全文获取类型
收费全文 | 1302篇 |
免费 | 37篇 |
国内免费 | 9篇 |
专业分类
化学 | 966篇 |
晶体学 | 19篇 |
力学 | 21篇 |
数学 | 236篇 |
物理学 | 106篇 |
出版年
2022年 | 13篇 |
2021年 | 16篇 |
2020年 | 16篇 |
2019年 | 15篇 |
2018年 | 8篇 |
2017年 | 13篇 |
2016年 | 26篇 |
2015年 | 32篇 |
2014年 | 34篇 |
2013年 | 47篇 |
2012年 | 86篇 |
2011年 | 87篇 |
2010年 | 46篇 |
2009年 | 44篇 |
2008年 | 76篇 |
2007年 | 72篇 |
2006年 | 90篇 |
2005年 | 83篇 |
2004年 | 93篇 |
2003年 | 63篇 |
2002年 | 72篇 |
2001年 | 21篇 |
2000年 | 26篇 |
1999年 | 14篇 |
1998年 | 5篇 |
1997年 | 16篇 |
1996年 | 15篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 4篇 |
1991年 | 5篇 |
1990年 | 6篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 16篇 |
1983年 | 6篇 |
1982年 | 18篇 |
1981年 | 11篇 |
1980年 | 16篇 |
1979年 | 12篇 |
1978年 | 6篇 |
1977年 | 12篇 |
1976年 | 4篇 |
1975年 | 7篇 |
1974年 | 10篇 |
1973年 | 6篇 |
1972年 | 5篇 |
排序方式: 共有1348条查询结果,搜索用时 0 毫秒
991.
The binding of propylene oxide (PO) to a series of metal cations LM(III)(+), where for L = tetraphenylporphyrin (TPP) M = Al, Ga, Cr, and Co, and for L = (R,R)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexenediamine (salen) M = Al and Cr, was studied in the gas phase by electrospray tandem mass spectroscopy, and the relative stabilities of LM(PO)(2)(+) and LM(PO)(+) cations were determined. The chromium(III) and aluminum(III) cations most tenaciously bind PO, and for M = Al, coordination to the TPP ligated metal center was favored relative to salen. For (TPP)M(PO)(2)(+), the dissociation of PO followed the order M = Al > Cr, but for (TPP)M(PO)(+) the dissociation was M = Cr > Al. The single-crystal structural determinations on (R,R-salen)AlOCHMe(S)CH(2)Cl.0.5PO and (R,R-salen)AlO(2)CMe.1.5py grown in neat PO and pyridine, respectively, reveal five-coordinate aluminum(III) centers with the alkoxide/acetate ligands in the axial position of a square-based pyramid. These results are discussed in terms of the reactivity of these metal complexes in ring-opening polymerizations and copolymerizations with PO and CO(2), respectively. 相似文献
992.
Luis J. González-Ortiz M. Judith Sánchez-Peña Carlos F. Jasso-Gastinel 《Polymer Degradation and Stability》2006,91(11):2715-2722
Effect of preheating of stearates on the processing and post-processing thermal stability of poly(vinyl chloride) compounds, plasticized with di(2-ethylhexyl) phthalate (DEHP) and epoxidized soybean oil (ESO), using several ratios of calcium/zinc stearates and DEHP/ESO is reported. The compounds were prepared as follows: (1) dry-blending the compound components, (2) pelletizing the dry-blend and (3) extruding the pellets to obtain a ribbon geometry. Processing stability was determined by: (a) mechanical characterization and (b) visual color comparison of extruded samples. Post-processing thermal stability was followed by: (a) measurement of HCl release from heated pellets and (b) color changes in heated ribbon samples. From a practical point of view, the preheating has a negligible effect on the initial color of formulations; except for the case of formulations without both ESO and CaSt2. However, the effect of the preheating on the post-processing thermal stability is strongly determined by the composition formulation. 相似文献
993.
David H. Shih Judith A. Fayter L.D. Cama Burton G. Christensen Jordan Hirshfield 《Tetrahedron letters》1985,26(5):583-586
The titled compounds are key synthetic intermediates in the structure-activity relationship studies of novel 1-methyl carbapenem antibiotics. Preparation and structural determination of these stereoisomers by x-ray crystallography and proton NMR spectroscopy are reported. 相似文献
994.
Subodh Bhatnagar Judith Polonsky Marc Vuilhorgne Thierry Prangé Claudine Pascard 《Tetrahedron letters》1982,23(49):5159-5162
Laurycolactone A and B are new quassinoids with a C18 basic skeleton isolated from the Vietnamese Simaroubaceae, Eurycoma longifolia Jack. The structure of Eurycomalactone, a C19 quassinoid isolated previously from the same plant, has been revised and shown to be . The structures have been established by spectral means and those of and confirmed by X-ray diffraction analysis. 相似文献
995.
Chisholm MH Click DR Gallucci JC Hadad CM Wilson PJ 《Journal of the American Chemical Society》2002,124(49):14518-14519
Alkynes are found to react with [W2(OCH2tBu)8] (M = M) in hydrocarbon solvents at room temperature or 45 degrees C to give 1:1 adducts. These are shown to be either bridged (mu-PhCCH and mu-MeCCMe) or terminal-bound (eta2-PhCCMe) in the solid state by single-crystal X-ray crystallography. In solution NMR spectroscopy reveals that bridged and terminal species exist in equilibrium for MeCCH, MeCCMe, and PhCCMe. By NMR spectroscopy the PhCCH and Me3SiCCH adducts are present in solution in bridging and terminally bonded species, respectively. The interconversion of bridged and terminal-bound adducts is chemically rapid but slow on the NMR time scale even though each type of adduct shows fluxional behavior. Calculations employing density functional theory have been carried out on alkyne adducts of the model template W2(OCH3)8 and reveal very small differences in energy between a mu-skewed structure and one having a terminal eta2-alkyne. 相似文献
996.
Bernadette Kuo Billings Judith A. Wagner Phillip Dan Cook Raymond N. Castle 《Journal of heterocyclic chemistry》1975,12(6):1221-1224
4-Deazatoxoflavin (1,6-dimethyl-1,5,6,7-tetrahydropyrimido[4,5-c]-5,7-pyridazinedione) ( 7 ) and several other 4-deazatoxoflavin and 4-deazafervenulin analogs have been prepared with the required intermediates. 3,5,7-Trimethyl-1,2,3,4-tetrahydropyrido[2,3-d]-2,4-pyrimidinedione ( 19 ) and 8-phenyl-3,5,7-trimethyl-2,3,4,8-tetrahydropyrido[2,3-d]-2,4-pyrimidinedione ( 20 ) were also prepared. 相似文献
997.
Christian Zidorn Bent O. Petersen Thomas O. Larsen Judith M. Rollinger Ernst P. Ellmerer 《Tetrahedron letters》2005,46(8):1291-1294
A phytochemical investigation of Podospermum laciniatum (L.) DC. (Asteraceae) yielded the new quinic acid derivative podospermic acid (1,3,5-tridihydrocaffeoylquinic acid), which was named after the genus it was isolated from. The structure was established by HR mass spectrometry and extensive 1D and 2D NMR spectroscopy. Podospermic acid is the first naturally occurring dihydrocaffeoylquinic acid derivative. The chemosystematic impact and the radical scavenging activity of the new compound are discussed briefly. 相似文献
998.
A calorimetric enthalpy of dilution technique has been applied to the investigation of the self-association of several chloro-substituted carboxylic acids in dilute solutions in anhydrous carbon tetrachloride at 25°C. Calorimetric data are expressed in terms of relative apparent molar enthalpies, ΦL. The values of ΦL are shown to be consistent with the monomer-dimer model. Values of the equilibrium constant, standard enthalpy, and standard entropy of dimerization are given for seven acids. Results are discussed in terms of the effect of substitution on the electrostatic nature of the hydrogen bond. 相似文献
999.
Vangala VR Bhogala BR Dey A Desiraju GR Broder CK Smith PS Mondal R Howard JA Wilson CC 《Journal of the American Chemical Society》2003,125(47):14495-14509
The crystal structures and packing features of a family of 13 aminophenols, or supraminols, are analyzed and correlated. These compounds are divided into three groups: (a) compounds 1-5 with methylene spacers of the general type HO-C6H4-(CH2)n-C6H4-NH2 (n = 1 to 5) and both OH and NH2 in a para position; (b) compounds 1a, 2a, 2b, 2c, and 3a in which one or more of the methylene linkers in 1 to 3 are exchanged with an S-atom; and (c) compounds 2d, 1b, and 6a prepared with considerations of crystal engineering and where the crystal structures may be anticipated on the basis of structures 1-5,1a, 2a, 2b, 2c, and 3a. These 13 aminols can be described in terms of three major supramolecular synthons based on hydrogen bonding between OH and NH2 groups: the tetrameric loop or square motif, the infinite N(H)O chain, and the beta-As sheet. These three synthons are not completely independent of each other but interrelate, with the structures tending toward the more stable beta-As sheet in some cases. Compounds 1-5 show an alternation in melting points, and compounds with n = even exhibit systematically higher melting points compared to those with n = odd. The alternating melting points are reflected in, and explained by, the alternation in the crystal structures. The n = odd structures tend toward the beta-As sheet as n increases and can be considered as a variable series whereas for n = even, the beta-As sheet is invariably formed constituting a fixed series. Substitution of a methylene group by an isosteric S-atom may causes a change in the crystal structure. These observations are rationalized in terms of geometrical and chemical effects of the functional groups. This study shows that even for compounds with complex crystal structures the packing may be reasonably anticipated provided a sufficient number of examples are available. 相似文献
1000.
Microbiological assays commonly use incubations of multiple tubes in a dilution series, and microorganism concentration is read as a most probable number (MPN) in standard tables for the observed pattern of positive tubes. Published MPN tables differ, sometimes substantially, because of use of approximate MPN calculation procedures, different rounding conventions in the results, and different methods of calculating confidence or credible intervals. We conclude that the first 2 issues can now be resolved by using recently developed exact MPN calculation methods and by reporting rounding conventions in standard tables. The third issue is not amenable to complete resolution, especially if credible interval (as opposed to confidence interval) limits are desired--as we think they most often are. In that case, Bayesian statistics are called for and the analyst must provide a distribution of concentration that was presumed to be true before the assay was performed. This is mathematically combined with the assay data, resulting in a posterior concentration distribution. These distributions may then be used to quantify the uncertainty in the MPN estimate, and the best approach is to use the highest posterior density regions of these distributions. If based on diffuse prior information (positing that, prior to an assay being performed, all positive concentrations are equally likely), then established procedures might be used to calculate the limits and publish them in standard tables. In the event that this prior assumption is held to be not satisfactory, we show results for an empirical Bayes procedure, with a Poisson prior distribution, giving credible interval widths much narrower than in the other cases examined. 相似文献