全文获取类型
收费全文 | 509篇 |
免费 | 17篇 |
国内免费 | 4篇 |
专业分类
化学 | 336篇 |
晶体学 | 3篇 |
力学 | 14篇 |
数学 | 36篇 |
物理学 | 141篇 |
出版年
2022年 | 3篇 |
2021年 | 5篇 |
2019年 | 6篇 |
2018年 | 4篇 |
2016年 | 4篇 |
2015年 | 16篇 |
2014年 | 4篇 |
2013年 | 29篇 |
2012年 | 27篇 |
2011年 | 28篇 |
2010年 | 16篇 |
2009年 | 18篇 |
2008年 | 32篇 |
2007年 | 27篇 |
2006年 | 22篇 |
2005年 | 25篇 |
2004年 | 14篇 |
2003年 | 24篇 |
2002年 | 22篇 |
2001年 | 15篇 |
2000年 | 8篇 |
1999年 | 9篇 |
1998年 | 6篇 |
1997年 | 6篇 |
1996年 | 8篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 6篇 |
1991年 | 7篇 |
1990年 | 9篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 9篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 13篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 7篇 |
1975年 | 2篇 |
1974年 | 6篇 |
1973年 | 11篇 |
1972年 | 2篇 |
1970年 | 5篇 |
排序方式: 共有530条查询结果,搜索用时 15 毫秒
41.
[reaction: see text] A formal total synthesis of the sex attractant of male dried bean beetle, methyl (R,E)-(-)-tetradeca-2,4,5-trienoate, was achieved by a new efficient route utilizing the Pd-catalyzed asymmetric allene synthesis reaction. It was found that the atropisomeric biaryl bisphosphine (R)-segphos showed better enantioselectivity than (R)-binap in the Pd-catalyzed reaction for preparing alkyl-substituted axially chiral allenes. 相似文献
42.
A catalytic system, Pd(OAc)2 (10 mol %)-P(n-Bu)3 (20 mol %)-Et3B (360 mol %), promotes allylic alcohols to undergo the allylation of anisidine-imines of aromatic and aliphatic aldehydes and furnishes homoallylamines in good to moderate yields. The reaction shows unique stereoselectivity, giving anti-isomers selectively. [reaction: see text] 相似文献
43.
Takeo Katami Tomokuni Hayakawa Masamichi Furukawa Shozo Shibata Tadashi Hara 《Analytica chimica acta》1986
An extraction-spectrophotometric method is described for the determination of traces of zinc with 2-[2-(3,5-dibromopyridyl)azo]-5-dimethylaminobenzoic acid. The reagent forms a stable, blue 1:2 zinc/reagent complex that can be extracted into chloroform. The apparent molar absorptivity of the zinc(II) complex is 1.26 × 105 l mol?1 cm?1 at 610 nm in chloroform. The reagent is relatively selective; interferences from cobalt, copper and nickel can be masked with dimethylglyoxime and aluminium and iron with a mixture of sodium fluoride and triethanolamine. The method is applied to the determination of zinc in coal fly ash and pond sediments with good precision and accuracy. 相似文献
44.
Rapid method for preparing a beta-glucan-specific sensitive fraction from Limulus (Tachypleus tridentatus) amebocyte lysate 总被引:1,自引:0,他引:1
By separating Limulus amebocyte lysate by cation-exchange chromatography with an SP-Toyopearl 650C column, a fraction insensitive to endotoxin, yet specifically sensitive to beta-glucan, was successfully obtained in the unadsorbed portion. This fraction showed beta-glucan dose-dependent clotting enzyme activity, although no sensitivity to endotoxin. This beta-glucan-dependent reaction showed no interference in the presence of endotoxin, with the fraction also showing sensitivity towards various kinds of beta-glucan, i.e. curdlan, pachyman, laminaran and lichenan. The sensitivity towards curdlan was approximately 10(-10) g/ml. 相似文献
45.
Kohji Tashiro Hitoshi Asanaga Kiyotaka Ishino Ryoko Tazaki Masamichi Kobayashi 《Journal of Polymer Science.Polymer Physics》1997,35(11):1677-1700
A software and some useful tools have been developed for identifying individual x-ray reflectional peaks recorded with an x-ray imaging plate system. These techniques were applied to analyze the crystal structure of uniaxially oriented polymer samples. Characteristic features of the present method may be summarized as follows. (1) The indexing of the observed reflections and the determination of the unit cell parameters can be made easily on the display of the computer. (2) The integrated intensity of the individual component of the overlapped reflections can be evaluated quantitatively through the curve separation technique. The Rmerge's for the equivalent reflections were 5–6%, indicating the exact evaluation of the integrated intensities. (3) The thus obtained reflectional data were successfully utilized for the extraction of the initial structural models by the direct method. The actual applications have been made for orthorhombic polyethylene, trigonal polyoxymethylene, and isotactic polybutene-1, giving the refined crystal structures including even the positions of hydrogen atoms in some cases. The reliability factors were 12, 5, and 15%, respectively, for these three polymer cyrstals. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1677–1700, 1997 相似文献
46.
S Ohmori K Nakata K Nishihara S Yamamoto M Kawase S Tsuboi 《Journal of chromatography. A》1992,574(1):35-40
Cystathionine was cleaved into 2-ketobutyric acid, cysteine and ammonia by cystathionase. 2-Ketobutyric acid was converted into 3-ethyl-2-hydroxy-6,7-dimethoxyquinoxaline (EHDQ) by reaction with 1,2-diamino-4,5-dimethoxybenzene. When EHDQ was measured in a mobile phase of pH 2.1 using high-performance liquid chromatography with ultraviolet detection, 250 pmol of L-cystathionine in 250 microliters of the reaction mixture could be determined. Because EHDQ has a strong fluorescence in a mobile phase of pH 6.5 at 447 nm, on excitation at 365 nm, as little as 2.5 pmol of cystathionine in 250 microliters of the reaction mixture could be determined by high-performance liquid chromatography with fluorimetric detection. Cystathionase activity was assayed on the basis of the same principle by determining cystathionine in as little as 63 ng of rat liver by fluorimetric detection. Cystathionine beta-synthase activity was measured by the same method by determining cystathionine formed in only 113 ng of wet weight of rat liver. Using these methods, both cystathionine beta- and gamma-lyase activities in Saccharomyces cerevisiae were determined, because quinoxaline derivatives from pyruvate and 2-ketobutyrate could be measured simultaneously by high-performance liquid chromatography. 相似文献
47.
Dr. Yuichi Kobayashi Yuji Takashima Yuuya Motoyama Yukari Isogawa Kyosuke Katagiri Atsuki Tsuboi Dr. Narihito Ogawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(11):3779-3785
The regioselectivity (r.s.) and enantiospecificity (e.s.) of the substitution reactions of secondary propargylic alcohol derivatives using reagents derived from ArMgBr and Cu salts were studied. First, the picolinate, 3-methylpicolinate, and diethylphosphonate derivatives of Ph(CH2)2CH(OH)C≡CTMS were reacted with PhMgBr/CuCN in ratios of 2.5:2.7–2.5:0.25. The use of 2.5:0.25 ratio in THF/DME (6:1) at 0 °C for 1 h afforded the α-substitution product from the phosphate with ≥98 % r.s. and 99 % e.s. CuBr⋅Me2S gave similar selectivity. The reaction system was then applied to phosphates derived from R1CH(OH)C≡CR2 and ArMgBr to obtain synthetically sufficient r.s. and e.s. values with R2=TMS, Ph, whereas iPr was borderline in terms of size as an R1 substituent. The presence of a substituent at the o-position of Ar marginally affected the selectivity. We also found that the use of PhMgBr/Cu(acac)2 in a 2:1 ratio in THF produced the γ-substitution products (allenes) with high r.s. and e.s. 相似文献
48.
Masamichi Furukawa 《Analytica chimica acta》1982,140(1):281-289
2-(2-ThiazolyIazo)-5-dimethylaminobenzoic acid (TAMB) and 2-(2-benzothiazolylazo)-5-dimethylaminobenzoic acid (BTAMB) have been synthesized, and their potential for determinations of metals has been studied spectrophotometrically. Both are extremely sensitive chromogenic reagents for the determination of nickel. Molar absorptivities in aqueous methanol are 0.95 × 105 (TAMB) and 1.2 × 105 (BTAMB). In aqueous methanol, at apparent pH 5–9.5, the system conforms to Beer's law for 0.05–0.5 ppm nickel; Cu, Cr, Co, Pd and Fe interfere, but they can easily be masked. 相似文献
49.
Masamichi Takase 《Mathematische Zeitschrift》2012,272(1-2):101-108
We give a formula to detect the oriented bordism class of a codimension one immersion of an oriented 7-manifold in terms of singularities of its singular Seifert surface, that is, a generic map from a compact 8-manifold which extends the given immersion. Our argument involves a study of a relative version of the Thom polynomials for certain singularities of generic maps from manifolds with non-empty boundaries. 相似文献
50.
Masamichi Takase 《Topology》2004,43(6):1425-1447
Haefliger has shown that a smooth embedding of the (4k−1)-sphere in the 6k-sphere can be knotted in the smooth sense. In this paper, we give a formula with which we can detect the isotopy class of such a Haefliger knot. The formula is expressed in terms of the geometric characteristics of an extension, analogous to a Seifert surface, of the given embedding. In particular, the Hopf invariant associated to the extension plays a crucial role. This leads us to a new characterisation of Haefliger knots. 相似文献