全文获取类型
收费全文 | 2352篇 |
免费 | 91篇 |
国内免费 | 6篇 |
专业分类
化学 | 1820篇 |
晶体学 | 28篇 |
力学 | 57篇 |
数学 | 68篇 |
物理学 | 476篇 |
出版年
2023年 | 10篇 |
2021年 | 22篇 |
2020年 | 40篇 |
2019年 | 43篇 |
2018年 | 33篇 |
2017年 | 13篇 |
2016年 | 46篇 |
2015年 | 39篇 |
2014年 | 36篇 |
2013年 | 100篇 |
2012年 | 116篇 |
2011年 | 118篇 |
2010年 | 41篇 |
2009年 | 76篇 |
2008年 | 127篇 |
2007年 | 113篇 |
2006年 | 141篇 |
2005年 | 95篇 |
2004年 | 98篇 |
2003年 | 84篇 |
2002年 | 76篇 |
2001年 | 57篇 |
2000年 | 54篇 |
1999年 | 32篇 |
1998年 | 15篇 |
1997年 | 20篇 |
1996年 | 30篇 |
1995年 | 35篇 |
1994年 | 30篇 |
1993年 | 26篇 |
1992年 | 44篇 |
1991年 | 31篇 |
1990年 | 36篇 |
1989年 | 46篇 |
1988年 | 39篇 |
1987年 | 34篇 |
1986年 | 27篇 |
1985年 | 56篇 |
1984年 | 53篇 |
1983年 | 16篇 |
1982年 | 29篇 |
1981年 | 25篇 |
1980年 | 29篇 |
1979年 | 39篇 |
1978年 | 31篇 |
1977年 | 22篇 |
1976年 | 28篇 |
1975年 | 22篇 |
1974年 | 16篇 |
1973年 | 16篇 |
排序方式: 共有2449条查询结果,搜索用时 15 毫秒
51.
Simple and sensitive determination of methylglyoxal in biological samples by gas chromatography with electron-capture detection 总被引:1,自引:0,他引:1
Methylglyoxal was allowed to react with 4,5-dichloro-1,2-phenylenediamine, and the 6,7-dichloro-2-methylquinoxaline formed was determined by gas chromatography with electron-capture detection. The standard curve of the quinoxaline was linear up to 160 pmol/ml. The recoveries of methylglyoxal from coffee and rat liver homogenate were 84.1 and 77.6%, respectively. This procedure was very selective and so sensitive that as little as 9 fmol of the quinoxaline could be measured in biological and food samples. 相似文献
52.
53.
Tanaka K Mori M Xu Q Helaleh MI Ikedo M Taoda H Hu W Hasebe K Fritz JS Haddad PR 《Journal of chromatography. A》2003,997(1-2):127-132
In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression. 相似文献
54.
55.
(-)-Pestalotin [(6S, l'S)-6-(1'-hydroxypentyl)-4-methoxy-5,6-d dihydro-2-pyrone 1a]and its three other stereoisomers were synthesized either by utilizing the Sharpless asymmetric epoxidation as the keystep or by derivation from D-(+)-glyceraldehyde acetonide. 相似文献
56.
57.
Miyashita T Baba M Shigeta S Mori K Shinozuka K 《Chemical & pharmaceutical bulletin》2003,51(6):630-634
A series of novel 10-thiaisoalloxazine derivatives bearing an alkoxymethyl or benzyloxymethyl moiety at the N-1 position has been synthesized through the bromination of 1-substituted-5-hydroxyuracils and subsequent condensation with aminobenzenethiol in a one-pot reaction. Contrary to the previous report, the formation of intermediary 5,6-diethoxy-5-hydroxy-5,6-dihydrouracil seems to be not the necessary factor for the formation of the thiaisoalloxazines, since the reaction proceeds in tetrahydrofuran (THF) or acetonitrile far more smoothly than in ethanol. The anti-human immunodeficiency virus (HIV)-1 activity of the resulted thiaisoalloxazine derivatives was evaluated in lymphocyte cells based on the inhibitory activity against the viral-induced cytopathic activity. Among the derivatives, compounds 6, 7, and 8 bearing an alkoxymethyl moiety at the N-1 position exhibited modest inhibitory activity towards the cytotopathic effect of HIV-1. 相似文献
58.
Three newly prepared [Ni(mnt)2] complexes, (HMTTF)[Ni(mnt)2], (ChSTF)[Ni(mnt)2], and (DBTTF)2[Ni(mnt)2], are reported (DBTTF = dibenzotetrathiafulvalene, ChSTF = 2,3-cyclohexylenedithio-1,4-dithia-5,8-diselanafulvalene, HMTTF = bis(trimethylene)-tetrathiafulvalene, and mnt = maleonitrile dithiolate). The former two compounds have usual DA-type (D = donor, A = acceptor) mixed stacks, whereas the DBTTF complex has DDDDAA-type 6-fold columns. These compounds are electrical insulators, but the HMTTF and ChSTF complexes exhibit chiT minima at 16 and 55 K, respectively, followed by chiT peaks at 8 and 16 K. Below these temperatures the ESR signal disappears, indicating antiferromagnetic transitions. The origin of the ferromagnetic interaction is explained either from the difference of the g values between the donor and the anion or from the intrinsic ferromagnetic interaction of the [Ni(mnt)2] anions. 相似文献
59.
Kitano H Tada S Mori T Takaha K Gemmei-Ide M Tanaka M Fukuda M Yokoyama Y 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11932-11940
The structure and hydrogen bonding of water in the vicinity of carboxybetaine homopolymer (poly[1-carboxy-N,N-dimethyl-N-(2'-methacryloyloxyethyl)methanaminium inner salt] (PolyCMB), and a random copolymer of CMB and n-butyl methacrylate, Poly(CMB-r-BMA), with various molecular weights were analyzed in their aqueous solutions and thin film with contours of O-H stretching of Raman and attenuated total reflection infrared (ATR-IR) spectra, respectively. The relative intensity of the collective band (C value) corresponding to a long-range coupling of O-H stretchings of the Raman spectra for aqueous solution of Poly(CMB-r-BMA) was very close to that for pure water, which is in contrast with the smaller C value in aqueous solution of ordinary polyelectrolytes. The number of hydrogen bonds collapsed by the presence of one monomer residue (N(corr) value) of PolyCMB and Poly(CMB-r-BMA) (CMB, 45 mol %) (M(w), 1.14 x 10(4) and 1.78 x 10(4), respectively) could be calculated from the C value. The N(corr) values were much smaller than those for ordinary polyelectrolytes and close to those for nonionic water-soluble polymers such as poly(ethylene glycol) and poly(N-vinylpyrrolidone). Furthermore, a water-insoluble Poly(CMB-r-BMA) with a large BMA content (M(w) = 347 kD, CMB 27 mol %) could be cast as a thin film (thickness, ca. 10 microm) on a ZnSe crystal for the ATR-IR analyses. At an early stage of sorption of water into the Poly(CMB-r-BMA) film, the O-H stretching band of IR spectra for the water incorporated in the film was similar to that for free water, which is in contrast with the drastic change in the O-H stretching band of water incorporated in polymer films such as poly(methyl methacrylate) (PMMA) and poly(n-butyl methacrylate) (PBMA). The theoretical vibrational frequency for water molecules hydrating a betaine molecule calculated by using a density functional method supported the experimental results. The adhesion of human platelets to Poly(CMB-r-BMA) films was much less than that to PMMA and PBMA. With an increase in the content of CMB residue, the number of platelets adhered to the Poly(CMB-r-BMA) film drastically decreased and then gradually increased, probably due to the increase in the roughness of the film surface. These results suggest that the carboxybetaine monomer residues with a zwitterionic structure do not significantly disturb the hydrogen bonding between water molecules in both aqueous solution and thin film systems, resulting in the excellent blood-compatibility of the carboxybetaine polymers. 相似文献
60.