全文获取类型
收费全文 | 1632篇 |
免费 | 27篇 |
国内免费 | 5篇 |
专业分类
化学 | 977篇 |
晶体学 | 35篇 |
力学 | 31篇 |
数学 | 101篇 |
物理学 | 520篇 |
出版年
2022年 | 18篇 |
2021年 | 30篇 |
2020年 | 25篇 |
2019年 | 25篇 |
2018年 | 23篇 |
2017年 | 23篇 |
2016年 | 40篇 |
2015年 | 34篇 |
2014年 | 50篇 |
2013年 | 136篇 |
2012年 | 87篇 |
2011年 | 98篇 |
2010年 | 48篇 |
2009年 | 56篇 |
2008年 | 65篇 |
2007年 | 67篇 |
2006年 | 82篇 |
2005年 | 52篇 |
2004年 | 52篇 |
2003年 | 34篇 |
2002年 | 45篇 |
2001年 | 25篇 |
2000年 | 20篇 |
1999年 | 14篇 |
1998年 | 15篇 |
1997年 | 14篇 |
1996年 | 11篇 |
1995年 | 15篇 |
1994年 | 16篇 |
1993年 | 15篇 |
1992年 | 26篇 |
1991年 | 16篇 |
1990年 | 19篇 |
1989年 | 19篇 |
1988年 | 16篇 |
1987年 | 10篇 |
1986年 | 17篇 |
1985年 | 23篇 |
1984年 | 18篇 |
1983年 | 21篇 |
1982年 | 19篇 |
1981年 | 18篇 |
1980年 | 25篇 |
1979年 | 23篇 |
1978年 | 20篇 |
1977年 | 18篇 |
1976年 | 10篇 |
1975年 | 15篇 |
1973年 | 12篇 |
1971年 | 9篇 |
排序方式: 共有1664条查询结果,搜索用时 296 毫秒
11.
G. R. Doshi S. N. Joshi K. C. Pillai 《Journal of Radioanalytical and Nuclear Chemistry》1991,155(2):115-127
Neutron activation analysis was used to determine129I in soil and grass samples around a reprocessing plant. The method involved wet oxidation of samples, using chromic acid, followed by distillation, collection of iodine in alkaline solution, loading on Dowex-1, irradiation and post-irradiation purification steps. The -activity of130I isotope of the purified samples was measured for quantitative determination of129I. The experimental results showed that129I and the129I/127I atomic ratio in soil samples varied from 1.09×10–4 to 5.33×10–3 pCi g–1 and 0.10×10–6 to 6.12×10–6, respectively. Further, the geometric mean of soil-to-plant transfer factor (Bv) for129I was found to be 0.16 which was comparable with other published values. 相似文献
12.
Tobacco protein separation by aqueous two-phase extraction 总被引:13,自引:0,他引:13
Tobacco has long been considered as a host to produce large quantity of high-valued recombinant proteins. However, dealing with large quantities of biomass is a challenge for downstream processing. Aqueous two-phase extraction (ATPE) has been widely used in purifying proteins from various sources. It is a protein-friendly process and can be scaled up easily. In this paper, ATPE was studied for its applicability to recombinant protein purification from tobacco with egg white lysozyme as the model protein. Separate experiments with poly(ethylene glycol) (PEG)-salt-tobacco extract and PEG-salt-lysozyme were carried out to determine the partition behavior of tobacco protein and lysozyme, respectively. Two-level fractional factorial designs were used to study the effects of factors such as, PEG molecular mass, PEG concentration, the concentration of phase forming salt, sodium chloride concentration and pH, on protein partitioning. The results showed that, among the studied systems, PEG-sodium sulfate system was most suitable for lysozyme purification. Detailed experiments were conducted by spiking lysozyme into the tobacco extract. The conditions with highest selectivity of lysozyme over native tobacco protein were determined using a response surface design. The purification factor was further improved by decreasing the phase ratio along the tie line corresponding to the phase compositions with the highest selectivity. Under selected conditions the lysozyme yield was predicted to be 87% with a purification factor of 4 and concentration factor of 14. From this study, ATPE was shown to be suitable for initial protein recovery and partial purification from transgenic tobacco. 相似文献
13.
Vikas V. Vaidya Santosh M. Yetal Shikha M. N. Roy Noel A. Gomes Santosh S. Joshi 《Chromatographia》2007,66(11-12):925-928
A rapid, sensitive and specific method to quantify pregabalin in human plasma using metaxalone as the internal standard is described. Sample preparation involved simple protein precipitation by using acetronitrile as solvent. The extract was analyzed by high-performance liquid chromatography coupled to electrospray tandem mass spectrometry (LC-MS–MS). Chromatography was performed isocratically on Thermo Hypurity C18 5 μm analytical column, (50 mm × 4.6 mm i.d.). The assay of pegabalin was linear calibration curve over the range 10.000–10000.000 ng mL?1. The lower limit of quantification was 10.000 ng mL?1 in plasma. The method was successfully applied to the bioequivalence study of pregabalin capsules (150.0 mg) administered as a single oral dose. 相似文献
14.
Xilin Ren Chingkuang Tu Deepa Bhatt J. Jefferson P. Perry John A. Tainer Diane E. Cabelli David N. Silverman 《Journal of Molecular Structure》2006,790(1-3):168-173
Incorporation of 3-fluorotyrosine and site-specific mutagenesis have been used with stopped-flow spectrophotometry and pulse radiolysis to investigate the catalytic properties of human manganese superoxide dismutase (MnSOD). All of the nine tyrosine residues in each of the four subunits of the homotetramer of human MnSOD were replaced with 3-fluorotyrosine. Previous studies showed that the crystal structures of the unfluorinated and fluorinated human MnSOD are nearly superimposable with the root-mean-square deviation for 198 -carbon atoms at 0.3 Å. However, the catalytic activity kcat/Km of the fluorinated MnSOD at 30 μM−1 s−1 was less than unfluorinated wild type at 800 μM−1 s−1. Comparison of the values of kcat/Km for fluorinated and unfluorinated wild-type andY34F MnSOD showed that this decrease for the fluorinated enzyme was in significant part due to 3-fluorotyrosine residues distant (>7 Å) from the active-site metal, not to 3-fluorotyrosine at position 34 close (5 Å) to the metal. Although many rate constants for the catalysis are decreased by this fluorination, the rate of dissociation of the product-inhibited complex appears unchanged by the presence of fluorinated tyrosines. These results suggest that Tyr34 is not a proton donor in the release of the product-inhibited complex, which involves protonation of a peroxo complex of the metal with release of hydrogen peroxide. 相似文献
15.
16.
We report a detailed density functional theory (B3LYP) analysis of the gas-phase H2O2 formation from H2 and O2 on Au3, Au4+, Au5, and Au5-. We find that H2, which interacts only weakly with the Au clusters, is dissociatively added across the Au-O bond, upon interaction with AunO2. One H atom is captured by the adsorbed O2 to form the hydroperoxy intermediate (OOH), while the other H atom is captured by the Au atom. Once formed, the hydroperoxy intermediate acts as a precursor for the closed-loop catalytic cycle. An important common feature of all the pathways is that the rate-determining step of the catalytic cycle is the second H2 addition to form H2O2. The H2O2 desorption is followed by O2 addition to AunH2 to form the hydroperoxy intermediate, thus leading to the closure of the cycle. On the basis of the Gibbs free energy of activation, out of these four clusters, Au4+ is most active for the formation of the H2O2. The 0 K electronic energy of activation and the DeltaGact at the standard conditions are 12.6 and 16.6 kcal/mol respectively. The natural bond orbital charge analysis suggests that the Au clusters remain positively charged (oxidic) in almost all the stages of the cycle. This is interesting in the context of the recent experimental evidence for the activity of cationic Au in CO oxidation and water-gas shift catalysts. We have also found preliminary evidence for a correlation between the activation barrier for the first H2 addition and the O2 binding energy on the Au cluster. It suggests that the minimum activation barrier for the first H2 addition is expected for the Au clusters with 7.0-9.0 kcal/mol O2 binding energy, i.e., in the midrange of the expected interaction energy. This represents a balance between more favorable H2 dissociation when the Aun-O2 interaction is weaker and high O2 coverage when the interaction is stronger. On the basis of this work, we predict that the hydroperoxy intermediate formation can be both thermodynamically and kinetically viable only in a narrow range of the O2 binding energy (10.0-12.0 kcal/mol)-a useful estimate for computationally screening Au-cluster-based catalysts. We also show that a competitive channel for the OOH desorption exists. Thus, in propylene epoxidation both OOH radicals and H2O2 can attack the active Ti in/on the Au/TS-1 and generate the Ti-OOH sites, which can convert propylene to propylene oxide. 相似文献
17.
The condensation products of 5-amino-1,3-disubstituted-pyrazoles with aromatic aldehydes were identified as 2,4-dihydro-2,5-diphenyl-4-(phenylmethylene)-3H-pyrazol-5-imine derivatives Treatment of these products with mercaptoacetic acid gave new fluorine containing 1H-pyrazolo[3,4-e][1,4]thiazepin-7-ones. 相似文献
18.
[reaction: see text] The TiCl4-mediated reaction of an ester with benzoyl chloride results in high yields of the alpha-benzoylated ester. Diazo transfer of the benzoylated ester utilizing p-acetoamidobenzenesulfonyl azide affords the alpha-diazo ester in good yield. Using this simplified procedure, it is easy to prepare gram quantities of alpha-diazo esters. 相似文献
19.
Summary The formation of violet coloured chelate of indium with Gallion has been studied. Indium forms only one chelate with Gallion at pH 4.5 having
max 610 nm. The composition of the complex formed has been determined by various methods and is found to be 11 (MR). The values of stability constant have been calculated by three methods and the average value of logK obtained is 5.6 ± 0.1. A procedure for the spectrophotometric determination of indium has been suggested.
Zusammenfassung Die Bildung eines violetten Chelates von Indium mit dem Reagens Gallion wurde studiert. In bildet damit ein einziges Chelat bei pH=4,5 und max=610 nm. Die Zusammensetzung des entstandenen Komplexes wurde nach verschiedenen Methoden ermittelt und gleich 11 (MetallReagens) gefunden. Die Stabilitätskonstante wurde nach drei Verfahren berechnet, wobei sich als Mittelwert logK=5,6±0,1 ergab. Eine Arbeitsvorschrift für die spektrophotometrische Bestimmung des In wird vorgeschlagen.相似文献
20.
Reinvestigation of the reaction of 3-aroylmethyleneindol-2-ones with hydrogen peroxide has revealed that a 1:1 isomeric mixture of spiro[3H-indole-3,2′-oxiran]-2(1H)-ones is formed. The structures of the two isomers have been confirmed by their ir, pmr and mass spectral studies. Mass fragmentation patterns of these compounds are discussed. 相似文献