全文获取类型
收费全文 | 432篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 383篇 |
晶体学 | 1篇 |
力学 | 2篇 |
数学 | 6篇 |
物理学 | 50篇 |
出版年
2022年 | 7篇 |
2021年 | 5篇 |
2020年 | 9篇 |
2019年 | 7篇 |
2018年 | 4篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 9篇 |
2014年 | 12篇 |
2013年 | 21篇 |
2012年 | 19篇 |
2011年 | 28篇 |
2010年 | 19篇 |
2009年 | 14篇 |
2008年 | 26篇 |
2007年 | 24篇 |
2006年 | 32篇 |
2005年 | 22篇 |
2004年 | 27篇 |
2003年 | 18篇 |
2002年 | 16篇 |
2001年 | 5篇 |
2000年 | 6篇 |
1999年 | 4篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 8篇 |
1991年 | 13篇 |
1990年 | 8篇 |
1989年 | 3篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 6篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 4篇 |
1975年 | 5篇 |
1973年 | 2篇 |
1968年 | 1篇 |
1942年 | 1篇 |
排序方式: 共有442条查询结果,搜索用时 15 毫秒
1.
Ryoko Chiba Ayako Ogasawara Teppei Kubo Hiroyuki Yamazaki Masuo Umino Yoichi Ishizuka 《Analytical sciences》2003,19(5):785-789
A column-switching high-performance liquid chromatographic method with fluorescence detection was developed for the simultaneous determination of four benzamide-type anti-psychotic drugs: sulpiride, tiapride, sultopride and metoclopramide in human serum. In this method, a TSKgel Super-ODS column was used as an analytical column, and a TSKgel G 2000SW was prepared as a pretreatment column. Under the optimized analytical conditions, four benzamide-type anti-psychotic drugs were eluted within 18 min. The detection limits (S/N = 3) for sulpiride, tiapride, sultopride and metoclopramide are 1 ng/ml, 4 ng/ml, 2 ng/ml and 0.5 ng/ml, respectively. Finally, the method was applied to the determination of sulpiride in human serum samples obtained after a single oral dose of sulpiride. 相似文献
2.
Momoko Ishida Rika Ohara Fuka Miyagawa Hiroe Kikuzaki Kosuke Nishi Hiroyuki Onda Nanami Yoshino Takuya Sugahara 《Molecules (Basel, Switzerland)》2022,27(13)
Cuminum cyminum L. (cumin) is an annual plant of the Umbelliferae family native to Egypt. We previously showed that the aqueous extract of cumin seeds suppresses degranulation by downregulating the activation of antigen-induced intracellular signaling molecules in rat basophilic leukemia RBL-2H3 cells. However, the active substances in the extract have not yet been identified. Accordingly, herein, we aimed to ascertain the water-soluble substances present in cumin seeds that inhibit degranulation, which led to the identification of umbelliferose, a characteristic trisaccharide present in plants of the Umbelliferae family. Our study is the first to reveal the degranulation-suppressing activity of umbelliferose, and quantification studies suggest that cumin seed powder contains 1.6% umbelliferose. Raffinose, an isomer of umbelliferose, was also found to significantly suppress antigen-induced degranulation, but less so than umbelliferose. Both umbelliferose and raffinose contain sucrose subunits in their structures, with galactose moieties bound at different sites. These differences in structure suggest that the binding of galactose to the sucrose subunit at the α1-2 bond contributes to its strong degranulation-inhibiting properties. 相似文献
3.
Ayako Imai Kenji Mawatari Nobuo Ueno Kazuyuki Sakamoto 《Applied Surface Science》2009,256(4):1156-1159
The thickness-dependent electronic structures of Dy silicide films grown on a Si(1 1 1) surface have been investigated by angle-resolved photoelectron spectroscopy. Two (1×1) periodic bands, both of them cross the Fermi level, have been observed in the silicide films formed by Dy coverages of 1.0 monolayer and below, and more than five () periodic bands have been observed in thicker films. Taking the () periodic structure of Dy atoms in the submonolayer silicide film into account, the periodicity of the two metallic bands indicate that they mainly originate from the orbitals of Si atoms, which form a (1×1) structure. Of the () periodic bands observed in thick films, four of them are well explained by the folding of the (1×1) bands into a () periodicity. Regarding the other band, the three () periodic bands would originate from the electronic states related to the inner Si layers that form a () structure, and the one observed in the 3.0 ML film only might originate from the electron located at the interface between bulk Si and the Dy silicide film. 相似文献
4.
ZrO2 thin films were produced by limited reaction sputtering process varying the deposition parameters. An interesting growth phenomenon was observed in the initial growth stage of amorphous samples, appearing to suppress film growth for the first several minutes. The structures of such ultrathin ZrO2 films were investigated by high-resolution Rutherford backscattering (HR-RBS) and X-ray photoelectron spectroscopy (XPS). The results suggest that the existence of interfacial suboxides due to the adsorption-induced surface reaction and diffusion-induced internal reaction, lead to the deteriorated interfacial performance. The mechanism and effects of the growth delay time on the interfacial characteristics are discussed in detail. 相似文献
5.
Mori M Oyama Y Suzuki A Takahashi K Yamada M Miyano K Miyata H Takei H Hirata KS Kajita T Kihara K Nakahata M Nakamura K Ohara S Sato N Suzuki Y Totsuka Y Yaginuma Y Koshiba M Suda T Tajima T Fukuda Y Nagashima Y Takita M Kaneyuki K Tanimori T Beier EW Frank ED Frati W Kim SB Mann AK Newcomer FM Van Berg R Zhang W 《Physical review D: Particles and fields》1991,43(9):2843-2846
6.
Ayako Tokiwa Masayasu Nagoshi Yasuhiko Syono 《Physica C: Superconductivity and its Applications》1990,170(5-6):437-442
Superconductivity and composition analysis of PbBaSr(Y, Ca)Cu3Oy with fixed ratio of Sr/Ba = 1 were studied. Synthesis condition and superconductivity of Pb(Ba, Sr)2(Y, Ca)Cu3Oy with various ratio of Sr/Ba and Ca/Y were also studied. It was found that Tc increased with increasing Ca concentration, and that Sr-rich specimens allowed to contain more Ca. PbBa0.8Sr1.2Y0.6Ca0.4Cu3O7 showed superconductivity with zero-resistance temperature of 42 K, which was higher than PbBaSrY0.7Ca0.3Cu3O7 with maximum Ca content for Sr/Ba = 1. Decrease in averaged ionic radii of Ba and Sr in Sr-rich compositions would be favorable for the contraction of Cu-O bonds by hole-doping via Ca substitution for Y. 相似文献
7.
8.
[Structure: see text] Beta-isocupreidine (beta-ICD)-catalyzed Baylis-Hillman reaction of chiral N-Boc-alpha-amino aldehydes and 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) takes place without racemization and exhibits the match-mismatch relationship between the substrate and the catalyst. In the case of acyclic amino aldehydes, L-substrates show excellent syn selectivity and high reactivity in contrast to D-substrates. On the other hand, in the case of cyclic amino aldehydes, D-substrates rather than L-substrates show excellent anti selectivity and high reactivity. 相似文献
9.
Diversity oriented synthesis of conjugate dienes and alkenylcyclopropanes by the sequential reactions using silyl group-substituted titanium carbene complexes was studied. Dienylsilanes were obtained by the olefination of carbonyl compounds with γ-silylvinylcarbene complexes. Cyclopropanation of 1-alkenes with the vinylcarbene complexes produced (E)-(β-silylvinyl)cyclopropanes with high stereoselectivity. The reaction of β-(trialkylsilyl)carbene complexes with zinc alkoxides of homopropargyl alcohols produced 6-silyl-3,5-hexadien-1-ols with high regio- and stereoselectivity. The (E)-alkenylsilanes thus obtained were transformed into a range of unsaturated compounds by the palladium-catalyzed or copper(I)-promoted cross-coupling with organic halides with retention of configuration. 相似文献
10.
Keikichi Uno Mutsuko Ohara Harold G. Cassidy 《Journal of polymer science. Part A, Polymer chemistry》1968,6(10):2729-2740
Ten vinylhydroquinone and one vinyl resorcinol derivatives are compared, particularly with respect to NMR spectra and copolymerizability with styrene. They are vinylhydroquinone dimethyl ether (I), vinyl-O,O′-bis(1-ethoxyethyl)hydroquinone (II), vinylhydroquinone di(2-pentyl)ether (III), 4-vinyl resorcinol bismethoxymethyl ether (IV), 2-vinyl-5-methylhydroquinone dimethyl ether (V), 2-vinyl-5-methyl-O,O′-bis(1-ethoxyethyl)hydroquinone (VI), 2-vinyl-6-methylhydroquinone dimethyl ether (VII), 2-vinyl-5-tert-butylhydroquinone dimethyl ether (VIII), 2-vinyl-5-chlorohydroquinone dimethyl ether (IX), 2-vinyl-3,6-dimethylhydroquinone dimethyl ether (X), and 2-vinyl-3,5,6-trimethylhydroquinone dimethyl ether (XI). All the vinyl protons have almost the same coupling constants. Though subtle distinctions are found among all the spectra, they can in general be put into two groups on the basis of the chemical shifts. Let the hydrogen on carbon-1 of the vinyl group be A, the hydrogen cis to A be B the hydrogen trans to A be C, then in the first group, (I) through (IX), the chemical shifts (τ) are (A) 3.02 ± 0.08, (C) 4.41 ± 0.05, and (B) 4.87 ± 0.07, and in the second group, (X) and (XI), they are (A) 3.30 ± 0.03, (C) 4.49 ± 0.01, and (B) 4.59 ± 0.03. It is supposed that in (X) and (XI) the vinyl group is out of the plane of the ring, because of the two ortho substituents, and this conformation is reflected in the NMR data. Ultraviolet spectra are consonant with this interpretation, since the λmax of (X) and (XI) correspond closely with those of nonvinyl reference compounds, while those of (II), (V), and (VIII) are shifted to longer wavelengths. When these compounds are copolymerized separately with styrene, the behaviors are classifiable into the following three groups, where r1 and r2 are monomer reactivity ratios with styrene as the first monomer: (i) r1 < 1 and r2 < 1 for compounds (II) and (III) and the reference compound O,O′-dibenzoylvinylhydroquinone, (ii) r1 < 1 and r2 > 1 for compounds (I), (V), (VII), (VIII), (IX), and (iii) r1 > 1 and r2 = 0 for compounds (X) and (XI). These behaviors are correlated with the effect of electronegativity of groups on the stability of the radical at the growing end of the chain and with the simultaneous effects of steric hindrance. 相似文献