全文获取类型
收费全文 | 977篇 |
免费 | 20篇 |
国内免费 | 3篇 |
专业分类
化学 | 749篇 |
晶体学 | 18篇 |
力学 | 7篇 |
数学 | 64篇 |
物理学 | 162篇 |
出版年
2023年 | 2篇 |
2022年 | 5篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 12篇 |
2018年 | 12篇 |
2017年 | 7篇 |
2016年 | 16篇 |
2015年 | 12篇 |
2014年 | 27篇 |
2013年 | 55篇 |
2012年 | 52篇 |
2011年 | 41篇 |
2010年 | 25篇 |
2009年 | 50篇 |
2008年 | 71篇 |
2007年 | 64篇 |
2006年 | 78篇 |
2005年 | 76篇 |
2004年 | 69篇 |
2003年 | 43篇 |
2002年 | 35篇 |
2001年 | 10篇 |
2000年 | 19篇 |
1999年 | 14篇 |
1998年 | 9篇 |
1997年 | 11篇 |
1996年 | 18篇 |
1995年 | 9篇 |
1994年 | 5篇 |
1993年 | 8篇 |
1992年 | 10篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 9篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 12篇 |
1980年 | 12篇 |
1979年 | 11篇 |
1978年 | 6篇 |
1977年 | 9篇 |
1976年 | 10篇 |
1975年 | 9篇 |
1974年 | 5篇 |
1973年 | 3篇 |
排序方式: 共有1000条查询结果,搜索用时 15 毫秒
101.
Iida T Satoh H Maeda K Yamamoto Y Asakawa K Sawada N Wada T Kadowaki C Itoh T Mase T Weissman SA Tschaen D Krska S Volante RP 《The Journal of organic chemistry》2005,70(23):9222-9229
[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1. 相似文献
102.
Kotaro Ishiji Tomoyuki Matsuda Hiroko Tokoro Toshiaki Iwazumi Shin-ichi Ohkoshi 《Journal of Physics and Chemistry of Solids》2007,68(11):2158-2161
Cesium manganese hexacyanoferrates exhibit an interesting phenomenon of temperature-induced phase transition accompanied by a variation in the magnetic susceptibility. We observed the variation in the electronic state of Mn during the phase transition by using X-ray absorption spectroscopy. The results of the analyses showed that the content ratio of FeII-CN-MnIII and FeIII-CN-MnII systematically varied during the phase transition. However, the ratio of FeII-CN-MnII remained constant at almost all temperatures. These results suggest that the charge transfer between Fe and Mn ions in the FeIII-CN-MnII or the FeII-CN-MnIII bond produces the phase transition. 相似文献
103.
The interaction between metal ions and bovine serum albumin (BSA) was studied by using a piezoelectric quartz crystal (PQC) arranged in the electrode-separated configuration. A silanized surface of the PQC was coated with a BSA membrane via a coupling reaction with glutaraldehyde. The frequency shifts obtained from PQC coated with a BSA membrane suggested that various kinds of metal ions could be adsorbed onto the BSA membrane from aqueous solutions containing a low concentration of metal ions (2 or 10 micromol dm(-3)), only when the BSA was denatured with an alkaline solution. Anionic species of Pt(IV) and Au(III) were adsorbed onto the denatured BSA membrane from an acetic acid solution at pH 2.2, and cationic species of Cd(II), Zn(II), Co(II), Ni(II), Cu(II), and Ag(I), and cations, such as Ca2+, Ba2+, and Mg2+, were adsorbed from ammonia buffer at pH 9.5, whereas Al(III), Cr(III), Fe(III), Hg(II), and Pb(II) were hardly adsorbed. The adsorption mechanisms of these metal ions are discussed, based on the electrostatic interaction between the metal ions and the denatured BSA membrane, and complex formation between the metal ions and amino acid residues of the denatured BSA. Further, the PQC coated with a denatured BSA membrane was applied to the determination of Pt and Cd, using large frequency shifts for Pt(IV) and Cd(II). 相似文献
104.
Yasuo Narukawa Toshiaki Murofushi 《Journal of Mathematical Analysis and Applications》2003,282(1):201-211
If the universal set X is not compact but locally compact, a comonotonically additive and monotone functional (for short c.m.) on the class of continuous functions with compact support is not represented by one Choquet integral, but represented by the difference of two Choquet integrals. The conditions for which a c.m. functional can be represented by one Choquet integral are discussed. 相似文献
105.
Kazuhiko Mase Mitsuru Nagasono Shin-ichiro Tanaka Tsuneo Urisu Eiji Ikenaga Tetsuji Sekitani Ken-ichiro Tanaka 《Surface science》1997,390(1-3):97-101
Ion desorption induced by a resonant excitation of O 1s of condensed amorphous H2O has been studied by total ion and total electron yield spectroscopy, nonderivative Auger electron spectroscopy (AES) and Auger electron photo-ion coincidence (AEPICO) spectroscopy. The spectrum of total ion yield divided by total electron yield exhibits a characteristic threshold peak at hν = 533.4 eV, which is assigned to the 4a1 ← O 1s resonant transition. The AES at the 4a1 ← O 1s resonance is interpreted as being composed of the spectator-AES of the surface H2O, and the normal-AES of the bulk H2O, where the 4a1 electron is delocalized before Auger transitions. H+ is found to be the only ion species in AEPICO spectra measured at the 4a1 ← O 1s resonance and at the O 1s ionization (hν = 560 eV). The electron kinetic energy dependence of the AEPICO yield (AEPICO yield spectrum) at the 4a1 ← O 1s resonance is found to be greatly different from that at the O 1s ionization. The peak positions of the AEPICO yield spectrum at the 4a1 ← O 1s resonance are found to correspond to those of the spectator-AES of the surface H2O, which is extracted from the AES at the 4a1 ← O 1s resonance. Furthermore, the AEPICO yield is greatly enhanced at the 4a1 ← O 1s resonance as compared with that at the O 1s ionization. On the basis of these results, a spectator-Auger-stimulated ion desorption mechanism and/or ultra-fast ion desorption mechanism are concluded to be responsible for the H+ desorption at the 4a1 ← O 1s resonance. The enhancement of the H+ yield is ascribed to the O---H anti-bonding character of the 4a1 orbital. 相似文献
106.
Osamu Kido Mami Kurumada Katsuya Kamitsuji Toshiaki Tanigaki Takeshi Sato Yuki Kimura Hitoshi Suzuki Yoshio Saito Chihiro Kaito 《Physica E: Low-dimensional Systems and Nanostructures》2006,31(2):169-173
The synthesis of Al–Cr single quasicrystal (QC) nanoparticles of the decagonal phase was achieved by introducing an advanced gas flow evaporation method. By obtaining successive electron diffraction patterns for single-QC nanoparticles, the phase transformation temperature of a single-QC nanoparticle was determined to be 700 °C. It was also determined that part of the QC nanoparticle decomposed into hex-Al8Cr5 and Al during the phase transformation. Since the grain growth did not occur during the phase transformation in the present experiment, the inherent phase transformation temperature could be measured. 相似文献
107.
We give a method for constructing all rigid local systems of semi‐simple type, which is different from the Katz–Dettweiler–Reiter algorithm. Our method follows from the construction of Fuchsian systems of differential equations with monodromy representations corresponding to such local systems, which give an explicit solution of the Riemann–Hilbert problem. Moreover, we show that every section of such local systems has an integral representation. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
108.
A novel procedure for an observation of a liquid crystal texture is proposed by using a UV curable liquid crystal. Optical observations from a cross-section of the Cano wedge cell are demonstrated and layered structures of cholesteric LC are visualized clearly. The structures near the Grandjean lines are then revealed in detail from images. From the observations, it is confirmed that the texture near the Grandjean line is similar to fingerprint texture 相似文献
109.
This paper describes the history and scheme of reference materials and standard solutions for titrimetry in Japan. Titrimetry
is one of the most fundamental and precise methods for determination of a constituent, based on the effective purity of reference
materials in stoichiometric analysis. It has wide-ranging applications based on titrimetric reactions such as neutralization,
redox, chelatometric, and precipitation titration processes, which are used in various analytical fields all over the world.
Japanese Industrial Standards (JIS) have played an important role in establishing a stable supply of reference materials for
titrimetry since the 1950s. There are several reports of preparations and their determination, including coulometric studies,
in order to establish highly reliable reference materials. This paper briefly reviews the schemes and studies of standardization
through the provision of reference materials and standard solutions based on JIS, and several applications in other standards.
Presented at Berm-11, October 2007, Tsukuba, Japan. 相似文献
110.
Akio Toshimitsu Toshiaki Aoai Hiroto Owada Sakae Uemura Masaya Okano 《Tetrahedron》1985,41(22):5301-5306
The reaction of phenylselenenyl chloride with olefins in aqueous acetonitrile affords β-hydroxyalkyl phenyl selenides in excellent yields, providing the most convenient method for hydroxyselenation of olefins so far reported. When the reaction was applied to conjugated dienes, monohydroxyselenated products were obtained in good to excellent yields. From non-conjugated dienes, on the other hand, cyclic ethers containing two phenylseleno groups were produced in good to excellent yields, the first step of this reaction being the hydroxyselenation of one double bond. 相似文献