全文获取类型
收费全文 | 2501篇 |
免费 | 85篇 |
国内免费 | 19篇 |
专业分类
化学 | 1785篇 |
晶体学 | 19篇 |
力学 | 20篇 |
数学 | 366篇 |
物理学 | 415篇 |
出版年
2023年 | 14篇 |
2022年 | 38篇 |
2021年 | 49篇 |
2020年 | 57篇 |
2019年 | 68篇 |
2018年 | 53篇 |
2017年 | 54篇 |
2016年 | 107篇 |
2015年 | 84篇 |
2014年 | 109篇 |
2013年 | 176篇 |
2012年 | 175篇 |
2011年 | 220篇 |
2010年 | 128篇 |
2009年 | 111篇 |
2008年 | 165篇 |
2007年 | 145篇 |
2006年 | 137篇 |
2005年 | 95篇 |
2004年 | 94篇 |
2003年 | 63篇 |
2002年 | 64篇 |
2001年 | 28篇 |
2000年 | 22篇 |
1999年 | 21篇 |
1998年 | 26篇 |
1997年 | 18篇 |
1996年 | 24篇 |
1995年 | 16篇 |
1994年 | 8篇 |
1993年 | 20篇 |
1992年 | 12篇 |
1991年 | 13篇 |
1990年 | 8篇 |
1989年 | 9篇 |
1988年 | 7篇 |
1987年 | 18篇 |
1986年 | 8篇 |
1985年 | 10篇 |
1984年 | 5篇 |
1983年 | 7篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1977年 | 6篇 |
1975年 | 8篇 |
1973年 | 5篇 |
1970年 | 5篇 |
1966年 | 6篇 |
1958年 | 6篇 |
1955年 | 9篇 |
排序方式: 共有2605条查询结果,搜索用时 15 毫秒
971.
An interlaboratory study in 12 laboratories was performed to prove the validation of the ELISA method developed for the quantitative determination of mustard protein in foods. The ELISA kit used for this study is based on rabbit polyclonal antibody. This kit did not produce any false-positive results or cross-reactivity with in-house validation for a broad range of food matrixes with no detectable mustard protein. All participants obtained the Mustard ELISA kit with standard operational procedures, a list of samples, samples, and a protocol for recording test results. The study included 15 food samples and two spiked samples. Seven food matrix samples of zero mustard content and four samples with mustard declared as an ingredient showed mustard protein content lower than that of the first standard (0.42 mg/kg). Four samples with mustard declared as an ingredient revealed mustard protein content above 12.5 mg/kg (the highest standard). The statistical tests (Cochran, Dixon, and Mandel) and analysis of variance were used to evaluate the interlaboratory study results. Repeatability and reproducibility limits, as well as an LOQ (1.8 mg mustard proteins/kg) and LOD (0.5 mg mustard proteins/kg), for the kit were calculated. 相似文献
972.
Duchácková L Roithová J Milko P Zabka J Tsierkezos N Schröder D 《Inorganic chemistry》2011,50(3):771-782
Mono- and binuclear complexes of N,N-dimethylformamide (DMF) with chlorides of the divalent, late 3d metals M = Co, Ni, Cu, and Zn are investigated by means of electrospray ionization (ESI). Specifically, ESI leads to monocations of the type [(DMF)(n)MCl](+) and [(DMF)(n)M(2)Cl(3)](+), of which the species with n = 2 and 3 were selected for in-depth studies. The latter include collision-induced dissociation experiments, gas-phase infrared spectroscopy, and calculations using density functional theory. The mononuclear complexes [(DMF)(n)MCl](+) almost exclusively lose neutral DMF upon collisional activation with the notable exception of the copper complex, for which also a reduction from Cu(II) to Cu(I) concomitant with the release of atomic chlorine is observed. For the dinuclear clusters, there exists a competition between loss of a DMF ligand and cluster degradation via loss of neutral MCl(2) with decreasing cluster stability from cobalt to zinc. For the specific case of [(DMF)(n)ZnCl](+) and [(DMF)(n)Zn(2)Cl(3)](+), ion-mobility mass spectrometry indicates the existence of two isomeric cluster ions in the case of [(DMF)(2)Zn(2)Cl(3)](+) which corroborates parallel theoretical predictions. 相似文献
973.
Demel J Pleštil J Bezdička P Janda P Klementová M Lang K 《Journal of colloid and interface science》2011,362(2):532-539
Herein, we report our analysis of the surface modification of polystyrene (PS) when treated under ambient conditions with a common biological buffer such as phosphate buffered saline (PBS) or aqueous solutions of the ionic constituents of PBS. Attenuated total reflection Fourier transform infrared spectroscopy was used for the analysis because the resultant spectra are very sensitive to minor changes in the chemical and structural properties of PS films. In addition, ultraviolet-visible spectroscopy was applied to characterize the surface modifications of PS. Treatment with PBS resulted in the most significant chemical and structural surface modifications of the PS films, as compared with each of the solutions of the constituents of PBS, which were tested separately. A multistep mechanism for the wet modification of PS is discussed. We postulate that the observed surface modifications are the result of photo-oxidation/reduction, swelling, and conformational changes and re-arrangement of the polymer chain. The resultant surface modifications could be similar to those produced by commonly used dry processes such as plasma treatments and electron, ion or ultraviolet irradiation. We found that the modifications that occurred in PBS were more stable than those initiated by dry processes. The formation of active groups on the surface of PS can be controlled by adsorption of bovine serum albumin or thermal annealing of PS before PBS treatment. This approach provides a simple and efficient method for the surface modification of PS for biomedical applications. 相似文献
974.
Gradient elution provides significant improvement in peak capacity with respect to isocratic conditions and therefore should be used in comprehensive two-dimensional LC×LC, both in the first and in the second dimension, where, however, gradients are limited to a short time period available for separation, usually 1 min or less. Gradient conditions spanning over a broad mobile phase composition range in each second-dimension fraction analysis are used with generic "full in fraction" (FIF) gradients. "Segment in fraction" (SIF) gradients cover a limited gradient range adjusted independently to suit changing lipophilicity range of compounds transferred to the second dimension during the first-dimension gradient run and to provide regular coverage of the two-dimensional retention space. Optimization of the gradient profiles is important tool for achieving high two-dimensional peak capacity and savings of the separation time in comprehensive LC×LC. Calculations based on the well-established gradient-elution theory can be used to predict the elution times and bandwidths in fast gradients, taking into account increased probability of pre-gradient or post-gradient elution. The fraction volumes transferred into the second dimension may significantly affect the second-dimension bandwidths, especially at high elution strength of the fraction solvent, which may cause even band distortion or splitting in combined normal-phase (HILIC)-RP systems, but also in some two-dimensional RP-RP systems. In the present work, the effects of the fast gradient profile, of the sample volume and solvent on the elution time and bandwidths were investigated on a short column packed with fused-core porous-shell particles, providing narrow bandwidths and fast separations at moderate operating pressure. 相似文献
975.
Multidrug resistance (MDR) is often associated with overexpression of the P-glycoprotein (P-gp, ABCB1). It was demonstrated that the P-gp mediated efflux decreases the drug concentration in cancer cells which results in the failure of chemotherapy. However, the MDR phenotype in cancer cells obviously involves various mechanisms. Therefore, if we want to estimate a contribution of the P-gp expression to the MDR phenotype, a clear quantitative relationship between the intracellular drug level and cell sensitivity must be established. To achieve this goal, a sensitive and non-radioactive assay for precise determination of intracellular levels of imatinib and its main metabolite N-desmethyl imatinib (CGP 74588) has been developed. The assay is based on an optimised extraction of cells with 4% formic acid after their separation from the growth medium by centrifugation through a layer of silicone oil. Cell extracts are subsequently analyzed by LC/MS/MS. Calibration curves were linear from 1 to 500 nmol/l for imatinib and from 2 to 500 nmol/l for CGP 74588, with correlation coefficients (r2) better than 0.998 and 0.996, respectively. The limit of quantitation (LOQ) was 1 nmol/l for imatinib and 2 nmol/l for CGP 74588. Our method has been successfully applied to the determination of intracellular levels of imatinib in sensitive K562 and their resistant variant, K562/Dox cells. 相似文献
976.
Petr Toman Emanuel Makrlík Petr Vaňura 《Monatshefte für Chemie / Chemical Monthly》2011,286(1):993-996
Abstract
The most probable structures of the cucurbit[6]uril·H3O+ and cucurbit[6]uril·(H3O+)2 cationic complex species have been derived by quantum mechanical DFT calculations. In these two complexes, each of the H3O+ ions is bound by three strong linear hydrogen bonds to three carbonyl oxygen atoms of the parent macrocycle. 相似文献977.
A novel long drop time mercury electrode has been constructed from common fused-silica capillary (50 μm I.D., 360 μm E.D.). Proposed device provides reproducible mercury drops with typical lifetime 40-120 s. The electrode was used for a set of electrocapillary measurements aimed at determination of critical micelle concentration of anionic surfactants by a convection controlled drop-time technique. A critical micelle concentration of sodium dodecyl sulfate 5.6 ± 0.4 mmol L−1 and 4.3 ± 0.4 mmol L−1 were obtained in 1 mmol L−1 and 5 mmol L−1 phosphate buffer (pH 7.0), respectively. The values were comparable to those obtained from conductometric measurements under the same conditions (7.0 ± 0.1 mmol L−1 and 5.2 ± 0.1 mmol L−1, respectively) and the difference was explained in accordance with theory of hemi-micelle formation. 相似文献
978.
Petr Zuman 《Journal of Solid State Electrochemistry》2011,15(7-8):1753-1759
After a brief introduction describing the main milestones in the development of DC polarography (DCP) as well as linear sweep (LSV) and cyclic voltammetry (CV), attention is paid to first applications of DCP in the reduction of organic compounds. In aqueous solutions the electron transfer (ET) is often accompanied by a proton transfer. Limiting currents in DCP enable investigation of kinetics of chemical reactions preceding ET. Dependence of the limiting current on concentration of a reagent, like H+ or OH??/sup> ions, enables determination of rate constants (k) of very fast reactions, with k values between 104 and 1010?L?mol???s??, comparable with those studied by relaxation methods. Application of CV is most advantageous for investigation of rates of chemical reactions following the ET. Comparison of analytical applications of DCP (reductions) with those of LSV (oxidations) is given. Apart from fast reactions taking place before the ET in the solution in the vicinity of the electrode surface, DCP can also be used for investigation of slower reactions, taking place in the bulk of the solution. Data obtained by DCP for determination of equilibrium (K) and rate (k) constants of reactions of organic compounds. Hence, DCP can be used in physical organic chemistry of solutions, in some cases complementing data obtained by UV–vis spectrophotometry. Some examples of determinations of K and k are given. Uncertain future of practical analytical applications of DCP and LSV is discussed as is the brighter future of applications in physical organic chemistry. As the main factor limiting successful applications is considered the limited opportunity for education of future research advisors in academia and group supervisors in industry. 相似文献
979.
Ferus M Kubelík P Kawaguchi K Dryahina K Španěl P Civiš S 《The journal of physical chemistry. A》2011,115(10):1885-1899
Time-resolved Fourier transform (FT) spectrometry was used to study the dynamics of radical reactions forming the HCN and HNC isomers in pulsed glow discharges through vapors of BrCN, acetonitrile (CH(3)CN), and formamide (HCONH(2)). Stable gaseous products of discharge chemistry were analyzed by selected ion flow tube mass spectrometry (SIFT-MS). Ratios of concentrations of the HNC/HCN isomers obtained using known transition dipole moments of rovibrational cold bands v(1) were found to be in the range 2.2-3%. A kinetic model was used to assess the roles the radical chemistry and ion chemistry play in the formation of these two isomers. Exclusion of the radical reactions from the model resulted in a value of the HNC/HCN ratio 2 orders of magnitude lower than the experimental results, thus confirming their dominant role. The major process responsible for the formation of the HNC isomer is the reaction of the HCN isomer with the H atoms. The rate constant determined using the kinetic model from the present data for this reaction is 1.13 (±0.2) × 10(-13) cm(3) s(-1). 相似文献
980.