in 20 mM sodium dodecyl sulfate (SDS) aqueous micellar solution. In the SDS micellar solution, a double half-filter NOESY experiment revealed that the distance between the H(19Z) and H(7) protons is significantly shorter than that of the corresponding distance calculated from the solid state (X-ray) structure of the free ligand. The NMR data in micelles reveals that 58 exists essentially completely in the alpha-conformer with the 3 beta-hydroxyl equatorially oriented, just as in the solid state. The shortened distance (H(19Z))-H(7)) in micellar solutions as compared to that in the solid state is most easily rationalized on the basis that the 5(10)-torsion angle in 58 is decreased in micellar solutions as compared to that in the solid state. 相似文献
14.
A bicyclic diphenyldisilane bearing two tetramethylene tethers reacts with lithium to form predominantly the disilanyllithium as a result of Si-CPh bond fission, while the pentamethylene homolog undergoes ordinary Si-Si bond cleavage to afford the expected phenylsilyllithium. The compressed Si-Si bond incorporated in the bicyclic ring system may be kinetically stabilized (compression effect), resulting in the unusual Si-C bond fission. When the reaction is carried out in the presence of chlorotrimethylsilane, a Calas-type reaction takes place on the phenyl rings. This result suggests that electron transfer to the phenyl group is the primary process in these bicyclic disilanes, followed by Si-Si or Si-C bond cleavage to afford the corresponding silyllithium species. 相似文献
15.
The surface free energies of polyethylene terepthalate fibers with different draw ratios were experimentally determined by contact angle measurements inn-alkane/water systems. The dispersive component of the surface free energy increased with increasing draw ratio, whereas the nondispersive one remained almost constant. After heat treatment, the dispersive surface free energy increased, but was reduced above 140°C. The nondispersive component increased by heat treatment at 190°C. The increases in the density and birefringence of the fibres due to the drawing and heat treatment suggested that the increase in the dispersive surface free energy was caused by the increase in the atomic density at the fiber surface due to drawing and heat treatment. ESCA results indicated that the increment in the nondispersive surface free energy due to heat treatment was caused by the addition of functional groups to the fiber surface due to heat treatment. 相似文献
16.
The reaction of [(trimethylsilyl)imino]methyldiphenylphosphorane: Ph2MePNSiMe3 (I) with several acid anhydrides or alkyl isocyanates took place by the simple cleavage of silicon-nitrogen bond. In contrast the interaction of (I) with phenyl isocyanate, isothiocyanate or carbon disulphide led to addition-elimination reactions of the Wittig type. Detailed investigation in the case of phenyl isocyanate indicated the usual elimination of Ph2MePO is suppressed by the strong affinity of the trimethylsilyl group for anionic oxygen atom. 相似文献
17.
Ar+ sputtering of an Cu(111) surface while simultaneously supplying Mo atoms is known to induce an oriented growth of Mo thin crystals, or seed-layers, on evolving conical Cu protrusions. The seed-layers thus formed are shown to be dual-oriented, or bicrystalline, consisting of columnar crystallites grown homo-epitaxially. The orientation relationship between the two types of crystallites was (100)I (111)II with [001]I [110]II, and this bicrystallinity probably resulted from a non-uniform charge-up of the layers' growth front. As concluded from high-resolution electron microscopy, the Mo(100) stacking is elastically converted into the Mo(111) stacking and vice versa, under the influence of tensile stress. The homo-epitaxy that the seed-layers exhibited is believed to reflect the mutual convertibility of the Mo(100) and (111) stackings. 相似文献
18.
Koiso T Yamamoto K Hata Y Takahashi Y Kita E Ohshima K Okamura FP 《J Phys Condens Matter》1996,8(38):7059-7065
A structural study of [Formula: see text], grown from aqueous solution, was performed using anomalous x-ray scattering near the Cs K absorption edge to determine an absolute configuration of constituent atoms. The sense of the helical structure of the [Formula: see text] chain was found to be predominantly right-handed through a comparison of observed Bragg Bijvoet ratios with calculated ones. Assuming that [Formula: see text] consists of the two domains (i.e. right- and left-handed helices), we estimate that the volume fraction for the right-handed helix is [Formula: see text]. 相似文献
19.
20.
Transition of the radial electric field by electron cyclotron heating in the CHS heliotron/torsatron