全文获取类型
收费全文 | 1904篇 |
免费 | 14篇 |
国内免费 | 3篇 |
专业分类
化学 | 1139篇 |
晶体学 | 18篇 |
力学 | 24篇 |
综合类 | 1篇 |
数学 | 57篇 |
物理学 | 682篇 |
出版年
2023年 | 6篇 |
2021年 | 5篇 |
2020年 | 12篇 |
2019年 | 16篇 |
2018年 | 9篇 |
2017年 | 9篇 |
2016年 | 16篇 |
2015年 | 15篇 |
2014年 | 19篇 |
2013年 | 77篇 |
2012年 | 57篇 |
2011年 | 80篇 |
2010年 | 43篇 |
2009年 | 48篇 |
2008年 | 95篇 |
2007年 | 120篇 |
2006年 | 108篇 |
2005年 | 121篇 |
2004年 | 112篇 |
2003年 | 98篇 |
2002年 | 88篇 |
2001年 | 56篇 |
2000年 | 54篇 |
1999年 | 35篇 |
1998年 | 28篇 |
1997年 | 32篇 |
1996年 | 36篇 |
1995年 | 36篇 |
1994年 | 29篇 |
1993年 | 36篇 |
1992年 | 48篇 |
1991年 | 23篇 |
1990年 | 21篇 |
1989年 | 29篇 |
1988年 | 19篇 |
1987年 | 30篇 |
1986年 | 18篇 |
1985年 | 28篇 |
1984年 | 28篇 |
1983年 | 12篇 |
1982年 | 20篇 |
1981年 | 21篇 |
1980年 | 19篇 |
1979年 | 22篇 |
1978年 | 17篇 |
1977年 | 12篇 |
1976年 | 10篇 |
1975年 | 12篇 |
1974年 | 10篇 |
1973年 | 10篇 |
排序方式: 共有1921条查询结果,搜索用时 15 毫秒
71.
The demand for more efficient methods of establishing the undetermined stereochemistries of peptidic natural products continues unabated. A new method for microscale stereochemical determination was devised by integrating solid-phase synthesis, split-and-mix randomization, 18O/16O-encoding of d /l -configurations, tandem mass spectrometry, and biological evaluation. Here we applied gramicidin A as the molecule for a blind test. Gramicidin A and its 31 diastereomers were randomly prepared in microgram scale with 18O/16O-stereochemical encoding and subjected to MS/MS-structural determination and cytotoxicity assay. Only the parent gramicidin A was selected from among the 32 stereoisomers, validating the high reliability of the present strategy. 相似文献
72.
Itoh Y Ezawa A Kikuchi K Tsuruta Y Niwa T 《Analytical and bioanalytical chemistry》2012,403(7):1841-1850
Cardiovascular disease (CVD) is prevalent in patients with chronic kidney disease (CKD). In hemodialysis (HD) patients, some protein-bound uremic toxins are considered to be associated with CVD. However, it is not yet known which uremic toxins are important in terms of endothelial toxicity. Serum samples were obtained from 45 HD patients before and after HD. Total and free serum concentrations of indoxyl sulfate, indoxyl glucuronide, indoleacetic acid, p-cresyl sulfate, p-cresyl glucuronide, phenyl sulfate, phenyl glucuronide, phenylacetic acid, phenylacetyl glutamine, hippuric acid, 4-ethylphenyl sulfate, and 3-carboxy-4-methyl-5-propyl-2-furanpropionic acid (CMPF) were simultaneously measured by liquid chromatography/electrospray ionization-mass spectrometry/mass spectrometry (LC/ESI-MS/MS). The effects of these solutes at their pre-HD mean and maximum serum concentrations on reactive oxygen species (ROS) production in human umbilical vein endothelial cells (HUVEC) were measured with a ROS probe. Serum levels of 11 of the solutes (all except 4-ethylphenyl sulfate) were significantly increased in HD patients compared to healthy subjects. All 12 solutes showed changes in their protein-binding ratios. In particular, indoxyl sulfate, p-cresyl sulfate, CMPF, and 4-ethylphenyl sulfate showed high protein-binding ratios (>95 %) and low reduction rates by HD (<35 %). Indoxyl sulfate at its mean and maximum pre-HD serum concentrations-even with 4 % albumin-stimulated ROS production in HUVEC most intensely, followed by CMPF. In conclusion, the serum levels of 11 protein-bound uremic toxins were increased in HD patients. Indoxyl sulfate, p-cresyl sulfate, and CMPF could not be removed efficiently by HD due to their high protein-binding ratios. Indoxyl sulfate most intensely induced endothelial ROS production, followed by CMPF. 相似文献
73.
Yoshihiro Itoh Masamitsu Inoue Tomoko Takahashi Akira Hachimori Satoshi Suzuki 《Journal of polymer science. Part A, Polymer chemistry》1995,33(7):1069-1074
Alternating and random copolymers of 9-phenanthrylmethyl methacrylate or 2-(9-carbazolyl)ethyl methacrylate with styrene were synthesized and their fluorescence properties were examined. There was no noticeable difference in the spectral features of the alternating and random copolymers in tetrahydrofuran (THF), demonstrating that this type of polymers have no quenching sites in the polymer chains. The fluorescence quenching studies indicated that the alternating copolymers permitted singlet-state energy migration as efficiently as the corresponding random copolymers but less efficiently than the random copolymers with higher chromophore contents. These results strongly suggest that to be chromophores close to each other is most important for facilitation of an intramolecular energy migration. © 1995 John Wiley & Sons, Inc. 相似文献
74.
Akihito Sakakibara Maki Itoh Itaru Mita 《Journal of polymer science. Part A, Polymer chemistry》1995,33(8):1293-1303
Aromatic polybenzobisoxazoles, having polydimethylsiloxane side chains (SCPBOs), were prepared using terephthaloyl chloride-terminated polydimethylsiloxane macromonomers and 3,3′-bis(trimethylsiloxy)-4,4′-bis(trimethylsilylamino)biphenyl for the purpose of dispersing rigid-rod molecules in silicone matrices for molecular reinforcement. The degree of polymerization of the side chain was varied from 7.8 to 45.4, and a small amount of (3-butenyloxy)terephthaloyl chloride was copolymerized to give the polymers a functionality that can be linked to the matrices. For all the SCPBOs, the WAXD pattern showed only diffuse reflections, suggesting limited structural regularity, although the polymers were optically anisotropic. No melting transition was observed below the side chain decomposition temperature, 350°C. A polydimethylsiloxane/polybenzobisoxazole composite elastomer was obtained first curing the polysiloxane matrix containing the prepolymer of the SCPBO, followed by in situ thermal ring closure of the prepolymer. Some reinforcement was observed, but the presence of plasticizing effect by the unbound SCPBO was suggested at the same time. © 1995 John Wiley & Sons, Inc. 相似文献
75.
Takahito Itoh Hiroki Saitoh Shouji Iwatsuki 《Journal of polymer science. Part A, Polymer chemistry》1995,33(10):1589-1596
1,1′-Dialkylferrocene-3,3′-dicarbaldehydes ( 1a–c ) with long alkyl chains such as ethyl, hexyl, and dodecyl groups were prepared in 13–25% yield via three-step reactions. The titanium-induced dicarbonyl-coupling reaction of 1a–c gave poly(1,1′-dialkyl-3,3′-ferrocenylenevi-nylene)s ( 2a–c ) in quantitative yields, which were the molecular weights of 3000–10,000 and highly soluble in chloroform, benzene, and hexane. The electrical conductivity and the third-order nonlinear optical susceptibility for poly(1,1′-dihexyl-3,3′-ferrocenylenevinylene) ( 2b ) were estimated to be 1 × 10?2 S/cm on doping with iodine and 1–4 × 10?12 esu at a wavelength of 1–2.4 μm, respectively. © 1995 John Wiley & Sons, Inc. 相似文献
76.
Kazuhiro Marumo Manabu Itoh Sungmin Kang Koichi Sakajiri Junji Watanabe 《Liquid crystals》2013,40(2):234-238
Galactose derivatives were explored as chiral dopants, effective for inducing chiral nematic liquid crystal (LC) phases. Galactose bearing O-isopropylidene substituents at the C3 and C4 and butoxybiphenyl substituents at the C2 and C6 positions exhibits a high helical twisting power (HTP) value of ?74.4 μm?1. Such a high HTP value for the galactose derivative is attributed to (1) linkage of the C3 and C4 carbons with the O-isopropylidene substituent, which places the C2 and C6 substitutes in a skew arrangement at a large angle and (2) enhancement of the affinity with the host nematic LCs by incorporating aromatic substituents at the C2 and C6 positions that are similar to those in the host. 相似文献
77.
A simple protocol that uses [OsIII(OH)(H2O)(L ‐N4Me2)](PF6)2 ( 1 ; L ‐N4Me2=N,N′‐dimethyl‐2,11‐diaza[3.3](2,6)pyridinophane) as a catalyst and H2O2 as a terminal oxidant for efficient cis‐1,2‐dihydroxylation of alkenes is presented. Unfunctionalized (or aliphatic) alkenes and alkenes/styrenes containing electron‐withdrawing groups are selectively oxidized to the corresponding vicinal diols in good to excellent yields (46–99 %). In the catalytic reactions, the stoichiometry of alkene:H2O2 is 1:1, and thus the oxidant efficiency is very high. For the dihydroxylation of cyclohexene, the catalytic amount of 1 can be reduced to 0.01 mol % to achieve a very high turnover number of 5500. The active oxidant is identified as the OsV(O)(OH) species ( 2 ), which is formed via the hydroperoxide adduct, an OsIII(OOH) species. The active oxidant 2 is successfully isolated and crystallographically characterized. 相似文献
78.
79.
80.
A new preconcentration method with yeast is presented. The method was evaluated for the determination of trace silver in river waters by graphite furnace atomic absorption spectrometry (GFAAS). A suitable cultivation bed for preconcentration of silver was 1.75 mg ml-1 2-ammonium hydrogen phosphate. The optimal cultivation time and temperature were 2 h and 25 degrees C. Under optimal conditions, silver in aqueous sample was concentrated to 6.9-fold by yeast. The detection limit was 4.6 pg ml-1 (3S/N) for silver in river water. The yeast preconcentration method was applied to the determination of silver in river waters. The recovery of spiked silver was in the range of 89 to 110%. By the preconcentration, it was found that ultra trace silver in river waters could be determined without interferences of matrix elements, after only the cultivation and with no chemical treatment. 相似文献