全文获取类型
收费全文 | 324篇 |
免费 | 4篇 |
国内免费 | 1篇 |
专业分类
化学 | 132篇 |
晶体学 | 11篇 |
力学 | 9篇 |
数学 | 29篇 |
物理学 | 148篇 |
出版年
2018年 | 4篇 |
2016年 | 6篇 |
2015年 | 4篇 |
2014年 | 3篇 |
2013年 | 8篇 |
2012年 | 9篇 |
2011年 | 11篇 |
2010年 | 4篇 |
2009年 | 4篇 |
2008年 | 20篇 |
2007年 | 22篇 |
2006年 | 9篇 |
2005年 | 7篇 |
2004年 | 6篇 |
2003年 | 7篇 |
2002年 | 12篇 |
2001年 | 5篇 |
2000年 | 15篇 |
1999年 | 6篇 |
1998年 | 8篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 6篇 |
1993年 | 10篇 |
1992年 | 6篇 |
1991年 | 7篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1981年 | 7篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1977年 | 7篇 |
1976年 | 6篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 5篇 |
1972年 | 2篇 |
1969年 | 3篇 |
1968年 | 3篇 |
1966年 | 3篇 |
1935年 | 7篇 |
1932年 | 2篇 |
1928年 | 2篇 |
排序方式: 共有329条查询结果,搜索用时 203 毫秒
81.
Geng Bang Jin Robert P. Guertin Travis H. Bray Thomas E. Albrecht-Schmitt 《Journal of solid state chemistry》2007,180(7):2129-2135
δ-Ln2−xLuxS3 (Ln=Ce, Pr, Nd; x=0.67-0.71) compounds have been synthesized through the reaction of elemental rare-earth metals and S using a Sb2S3 flux at 1000 °C. These compounds are isotypic with CeTmS3, which has a complex three-dimensional structure. It includes four larger Ln3+ sites in eight- and nine-coordinate environments, two disordered seven-coordinate Ln3+/Lu3+ positions, and two six-coordinate Lu3+ ions. The structure is constructed from one-dimensional chains of LnSn (n=6-9) polyhedra that extend along the b-axis. These polyhedra share faces or edges with two neighbors within the chains, while in the [ac] plane they share edges and corners with other chains. Least square refinements gave rise to the formulas of δ-Ce1.30Lu0.70S3, δ-Pr1.29Lu0.71S3 and δ-Nd1.33Lu0.67S3, which are consistent with the EDX analysis and magnetic susceptibility data. δ-Ln2−xLuxS3 (Ln=Ce, Pr, Nd; x=0.67-0.71) show no evidence of magnetic ordering down to 5 K. Optical properties measurements show that the band gaps for δ-Ce1.30Lu0.70S3, δ-Pr1.29Lu0.71S3, and δ-Nd1.33Lu0.67S3 are 1.25, 1.38, and 1.50 eV, respectively. Crystallographic data: δ-Ce1.30Lu0.70S3, monoclinic, space group P21/m, a=11.0186(7), b=3.9796(3), c=21.6562(15) Å, β=101.6860(10), V=929.93(11), Z=8; δ-Pr1.29Lu0.71S3, monoclinic, space group P21/m, a=10.9623(10), b=3.9497(4), c=21.5165(19) Å, β=101.579(2), V=912.66(15), Z=8; δ-Nd1.33Lu0.67S3, monoclinic, space group P21/m, a=10.9553(7), b=3.9419(3), c=21.4920(15) Å, β=101.5080(10), V=909.47(11), Z=8. 相似文献
82.
García Ruano JL Gamboa AE Gutiérrez LG Martín Castro AM Rodríguez Ramos JH Yuste F 《Organic letters》2000,2(6):733-736
A new kind of chiral dienophiles, cyclic vinyl-p-tolylsulfilimines (2a and 2b), were obtained from the corresponding (Z)-sulfinylacrylonitriles with HBF(4) and methanol. The asymmetric Diels-Alder reaction of optically pure 2a with cyclopentadiene under mild thermal or catalyzed conditions afforded only the endo-4a adduct with complete endo and pi-facial selectivities. The ability of the sulfilimine moiety to enhance the dienophilic reactivity of the double bond is similar to that of the sulfinyl group. 相似文献
83.
Parsons JG Stachurska-Buczek D Choi N Griffiths PG Huggins DA Krywult BM Marino ST Nguyen T Sheehan CS James IW Bray AM White JM Boyce RS 《Molecules (Basel, Switzerland)》2004,9(6):449-458
The synthesis of (2S)-2-benzyloxymethyl-3-(2-fluoro-4-methoxyphenyl)- propionic acid, (2S)-2-benzyloxymethyl-3-(2-fluoro-4-methylphenyl)propionic acid and (2S)-2-benzyl-oxymethyl-3-(2,4-dimethylphenyl)propionic acid has been achieved by TiCl4 mediated alkylation of the corresponding (4R)-4-benzyl-3-[3-(2-fluoro-4-methoxyphenyl-, 2-fluoro-4-methylphenyl-, 2,4- dimethylphenyl-)propionyl]-2-oxazolidinones, followed by hydrolysis of the chiral auxiliary. The stereochemistry of the alkylation reaction was confirmed by an X-ray crystal structure of (4R)-4-benzyl-3-[(2S)-2-benzyloxymethyl-3-(2- fluoro-4-methylphenyl)propionyl]-2-oxazolidinone. 相似文献
84.
NMR techniques are employed to determine the relative fractions of boron atoms in Na2OB2O3SiO2 glasses of high soda content. The data show that if enough Na2O is added, four-coordinated borons are destroyed and borons with one or two non-bridging oxygens are created, but that both the beginning point and the rate of these processes depend strongly on the amount of silica present. These findings are shown to be quantitatively inconsistent with structural models previously suggested in the literature. Utilizing the concept of proportionate atomic sharing of the additional Na2O, a new structural model is proposed for K 8 (K = mol% SiO2/mol% B2O3) which is consistent with all the data including previously reported data for glasses in the region of relatively low soda content. Using R = mol% Na2O/mol% B2O3, the new model states that for , all the additional Na2O is employed in forming non-bridging oxygens on the silica tetrahedra; then for RD1 R RD3 = 2 + K, the fraction of the additional Na2O destroys reedmernerite groups and forms pyroborate units plus silica tetrahedra with two non-bridging oxygens per Si atom, while the fraction of the additional Na2O destroys diborate groups and forms additional pyroborate units. 相似文献
85.
Mark R. Bray Robert J. Deeth Veronica J. Paget Paul D. Sheen 《International journal of quantum chemistry》1997,61(1):85-91
Optimized metal-ligand (M-L) bond lengths for 17 classical Werner-type transition-metal complexes were calculated using the local density approximation (LDA) and a gradient-corrected (GC) extension. GCs lengthen the bonds by between 0.02 and 0.09 Å relative to the LDA results. The latter range from 0.02 Å shorter than observed to 0.05 Å longer, while the GC data range from exact agreement with experiment to some 0.12 Å too long. The LDA rms deviation is 0.025 Å compared to the GC error of 0.070 Å. In contrast, data from the literature for organometallic species show that the LDA gives systematically too short M-L distances and GCs lead to a better agreement with experiment. The relative performance of LDA and GC functionals reflects the qualitatively different chemistries of organometallic and Werner-type complexes. The magnitude of the GC bond-length expansion for the latter correlates with the ionicity of the M-L interaction. © 1997 John Wiley & Sons, Inc. 相似文献
86.
The quadrupole coupling constant (Qcc) and asymmetry parameter (eta) of 11B in crystalline CaO.B2O3 have been measured employing three different NQR and NMR methods: (1) 11B and 10B NQR; (2) 11B NQR and NMR; and (3) the 11B Zeeman NQR powder pattern. It is found that Qcc = 2594.3 +/- 0.5 kHz and eta = 0.515 +/- 0.001 at 77 K, and Qcc = 2573.5 +/- 0.5 kHz and eta = 0.511 +/- 0.002 at 300 K. These values are in agreement with, but far more accurate than, values obtained from a fourth procedure: measurement of the second-order quadrupolar effects evident in the m = + 1/2<-->m = - 1/2 transition of the 11B NMR spectrum. 相似文献
87.
Nitrogen-14 nuclear quadrupole resonance (NQR) spectra for eleven local anesthetics in the solid state are reported and analyzed using the Townes and Dailey approach. The changes in the electron distributions at various nitrogen sites, produced by protonating the tertiary amino nitrogen, are discussed and shown to be in general agreement with expectations based on the increased electrophilic character of the protonated amino group. 相似文献
88.
E. Benesch P. P. Wiktorow R. Dubrisay M. A. Heath M. W. Bray C. E. Curran C. J. Hansen H. Werres G. Hiller K. Voituret D. Harris F. A. Eustis F. B. Downing L. S. Larsen A. K. Scribner G. Brédemann R. Radeloff A. Ponte A. Grounds W. I. Minajew S. S. Frolow und G. M. Majorow 《Fresenius' Journal of Analytical Chemistry》1935,101(7-8):290-294
Ohne Zusammenfassung 相似文献
89.
Czasch A Schöffler M Hattass M Schössler S Jahnke T Weber T Staudte A Titze J Wimmer C Kammer S Weckenbrock M Voss S Grisenti RE Jagutzki O Schmidt LP Schmidt-Böcking H Dörner R Rost JM Schneider T Liu CN Bray I Kheifets AS Bartschat K 《Physical review letters》2005,95(24):243003
Partial photoionization cross sections sigmaN(Egamma) and photoelectron angular distributions betaN(Egamma) were measured for the final ionic states He+ (N > 4) in the region between the N = 8 and N = 13 thresholds (Egamma > 78.155 eV) using the cold target recoil ion momentum spectroscopy technique (COLTRIMS). Comparison of the experimental data with two independent sets of theoretical predictions reveals disagreement for the branching ratios to the various HeN(+) states. The angular distributions just below the double ionization threshold suggest an excitation process for highly excited N states similar to the Wannier mechanism for double ionization. 相似文献
90.
Toledano P Figueiredo Neto AM de Sant'Ana ZA 《Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics》2000,61(1):486-492
Experimental investigations of lyotropic cholesterics fluids are presented which show that changes in the shape anisotropy and chirality of the micellar population determine the topology of the temperature-concentration phase diagrams. For given amounts of the substances which induce the chirality and modify the shape anisotropy of the micelles, two distinct biaxial cholesteric phases are disclosed in the phase diagrams. This is interpreted in the framework of the catastrophe theory of phase transitions. 相似文献