全文获取类型
收费全文 | 1654篇 |
免费 | 30篇 |
国内免费 | 3篇 |
专业分类
化学 | 792篇 |
晶体学 | 10篇 |
力学 | 34篇 |
数学 | 164篇 |
物理学 | 687篇 |
出版年
2021年 | 10篇 |
2020年 | 17篇 |
2019年 | 20篇 |
2018年 | 13篇 |
2017年 | 20篇 |
2016年 | 27篇 |
2015年 | 21篇 |
2014年 | 26篇 |
2013年 | 68篇 |
2012年 | 67篇 |
2011年 | 63篇 |
2010年 | 47篇 |
2009年 | 35篇 |
2008年 | 64篇 |
2007年 | 71篇 |
2006年 | 69篇 |
2005年 | 66篇 |
2004年 | 51篇 |
2003年 | 24篇 |
2002年 | 53篇 |
2001年 | 36篇 |
2000年 | 38篇 |
1999年 | 18篇 |
1998年 | 21篇 |
1997年 | 27篇 |
1996年 | 46篇 |
1995年 | 47篇 |
1994年 | 37篇 |
1993年 | 53篇 |
1992年 | 42篇 |
1991年 | 23篇 |
1990年 | 38篇 |
1989年 | 16篇 |
1988年 | 20篇 |
1987年 | 16篇 |
1986年 | 17篇 |
1985年 | 20篇 |
1984年 | 17篇 |
1983年 | 18篇 |
1982年 | 20篇 |
1981年 | 23篇 |
1980年 | 18篇 |
1979年 | 25篇 |
1978年 | 21篇 |
1977年 | 19篇 |
1976年 | 16篇 |
1975年 | 20篇 |
1974年 | 13篇 |
1973年 | 10篇 |
1972年 | 10篇 |
排序方式: 共有1687条查询结果,搜索用时 15 毫秒
81.
Campbell R Carrella LM Clegg W Mulvey RE Rentschler E Robertson SD Russo L 《Inorganic chemistry》2011,50(10):4656-4659
One of the milestone structures in the development of transition-metal complexes with metal-metal bonds of multiple bond order was the lithium methylchromate dimer Me(8)Cr(2)[Li(donor)](4) (donor = THF or Et(2)O). Using a simple salt metathesis reaction mixing this compound with sodium tert-butoxide, the sodium congener Me(8)Cr(2)[Na(OEt(2))](4) has been synthesized as a green crystalline compound and isolated in 51% yield. Its solid-state structure was determined by single-crystal X-ray diffraction. Exhibiting exact crystallographic C(4h) symmetry, this heavier alkali-metal chromate structure is also dimeric, formally comprising a (Me(8)Cr(4))(4-) tetranionic core with four peripheral Na(+) cations carrying supporting ether ligands. Its salient feature is the long Cr···Cr distance of 3.263(2) ?, which is remarkably elongated compared to that in the lithium THF-solvated congener [1.968(2) ?]. With respect to the methyl C atoms, the Cr coordination is distorted-square-planar. Each Na(+) interacts with four methyl C atoms, and there are also some short Na···H(C) contacts. Unlike for lithium chromate, no NMR spectroscopic data could be obtained for sodium chromate. The paramagnetic character of sodium chromate was confirmed by variable-temperature magnetization measurements, which indicated antiferromagnetic behavior. 相似文献
82.
Quantitative assessment of the enzymatic degradation of amorphous cellulose by using a quartz crystal microbalance with dissipation monitoring 总被引:1,自引:0,他引:1
Suchy M Linder MB Tammelin T Campbell JM Vuorinen T Kontturi E 《Langmuir : the ACS journal of surfaces and colloids》2011,27(14):8819-8828
The systematic evaluation of the degradation of an amorphous cellulose film by a monocomponent endoglucanase (EG I) by using a quartz crystal microbalance with dissipation monitoring (QCM-D) identified several important aspects relevant to the study the kinetics of cellulose degradation by enzymes. It was demonstrated that, to properly evaluate the mechanism of action, steady state conditions in the experimental set up need to be reached. Rinsing or diluting the enzyme, as well as concentration of the enzyme, can have a pronounced effect on the hydrolysis. Quantification of the actual hydrolysis was carried out by measuring the film thickness reduction by atomic force microscopy after the enzymatic treatment. The values correlated well with the frequency data obtained by QCM-D measurement for corresponding films. This demonstrated that the evaluation of hydrolysis by QCM-D can be done quantitatively. Tuning of the initial thickness of films enabled variation of the volume of substrate available for hydrolysis which was then utilized in establishing a correlation between substrate volume and hydrolytic activity of EG I as measured by QCM-D. It was shown that, although the amount of substrate affects the absolute rate of hydrolysis, the relative rate of hydrolysis does not depend on the initial amount of substrate in steady state system. With this experimental setup it was also possible to demonstrate the impact of concentration on crowding of enzyme and subsequent hydrolysis efficiency. This effort also shows the action of EG I on a fully amorphous substrate as observed by QCM-D. The enzyme was shown to work uniformly within the whole volume of swollen film, however being unable to fully degrade the amorphous film. 相似文献
83.
Hanna C. Wentz Grigorii Skorupskii Ana B. Bonfim Jenna L. Mancuso Christopher H. Hendon Evan H. Oriel Graham T. Sazama Michael G. Campbell 《Chemical science》2020,11(5):1342
Redox-active metal–organic frameworks (MOFs) are promising materials for a number of next-generation technologies, and recent work has shown that redox manipulation can dramatically enhance electrical conductivity in MOFs. However, ligand-based strategies for controlling conductivity remain under-developed, particularly those that make use of reversible redox processes. Here we report the first use of ligand n-doping to engender electrical conductivity in a porous 3D MOF, leading to tunable conductivity values that span over six orders of magnitude. Moreover, this work represents the first example of redox switching leading to reversible conductivity changes in a 3D MOF.Redox-active ligands are used to reversibly tune electrical conductivity in a porous 3D metal–organic framework (MOF). 相似文献
84.
Raynald Gauvin Eric Lifshin Hendrix Demers Paula Horny Helen Campbell 《Microscopy and microanalysis》2006,12(1):49-64
A new Monte Carlo program, Win X-ray, is presented that predicts X-ray spectra measured with an energy dispersive spectrometer (EDS) attached to a scanning electron microscope (SEM) operating between 10 and 40 keV. All the underlying equations of the Monte Carlo simulation model are included. By simulating X-ray spectra, it is possible to establish the optimum conditions to perform a specific analysis as well as establish detection limits or explore possible peak overlaps. Examples of simulations are also presented to demonstrate the utility of this new program. Although this article concentrates on the simulation of spectra obtained from what are considered conventional thick samples routinely explored by conventional microanalysis techniques, its real power will be in future refinements to address the analysis of sample classifications that include rough surfaces, fine structures, thin films, and inclined surfaces because many of these can be best characterized by Monte Carlo methods. The first step, however, is to develop, refine, and validate a viable Monte Carlo program for simulating spectra from conventional samples. 相似文献
85.
Victoria E. Campbell Xavier de Hatten Dr. Nicolas Delsuc Dr. Brice Kauffmann Dr. Ivan Huc Dr. Jonathan R. Nitschke Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(25):6138-6142
Systemic change : A system of transformations between helical structures was observed to be governed by interactions mediated by the electronic effects of substituents, entropic effects, the conformational preferences of organic building blocks, and the coordinative preferences of the metal ion. All of these effects were important, but all must be considered together to allow the prediction of the product observed (see scheme).
86.
87.
88.
89.
90.
Agathe Szkola Katrina Campbell Christopher T. Elliott Reinhard Niessner Michael Seidel 《Analytica chimica acta》2013
A novel multiplexed immunoassay for the analysis of phycotoxins in shellfish samples has been developed. Therefore, a regenerable chemiluminescence (CL) microarray was established which is able to analyze automatically three different phycotoxins (domoic acid (DA), okadaic acid (OA) and saxitoxin (STX)) in parallel on the analysis platform MCR3. As a test format an indirect competitive immunoassay format was applied. These phycotoxins were directly immobilized on an epoxy-activated PEG chip surface. The parallel analysis was enabled by the simultaneous addition of all analytes and specific antibodies on one microarray chip. After the competitive reaction, the CL signal was recorded by a CCD camera. Due to the ability to regenerate the toxin microarray, internal calibrations of phycotoxins in parallel were performed using the same microarray chip, which was suitable for 25 consecutive measurements. For the three target phycotoxins multi-analyte calibration curves were generated. In extracted shellfish matrix, the determined LODs for DA, OA and STX with values of 0.5 ± 0.3 μg L−1, 1.0 ± 0.6 μg L−1, and 0.4 ± 0.2 μg L−1 were slightly lower than in PBS buffer. For determination of toxin recoveries, the observed signal loss in the regeneration was corrected. After applying mathematical corrections spiked shellfish samples were quantified with recoveries for DA, OA, and STX of 86.2%, 102.5%, and 61.6%, respectively, in 20 min. This is the first demonstration of an antibody based phycotoxin microarray. 相似文献