全文获取类型
收费全文 | 600篇 |
免费 | 7篇 |
国内免费 | 1篇 |
专业分类
化学 | 359篇 |
晶体学 | 6篇 |
力学 | 15篇 |
数学 | 35篇 |
物理学 | 193篇 |
出版年
2022年 | 3篇 |
2021年 | 4篇 |
2019年 | 3篇 |
2018年 | 5篇 |
2016年 | 3篇 |
2015年 | 8篇 |
2014年 | 7篇 |
2013年 | 39篇 |
2012年 | 29篇 |
2011年 | 40篇 |
2010年 | 11篇 |
2009年 | 15篇 |
2008年 | 20篇 |
2007年 | 15篇 |
2006年 | 31篇 |
2005年 | 34篇 |
2004年 | 29篇 |
2003年 | 21篇 |
2002年 | 17篇 |
2001年 | 13篇 |
2000年 | 16篇 |
1999年 | 20篇 |
1998年 | 10篇 |
1997年 | 6篇 |
1996年 | 9篇 |
1995年 | 6篇 |
1994年 | 8篇 |
1993年 | 6篇 |
1992年 | 12篇 |
1991年 | 8篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 3篇 |
1987年 | 8篇 |
1986年 | 7篇 |
1985年 | 16篇 |
1984年 | 12篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 11篇 |
1979年 | 9篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 7篇 |
1975年 | 3篇 |
1974年 | 6篇 |
1973年 | 5篇 |
1972年 | 3篇 |
1897年 | 3篇 |
排序方式: 共有608条查询结果,搜索用时 78 毫秒
81.
In Part I of this work, we developed a method for the detection of drugs of abuse in biological samples based on fast gradient elution liquid-chromatography coupled with diode array spectroscopic detection (LC-DAD). In this part of the work, we apply the chemometric method of target factor analysis (TFA) to the chromatograms. This algorithm identifies the target compounds present in chromatograms based on a spectral library, resolves nearly co-eluting components, and differentiates between drugs with similar spectra. The ability to resolve highly overlapped peaks using the spectral data afforded by the DAD is what distinguishes the present method from conventional library searching methods. Our library has a mean list length (MLL) of 1.255 and a discriminating power of 0.997 when both retention index and spectral factors are considered. The algorithm compares a library of 47 different compounds of toxicological relevance to unknown samples and identifies which compounds are present based on spectral and retention index matching. The application of a corrected retention index for identification rather than raw retention times compensates for long-term and column-to-column retention time shifts and allows for the use of a single library of spectral and retention data. Training data sets were used to establish the search and identification parameters of the method. A validation data set of 70 chromatograms was used to calculate the sensitivity (correct identification of positives) and specificity (correct identification of negatives) of the method, which were found to be 92% and 94%, respectively. 相似文献
82.
Jeremy M. Carr 《Tetrahedron》2008,64(13):2897-2905
Reductive desymmetrization of 2-methyl-2-substituted-cycloalkane-1,3-diones can be effected using either NaBH4 in DME or lithium tri-tert-butoxyaluminum hydride (LTBA) in THF at −60 °C. The former is a new approach that offers slightly greater diastereoselectivity in the reduction of 2,2-disubstituted-cyclopentane-1,3-diones while LTBA is superior with 2,2-disubstituted-cyclohexane-1,3-diones. Both conditions minimize subsequent reduction to diols thereby furnishing high yields of 1,3-ketols. Particularly rapid monoreductions are observed with 2-methyl-2-nitroethylcyclopentane-1,3-dione and 2-cyanoethyl-2-methylcyclopentane-1,3-dione when treated with NaBH4 in DME at −60 °C. As expected, diastereoselectivity varies considerably with the substitution at C-2. 相似文献
83.
The uptake of ascorbate by neuroblastoma cells using a ruthenium oxide hexacyanoferrate (RuOHCF)-modified carbon fiber disc (CFD) microelectrode (r = 14.5 microm) was investigated. By use of the proposed electrochemical sensor the amperometric determination of ascorbate was performed at 0.0 V in minimum essential medium (MEM, pH = 7.2) with a limit of detection of 25 micromol L(-1). Under the optimum experimental conditions, no interference from MEM constituents and reduced glutathione (used to prevent the oxidation of ascorbate during the experiments) was noticed. The stability of the RuOHCF-modified electrode response was studied by measuring the sensitivity over an extended period of time (120 h), a decrease of around 10% being noticed at the end of the experiment. The rate of ascorbate uptake by control human neuroblastoma SH-SY5Y cells, and cells transfected with wild-type Cu,Zn-superoxide dismutase (SOD WT) or with a mutant typical of familial amyotrophic lateral sclerosis (SOD G93A), was in agreement with the level of oxidative stress in these cells. The usefulness of the RuOHCF-modified microelectrode for in vivo monitoring of ascorbate inside neuroblastoma cells was also demonstrated. 相似文献
84.
Elevated levels of trans‐indolyl‐3‐acryloylglycine (IAcrGly) have been reported in the urine of people with various conditions including pervasive developmental disorders (PDDs) such as autism and Asperger syndrome. Reversed‐phase high‐performance liquid chromatography with ultra‐violet detection using traditional particle silica‐based columns subsequent to solid‐phase extraction (SPE) has been the preferred assay method; requiring long analytical run times, high flow rates and high solvent usage. Recent developments in monolithic HPLC column technology facilitated the development of a novel analytical method, for the detection and quantification of urinary IAcrGly. The revised method eliminates the requirement for SPE pre‐treatment, reduces sample run‐time and decreases solvent volumes. Five urine samples from people diagnosed with PDD were run in quadruplicate to test the intra‐ and inter‐day reliability of the new method based on retention time, peak area and peak height for IAcrGly. Detection was by UV with IAcrGly confirmation by MS/MS‐MS. Relative standard deviations showed significant improvement with the new method for all parameters. The new method represents a major advancement in the detection and quantification of IAcrGly by reducing time and cost of analysis whilst improving detection limits and reproducibility. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
85.
Kevin P. Cole David Mitchell M. Austin Carr James R. Stout Matthew D. Belvo 《Tetrahedron: Asymmetry》2009,20(11):1262-1266
A route for the synthesis of (S,S)-7-amino-5-methyl-5H-dibenzo[b,d]azepin-6(7H)-one hydrochloride is disclosed. The synthesis includes a Friedel–Crafts alkylation to form the seven-membered ring and a highly efficient classical resolution. Additional studies on the enantiopure material showed the amine to be highly resistant to racemization, which led us to investigate the unexpected stability. We propose that the inherent axial chirality contained in the dibenzazepinone works to produce an interesting chirality transfer mechanism, which accounts for the observed robustness of the stereocenter. This previously unrecognized stereochemical element exists within this specific class of molecules, and they should be drawn in a manner which displays the axial chirality. 相似文献
86.
A thermogravimetry-microchromatography assembling has been developed and tested for solvent vaporization studies. Cyclodextrine
and calcium sulfate dehydrations as well as cobalt carbonate decomposition were studied.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
87.
This paper describes results of a recent study that characterizes effective index of refraction for commercially available matched-clad, single-mode optical fibers. Effects of product parameter, stress, and temperature ranges on the index are reported. Direct measurements of flight times, fiber lengths, tensile loads, elongations, and temperatures provide index of refraction accuracy to four decimal places. Nominal effective index of refraction values found for unshifted fiber were 1.4675 and 1.4681 at 1300 nm and 1550 nm wavelengths, respectively; values for dispersion-shifted fiber were 1.4718 and 1.4711. Both fiber types at each wavelength displayed index versus stress slopes of -0.000024/kpsi, and index versus temperature slopes of 0.000012/°C. 相似文献
88.
Part I. Chromatography using ultra-stable metal oxide-based stationary phases for HPLC 总被引:1,自引:0,他引:1
The first part of the review contrasts the main drawbacks of silica-based packings such as their relative thermal and chemical instability with excellent stability of metal oxides. The paper concerns mainly ZrO2, TiO2 and Al2O3. Methods of preparation of spherical particles for HPLC are described. Surface chemistry of the oxides is, however, very different from that of silica. Ability of the oxides to ion- and ligand exchange is discussed from a chromatographic point of view. 相似文献
89.
90.
Comprehensive two-dimensional liquid chromatography (LC×LC) has received a great deal of attention during the past few years because of its extraordinary resolving power. The biggest advantage of this technique is that very high peak capacities can be generated in a relatively short time. Numerous approaches to maximize the peak capacity in LC×LC have been employed. In this work we investigate the impact of the first dimension mobile phase on selectivity. LC×LC has several potential advantages over one-dimensional LC (1DLC) in that unconventional solvents, at least in reversed-phase LC, can be used. For example, solvents which strongly adsorb in the UV in the first dimension are not problematic in LC×LC. This so because the UV detector is placed after the second dimensional column, as pulses of the first dimension eluent arrive at the second dimensional column, they elute well before the solutes of interest and therefore do not interfere at all with detection of solute peaks. So far, the most widely used solvents in reversed-phase 1DLC are methanol and acetonitrile. However, the "UV advantage" of 2DLC allows us to employ UV active solvents, such as acetone. We compare their differential selectivities to that of acetonitrile for the separation of 23 indole acetic acids of interest in plant biology. We also apply them to the separation of a maize seed extract, a very complex sample. In both sample sets, mobile phase composition can be an important parameter to increase the orthogonality of the two dimensions and thus, to increase the effective peak capacity of LC×LC. 相似文献