全文获取类型
收费全文 | 947篇 |
免费 | 42篇 |
专业分类
化学 | 744篇 |
晶体学 | 21篇 |
力学 | 13篇 |
数学 | 63篇 |
物理学 | 148篇 |
出版年
2023年 | 8篇 |
2022年 | 21篇 |
2021年 | 27篇 |
2020年 | 32篇 |
2019年 | 41篇 |
2018年 | 40篇 |
2017年 | 30篇 |
2016年 | 51篇 |
2015年 | 34篇 |
2014年 | 59篇 |
2013年 | 62篇 |
2012年 | 80篇 |
2011年 | 95篇 |
2010年 | 36篇 |
2009年 | 37篇 |
2008年 | 50篇 |
2007年 | 41篇 |
2006年 | 23篇 |
2005年 | 28篇 |
2004年 | 23篇 |
2003年 | 16篇 |
2002年 | 14篇 |
2001年 | 5篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1995年 | 9篇 |
1991年 | 6篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1987年 | 5篇 |
1985年 | 7篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1976年 | 6篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1971年 | 2篇 |
1969年 | 2篇 |
1968年 | 4篇 |
1967年 | 3篇 |
1964年 | 2篇 |
1962年 | 2篇 |
1961年 | 5篇 |
排序方式: 共有989条查询结果,搜索用时 15 毫秒
11.
A new sphingolipid, (2S,3R,4E)-1,3-dihydroxy-2-[(nonadecanoyl) amino]-octadec-4-ene (1) along with ubiquitous batyl alcohol is isolated from the gorgonian, Junceella juncea Pallas (Gorgonaceae) of the Indian Ocean. The structure of 1 is determined on the basis of 1H- and 13C-NMR, COSY, FABMS, and GC-EIMS experiments. 相似文献
12.
Cobalt(II) reacts instantaneously with the reagent at pH 5.0. The yellow complex has a molar absorptivity of 1.1 × 104 1 mol?1 cm?1. The method is applied to the determination of cobalt in steels after removal of iron with phosphate. 相似文献
13.
A simple, sensitive and selective Spectrophotometric method has been developed for the determination of cobalt using indane 1,2,3-trionetrioxime (ITT): The method is based on the colour reaction between ITT and cobalt(II) in sodium acetate-acetic acid buffer (pH 4.5–7.5) medium. The calibration graph for measurement at 320 nm is linear in the range 1.18–23.60g of cobalt per 25 ml, with molar absorptivity of 5.32×1041mol–1 cm–1. The effect of interfering ions has been studied and the method was applied to the determination of cobalt in alloys, with good results. 相似文献
14.
Chary KV Sagar GV Naresh D Seela KK Sridhar B 《The journal of physical chemistry. B》2005,109(19):9437-9444
A series of copper catalysts supported on TiO2-ZrO2 with copper loading varying from 1.0 to 21.6 wt % were prepared by a wet impregnation method. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy, electron spin resonance (ESR), temperature programmed reduction (TPR), and Brunauer-Emmett-Teller specific surface area measurements. Copper dispersion and metal area were determined by N2O decomposition by the passivation method. XRD results suggest that the copper oxide is present in a highly dispersed amorphous state at copper loadings <16.8 wt % in the sample and as a crystalline CuO phase at higher Cu loadings. Copper dispersion increases with Cu loading up to 5.1 wt % and levels off at higher loadings. The XPS peak intensity ratios of Cu 2p(3/2)/Ti 2p(3/2) and Cu 2p(3/2)/Zr 3d(5/2) were compared with the copper dispersion calculated from N2O decomposition. ESR results suggest the presence of two types of copper species on the TiO2-ZrO2 support. TPR profiles reveal the presence of highly dispersed copper oxide at lower temperatures and bulk CuO at higher temperatures. The catalytic properties were evaluated for the vapor-phase dehydrogenation of cyclohexanol to cyclohexanone and related to the dispersion of Cu on TiO2-ZrO2. 相似文献
15.
Mohamed Ariff Md. Jainuddin V. Gopalan K. Venkata Rao 《Journal of polymer science. Part A, Polymer chemistry》1985,23(7):2063-2071
The polymerization of acrylonitrile initiated by an ascorbic acid–peroxodisulfate redox system was studied in an aqueous solution at 35°C in the presence of air. Molecular oxygen was found to have no effect on the polymerization reaction. An increase in ionic strength slightly increased the rate. The overall rate of polymerization, Rp, showed a square dependence on [monomer] and a half-order dependence on [peroxodisulfate]. A first-order dependence on [ascorbic acid] at low concentrations (<3.0 × 10?3 mol L?1) followed by a decrease in Rp at higher concentrations of ascorbic acid (>3.0 × 10?3 mol L?1) was also noted. Rp remained unchanged up to 40°C and showed a decline thereafter. Addition of catalytic amounts of cupric ions decreased the rate whereas ferric ions were found to increase the rate. Added sulfuric acid in the range (6.0?50.0) × 10?5 mol L?1 decreased the Rp. 相似文献
16.
On-line preconcentration on a chelating resin (Dowex A-1) and elution with 0.1 M hydorchloric acid is followed by spectrophotometry based on the metal complexes formed with 1- (2-hydroxy-4-diethylamino-1-phenylazo)-2-hydroxynaphthalene-3,6-disulfonic acid. The total concentration of calcium and magnesium is determined; in a second sample, calcium is masked with a ligand buffer containing excess of barium(II) and EGTA, and magnesium is determined. The calcium concentration is measured by difference. Magnesium (1–30 μg l?1 and calcium (8– 10 μg l?1) in 2.5 M sodium chloride can be determined. Calcium and magnesium in analytical reagent-grade sodium chloride and potassium chloride and primary standard sodium chloride are aslo determined. The method based on the exchange between calcium ions and Mg(EDTA) is proposed to enchance the sensitivity for calcium. 相似文献
17.
Bassil BS Nellutla S Kortz U Stowe AC van Tol J Dalal NS Keita B Nadjo L 《Inorganic chemistry》2005,44(8):2659-2665
The 15-cobalt-substituted polyoxotungstate [Co(6)(H(2)O)(30){Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}](5-) (1) has been characterized by single-crystal XRD, elemental analysis, IR, electrochemistry, magnetic measurements, and EPR. Single-crystal X-ray analysis was carried out on Na(5)[Co(6)(H(2)O)(30){Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}].37H(2)O, which crystallizes in the hexagonal system, space group P6(3)/m, with a = 19.8754(17) A, b = 19.8754(17) A, c = 22.344(4) A, alpha= 90 degrees, beta = 90 degrees, gamma = 120 degrees, and Z = 2. The trimeric polyanion 1 has a core of nine Co(II) ions encapsulated by three unprecedented (beta-SiW(8)O(31)) fragments and two Cl(-) ligands. This central assembly {Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}(17-) is surrounded by six antenna-like Co(II)(H(2)O)(5) groups resulting in the satellite-like structure 1. Synthesis of 1 is accomplished in a simple one-pot procedure by interaction of Co(II) ions with [gamma-SiW(10)O(36)](8-) in aqueous, acidic NaCl medium (pH 5.4). Polyanion 1 was studied by cyclic voltammetry as a function of pH. The current intensity of its Co(II) centers was compared with that of free Co(II) in solution. Our results suggest that 1 keeps its integrity in solution. Magnetic susceptibility results show the presence of both antiferro- and ferromagnetic coupling within the (Co(II))(9) core. A fully anisotropic Ising model has been employed to describe the exchange-coupling and yields g = 2.42 +/- 0.01, J(1) = 17.0 +/- 1.5 cm(-1), and J(2) = -13 +/- 1 cm(-(1). Variable frequency EPR studies reveal an anisotropic Kramer's doublet. 相似文献
18.
19.
The glucose‐, mannose‐, and galactose‐derived spirocyclic cyclopropylammonium chlorides 1a – 1d, 2a – 2d and 3a – 3d were prepared as potential glycosidase inhibitors. Cyclopropanation of the diazirine 5 with ethyl acrylate led in 71% yield to a 4 : 5 : 1 : 20 mixture of the ethyl cyclopropanecarboxylates 7a – 7d , while the Cu‐catalysed cycloaddition of ethyl diazoacetate to the exo‐glycal 6 afforded 7a – 7d (6 : 2 : 5 : 3) in 93–98% yield (Scheme 1). Saponification, Curtius degradation, and subsequent addition of BnOH or t‐BuOH led in 60–80% overall yield to the Z‐ or Boc‐carbamates 11a – 11d and 12a – 12d , respectively. Hydrogenolysis of 11a – 11d afforded 1a – 1d , while 12a – 12d was debenzylated to 13a – 13d prior to acidic cleavage of the N‐Boc group. The manno‐ and galacto‐isomers 2a – 2d and 3a – 3d , respectively, were similarly obtained in comparable yields (Schemes 2 and 4). Also prepared were the differentially protected manno‐configured esters 24a – 24d ; they are intermediates for the synthesis of analogous N‐acetylglucosamine‐derived cyclopropanes (Scheme 3). The cyclopropylammonium chlorides 1a – 1d, 2a – 2d and 3a – 3d are very weak inhibitors of several glycosidases (Tables 1 and 2). Traces of Pd compounds, however, generated upon catalytic debenzylation, proved to be strong inhibitors. PdCl is, indeed, a reversible, micromolar inhibitor for the β‐glucosidases from C. saccharolyticum and sweet almonds (non‐competitive), the β‐galactosidases from bovine liver and from E. coli (both non‐competitive), the α‐galactosidase from Aspergillus niger (competitive), and an irreversible inhibitor of the α‐glucosidase from yeast and the α‐galactosidase from coffee beans. The cyclopropylamines derived from 1a – 1d or 3a – 3d significantly enhance the inhibition of the β‐glucosidase from C. saccharolyticum by PdCl , lowering the Ki value from 40 μM (PdCl ) to 0.5 μM for a 1 : 1 mixture of PdCl and 1d . A similar effect is shown by cyclopropylamine, but not by several other amines. 相似文献
20.
Salicylaldehyde thiosemicarbazone instantaneously forms a green complex with copper(II) in the optimum pH range 5–7. A fivefold molar excess of the reagent is sufficient for the full development of the color. Beer's law is obeyed in the range 0.5–6.0 ppm of copper. The optimum concentration range as evaluated by Ringbom's method is 1.4–5.8 ppm. At 375 nm the sensitivity of the reaction and the molar absorptivity are 0.006 μg cm?2 and 9.2 × 103 liters mol?1 cm?1, respectively. The effects of pH, reagent concentration, time, order of addition of the solutions, and the interference of various ions were investigated. Copper in plant samples, containing zinc, iron, and manganese, was determined. 相似文献