全文获取类型
收费全文 | 526篇 |
免费 | 16篇 |
国内免费 | 1篇 |
专业分类
化学 | 469篇 |
晶体学 | 6篇 |
力学 | 1篇 |
数学 | 24篇 |
物理学 | 43篇 |
出版年
2023年 | 4篇 |
2022年 | 27篇 |
2021年 | 40篇 |
2020年 | 17篇 |
2019年 | 8篇 |
2018年 | 10篇 |
2017年 | 8篇 |
2016年 | 27篇 |
2015年 | 15篇 |
2014年 | 32篇 |
2013年 | 41篇 |
2012年 | 32篇 |
2011年 | 43篇 |
2010年 | 21篇 |
2009年 | 23篇 |
2008年 | 29篇 |
2007年 | 30篇 |
2006年 | 28篇 |
2005年 | 14篇 |
2004年 | 20篇 |
2003年 | 19篇 |
2002年 | 15篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1999年 | 5篇 |
1998年 | 8篇 |
1997年 | 5篇 |
1996年 | 2篇 |
1995年 | 7篇 |
1994年 | 1篇 |
1992年 | 2篇 |
1985年 | 1篇 |
1981年 | 3篇 |
1980年 | 1篇 |
排序方式: 共有543条查询结果,搜索用时 31 毫秒
461.
Justyna Majewska Beata Michalkiewicz 《Applied Physics A: Materials Science & Processing》2013,111(4):1013-1016
The one-step method of carbon nanotubes filled with continuous cobalt nanowires (CoF-CNT) synthesis is presented. Co/ZSM-5 (8 wt% Co) was used as catalyst for CoF-CNT production by methane decomposition at the temperature of 400 °C and 800 °C at atmospheric pressure in a conventional gas-flow system. The average diameter of the CoF-CNT is about 25 and 40 nm for products obtained at 400 °C and at 800 °C, respectively. The average size of coherently scattering domains along the normal to graphite layers L c , the interlayer spacing d 002, the graphitization degree of carbon, and the relative intensities of the G and D bands in Raman spectroscopy were determined to characterize the quality of carbon. It was proved that cobalt-filled carbon nanotubes can be produced by a simple method. The results of XRD, FE-SEM, and TEM show that CoF-CNT can be obtained even at 400 °C by catalytic decomposition of methane. On the basis of XRD, TEM, Raman spectroscopy was found that at a temperature of 800 °C, a better quality of carbon was produced. 相似文献
462.
463.
Diamond D5 is a hyperdiamond with the rings being mostly pentagonal and built up on the frame of mtn structure, appearing in clathrate hydrates of type II. As the seed of D5, the centrohexaquinane C17 was proposed (Diudea, Stud Univ Babes-Bolyai Chem 55(4):11–17, 2010). In this article, we study the molecular dynamics MD of four structures based on C17 skeleton, as all carbon or partly oxygenated derivatives. The results are discussed in terms of structural stability as given
by DFT calculations as well as by the stable fluctuations of root mean square deviations and total, potential and kinetic
energies provided by MD calculations. 相似文献
464.
Fabian Kallmeier Dr. Beata Dudziec Dr. Torsten Irrgang Prof. Dr. Rhett Kempe 《Angewandte Chemie (International ed. in English)》2017,56(25):7261-7265
The development of reactions that convert alcohols into important chemical compounds saves our fossil carbon resources as alcohols can be obtained from indigestible biomass such as lignocellulose. The conservation of our rare noble metals is of similar importance, and their replacement by abundantly available transition metals, such as Mn, Fe, or Co (base or nonprecious metals), in key technologies such as catalysis is a promising option. Herein, we report on the first base-metal-catalyzed synthesis of pyrroles from alcohols and amino alcohols. The most efficient catalysts are Mn complexes stabilized by PN5P ligands whereas related Fe and Co complexes are inactive. The reaction proceeds under mild conditions at catalyst loadings as low as 0.5 mol %, and has a broad scope and attractive functional-group tolerance. These findings may inspire others to use Mn catalysts to replace Ir or Ru complexes in challenging dehydrogenation reactions. 相似文献
465.
466.
Krzysztof Drwal Zuzanna Górska Patrycja Bończak Beata Krasnodębska-Ostręga 《Electroanalysis》2023,35(5):e202200397
The stripping voltammetry at HMDE is proposed for Cd and Pb (undesirable ingredients) determination in the natural brine (CCl >43 g L−1). Samples with so high salinity have to be significantly diluted. For ICP MS, a 105–6 times dilution is required, which disqualifies this method. The proposed procedure allows to determine Cd (0.001 μg L−1) and Pb (0.005 μg L−1) after only 100 times dilution. The thermal chloride stripping or isolation by Chelex 100 increase the quality of obtained data. The recovery study was performed. The LOQs are below recommendations related to the use of brines in balneology. 相似文献
467.
Energy-dispersive X-ray fluorescence spectrometer (EDXRF) with primary radiation monochromatized by LiF(200) crystal was developed. In the constructed spectrometer, the radiation from the Ag target X-ray tube operated at 50 kV and 40 mA excites the secondary target (Cu, Se, Zr or Mo). The characteristic radiation (Cu Kα, Se Kα, Zr Kα or Mo Kα) of the target is monochromatized with LiF(200) crystal and excites elements in the analyzed sample. The X-ray spectra are collected by thermoelectrically cooled Si-PIN detector with resolution of 145 eV at 5.9 keV. The pinhole collimator placed in front of the X-ray detector allows reducing size of the analyzed area. Quantitative analysis is performed using standardless fundamental parameters (FP) method. Because sample is excited using highly monochromatized radiation, the calculations are much simpler and analysis error resulting from uncertainty of X-ray tube spectral distribution is completely eliminated. Moreover, EDXRF system allows obtaining very low background and appropriate secondary target can be selected for the best excitation of the determined elements and to avoid overlapping of the analyte peaks with characteristic radiation originating from the secondary target. The FP calculations were verified using several certified reference materials of stainless steel. The spectrometer was used for nondestructive analysis of mono- and polycrystals of selenide spinels of general formula MxNyCrzSe4 (where M, N are Cu2+, Zn2+, Cd2+, Mn2+, Ge2+, Ni2+, V3+, Sb3+, Ga3+). The results from EDXRF were compared with those obtained by means of the wavelength-dispersive X-ray fluorescence spectrometry (WDXRF). 相似文献
468.
Corvis Y Korchowiec B Brezesinski G Follot S Rogalska E 《Langmuir : the ACS journal of surfaces and colloids》2007,23(6):3338-3348
There is evidence that serious pathologies are associated with aluminum (Al). In the present work, the influence of Al on enzymatic lipolysis was studied with the aim to get more insight into the possible link between the Al-induced membrane modification and the cytotoxicity of the trivalent cation (AlIII). Lipid monolayers were used as model membranes. The monomolecular film technique allowed monitoring the Al-dependent modifications of the lipid monolayer properties and enzyme kinetics. Two enzymes, namely, Candida rugosa lipase and a calcium (CaII)-dependent phospholipase A2 from porcine pancreas, were used to catalyze the lipolysis of triglyceride and phosphoglyceride monolayers, respectively. The results obtained show that Al modifies both the monolayer structure and enzymatic reaction rates. While the enzymes used in this study can be considered as probes detecting lipid membrane properties, it cannot be excluded that in physiological conditions modulation of the enzyme action by the Al-bound membranes is among the reasons for Al toxicity. 相似文献
469.
Monofluorophosphate was found to be a specific substrate for alkaline phosphatase (EC 3.1.3.1) forming novel biosensing schemes with potentiometric detection. Several utilities of this substrate/enzyme system in analytical chemistry will be demonstrated. The system is useful for direct detection of enzymes and substrates as well as for indirect determination of enzyme inhibitors and cofactors using common potentiometric instrumentation. The analytical values of reported biosensing schemes are significantly improved by their implementation into flow injection analysis. This paper presents recent developments in this area and suggests important prospects for further investigations and applications. 相似文献
470.
Korchowiec B Corvis Y Viitala T Feidt C Guiavarch Y Corbier C Rogalska E 《The journal of physical chemistry. B》2008,112(43):13518-13531
Interactions of phenantrene, anthracene, pyrene, chrysene, and benzo[a]pyrene (polyaromatic hydrocarbons) with model phospholipid membranes were probed using the Langmuir technique. The lipid monolayers were prepared using 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine, 1,2-dipalmitoyl-sn-glycero-3-phosphoglycerol, 1,2-dipalmitoyl-sn-glycero-3-phosphoserine, 1,2-myristoyl-sn-glycero-3-phosphoethanolamine, 1,2-dilauroyl-sn-glycero-3-phosphocholine, and cholesterol. Surface pressure and electrical surface potential were measured on mixed phospholipid/PAH monolayers spread on a pure water subphase. The morphology of the mixed monolayers was followed with Brewster angle microscopy. Polarization-modulation infrared reflection-absorption spectroscopy spectra obtained on DPPE/benzo[a]pyrene showed that the latter interacts with the carbonyl groups of the phospholipid. On the other hand, the activity of phospholipase A2 toward DLPC used as a probe to locate benzo[a]pyrene in the monolayers indicates that the polyaromatic hydrocarbons are not accessible to the enzyme. The results obtained show that all PAHs studied affect the properties of the pure lipid, albeit in different ways. The most notable effects, namely, film fluidization and morphology changes, were observed with benzo[a]pyrene. In contrast, the complexity of mixed lipid monolayers makes the effect of PAHs difficult to detect. It can be assumed that the differences observed between PAHs in monolayers correlate with their toxicity. 相似文献