全文获取类型
收费全文 | 2086篇 |
免费 | 103篇 |
国内免费 | 15篇 |
专业分类
化学 | 1747篇 |
晶体学 | 10篇 |
力学 | 28篇 |
数学 | 195篇 |
物理学 | 224篇 |
出版年
2024年 | 2篇 |
2023年 | 36篇 |
2022年 | 109篇 |
2021年 | 98篇 |
2020年 | 77篇 |
2019年 | 80篇 |
2018年 | 53篇 |
2017年 | 43篇 |
2016年 | 116篇 |
2015年 | 103篇 |
2014年 | 78篇 |
2013年 | 133篇 |
2012年 | 169篇 |
2011年 | 190篇 |
2010年 | 113篇 |
2009年 | 85篇 |
2008年 | 109篇 |
2007年 | 107篇 |
2006年 | 99篇 |
2005年 | 86篇 |
2004年 | 65篇 |
2003年 | 57篇 |
2002年 | 45篇 |
2001年 | 11篇 |
2000年 | 13篇 |
1999年 | 8篇 |
1998年 | 9篇 |
1997年 | 4篇 |
1996年 | 8篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 7篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1983年 | 7篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1925年 | 1篇 |
1924年 | 1篇 |
排序方式: 共有2204条查询结果,搜索用时 0 毫秒
61.
Abbas Pardakhty Mehdi Ranjbar Mohammad Hasan Moshafi Sara Abbasloo 《Journal of Cluster Science》2018,29(6):1061-1068
In this work we synthesized ZnO/CuO nanostructures pegylated by simple and fast microwave method assistant reverse micelles, Reverse micelles protocol creates many advantages in stability, particle size control, morphology, density, loading level, distribution, uniformity, charge and purification. Based on the statistical results ZnO/CuO nanostructures placed in the hydrophilic substrate. The effect of microwave and concentration of surfactant on the surface area, pore diameter and pore volume of the final product was systematically studied using Taguchi technique. ZnO/CuO core/shell pegylated nanostructures, indicating a ZnO as core and CuO as shell and continuous micelles chains around this structures. Products were characterized by UV–Vis spectra, X-ray diffraction, scanning electron microscopy, Dynamic light scattering, Energy-dispersive X-ray spectroscopy, transmission electron microscopy and nitrogen adsorption (i.e. Brunauer–Emmett–Teller surface area analysis). 相似文献
62.
Yeast cell wall particles: a promising class of nature-inspired microcarriers for multimodal imaging
Figueiredo S Moreira JN Geraldes CF Rizzitelli S Aime S Terreno E 《Chemical communications (Cambridge, England)》2011,47(38):10635-10637
This communication demonstrates that yeast cell wall particles (YCWPs) are a promising class of nature-inspired biocompatible microcarriers for the delivery of amphipathic/lipophilic imaging reporters. When a paramagnetic MRI agent is loaded, the longitudinal relaxivity per particle at 0.5 T is the highest ever reported for Gd-based systems. 相似文献
63.
Sara Chumillas Carlos Busó-Rogero José Solla-Gullón Francisco J. Vidal-Iglesias Enrique Herrero Juan M. Feliu 《Electrochemistry communications》2011,13(11):1194-1197
Formic acid and ethanol oxidations on spherical platinum nanoparticles dispersed on carbon with different loadings have been studied. The increasing loading of the catalyst leads to a lower diffusion flux of reactants in the internal parts of the catalyst layer, resulting in a lower apparent activity. In some cases, as in ethanol oxidation, it may also affect the diffusion of the products. As a practical consequence, the structure of the supporting layer and the catalyst loading should be optimized so that the maximum catalyst utilization is obtained. Finally, these diffusion effects may mask some important catalytic activity increase of the nanoparticles. In the case of formic acid, a significant increase in the activity is obtained for very small nanoparticles. 相似文献
64.
A triazolyl-di-ylidene ligand has been used for the preparation of a homodimetallic complex of gold, and a heterodimetallic compound of gold and iridium. Both complexes have been fully characterized and their molecular structures have been determined by means of X-ray diffraction. The catalytic properties of these two complexes have been evaluated in the reduction of nitroarenes by transfer hydrogenation using primary alcohols. The two complexes afford different reaction products; whereas the Au(I)-Au(I) catalyst yields a hydroxylamine, the Ir(III)-Au(I) complex facilitates the formation of an imine. 相似文献
65.
Sara TunstallDulasiri Amarasiriwardena 《Microchemical Journal》2002,73(3):335-347
Ingestion of relatively small amounts of lead is now recognized to cause significant neurological and cognitive effects in humans. Large quantities may be fatal, yet lead poisoning, especially of children, is still a major public health concern in many parts of the world. In rural Mexican communities lead oxide (PbO) is added to ceramic glaze as a fluxing agent, lowering starting firing temperatures to 500 °C. The purpose of this study is to characterize the lead chemical forms in ceramic glazes from the Solis Valley, Mexico, to investigate lead leaching properties of these ceramics, and to demonstrate the applicability of lead isotope signatures as a means of tracing lead source origins. Ceramics were collected from the rural village of Santa Maria de Canchesda, State of Mexico, Mexico. Dried liquid glazes, post-fired glaze material, and pure PbO were analyzed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). Results from DRIFT analysis indicate that PbO (1429 cm−1 band) is the active form of lead found in liquid glazes and ceramics. Some shifting of 1429 cm−1 PbO peak to lower wavenumbers occurs in post-fired ceramics, and this may be due to the formation of lead bisilicate during firing. Ceramics samples were leached in 0.02 M citric acid solution for 1 min, and leached lead concentrations were measured using inductively coupled plasma-mass spectrometry (ICP-MS). Lead concentrations in these leachates varied from 0.4-80.4 μg ml−1, while the control pottery from the US leached only 0.1 μg ml−1 lead. Elemental distributions on glaze surfaces were identified by laser ablation (LA)-ICP-MS. Nitric acid extracts of soils, teeth, and ceramic glazes were analyzed for lead isotope ratios (207Pb/206Pb vs. 208Pb/206Pb) using ICP-MS. Similarities of tooth and ceramic lead isotope ratios indicate that ceramics may be a substantial source of body lead burden in the Solis Valley. This study demonstrates the applicability of lead isotope ratios for lead source identification, and it identifies potential health risks from ceramic use induced lead toxicity within the Solis Valley. 相似文献
66.
Nucleophilic addition of the peroxynitrite anion, ONOO(-), to the two prototypical carbonyl compounds, acetaldehyde and acetone, was investigated in the pH interval 7.4-14. The process is initiated by fast equilibration between the reactants and the corresponding tetrahedral adduct anion, the equilibrium being strongly shifted to the reactant side. The adduct anion also undergoes fast protonation by water and added buffers. Consequently, the rate of the bimolecular reaction between ONOO(-) and the carbonyl is strongly dependent on the pH and on the concentration of the buffer. The pK(a) of the carbonyl-ONOO adduct was estimated to be approximately 11.8 and approximately 12.3 for acetone and acetaldehyde, respectively. It is shown that both the anionic and the neutral adducts suffer fast homolysis along the weak O-O bond to yield free alkoxyl and nitrogen dioxide radicals. The yield of free radicals was determined to be about 15% with both carbonyl compounds at low and high pH, while the remainder collapses to molecular products in the solvent cage. The rate constants for the homolysis of the adducts vary from ca. 3 x 10(5) to ca. 5 x 10(6) s(-1), suggesting that they cannot act as oxidants in biological systems. This small variation around a mean value of about 10(6) s(-1) suggests that the O-O bond in the adduct is rather insensitive to its protonation state and to the nature of its carbonyl precursor. An overall reaction scheme was proposed, and all the corresponding rate constants were evaluated. Finally, thermokinetic considerations were employed to argue that the formation of dioxirane as an intermediate in the reaction of ONOO(-) with acetone is an unlikely process. 相似文献
67.
Massimo Chessa Mario Panebianco Sara Corbu Milena Lussu Angelica Dessì Roberta Pintus Flaminia Cesare Marincola Vassilios Fanos 《Molecules (Basel, Switzerland)》2021,26(14)
Bicuspid aortic valve (BAV) is the most common congenital heart defect responsible for valvular and aortic complications in affected patients. Causes and mechanisms of this pathology are still elusive and thus the lack of early detection biomarkers leads to challenges in its diagnosis and prevention of associated cardiovascular anomalies. The aim of this study was to explore the potential use of urine Nuclear Magnetic Resonance (NMR) metabolomics to evaluate a molecular fingerprint of BAV. Both multivariate and univariate statistical analyses were performed to compare the urinary metabolome of 20 patients with BAV with that of 24 matched controls. Orthogonal partial least squared discriminant analysis (OPLS-DA) showed statistically significant discrimination between cases and controls, suggesting seven metabolites (3-hydroxybutyrate, alanine, betaine, creatine, glycine, hippurate, and taurine) as potential biomarkers. Among these, glycine, hippurate and taurine individually displayed medium sensitivity and specificity by receiver operating characteristic (ROC) analysis. Pathway analysis indicated two metabolic pathways likely perturbed in BAV subjects. Possible contributions of gut microbiota activity and energy imbalance are also discussed. These results constitute encouraging preliminary findings in favor of the use of urine-based metabolomics for early diagnosis of BAV. 相似文献
68.
69.
Samskog J Bergström SK Jönsson M Klett O Wetterhall M Markides KE 《Electrophoresis》2003,24(11):1723-1729
A method for coupling an electrophoretic driven separation to a liquid flow, using conventional fused-silica capillaries and a soft polymeric interface is presented. A novel design of the electrode providing high voltage to the electrophoretic separation was also developed. The electrode consisted of a conductive polyimide/graphite imbedded coating immobilized onto the capillary electrophoresis (CE) column inlet. This integrated electrode gave the same separation performance as a commonly used platinum electrode. The on-column electrode also showed good electrochemical stability in chronoamperometric experiments. In addition, with this electrode design, the electrode position relative to the inlet end of the CE column will always be constant and well defined. The on-line flow injection analysis (FIA)-CE system was used with electrospray ionization (ESI)-time of flight (TOF)-mass spectrometry detection. The preparation of the PDMS (poly(dimethylsiloxane)) interface for FIA-CE is described in detail and used for initial tests of the on-column polymer-imbedded graphite inlet electrode. In this interface, a pressure-driven liquid flow, a make up CE electrolyte and a CE column inlet meet in a two-level cross (95 microm ID) in the PDMS structure, enabling independent flow characterization. 相似文献
70.
Kittaka A Kurihara M Peleg S Suhara Y Takayama H 《Chemical & pharmaceutical bulletin》2003,51(3):357-358
Hereditary vitamin D-resistant rickets (HVDRR) is a genetic disorder caused by mutations in the vitamin D receptor, which lead to resistance to 1alpha,25-dihydroxyvitamin D(3) [1alpha,25(OH)(2)D(3)]. We found that the A ring-modified analogues, 2alpha-(3-hydroxypropyl)- and 2alpha-(3-hydroxypropoxy)-1alpha,25(OH)(2)D(3), (O1C3 and O2C3) can bind better than the natural hormone to the mutant VDR (R274A), which similar to the HVDRR mutant, R274L, had lost the hydrogen bond to the 1alpha-hydroxyl group of 1alpha,25(OH)(2)D(3). 相似文献