全文获取类型
收费全文 | 1746篇 |
免费 | 36篇 |
国内免费 | 3篇 |
专业分类
化学 | 1332篇 |
晶体学 | 22篇 |
力学 | 12篇 |
数学 | 149篇 |
物理学 | 270篇 |
出版年
2021年 | 10篇 |
2020年 | 13篇 |
2019年 | 28篇 |
2018年 | 20篇 |
2017年 | 8篇 |
2016年 | 29篇 |
2015年 | 26篇 |
2014年 | 23篇 |
2013年 | 87篇 |
2012年 | 58篇 |
2011年 | 83篇 |
2010年 | 39篇 |
2009年 | 49篇 |
2008年 | 78篇 |
2007年 | 79篇 |
2006年 | 88篇 |
2005年 | 100篇 |
2004年 | 73篇 |
2003年 | 87篇 |
2002年 | 81篇 |
2001年 | 49篇 |
2000年 | 34篇 |
1999年 | 19篇 |
1998年 | 13篇 |
1997年 | 24篇 |
1996年 | 20篇 |
1995年 | 20篇 |
1994年 | 25篇 |
1993年 | 16篇 |
1992年 | 28篇 |
1991年 | 28篇 |
1990年 | 24篇 |
1989年 | 22篇 |
1988年 | 14篇 |
1987年 | 18篇 |
1986年 | 26篇 |
1985年 | 30篇 |
1984年 | 46篇 |
1983年 | 15篇 |
1982年 | 22篇 |
1981年 | 21篇 |
1980年 | 28篇 |
1979年 | 36篇 |
1978年 | 25篇 |
1977年 | 18篇 |
1976年 | 20篇 |
1975年 | 23篇 |
1974年 | 13篇 |
1973年 | 7篇 |
1972年 | 12篇 |
排序方式: 共有1785条查询结果,搜索用时 15 毫秒
41.
Kiyoshi Ozawa Yoshio Sakka Muneyuki Amano 《Journal of Sol-Gel Science and Technology》2000,19(1-3):595-598
Cubic antimonic acid (Sb2O5·nH2O) films were successfully prepared on stainless steel and Si(100) substrates by electrophoretic deposition (EPD) using two types of sols. The sols were prepared by reacting an H2O2 aqueous solution with Sb(O-i-C3H7)3 or metallic Sb powder. The resulting films were found to consist of fine particles of cubic Sb2O5·nH2O single crystals with uniform particle sizes of 30 nm and 150 nm. The weight of the Sb2O5·nH2O deposit on the anode Si(100) substrate by EPD increased linearly with the current density in the range of 0–0.67 mA cm–2, when the sol pH was over 7. The proton conductivity of the polycrystalline Sb2O5·nH2O discs, formed from the two types of sols, was evaluated by an ac impedance method at room temperature under controlled levels of relative humidity. 相似文献
42.
Keiichi Satoh Zhang Xiang-Yu Masashi Miya-iri Akiko Honma Kiyoshi Sawada 《Monatshefte für Chemie / Chemical Monthly》2006,137(11):1375-1383
Summary. The ion-pair solvent extraction behavior of ethylenediaminetetraacetate (EDTA) anion by various tetraalkylammonium ions was investigated at 25.0 ± 0.1°C. The extraction of EDTA exceeded 90% from the basic aqueous solution into the organic solvents such as n-hexane and benzene derivatives containing tri-n-octylmethylammonium chloride, but EDTA was hardly extracted from acidic solution. Among the chemical species of EDTA in aqueous solution, edta
4− is the most extractable one. On the other hand, the extraction of EDTA was less than 1% into chloroform and 1,2-dichloroethane even from the basic aqueous solution. The effect of the structure
of alkylammonium ion was also examined. Tetra-n-hexylammonium and tetra-n-octylammonium ions could not extract EDTA even from the basic aqueous solution, while the use of tri-n-octylmethylammonium and di-n-lauryldimethylammonium ions enhances the extraction of EDTA. These results suggest that the steric hindrance in the ion-pair of alkylammonium and EDTA anion in the organic phase affects the extractability of EDTA containing ion-pair. The solution structure of ion-pair in the organic phase was calculated by MMFF force field and the steric
effect in the ion-pair was also suggested. From the extraction constants obtained, the possibility of the extraction separation
of EDTA has been shown.
Present address: Chemistry Department, Heilongjiang University, Harbin, China 相似文献
43.
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
44.
Kiyoshi Tanemura Yoko Nishida Tsuneo Suzuki Koko Satsumabayashi Takaaki Horaguchi 《Journal of heterocyclic chemistry》1997,34(2):457-460
1,3-Dithianes 1 , 1,3-dithiolanes 2 , and diphenyl dithioacetals 3 derived from cinnamaldehydes reacted with 2,3-dichloro-5,6-dicyano-p-benzoquinone in aqueous solvents to give benzaldehydes 4 . Hydride transfer from 1–3 to 2,3-dichloro-5,6-dicyano-p-benzoquinone followed by hydrolysis and oxidative carbon-carbon bond cleavage would produce benzaldehydes 4 . 相似文献
45.
Miyauchi M Hoshino T Yamaguchi H Kamitori S Harada A 《Journal of the American Chemical Society》2005,127(7):2034-2035
A [2]rotaxane capped by a beta-cyclodextrin and a 2,4,6-trinitrophenyl group has been prepared by dissolving 6-aminocinnamoyl beta-cyclodextrin in water with 1-adamantane carboxylic acid and complexation with alpha-cyclodextrin followed by the reaction with 2,4,6-trinitrobenzene sulfonic acid sodium salt. The [2]rotaxane has been found to form supramolecular polymers by host-guest interactions. 相似文献
46.
The reaction of lithium ester enolate with enones provides a challenge for chemoselectivity, that is, discrimination between a conjugate addition and a 1,2-addition. Asymmetric conjugate addition of a lithium enolate of alpha-trimethylsilanylacetate to acyclic and cyclic alpha,beta-unsaturated ketones was mediated by an external chiral ligand to give the corresponding 1,4-adducts in good enantioselectivity of 74% and good chemoselectivity. 相似文献
47.
Potentiometric stripping determination of Cd, Cu and Zn using a vibrating electrode (VE) is presented. A simple VE was constructed
by using a piezoelectric bimorph oscillator and an inexpensive graphite-reinforcement carbon (GRC) rod (a mechanical pencil).
Experimental results obtained with the simple VE follow the equation valid for quantitative application of potentiometric
stripping analysis (PSA) in large solutions. It was found that the GRC vibrating electrode is suitable for multielement trace
analysis of small samples of 0.05 mL. The relative standard deviations for divalent metals are better than 2%.
Received: 3 February 1997 / Revised: 2 June 1997 / Accepted: 7 June 1997 相似文献
48.
The synthesis and properties of novel anthracene-bridged porphyrin dimers having an oxomolybdenum(V) porphyrin unit, H(2)(DPA)[Mo(V)O(OMe)] (1) and (DPA)[Mo(V)O(OMe)][Zn(II)(MeOH)] (2), and the relevant monomer porphyrin complexes Mo(V)O(MPP)OMe (3) and Zn(II)(MPP) (4) are presented. An oxomolybdenum(V) unit was introduced into one of the two porphyrins in DPA to give 1, which has a free-base porphyrin unit. By introducing a zinc(II) ion to the free-base part, a mixed-metal complex of 2 was prepared and isolated. The structure of 2 was analyzed by X-ray crystallography (2.(7)/(6)CH(2)Cl(2), triclinic, P(-)1 (no. 2), a = 15.2854(12) A, b = 19.9640(15) A, c = 13.6915(12) A, alpha = 90.968(3), beta = 113.108(4), gamma = 96.501(4), Z = 2, R1 = 9.9, wR2 = 19.2). The structure of 2 demonstrated that a methanol is stably coordinated to the Zn(II) ion with the aid of a hydrogen bond to the methoxo ligand on the Mo(V) ion in the binding pocket of DPA. The electrochemical measurements of 2 suggested that the methanol was kept in the pocket of DPA in solution even at the reduced state of the molybdenum ion. 相似文献
49.
Arakawa M Hasegawa K Funatsu K 《Journal of chemical information and computer sciences》2003,43(5):1390-1395
Molecular alignment is an important step in three-dimensional quantitative structure-activity relationship (3D-QSAR) such as comparative molecular field analysis (CoMFA). A reasonable molecular alignment is necessary for building a 3D-QSAR model. In this paper, a novel method for molecular alignment using the Hopfield Neural Network (HNN) is introduced. Four kinds of chemical properties are assigned to each atom of a molecule. Then, those properties between two molecules correspond to each other using HNN. To validate our method, HNN was applied to 12 pairs of enzyme inhibitors cited from the Protein Data Bank (PDB). As a result, our method could successfully reproduce the real molecular alignments obtained from X-ray crystallography. 相似文献
50.
A simple, accurate and reproducible reversed-phase high-performance liquid chromatography (HPLC) method was developed for the separation and characterisation of alkylphenols (APs) and alkylphenol polyethoxylates (APEOs), using a C18 octadecyl silica (ODS) column. APs and each APEO oligomer were separated successfully within a reasonable time without gradient elution. An excellent resolution was obtained, even for mixtures of APs and low EO number APEOs, which are otherwise difficult to separate using conventional normal-phase HPLC methods. This method, combined with solid-phase extraction, was highly applicable for the simultaneous determination of alkylphenols and alkylphenol ethoxylates in real samples. 相似文献