全文获取类型
收费全文 | 528篇 |
免费 | 24篇 |
国内免费 | 3篇 |
专业分类
化学 | 378篇 |
力学 | 2篇 |
数学 | 94篇 |
物理学 | 81篇 |
出版年
2023年 | 3篇 |
2022年 | 11篇 |
2021年 | 8篇 |
2020年 | 17篇 |
2019年 | 9篇 |
2018年 | 6篇 |
2017年 | 7篇 |
2016年 | 14篇 |
2015年 | 19篇 |
2014年 | 19篇 |
2013年 | 36篇 |
2012年 | 42篇 |
2011年 | 57篇 |
2010年 | 35篇 |
2009年 | 31篇 |
2008年 | 40篇 |
2007年 | 36篇 |
2006年 | 35篇 |
2005年 | 19篇 |
2004年 | 16篇 |
2003年 | 13篇 |
2002年 | 16篇 |
2001年 | 5篇 |
2000年 | 3篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1986年 | 1篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有555条查询结果,搜索用时 15 毫秒
1.
2.
Screening of 400 Streptomyces strains for biotransformation of the natural lignan matairesinol led to the identification of Streptomyces sp. LS136, capable of producing a single metabolite in moderate yields. Isolation and purification by preparative HPLC, followed by structural analyses by LC-MS and NMR, established the structure as matairesinol-4-O-rhamnoside. This bacterial strain was also used for rhamnosylation of the abundant natural lignans, hydroxymatairesinol and secoisolariciresinol. 相似文献
3.
Daniel Tholen Roderick Chappel Barbara Francis 《Accreditation and quality assurance》2006,11(8-9):400-407
International requirements for PT and EQA state that providers must demonstrate that samples are homogeneous and stable. However, testing for homogeneity and stability can be expensive, use samples that could otherwise serve as quality-control materials, and can also fail to detect significant inhomogeneity and instability. In some situations it may be preferable to use the results from participants to identify problems with sample lots, if historic results follow predictable distributions and a statistical decision rule can be produced. An unusually high proportion of incorrect results may indicate that samples were inhomogeneous or unstable. Conditions under which this can be demonstrated are discussed, and the efficacy of the proposal is demonstrated with two examples. This procedure is especially effective when there are a large number of participants and/or a historic small proportion of incorrect results. Providers who adopt this proposal will need to retain samples for testing and assume the risk of distributing bad samples.Presented at the Eurachem PT Workshop September 2005, Portorož, Slovenia 相似文献
4.
Hybrid quantum mechanical-molecular mechanics (dynamics) were performed on flavin reductase (Fre) and flavodoxin reductase (Fdr), both from Escherichia coli. Each was complexed with riboflavin (Rbf) or flavin mononucleotide (FMN). During 50 ps trajectories, the relative energies of the fluorescing state (S1) of the isoalloxazine ring and the lowest charge transfer state (CT) were assessed to aid prediction of fluorescence lifetimes that are shortened due to quenching by electron transfer from tyrosine. The simulations for the four cases display a wide range in CT–S1 energy gap caused by the presence of phosphate, other charged and polar residues, water, and by intermolecular separation between donor and acceptor. This suggests that the Gibbs energy change (ΔG0) and reorganization energy (λ) for the electron transfer may differ in different flavoproteins. 相似文献
5.
Daniel William Tholen 《Accreditation and quality assurance》1998,3(9):362-366
There are three stages to evaluating a laboratory's results in an interlaboratory proficiency test: establishing the correct
result for the test item, determining an evaluation statistic for the particular result, and establishing an acceptable range.
There are a wide variety of procedures for accomplishing these three stages and a correspondingly wide variety of statistical
techniques in use. Currently in North America the largest number of laboratory proficiency test programs are in the clinical
laboratory field, followed by programs for environmental laboratories that test drinking water and waste water. Proficiency
testing in both of these fields is under the jurisdiction of the federal government and other regulatory and accreditation
agencies. Many of the statistical procedures are specified in the regulations, to assure comparability of different programs
and a fair evaluation of performance. In this article statistical procedures recommended in International Organization for
Standardization Guide 43, Part 1, are discussed and compared with current practices in North America.
Received: 22 April 1998 · Accepted: 12 May 1998 相似文献
6.
Chemical studies on antioxidant mechanisms and free radical scavenging properties of lignans 总被引:1,自引:0,他引:1
Eklund PC Långvik OK Wärnå JP Salmi TO Willför SM Sjöholm RE 《Organic & biomolecular chemistry》2005,3(18):3336-3347
The antioxidant activity, in terms of radical scavenging capacity, of altogether 15 different lignans was measured by monitoring the scavenging of the free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH). The effect of differences in skeletal arrangement or the degree of oxidation of the lignans was investigated in a structure-activity relationship study. A large variety in the radical scavenging capacities of the different lignans was observed and related to some structural features. Lignans with catechol (3,4-dihydroxyphenyl) moieties exhibited the highest radical scavenging capacity, while the corresponding guaiacyl (3-methoxy-4-hydroxyphenyl) lignans showed a slightly weaker scavenging capacity. In addition, the butanediol structure was found to enhance the activity, whereas a higher degree of oxidation at the benzylic positions decreased the activity. Additionally, the readily available lignans (-)-secoisolariciresinol, a mixture of hydroxymatairesinol epimers and (-)-matairesinol were studied in more detail, including kinetic measurements and identification of oxidation products in the reactions with DPPH and ABAP (2,2-azobis(2-methylpropionamidine) dihydrochloride. The identification of reaction products, by GC-MS, HPLC-MS and NMR spectroscopy, showed that dimerisation of the two aromatic moieties was the major radical termination reaction. Also, the formation of adducts was a predominant reaction in the experiments with ABAP. The kinetic data obtained from the reactions between the lignans and DPPH indicated a complex reaction mechanism. 相似文献
7.
Dissociative recombination of the weakly bound NO-dimer cation: cross sections and three-body dynamics 总被引:1,自引:0,他引:1
Petrignani A Andersson PU Pettersson JB Thomas RD Hellberg F Ehlerding A Larsson M van der Zande WJ 《The Journal of chemical physics》2005,123(19):194306
Dissociative recombination (DR) of the dimer ion (NO)(2) (+) has been studied at the heavy-ion storage ring CRYRING at the Manne Siegbahn Laboratory, Stockholm. The experiments were aimed at determining details on the strongly enhanced thermal rate coefficient for the dimer, interpreting the dissociation dynamics of the dimer ion, and studying the degree of similarity to the behavior in the monomer. The DR rate reveals that the very large efficiency of the dimer rate with respect to the monomer is limited to electron energies below 0.2 eV. The fragmentation products reveal that the breakup into the three-body channel NO+O+N dominates with a probability of 0.69+/-0.02. The second most important channel yields NO+NO fragments with a probability of 0.23+/-0.03. Furthermore, the dominant three-body breakup yields electronic and vibrational ground-state products, NO(upsilon=0)+N((4)S)+O((3)P), in about 45% of the cases. The internal product-state distribution of the NO fragment shows a similarity with the product-state distribution as predicted by the Franck-Condon overlap between a NO moiety of the dimer ion and a free NO. The dissociation dynamics seem to be independent of the NO internal energy. Finally, the dissociation dynamics reveal a correlation between the kinetic energy of the NO fragment and the degree of conservation of linear momentum between the O and N product atoms. The observations support a mechanism in which the recoil takes place along one of the NO bonds in the dimer. 相似文献
8.
A new method has been developed for the determination of the isotope abundance ratios of deuterium, D, and oxygen-18, 18O, in water vapor (and water) using selected ion flow tube mass spectrometry (SIFT-MS). H3O+ ions are injected into the helium carrier gas where they associate with the H2O and HDO molecules in a sample of water introduced into the carrier gas. The D and 18O contents of the product cluster ions H8DO4+ and H9(18)OO3+ at m/e = 74 and 75, respectively, are determined by reference to the majority cluster ion H9O4+ at m/e = 73. Allowance is made for the contribution of the H8(17)OO3+ ions to the m/z = 74 ions. Absolute isotopic ratios are measured within seconds without the need for precalibration of the SIFT-MS instrument, currently to an accuracy of better than 2%. 相似文献
9.
Pastor IM Västilä P Adolfsson H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4031-4045
A library of novel dipeptide-analogue ligands based on the combination of tert-butoxycarbonyl(N-Boc)-protected alpha-amino acids and chiral vicinal amino alcohols were prepared. These highly modular ligands were combined with [[RuCl(2)(p-cymene)](2)] and the resulting metal complexes were screened as catalysts for the enantioselective reduction of acetophenone under transfer hydrogenation conditions using 2-propanol as the hydrogen donor. Excellent enantioselectivity of 1-phenylethanol (up to 98 % ee) was achieved with several of the novel catalysts. Although most of the ligands contained two stereocenters, it was demonstrated that the absolute configuration of the product alcohol was determined by the configuration of the amino acid part of the ligand. Employing ligands based on L-amino acids generated S-configured products, and catalysts based on D-amino acids favored the formation of the R-configured alcohol. The combination N-Boc-L-alanine and (R)-phenylglycinol (Boc-L-Ab) or its enantiomer (N-Boc-D-alanine and (S)-phenylglycinol, Boc-D-Aa) proved to be the best ligands for the reduction process. Transfer hydrogenation of a number of aryl alkyl ketones were evaluated and excellent enantioselectivity, up to 96 % ee, was obtained. 相似文献
10.
用选择离子流动管质谱测定汽油和柴油蒸汽成分 总被引:2,自引:0,他引:2
采用选择离子流动管质谱(SIFT/MS)装置,以H30^ 、N0^ 为初始离子对汽油和柴油蒸汽进行了研究,质谱分析表明,汽油和柴油主要由C—H化合物组成,包括烷烃、环烷烃、烯烃、炔烃、二烯烃以及芳香烃。在这几种成分中,烷烃都占有最大的比例;汽油蒸汽和柴油蒸汽最大的区别是柴油蒸汽中长链大分子的挥发性C—H化合物所占的比例远远高于汽油蒸汽。文中还给出了以H30^ 、N0^ 为初始离子所得到的汽油蒸汽的质谱图,以及汽油、柴油蒸汽中各种成分的定量分析结果。 相似文献