全文获取类型
收费全文 | 613篇 |
免费 | 13篇 |
国内免费 | 3篇 |
专业分类
化学 | 428篇 |
晶体学 | 4篇 |
力学 | 13篇 |
数学 | 63篇 |
物理学 | 121篇 |
出版年
2023年 | 5篇 |
2022年 | 13篇 |
2021年 | 8篇 |
2020年 | 13篇 |
2019年 | 9篇 |
2018年 | 14篇 |
2017年 | 7篇 |
2016年 | 20篇 |
2015年 | 9篇 |
2014年 | 12篇 |
2013年 | 31篇 |
2012年 | 32篇 |
2011年 | 54篇 |
2010年 | 35篇 |
2009年 | 30篇 |
2008年 | 36篇 |
2007年 | 48篇 |
2006年 | 34篇 |
2005年 | 29篇 |
2004年 | 33篇 |
2003年 | 26篇 |
2002年 | 21篇 |
2001年 | 13篇 |
2000年 | 13篇 |
1999年 | 10篇 |
1998年 | 8篇 |
1997年 | 4篇 |
1996年 | 9篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有629条查询结果,搜索用时 15 毫秒
111.
Vitamin K(1) is a fat-soluble vitamin required for the gamma-carboxylation of vitamin K-dependent proteins. Recent work has suggested an important role for vitamin K(1) in bone health beyond its more established function in the control and regulation of blood coagulation. However, current UK recommended intakes do not reflect this recent evidence. The use of stable isotopes provides a powerful tool to investigate vitamin K kinetics, turnover and absorption in man, although published methods have reported difficulties in the extraction and analysis of isotope ratios of vitamin K in human plasma. In this paper, we report a new methodology for the extraction and measurement of isotope ratios in vitamin K(1). Sample clean-up is achieved with liquid-liquid extraction, enzyme hydrolysis with lipase and cholesterol esterase, and solid-phase extraction. Isotopic analysis of the pentafluoropropionyl derivative of vitamin K(1) is performed by gas chromatography/mass spectrometry (GC/MS). The limit of quantitation is equivalent to at least 0.3 nmol/L and the method is demonstrated to be linear over a range of enrichments. This method provides a robust alternative to previous work requiring the use of semi-preparative high-performance liquid chromatography (HPLC). 相似文献
112.
A separation method is reported for particle and biochemical analysis based on affinity interactions between particle surfaces under magnetic field. In this method, magnetic particles with immunoglobulin G (IgG) or streptavidin on the surface are flowed through a separation channel to form a deposition matrix for selectively capturing nonmagnetic analytes with protein A or biotin on the surface due to specific antigen (Ag)--antibody (Ab) interactions. This separation method was demonstrated using model reactions of IgG--protein A and streptavidin-biotin on particle surface. The features of this new separation method are (1) the deposited Ag-Ab complex can be examined and further analyzed under the microscope, (2) a kinetic study of complex binding is possible, and (3) the predeposited matrix can be formed selectively and changed easily. The detection limits were about 10(-11) g. The running time was less than 10 min. The selectivities of studied particles were 94% higher than those of label-controlled particles. This method extends the applications of analytical magnetapheresis to nonmagnetic particles. Preliminary study shows that this separation method has a great potential to provide a simple, fast, and selective analysis for particles, blood cells, and immunoassay related applications. 相似文献
113.
Tsai HY Chang CM Shen JL Chen LJ Yang TF Bor Fuh C 《Journal of chromatographic science》2006,44(6):354-358
beta-Carotene in vegetables and nutritional products is analyzed using solid-phase microextraction (SPME) coupled with liquid chromatography (LC) to improve the speed of analysis and to reduce the consumption of organic solvents. The relative standard deviations (RSDs) of this analytical method for beta-carotene determinations in vegetables and nutritional products are approximately 10% and 5%, respectively. The amount of beta-carotene was found to vary from 0.35 +/- 0.05 ppm to 76.5 +/- 6.9 ppm for several vegetables in Taiwan. This method was linear over the range of 0.4-40 ppm with correlation coefficients higher than 0.997. The experimentally determined level of beta-carotene in nutritional products varied from 3.8 +/- 0.2 ppm to 24.6 +/- 1.1 ppm following SPME-LC. The recoveries of beta-carotene for these measurements following SPME were all higher than 97% +/- 2% (n = 3). The detection limits of beta-carotene for this method were from 0.027 to 0.054 ppm. Conventional solvent extractions take approximately 4-6 h for extraction and reconcentration but SPME takes approximately 1 h. From several tens to hundreds of milliliters, organic solvents can be saved using SPME. SPME provides better analyses on beta-carotene than conventional solvent extraction for nutritional products in terms of speed, precision, simplicity, and solvent consumption. 相似文献
114.
We report a new method of blood typing based on the agglutination of red blood cell (RBC) with serum-treated magnetic particles in analytical magnetapheresis. Blood typing of ABO was demonstrated. The agglutination patterns of RBCs are different for different blood types and can be used to determine the ABO blood typing in analytical magnetapheresis. Six samples can be tested in each run. The running time was less than 10 min. Magnetic particles were prepared in the laboratory. The amount of RBCs needed for the agglutination test was about 1.0 microl of adult blood. The blood typing of ABO was used to illustrate the capable applications of analytical magnetapheresis to nonmagnetic samples like cells without magnetic labels. Analytical magnetapheresis has a great potential for cell related analysis. 相似文献
115.
Two inline matrix diversion methods were developed for the sensitive analysis of perchlorate in a matrix comprising up to 1000 mg l−1 of chloride, sulfate and bicarbonate ions using suppressed ion chromatography and conductivity detection. The first method used a cryptand C1 concentrator column, which exhibited a high selectivity for perchlorate ion over the other matrix anions. After retaining the sample anions in a concentrator column derivatized with a crytpand phase, a rinse step was implemented with a weak base to divert the matrix ions to waste while selectively retaining perchlorate in the concentrator column for subsequent analysis. The analysis was done using a 2 mm IonPac® AS16 or 2 mm IonPac® AS20 separator column. The second method was a two-dimensional matrix diversion method with a focus on improving the detection sensitivity. The first dimension was used to achieve some resolution of the matrix ions from perchlorate. The perchlorate ion was then diverted into a concentrator column for subsequent analysis in the second dimension. By pursuing analysis using a 4 mm IonPac® AS16 or IonPac® AS20 column in the first dimension and subsequently pursuing analysis using a 2 mm IonPac® AS16 or IonPac® AS20 column format, excellent sensitivities were achieved when the first and second dimensions were operated at the same linear flow velocity (cm min−1). While sensitive detection of perchlorate in the low μg l−1 regime was achieved by the above methods in the presence of matrix ions, superior recovery for perchlorate was demonstrated under a variety of matrix concentrations by the second method. 相似文献
116.
Combined use of elevated pressure in the liquid phase (15 kbar), a metal template and the sulfur nucleophilicity of [Pt2(μ-S)2(P-P)2] (P-P = diphosphine or 2 · monophosphine) facilitates the one-pot synthesis of 3,8-dibenzo-1,6-dithiacyclodecane. Under r.t.p., nucleophilic addition of [Pt2(μ-S)2(P-P)2] [P-P = 2 · PPh3; Ph2P(CH2)nPPh2, n = 2, 1,2-bis(diphenylphosphino)ethane (dppe), 3, 1,3-bis(diphenylphosphino)propane (dppp)] with α-α′-dichloro-o-xylene would terminate as a dithiolato bridged cation viz. [Pt2(μ-SCH2C6H4CH2S)(P-P)2]2+. Under high pressure (15 kbar) at r.t., these stoichiometric reactions progress via a “catalytic-like” pathway to yield 3,8-dibenzo-1,6-dithiacyclodecane (up to 35%), and a series of mechanistically relevant intermediates and byproducts. The dithiolated intermediates [Pt2(μ-SCH2C6H4CH2S)(P-P)2]2+ for PPh3 and dppp have been isolated as complexes and their crystal structure determined. The formation of 3,8-dibenzo-1,6-dithiacyclodecane demonstrates a convenient synthetic strategy over the multi-step synthesis of this macrocyclic dithioether. 相似文献
117.
This paper describes a liquid chromatography-electrospray-tandem mass spectrometry (LC-ESI-MS/MS) for the qualitative and quantitative analysis of three isoflavone aglycones (glycitein, daidzein and genistein) in human serum. Positive ion mode was used for the detection of these compounds and selective reaction monitoring (SRM) was employed for quantitative measurement. The SRM transitions monitored were as 285.0 → 242.0, 270.0 for glycitein, 255.0 → 137.0, 153.0, 181.0, 199.0 for daidzein and 271.0 → 153.0, 215.0 for genistein. d3-Daidzein was used as an internal standard for quantitative measurement. The linearity was good from 0.5 to 500 ng/ml. The detection limit based on a signal-to-noise ratio of three was 0.27, 0.38 and 0.29 ng/ml for glycitein, daidzein and genistein, respectively. A newly developed solid phase extraction (SPE) procedure was developed for sample pre-treatment. Good recovery, 92.3-103.2%, for three isoflavone aglycones were obtained. This newly developed method was successfully applied to evaluate isoflavone pharmacokinetic in human serum after oral administration. 相似文献
118.
Chen C Nagy G Walker AV Maurer K McShea A Moeller KD 《Journal of the American Chemical Society》2006,128(50):16020-16021
Time-of-flight secondary ion mass spectrometry (TOF SIMS) has been used in conjunction with a mass spectrometry cleavable linker to determine the percent conversion of reactions that were conducted site-selectively on an addressable microelectrode array. When combined with fluorescence techniques for analysis of the reactions, the TOF SIMS experiment provides a means for optimization of both reaction confinement and reaction efficiency on the microelectrode arrays. 相似文献
119.
Improving Li-ion battery charge rate acceptance through highly ordered hierarchical electrode design
Yunsung Kim Andy Drews Rajeswari Chandrasekaran Ted Miller Jeff Sakamoto 《Ionics》2018,24(10):2935-2943
In Li-ion technology, increasing electrode loading (thickness) is one approach to improve performance; however, this approach typically compromises power density and safety. To achieve the goal of decoupling energy and power density, a novel electrode architecture is proposed. The electrode design enhances uniform ionic current, especially in thick electrodes. A highly ordered and hierarchical (HOH) graphite anode concept was designed, fabricated, and tested for efficacy. The HOH electrodes consisted of ordered arrays of macro-scale line-of-sight linear channels made through laser ablation. SEM and Raman spectroscopy demonstrated that laser ablation is a feasible approach to fabricate HOH electrodes without affecting the graphite anode chemistry, respectively. A 65–120% improvement in charge rate acceptance (5.5 mAh/cm2) was achieved in the HOH electrodes compared to conventional electrodes. A restricted diffusion direct current polarization test determined that the HOH design improved ionic flow throughout porous electrodes. Altogether, the results of this study suggest that improved charge rate acceptance can be achieved by engineering electrode porosity to mitigate the effects of concentration polarization in high energy density graphite anodes. These findings can facilitate the development of higher energy and power density Li-ion batteries, while improving resilience against Li plating under severe charge conditions. 相似文献
120.
ColliderBit: a GAMBIT module for the calculation of high-energy collider observables and likelihoods
The GAMBIT Scanner Workgroup: Csaba Balázs Andy Buckley Lars A. Dal Ben Farmer Paul Jackson Abram Krislock Anders Kvellestad Daniel Murnane Antje Putze Are Raklev Christopher Rogan Aldo Saavedra Pat Scott Christoph Weniger Martin White 《The European Physical Journal C - Particles and Fields》2017,77(11):795
We describe ColliderBit, a new code for the calculation of high energy collider observables in theories of physics beyond the Standard Model (BSM). ColliderBit features a generic interface to BSM models, a unique parallelised Monte Carlo event generation scheme suitable for large-scale supercomputer applications, and a number of LHC analyses, covering a reasonable range of the BSM signatures currently sought by ATLAS and CMS. ColliderBit also calculates likelihoods for Higgs sector observables, and LEP searches for BSM particles. These features are provided by a combination of new code unique to ColliderBit, and interfaces to existing state-of-the-art public codes. ColliderBit is both an important part of the GAMBIT framework for BSM inference, and a standalone tool for efficiently applying collider constraints to theories of new physics. 相似文献