全文获取类型
收费全文 | 1572篇 |
免费 | 33篇 |
国内免费 | 8篇 |
专业分类
化学 | 1232篇 |
晶体学 | 6篇 |
力学 | 23篇 |
数学 | 110篇 |
物理学 | 242篇 |
出版年
2023年 | 10篇 |
2022年 | 11篇 |
2021年 | 9篇 |
2020年 | 18篇 |
2019年 | 15篇 |
2018年 | 17篇 |
2017年 | 10篇 |
2016年 | 28篇 |
2015年 | 22篇 |
2014年 | 29篇 |
2013年 | 83篇 |
2012年 | 91篇 |
2011年 | 115篇 |
2010年 | 55篇 |
2009年 | 71篇 |
2008年 | 81篇 |
2007年 | 92篇 |
2006年 | 103篇 |
2005年 | 87篇 |
2004年 | 78篇 |
2003年 | 65篇 |
2002年 | 75篇 |
2001年 | 25篇 |
2000年 | 29篇 |
1999年 | 18篇 |
1998年 | 18篇 |
1997年 | 21篇 |
1996年 | 15篇 |
1995年 | 13篇 |
1994年 | 17篇 |
1993年 | 14篇 |
1992年 | 15篇 |
1991年 | 18篇 |
1990年 | 26篇 |
1989年 | 14篇 |
1988年 | 10篇 |
1987年 | 7篇 |
1986年 | 12篇 |
1985年 | 22篇 |
1984年 | 16篇 |
1983年 | 13篇 |
1982年 | 18篇 |
1981年 | 13篇 |
1980年 | 15篇 |
1979年 | 19篇 |
1977年 | 8篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1971年 | 10篇 |
排序方式: 共有1613条查询结果,搜索用时 171 毫秒
41.
An on-column fluorometric derivatization method was developed for the determination of histamine and 1-methylhistamine (HMs) by high-performance liquid chromatography. The system for the derivatization consisted only of a commercially available single-plunger pump and a reversed-phase C18 column supported on synthetic polymer with a mobile phase of acetonitrile and alkaline borate buffer solution containing o-phthalaldehyde as a derivatization reagent. It required no additional reaction system as for a post-column derivatization method. Injected HMs might be derivatized to a fluorophore on the inlet site of the high-performance liquid chromatographic column, followed by chromatography on the same column. Optimization of the on-column reaction conditions resulted in a simple and sensitive analytical method for the determination of HMs with excellent reproducibility and linearity of 0.05-5 micrograms/ml of both HMs. Application of this method to the determination of HMs in food samples resulted in a limit of quantification of 0.05 mg/100 g and in a greater than 95% overall mean recovery at a fortification of 0.1 mg/g of both HMs. This method was furthermore applicable to the determination of histamine released from rat peritoneal mast cells. 相似文献
42.
43.
Toshio Takido Sachiko Tamura Kenji Sato Haruo Kamijo Toshikatsu Nakazawa Manabu Seno Tadashi Hata 《Journal of heterocyclic chemistry》1998,35(2):437-443
The synthesis of hexahydrooxoepithiopyridinedicarboxyimide (5: X2 = N-Ph) by the reaction of thioamides 1 with N-substituted maleimide ( 2a ) was examined. The reaction of primary thioamides, such as thiobenzamide and p-toluthioamide with N-phenylmaleimide gives compounds 5 together with corresponding 4-hydroxy-1,3-thiazoles 4 . However, a similar reaction of secondary thioamides, such as N-methylthioacetamide, thiobenzanilide, with N-phenylmaleimide did not provide compounds 5 without addition of acid. The reaction pathway and the configuration of 5 were also investigated. 相似文献
44.
Riki Seki Etsuko Kimura Toshiyuki Takahashi Nagao Ikeda 《Journal of Radioanalytical and Nuclear Chemistry》1990,138(1):17-31
The concentration of129I in soil in Japan was determined by neutron activation analysis. For the activation analysis, pre-irradiation chemical separation of the iodine was carried out by acid decomposition and distillation and post-irradiation treatment was performed by ion exchange and solvent extraction. The concentration of stable iodine and137Cs were also determined and compared with the behavior of129I in soil.Soil samples from Ibaraki, Fukui, Fukushima, and Nagasaki Prefectures were analyzed and129I was detected in amounts ranging from 10–7 to 10–5 Bq/g soil in uncultivated surface soil. There are apparently small variations in the129I concentrations in each of the regions analyzed.From depth profile studies in sandy soil, the iodide form of129I was found to migrate downward at a relatively rapid rate while other species remain longer in the surface soil. 相似文献
45.
Tetsuro Ito Toshiyuki TanakaMunekazu Iinuma Ibrahim IliyaKen-ichi Nakaya Zulfiqar AliYoshikazu Takahashi Ryuichi SawaYoshiaki Shirataki Jin MurataDedy Darnaedi 《Tetrahedron》2003,59(28):5347-5363
Five new resveratrol oligomers; pauciflorols A-C (1-3), isovaticanols B (6) and C (8), and three new oligostilbene glucosides; pauciflorosides A (11), B (13), C (14), were isolated from the stem bark of Vatica pauciflora (Dipterocarpaceae) together with known 17 resveratrol oligomers (4, 5, 7, 9, 10, 12 and 15-25) and bergenin (26). The structures of isolates were established on the basis of detailed spectroscopic analysis. The typical and characteristic spectral properties of some resveratrol oligomers were also discussed. 相似文献
46.
Jun Suzuki Kenjiro Fujimoto Toshiyuki Mori Mamoru Watanabe Yoshio Hasegawa 《Journal of Sol-Gel Science and Technology》2000,19(1-3):775-778
The photocatalytic reduction of nitrogen monoxide (NO) with ethane on the hollandite type catalyst (K2Ga2Sn6O16KGSO) was investigated. Using a closed-gas circulating system equipped with a Q-MASS detector and in-situ diffuse reflectance FT-IR spectroscopy. The reactant gases of NO and 13C2H6 decreased with the increasing irradiation time. In contrast, the N2 yield increased proportionally to the conversion of 13C2H6. Nitrogen oxides such as N2O did not reach their detectable levels. The NO adsorbed on KGSO was found to change to its activated species by UV irradiation. The oxidized products of C2H6 such as CH3CHO increased in proportion to the reaction time. The present results strongly suggest that KGSO has remarkable photocatalytic activity for the reduction of NO with C2H6. 相似文献
47.
Nishimura K Suzuki T Momchilova S Miyashita K Katsura E Itabashi Y 《Journal of chromatographic science》2005,43(9):494-499
A simple and highly sensitive method for determining the fatty acid composition of food lipids containing conjugated linoleic acid (CLA) is described. The method is based on the separation of the 9-anthrylmethyl ester derivatives of saturated and unsaturated (conjugated and non-conjugated) fatty acids by reversed-phase high-performance liquid chromatography with fluorescence detection. Just like the other fatty acids, CLA reacts readily with 9-anthryldiazomethane at room temperature to produce 9-anthrylmethyl esters without isomerization and decomposition of the conjugated double bonds. Clear resolution of the individual fatty acids as their 9-anthrylmethyl esters is achieved on a highly efficient octadecylsilylated silica column (150- x 3-mm i.d., 3-microm particle size) using a stepwise gradient elution with methanol-water. The method is standardized with commercially available CLA isomers (cis-9, trans-11 and trans-10, cis-12-octadecadienoic acids, and their cis,cis and trans,trans isomers) and applied for determination of the fatty acid compositions of milk and sdairy products. 相似文献
48.
Hiroshi Takeuchi Makoto Nakagawa Takayuki Saito Toru Egawa Kiyoshi Tanaka Shigehiro Konaka Toshiyuki Mitsuhashi 《International journal of quantum chemistry》1994,52(6):1339-1348
The energy spectra of free water molecules were measured at scattering angles 2θ ranging from 10.5° to 75.7°, using an angle-dispersive-type diffractometer and synchrotron radiation as an X-ray source. A silicon (111) monochrometer was used to obtain incident X-rays with the wavelengths of (1.543/n) Å (n = 1,3,4,5). Observed inelastic scattering peaks are clearly separated from eleastic ones at s values [s = (4π/λ) sin Å] larger than 8 Å?1. The increase of the separation with an increasing s value was consistent with the classical theory of the Compton shift. The total (elastic plus inelastic) intensities were obtained over a range of s = 0.74–5.0 Å?1. Experimental difference intensities Δσee and Δσne were obtained separately by combining the X-ray and high-energy electron scattering data. The experimental results are in reasonable agreement with the theoretical intensities calculated from SCF and CI molecular wave functions with a basis set of double-zeta plus polarization functions. © 1994 John Wiley & Sons, Inc. 相似文献
49.
Shimizu T Kimura T Funahashi T Watanabe K Ho IK Yamamoto I 《Chemical & pharmaceutical bulletin》2005,53(3):313-318
Seventy eight N(3)-substituted derivatives of uridine (1), thymidine (2), 2'-deoxyuridine (3), 6-azauridine (4), 2',3'-O-isopropylideneuridine (5), and arabinofuranosyluracil (6) were synthesized and their antinociceptive effects were evaluated. N(3)-(2',4'-Dimethoxyphenacyl)uridine (1l), N(3)-(2',4'-dimethoxyphenacyl)2'-deoxyuridine (3l), and N(3)-(2',5'-dimethoxyphenacyl)arabinofuranosyluracil (6m) possessed 93, 86, and 82% of the antinociceptive effects tested by hot plate, respectively. The antinociceptive effects of three derivatives were 5.8, 5.4, and 5.1-folds of the effect of N(3)-phenacyluridine (1h) (16%), respectively. The structure-activity relationship of N(3)-substituted pyrimidine nucleosides was also discussed. 相似文献
50.
Toshiyuki Katagi 《Journal of computational chemistry》1990,11(4):524-530
The reaction mechanisms of the alkaline hydrolysis of N-methylcarbamates were studied using the AM1 method by assuming two possible pathways: (1) nucleophilic attack of hydroxide ion on the carbonyl carbon to give a tetrahedral complex followed by its breakdown to carbamic acid (BAC2); and (2) proton abstraction by hydroxide ion at the nitrogen atom followed by elimination of the alkoxide ion to form N-methyl isocyanate (E1cB). Reaction coordinate analysis showed that the reaction mechanism is determined by both the stability of an intermediate and the energy barrier for elimination. 相似文献