全文获取类型
收费全文 | 956篇 |
免费 | 14篇 |
国内免费 | 2篇 |
专业分类
化学 | 710篇 |
晶体学 | 7篇 |
力学 | 5篇 |
数学 | 76篇 |
物理学 | 174篇 |
出版年
2021年 | 7篇 |
2020年 | 5篇 |
2019年 | 9篇 |
2018年 | 12篇 |
2017年 | 5篇 |
2016年 | 14篇 |
2015年 | 10篇 |
2014年 | 9篇 |
2013年 | 27篇 |
2012年 | 28篇 |
2011年 | 43篇 |
2010年 | 22篇 |
2009年 | 31篇 |
2008年 | 66篇 |
2007年 | 42篇 |
2006年 | 55篇 |
2005年 | 55篇 |
2004年 | 52篇 |
2003年 | 48篇 |
2002年 | 45篇 |
2001年 | 17篇 |
2000年 | 24篇 |
1999年 | 19篇 |
1998年 | 11篇 |
1997年 | 16篇 |
1996年 | 14篇 |
1995年 | 8篇 |
1994年 | 11篇 |
1993年 | 9篇 |
1992年 | 11篇 |
1991年 | 7篇 |
1990年 | 13篇 |
1989年 | 5篇 |
1986年 | 13篇 |
1985年 | 14篇 |
1984年 | 30篇 |
1983年 | 9篇 |
1982年 | 20篇 |
1981年 | 16篇 |
1980年 | 14篇 |
1979年 | 17篇 |
1978年 | 7篇 |
1977年 | 8篇 |
1976年 | 10篇 |
1975年 | 11篇 |
1974年 | 5篇 |
1973年 | 7篇 |
1969年 | 4篇 |
1968年 | 7篇 |
1967年 | 5篇 |
排序方式: 共有972条查询结果,搜索用时 0 毫秒
21.
Yoko Kuwae Nobuo Kushibiki 《Journal of polymer science. Part A, Polymer chemistry》1989,27(12):3969-3975
The microstructure of the polymer formed by the hydrosilation of styrene with poly(hydrogenmethylsiloxane) was studied by 1H- and 13C-NMR spectra. Two modes of addition in hydrosilation were found to occur randomly without the influence of the adjacent monomer unit by statistical analysis of sequence distribution of 29Si-NMR spectrum. 相似文献
22.
Design and preparation of pulsatile release tablet as a new oral drug delivery system. 总被引:6,自引:0,他引:6
To achieve time-controlled or site specific delivery of a drug in the gastrointestinal tract, an orally applicable pulsatile drug release system with the dry-coated tablet form was developed. The system consisted of a less water permeable outer shell and a swellable core tablet; from such a system, the drug was expected to be rapidly released after a certain period of time on the basis of time-controlled disintegration mechanism. Various model disks of outer shell, consisting of hydrogenated castor oil and polyethyleneglycol 6000, were tested for their water penetration rate. The experimental results showed that water penetration proceeded obeying the boundary retreating mechanism, so that the lag time of the system could be controlled by changing either the thickness or the composition of the outer shell. The swelling force of various commercially available disintegrants was quantitatively compared, and it was found that carboxymethylcellulose calcium was the preferable disintegrant to be used for the core tablet. On the basis of the results of a series of fundamental studies, various pulsatile release tablets of isoniazide with different lag times were designed. In the in vitro dissolution test, typical pulsatile release was achieved for all the tablets prepared, and a good correlation was found between the observed lag time and the estimated lag time calculated from an empirical equation deduced from the thickness and polyethyleneglycol 6000 content of the outer shell. 相似文献
23.
Nobuo Ishikawa Tomoya Kitazume Kunitake Chino Mohamed El-Said Mustafa 《Journal of fluorine chemistry》1981,18(4):447-457
The reactions of -2-methyl-2-pentene (1) with several - difunctional benzenes afforded eight- and nine-membered benzoheterocyclic compounds carrying perfluoroalkyl groups. Salicylic acid, salicylaldehyde, and their methyl or chloro derivatives reacted in triethylamine-acetonitrile system giving perfluoroalkylated 2H,6H-1,5-benzodioxocin-2,6-dione (8) and 4H,6H-1,5-benzodioxocin (9) compounds respectively, while phthalyl alcohol and o-hydroxyphenethyl alcohol in triethylamine-diethyl ether system gave perfluoroalkylated 1H,3H,7H-2,6- and 4H,6H,7H-1,5-benzodioxonin compounds, (10) and (11). o-Aminobenzyl alcohol and (1) in diethyl ether afforded a perfluoroalkylated benzoxazocinobenzoxazocinone compound (15). 相似文献
24.
Ohki Y Matsuura N Marumoto T Kawaguchi H Tatsumi K 《Journal of the American Chemical Society》2003,125(26):7978-7988
A series of sulfido-bridged tungsten-ruthenium dinuclear complexes Cp*W(mu-S)(3)RuX(PPh(3))(2) (4a; X = Cl, 4b; X = H), Cp*W(O)(mu-S)(2)RuX(PPh(3))(2) (5a; X = Cl, 5b; X = H), and Cp*W(NPh)(mu-S)(2)RuX(PPh(3))(2) (6a; X = Cl, 6b; X = H) have been synthesized by the reactions of (PPh(4))[Cp*W(S)(3)] (1), (PPh(4))[Cp*W(O)(S)(2)] (2), and (PPh(4))[Cp*W(NPh)(S)(2)] (3), with RuClX(PPh(3))(3) (X = Cl, H). The heterolytic cleavage of H(2) was found to proceed at room temperature upon treating 5a and 6a with NaBAr(F)(4) (Ar(F) = 3, 5-C(6)H(3)(CF(3))(2)) under atmospheric pressure of H(2), which gave rise to [Cp*W(OH)(mu-S)(2)RuH(PPh(3))(2)](BAr(F)(4)) (7a) and [Cp*W(NHPh)(mu-S)(2)RuH(PPh(3))(2)](BAr(F)(4)) (8), respectively. When Cp*W(O)(mu-S)(2)Ru(PPh(3))(2)H (5b) was treated with a Br?nstead acid, [H(OEt(2))(2)](BAr(F)(4)) or HOTf, protonation occurred exclusively at the terminal oxide to give [Cp*W(OH)(mu-S)(2)RuH(PPh(3))(2)](X) (7a; X = BAr(F)(4), 7b; X = OTf), while the hydride remained intact. The analogous reaction of Cp+W(mu-S)(3)Ru(PPh(3))(2)H (4b) led to immediate evolution of H(2). Selective deprotonation of the hydroxyl group of 7a or 7b was induced by NEt(3) and 4b, generating Cp*W(O)(mu-S)(2)Ru(PPh(3))(2)H (5b). Evolution of H(2) was also observed for the reactions of 7a or 7b with CH(3)CN to give [Cp*W(O)(mu-S)(2)Ru(CH(3)CN)(PPh(3))(2)](X) (11a; X = BAr(F)(4), 11b; X = OTf). We examined the H/D exchange reactions of 4b, 5b, and 7a with D(2) and CH(3)OD, and found that facile H/D scrambling over the W-OH and Ru-H sites occurred for 7a. Based on these experimental results, the mechanism of the heterolytic H(2) activation and the reverse H(2) evolution reactions are discussed. 相似文献
25.
The crystal structures of the series of four ternary complexes, [Pd(phen)(2,6-PDCA)].4H(2)O (1) (phen=1,10-phenanthroline; 2,6-PDCA=2,6-pyridinedicarboxylic acid), [Pd(bpy)(2,3-PDCA)].3H(2)O (2) (bpy=2,2'-bipyridineand; 2,3-PDCA=2,3-pyridinedicarboxylic acid) and [Pd(phen)(PHT)].2.5H(2)O (3) (PHT=o-phthalic acid ) and [Pd(bpy)(PHT)].1.5H(2)O (4), are determined and the coordination modes of palladium(II) ternary complexes are characterized. All complexes take the mononuclear Pd(II) complexes, in which central Pd(II) atom of each complex has a similar distorted square-planar four coordination geometry. In all complexes, the aromatic heterocyclic compounds, phen and bpy, behave as a bidentate N, N' ligand. In the complex 1 and 2, 2,6-PDCA and 2,3-PDCA behave as a bidentate N, O ligand, and in complex 3 and 4, PHT behaves as a bidentate O, O' ligand. 相似文献
26.
Junling Bai Toshifumi Nakatani Yuuki Sasaki Sadanobu Inoue Nobuo Takahashi 《International journal of environmental analytical chemistry》2013,93(9):856-865
Effectiveness of Pd/Mg chemical modifier for the accurate direct determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry (GF-AAS) using slurry samples was evaluated. A calibration curve prepared by aqueous zinc standard solution with addition of Pd/Mg chemical modifier is used to determine the zinc concentration in the sediment. The accuracy of the proposed method was confirmed using Certified Reference Materials, NMIJ CRM 7303-a (lacustrine sediment) from National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology, Japan, and MESS-3 (marine sediment) and PACS-2 (marine sediment) from National Research Council, Canada. The analytical results obtained by employing Pd/Mg modifier are in good agreement with the certified values of all the reference sediment materials. Although for NRC MESS-3 an accurate determination of zinc is achieved even without the chemical modifier, the use of Pd/Mg chemical modifier is recommended as it leads to establishment of a reliable and accurate direct analytical method. One quantitative analysis takes less than 15 minutes after we obtain dried sediment samples, which is several tens of times faster than conventional analytical methods using acid digested sample solutions. The detection limits are 0.13?µg?g?1 (213.9?nm) and 16?µg?g?1 (307.6?nm), respectively, in sediment samples, when 40?mg of dried powdered samples are suspended in 20?mL of 0.1?mol?L?1 nitric acid and a 10?µl portion of the slurry sample is measured. The precision of the proposed method is 8–15% (RSD). 相似文献
27.
Koichi Hatada Koichi Ute Tatsuki Kitayama Takafumi Nishiura Nobuo Miyatake 《Macromolecular Symposia》1994,85(1):325-338
Highly isotactic (it-) and highly syndiotactic (st-) poly(methyl methacrylate)s (PMMAs) uniform with respect to molecular weight (stereoregular, uniform PMMAs) were isolated up to the 100mer from it- and st-PMMAs by supercritical fluid chromatography (SFC) and characterized by NMR and mass spectroscopies. Glass transition temperatures (Tg's) of the uniform it- and st-PMMAs were higher than those of the corresponding PMMAs with MWD and with similar molecular weight on average. The Tg values of the uniform it-and st-PMMAs series obeyed the relationship, Tg = Tg∞ - K/M, where M and Tg∞ denote molecular weight and Tg at infinite M, respectively. The reciprocal melting points (1/Tm) of uniform it-PMMA (degree of polymerization, DP = 28–44), obtained from methanol solutions by evaporating the solvent, increased linearly with increasing 1/DP. Extrapolation of the linear relation to 1/DP = 0 gave the Tm of it-PMMA with infinite DP; Tm∞ = 171.1°C. Thermal degradation behavior was studied by thermogravimetry and by SFC analysis of degradation products. In gel-permeation chromatography (GPC) measurements, the it-50mer eluted faster than the st-50mer. Calibration curves for it- and st-PMMAs could be obtained using series of the uniform PMMAs. The instrumental spreading factor determined using it-25mer, it-50mer, st-25mer and st-50mer for our GPC chromatograph was 0.070 ml when the volume of the sample solution was 0.003ml. GPC analysis of a mixture of the it- and st-50mers in tetrahydrofuran indicated formation of a stereocomplex in the solution, and was found quite useful to elucidate the minimum sequence length required for complex formation. 相似文献
28.
29.
In the atmospheric correction of satellite data in the visible and near-infrared bands, it is necessary to remove the adjacency effect due to the reflection from contiguous pixels. Evaluation of the influence of aerosol vertical distributions on the adjacency effect is done by calculating the single-scattering light intensity which, after the reflection at the ground surface, reaches the satellite sensor via a single scattering with a molecule or an aerosol particle. In the simulation, we assume aerosol vertical profiles similar to those used in the MODTRAN radiation transfer code, and those having a mixed layer with a uniform value of the aerosol extinction coefficient. We assume for the ground surface a simple model representing a border of land/sea surfaces. In spite of the single scattering approximation, it is confirmed that even if the optical thickness is the same, we have a larger adjacency effect when the extinction coefficient is large at higher altitudes. We also discuss the dependence of the adjacency effect on the aerosol optical thickness and that on the difference in the reflectances of the land and sea surfaces along the border. 相似文献
30.
A laser Doppler imaging system with a TV camera has been constructed and velocity distributions of fluid flow in cross sections of a rectangular channel have been measured. Consequently, it has been found that the system has some advantages in comparison with usual laser Doppler velocimeters, for example, the visualization of flow can be easily achieved. 相似文献