全文获取类型
收费全文 | 2829篇 |
免费 | 101篇 |
国内免费 | 3篇 |
专业分类
化学 | 1921篇 |
晶体学 | 16篇 |
力学 | 53篇 |
数学 | 370篇 |
物理学 | 573篇 |
出版年
2023年 | 45篇 |
2022年 | 62篇 |
2021年 | 78篇 |
2020年 | 84篇 |
2019年 | 94篇 |
2018年 | 65篇 |
2017年 | 61篇 |
2016年 | 146篇 |
2015年 | 110篇 |
2014年 | 123篇 |
2013年 | 135篇 |
2012年 | 202篇 |
2011年 | 209篇 |
2010年 | 144篇 |
2009年 | 109篇 |
2008年 | 171篇 |
2007年 | 158篇 |
2006年 | 125篇 |
2005年 | 137篇 |
2004年 | 111篇 |
2003年 | 65篇 |
2002年 | 49篇 |
2001年 | 28篇 |
2000年 | 29篇 |
1999年 | 36篇 |
1998年 | 24篇 |
1997年 | 26篇 |
1996年 | 24篇 |
1995年 | 11篇 |
1994年 | 23篇 |
1993年 | 10篇 |
1992年 | 23篇 |
1991年 | 7篇 |
1990年 | 11篇 |
1988年 | 11篇 |
1987年 | 8篇 |
1986年 | 14篇 |
1985年 | 9篇 |
1983年 | 15篇 |
1982年 | 9篇 |
1981年 | 12篇 |
1980年 | 8篇 |
1979年 | 13篇 |
1977年 | 4篇 |
1976年 | 16篇 |
1975年 | 6篇 |
1974年 | 6篇 |
1973年 | 13篇 |
1969年 | 4篇 |
1968年 | 4篇 |
排序方式: 共有2933条查询结果,搜索用时 31 毫秒
61.
Woldegiorgis A von Kieseritzky F Dahlstedt E Hellberg J Brinck T Roeraade J 《Rapid communications in mass spectrometry : RCM》2004,18(8):841-852
The use of non-polar, small polymers as matrices for the analysis of low molecular weight compounds in polymer-assisted laser desorption/ionization mass spectrometry (PALDI-MS) is demonstrated. The matrices evaluated were either based on an oligothiophene or a benzodioxin backbone. Metallocenes, polycyclic hydrocarbons, a fluorosurfactant, and a subset of small organic compounds with various functionalities, served as model analytes. The mechanism of ionization charge transfer is discussed and ionization potentials for the matrices in the study have been estimated using density functional theory (DFT) calculations. Some of the results are possibly contradictory to the generally accepted limiting conditions for gas-phase charge-transfer reactions. These results are interpreted in the light of energy pooling. Also a new mass calibration procedure for the low-mass region in positive ion mode is presented, and some aspects of the ionization/desorption process leading to radical cations are studied. 相似文献
62.
Juliana Vaz Bevilaqua Lidia M. Lima Aline Gomes Cunha Eliezer J. Barreiro Tito L. M. Alves Lucia Moreira Campos Paiva Denise M.Guimarães Freire 《Applied biochemistry and biotechnology》2005,121(1-3):117-128
The last step of the production of four phthalimide-derived acids, designed to act as antiasthma drugs, was performed by enzymatic hydrolysis of the respective methyl or ethyl esters. The esters 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic methyl ester (PHT-MET), 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic ethyl ester, 4-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester, and 2-(1,3-dioxo-1, 3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester were hydrolyzed by immobilized lipase. The enzymatic reaction could be used only to produce the desired 4-substituted compounds. The best result that was found to hydrolysis of PHT-MET, and, therefore, that ester was selected for optimization experiments in a three-phase system. Reactions were performed with solid biocatalyst (Lipozyme® RM IM), organic solvent phase (ethyl acetate), and aqueous phase (saturated Na2CO3 solution). To optimize the reaction conditions, an experimental design optimization procedure was used. The variables studied were the amount of enzyme, the temperature, and the volume of the aqueous solution. Time course experiments were then performed for different initial enzyme concentrations (0.5, 0.9, and 1.4 UH/mL of solvent). The optimized reaction conditions found were 20 mg of Lipozyme (0.9 UH/mLsolvent) and 5.0 mL of Na2CO3(sat) at 40°C for 6 h. 相似文献
63.
de Farias RF de Souza JM de Melo JV Airoldi C 《Journal of colloid and interface science》1999,212(1):123-129
The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press. 相似文献
64.
The pressure dependence of the reorientational correlation function for chloroform has been measured by analysis of the Raman 3019 cm? 1 A1 CH stretching lineshape at 1, 1000, and 2000 bar and 23°C. These reorientational correlation functions were obtained using the method of spectral Fourier deconvolution introduced by Bratos. The results are compared to the correlation times obtained from the NMR deuteron T1 relaxation times for CDCl3 and those calculated from high pressure viscosity measurements. 相似文献
65.
Comprehensive two-dimensional liquid chromatography-size-exclusion chromatography (LC x SEC) was investigated as a tool for the characterization of functional poly(methyl methacrylate) (PMMA) polymers. Ultraviolet-absorbance and evaporative light-scattering detection (ELSD) were used. A simple method to quantify ELSD data is presented. Each data point from the ELSD chromatogram can be converted into a mass concentration using experimental calibration curves. The qualitative and quantitative information obtained on two representative samples is used to demonstrate the applicability of LC x SEC for determining the mutually dependent molar-mass distributions (MMD) and functionality-type distributions (FTD) of functional polymers. The influence of the molar mass on the retention behavior in LC was investigated using LC x SEC for hydroxyl-functional PMMA polymers. The critical conditions, at which retention is--by definition--independent of molar mass, were not exactly the same for PMMA series with different end-groups. Our observations are in close agreement with theoretical curves reported in the literature. However, for practical applications of LC x SEC it is not strictly necessary to work at the exact critical solvent composition. Near-critical conditions are often sufficient to determine the mutually dependent distributions (MMD and FTD) of functional polymers. 相似文献
66.
Michelin SE Oliveira HL Kroin T Soares LS Veiteinheimer E Luz CA Lima MF Fujimoto MM Lee MT 《The Journal of chemical physics》2005,122(9):094309
In this work, we present a theoretical study on elastic electron collisions from three isoelectronic free radicals (CNN, NCN, and CCO) in the low incident energy range. More specifically, calculated differential, integral, and momentum transfer cross sections are reported in the 1-30 eV energy range. Calculations are performed in the static-exchange and static-exchange-polarization levels. The iterative Schwinger variational method is used to solve the scattering equations. Our study reveals that the calculated cross sections for the three targets are significantly different at incident energies below 10 eV. Above that energy, a remarkable similarity among the calculated results is seen. 相似文献
67.
A Cu2N2 diamond core structure, {(PNP)CuI}2 (2), supported by a [PNP]- ligand (1) ([PNP]- = bis(2-(diisobutylphosphino)phenyl)amide) has been prepared. 2 is highly emissive at ambient temperature in both the solid and solution states and is characterized by a relatively long-lived excited state (tau > 10 mus) and an unusually high quantum yield (phi > 0.65). These observations are consistent with a low degree of structural reorganization between the ground state of 2 and its excited state *2, and also with a high degree of steric protection of the two copper centers of 2 afforded by the bulky [PNP]- ligand. An estimate for the excited-state reduction potential of *2 (ca. -3.2 V vs Fc+/Fc), and the availability of two well-separated and reversible ground-state redox processes, suggests that bimetallic copper systems of these types may be interesting candidates to consider for photochemically driving multielectron redox transformations. 相似文献
68.
Rodrigues e Silva AA da Silva Góes AJ de Lima WT de Souza Maia MB 《Chemical & pharmaceutical bulletin》2003,51(12):1351-1355
The search for new anti-inflammatory drugs has been constant in several research centers. The use of the Bioisostery concept allows the elaboration of new bioactive compounds with different properties through the introduction of substitute groups in one or more positions of a main molecule with known biological activity. Preliminary works accomplished at our laboratory with 2,4-thiazolidinedione isosters demonstrated inhibitory activity on edema formation for N-tryptophyl-5-(3,5-di-tert-butyl-4-hydroxybenzylidene)-2,4-thiazolidinedione (GS28) and N-tryptophyl-5-(3,5-di-tert-butyl-4-hydroxybenzylidene) rhodanine (GS26). We verified the antiedematogenic and ulcerogenic activity of these two compounds in Wistar rats. The carrageenan induced paw edema suffered significant (p<0.05) inhibition (28.36% on average) for GS28 (100 mg/kg; v.o.) during the entire time of the experiment. GS26 (50 and 100 mg/kg; v.o.) significantly inhibited (p<0.05) the paw edema dextran induced (22.1 and 27.8%, for the respective doses) after 180 min. The compounds GS26 and GS28 did not show ulcerogenic activity on gastric mucous. The results suggest antiedematogenic action for both compounds without the appearance of gastric lesions. 相似文献
69.
Jose′ L. F. C. Lima Antoacutenio O. S. S. Rangel M. Renata S. Souto 《Fresenius' Journal of Analytical Chemistry》1997,358(5):657-662
A flow injection system was developed for the sequential determination of total nitrogen and phosphorus in digests of vegetables
using potentiometric and spectrophotometric detection systems, respectively. A tubular ammonium selective electrode with a
sensor system composed of nonactin/monactin in tris(2-ethylhexyl) phosphate was used. The selectivity limitations of this
electrode were overcome by the inclusion of a gas-diffusion unit in the system that separated ammonium from the rest of the
sample matrix and allowed the determination of total nitrogen and phosphorus by the partition of the sample plug between two
streams.
The results obtained with the developed FIA system were in good agreement with those of the reference methods. Sampling rates
from 40 to 60 samples per hour and relative standard deviations below 3.5% were achieved.
Received: 17 October 1996/Revised: 21 November 1996/Accepted: 27 November 1996 相似文献
70.
Inductively coupled plasma optical emission spectrometry (ICP-OES) was applied to the analysis of major and minor elements of Ni-Nb alloys obtained by aluminothermic reduction process. Digestion of samples was made using a mixture of HF+HNO3. Minor and trace elements were determined without matrix separation. The precision for all constituents was <3%. Recoveries for the analyte-spiked samples were 95%. 相似文献