全文获取类型
收费全文 | 3517篇 |
免费 | 210篇 |
国内免费 | 17篇 |
专业分类
化学 | 2476篇 |
晶体学 | 14篇 |
力学 | 78篇 |
数学 | 605篇 |
物理学 | 571篇 |
出版年
2023年 | 29篇 |
2022年 | 36篇 |
2021年 | 61篇 |
2020年 | 79篇 |
2019年 | 78篇 |
2018年 | 70篇 |
2017年 | 77篇 |
2016年 | 178篇 |
2015年 | 139篇 |
2014年 | 127篇 |
2013年 | 227篇 |
2012年 | 272篇 |
2011年 | 287篇 |
2010年 | 166篇 |
2009年 | 118篇 |
2008年 | 232篇 |
2007年 | 195篇 |
2006年 | 164篇 |
2005年 | 170篇 |
2004年 | 152篇 |
2003年 | 138篇 |
2002年 | 125篇 |
2001年 | 40篇 |
2000年 | 30篇 |
1999年 | 39篇 |
1998年 | 37篇 |
1997年 | 26篇 |
1996年 | 38篇 |
1995年 | 12篇 |
1994年 | 21篇 |
1993年 | 28篇 |
1992年 | 18篇 |
1991年 | 17篇 |
1990年 | 17篇 |
1989年 | 11篇 |
1988年 | 18篇 |
1987年 | 14篇 |
1986年 | 14篇 |
1985年 | 32篇 |
1984年 | 26篇 |
1983年 | 11篇 |
1982年 | 16篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1979年 | 21篇 |
1978年 | 12篇 |
1977年 | 14篇 |
1975年 | 11篇 |
1974年 | 15篇 |
1973年 | 13篇 |
排序方式: 共有3744条查询结果,搜索用时 15 毫秒
191.
Klaus Bieger Miguel Tomás José Barluenga Rafael Santiago Santiago García-Granda 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract The title compound is the main product of the 2:1 reaction of DMAD with diazaphosphinines. The supposed mechanisms with intermediates and related products will be presented. 相似文献
192.
Agnes M Modro Tom A Modro P. Bernatowicz Wojciech Schilf Lech Stefaniak 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract A series of phosphoric amidodiesters, diamidoesters and triamides was prepared and their 31P and15 N NMR spectra were recorded in order to evaluate the major structural factors that determine the chemical shifts and coupling contants values. Considering the equation expressing the structural effects on shielding[1]. 相似文献
193.
Tomáš Bříza Martin Havlík Bohumil Dolenský Zdeněk Kejík Pavel Martásek 《Supramolecular chemistry》2013,25(3):237-242
Highly functionalized fluorinated porphyrins were synthesized by a convergent strategy. Nucleophilic substitution using fluorinated branched unit and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin afforded highly functionalized fluorinated porphyrin 8 containing 24 fluorinated chains in the peripheral region. 相似文献
194.
Fabian Benz Christoph Roderburg David Vargas Cardenas Mihael Vucur Jérémie Gautheron Alexander Koch Henning Zimmermann J?rn Janssen Lukas Nieuwenhuijsen Mark Luedde Norbert Frey Frank Tacke Christian Trautwein Tom Luedde 《Experimental & molecular medicine》2013,45(9):e42
MicroRNA (miRNA) levels in serum have recently emerged as potential novel biomarkers for various diseases. miRNAs are routinely measured by standard quantitative real-time PCR (qPCR); however, the high sensitivity of qPCR demands appropriate normalization to correct for nonbiological variation. Presently, RNU6B (U6) is used for data normalization of circulating miRNAs in many studies. However, it was suggested that serum levels of U6 themselves might differ between individuals. Therefore, no consensus has been reached on the best normalization strategy in ‘circulating miRNA''. We analyzed U6 levels as well as levels of spiked-in SV40-RNA in sera of 44 healthy volunteers, 203 intensive care unit patients and 64 patients with liver fibrosis. Levels of U6 demonstrated a high variability in sera of healthy donors, patients with critical illness and liver fibrosis. This high variability could also be confirmed in sera of mice after the cecal ligation and puncture procedure. Most importantly, levels of circulating U6 were significantly upregulated in sera of patients with critical illness and sepsis compared with controls and correlated with established markers of inflammation. In patients with liver fibrosis, U6 levels were significantly downregulated. In contrast, levels of spiked-in SV40 displayed a significantly higher stability both in human cohorts (healthy, critical illness, liver fibrosis) and in mice. Thus, we conclude that U6 levels in the serum are dysregulated in a disease-specific manner. Therefore, U6 should not be used for data normalization of circulating miRNAs in inflammatory diseases and previous studies using this approach should be interpreted with caution. Further studies are warranted to identify specific regulatory processes of U6 levels in sepsis and liver fibrosis. 相似文献
195.
Martin T. Palou Ľubomír Bágeľ Vladimír Živica Marta Kuliffayová Tomáš Ifka 《Journal of Thermal Analysis and Calorimetry》2013,113(1):385-394
Various hydrothermal curing regimes were used to investigate the hydration and physical characteristics of two kinds of inorganic binder composites: high alumina cement–silica fume–Portland cement and high alumina cement–silica fume–sodium polyphosphate. Simultaneous thermal analysis (DTA and TG) was used to identify temperature ranges of thermal decomposition of cured samples and to characterize the nature of hydrate products. Two kinds of products are formed. The first ones consist of C3AH6, AH3, calcium carbonate (C–C) as a product of carbonation, and C3AH1.5 resulted from the partial decomposition of C3AH6 under higher hydrothermal pressure. The second ones are the products formed by acid–base reaction between monocalcium aluminate and sodium polyphosphate to form NaCaPO4·xH2O and Al2O3·xH2O that could convert to chemically bonded ceramic binders like hydroxyapatite (Ca5(PO4)3OH) and gibbsite (Al(OH)3). These two hydroceramic products formed under these conditions act also as binder and could be useful as cement binders for the protection of petroleum, gas, or geothermal wells. Mercury intrusion porosimeter was used for the estimation of the pore structure parameters of the composites. It turned up that longer curing time coupled with higher hydrothermal pressure has improved the pore structure of the first composite, while that of the second has remained unchanged. 相似文献
196.
197.
Giovanni Bottari Claudia Dammann Tomás Torres Thomas Drewello 《Journal of the American Society for Mass Spectrometry》2013,24(9):1413-1419
Two novel monofunctionalized fulleropyrrolidine derivatives (Prato adducts) were prepared and characterized by matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI). MALDI experiments conducted in the positive-ion mode on pure and mixed samples of both monofunctionalized fullerene derivatives revealed the efficient formation of bisadducts (in the case of the pure samples) and mixed bisadducts (in the case of a mixed sample). Bisadducts were not observed in the ESI experiments and thus not present in the sample. A mechanism for the MALDI formation of these bisadduct ions is proposed in which an azomethine ylide fragment is formed in situ from the monofunctionalized fulleropyrrolidine species upon laser irradiation. This fragment, which can survive as an intact moiety in the gas phase in the special environment provided by the MALDI experiment, is then able to attach to a fulleropyrrolidine monoadduct which acts as a dipolarophile, thus leading to the formation of a bisadduct fullerene derivative. The unprecedented re-attachment of the azomethine ylide implies that the establishment of the ligand attainment of Prato adducts based on MALDI analysis alone can lead to wrong assignments. Figure
? 相似文献
198.
Roberto Terzano Matthias Alfeld Koen Janssens Bart Vekemans Tom Schoonjans Laszlo Vincze Nicola Tomasi Roberto Pinton Stefano Cesco 《Analytical and bioanalytical chemistry》2013,405(10):3341-3350
Iron (Fe) is an essential element for plant growth and development; hence determining Fe distribution and concentration inside plant organs at the microscopic level is of great relevance to better understand its metabolism and bioavailability through the food chain. Among the available microanalytical techniques, synchrotron μ-XRF methods can provide a powerful and versatile array of analytical tools to study Fe distribution within plant samples. In the last years, the implementation of new algorithms and detection technologies has opened the way to more accurate (semi)quantitative analyses of complex matrices like plant materials. In this paper, for the first time the distribution of Fe within tomato roots has been imaged and quantified by means of confocal μ-XRF and exploiting a recently developed fundamental parameter-based algorithm. With this approach, Fe concentrations ranging from few hundreds of ppb to several hundreds of ppm can be determined at the microscopic level without cutting sections. Furthermore, Fe (semi)quantitative distribution maps were obtained for the first time by using two opposing detectors to collect simultaneously the XRF radiation emerging from both sides of an intact cucumber leaf. Figure
Elemental distribution maps within intact tomato roots as determined by confocal micro X‐ray fluorescence 相似文献
199.
Robert Jirásko Tomáš Mikysek Vitaliy Chagovets Ivan Vokřál Michal Holčapek 《Analytical and bioanalytical chemistry》2013,405(23):7181-7193
Ultrahigh-performance liquid chromatography coupled with high-mass-accuracy tandem mass spectrometry (UHPLC–MS–MS) has been used for elucidation of the structures of oxidation products of atorvastatin (AT), one of the most popular commercially available drugs. The purpose of the study was identification of AT metabolites in rat hepatocytes and comparison with electrochemically generated oxidation products. AT was incubated with rat hepatocytes for 24 h. Electrochemical oxidation of AT was performed by use of a three-electrode off-line system with a glassy carbon working electrode. Three supporting electrolytes (0.1 mol L?1 H2SO4, 0.1 mol L?1 HCl, and 0.1 mol L?1 NaCl) were tested, and dependence on pH was also investigated. AT undergoes oxidation by a single irreversible process at approximately +1.0 V vs. Ag/AgCl electrode. The results obtained revealed a simple and relatively fast way of determining the type of oxidation and its position, on the basis of characteristic neutral losses (NLs) and fragment ions. Unfortunately, different products were obtained by electrochemical oxidation and biotransformation of AT. High-mass-accuracy measurement combined with different UHPLC–MS–MS scans, for example reconstructed ion-current chromatograms, constant neutral loss chromatograms, or exact mass filtering, enable rapid identification of drug-related compounds. β-Oxidation, aromatic hydroxylation of the phenylaminocarbonyl group, sulfation, AT lactone and glycol formation were observed in rat biotransformation samples. In contrast, a variety of oxidation reactions on the conjugated skeleton of isopropyl substituent of AT were identified as products of electrolysis. Figure
Chemical structure of atorvastatin (AT) composed of four main parts assigned as A, B, C and D including the list of identified oxidation reactions for both electrochemical and in vitro experiments 相似文献
200.
Tomáš Křížek Veronika Doubnerová Helena Ryšlavá Pavel Coufal Zuzana Bosáková 《Analytical and bioanalytical chemistry》2013,405(8):2425-2434
Enzyme assays of β-N-acetylhexosaminidase from Aspergillus oryzae using capillary electrophoresis in the offline and online setup have been developed. The pH value and concentration of the borate-based background electrolyte were optimized in order to achieve baseline separation of N,N′,N″-triacetylchitotriose, N,N′-diacetylchitobiose, and N-acetyl-d-glucosamine. The optimized method using 25 mM tetraborate buffer, pH 10.0, was evaluated in terms of repeatability, limits of detection, quantification, and linearity. The method was successfully applied to the offline enzyme assay of β-N-acetylhexosaminidase, which was demonstrated by monitoring the hydrolysis of N,N′,N″-triacetylchitotriose. The presented method was also utilized to study the pH dependence of enzyme activity. An online assay with N,N′-diacetylchitobiose as a substrate was developed using the Transverse Diffusion of Laminar Flow Profiles model to optimize the injection sequence and in-capillary mixing of substrate and enzyme plugs. The experimental results were in good agreement with predictions of the model. The online assay was successfully used to observe the inhibition effect of N,N′-dimethylformamide on the activity of β-N-acetylhexosaminidase with nanoliter volumes of reagents used per run and a high degree of automation. After adjustment of background electrolyte pH, an online assay with N,N′,N″-triacetylchitotriose as a substrate was also performed. Figure
Electropherograms resulting from online enzyme assays of β-N-acetylhexosaminidase for chitobiose as a substrate with 10-min (red line), 5-min (blue line) and 0-min (black line) reaction time. Peak identification: 1 chitobiose, 2 N-acetylglucosamine 相似文献