全文获取类型
收费全文 | 1881篇 |
免费 | 70篇 |
国内免费 | 12篇 |
专业分类
化学 | 1508篇 |
晶体学 | 6篇 |
力学 | 32篇 |
数学 | 207篇 |
物理学 | 210篇 |
出版年
2023年 | 20篇 |
2022年 | 78篇 |
2021年 | 114篇 |
2020年 | 49篇 |
2019年 | 57篇 |
2018年 | 28篇 |
2017年 | 21篇 |
2016年 | 67篇 |
2015年 | 64篇 |
2014年 | 60篇 |
2013年 | 92篇 |
2012年 | 124篇 |
2011年 | 138篇 |
2010年 | 93篇 |
2009年 | 75篇 |
2008年 | 126篇 |
2007年 | 129篇 |
2006年 | 84篇 |
2005年 | 123篇 |
2004年 | 101篇 |
2003年 | 58篇 |
2002年 | 53篇 |
2001年 | 17篇 |
2000年 | 12篇 |
1999年 | 18篇 |
1998年 | 7篇 |
1997年 | 11篇 |
1996年 | 13篇 |
1995年 | 5篇 |
1994年 | 17篇 |
1993年 | 8篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 4篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1980年 | 11篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1973年 | 3篇 |
1968年 | 3篇 |
排序方式: 共有1963条查询结果,搜索用时 46 毫秒
941.
Determination of polar organic compounds in atmospheric aerosols by gas chromatography with ion trap tandem mass spectrometry
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
A gas chromatography with ion trap mass spectrometry method has been developed and validated for the analysis of 27 polar organic compounds in atmospheric aerosols. The target analytes were low‐molecular‐weight carboxylic acids and methoxyphenols, as relevant markers of source emissions and photochemical processes of organic aerosols. The operative parameters were optimized in order to achieve the best sensitivity and selectivity for the analysis. In comparison with the previous gas chromatography with mass spectrometry procedure based on single ion monitoring detection, the tandem mass spectrometry technique increased the analytical sensitivity by reducing detection limits for standard solutions from 1–2.6 to 0.1–0.4 ng/μL ranges (concentrations in the injected solution). In addition, it enhanced selectivity by reducing matrix interferences and chemical noise in the chromatogram. The applicability of the developed method in air quality monitoring campaigns was effectively checked by analyzing environmental samples collected in the Po Valley (Northern Italy) in different seasons. The obtained results indicate that the ion trap mass spectrometer may be an ideal alternative to high‐resolution mass spectrometers for the user‐friendly and cost‐effective determination of a wide range of molecular tracers in airborne particulate matter. 相似文献
942.
Pamela D. Noyes Sean C. Lema Simon C. Roberts Ellen M. Cooper Heather M. Stapleton 《Analytical and bioanalytical chemistry》2014,406(3):715-726
Thyroid hormones are critical regulators of normal development and physiological functioning in all vertebrates. Radioimmunoassay (RIA) approaches have been the method of choice for measuring circulating levels of thyroid hormones in vertebrates. While sensitive, RIA-based approaches only allow for a single analyte measurement per assay, can lack concordance across platforms and laboratories, and can be prone to analytical interferences especially when used with fish plasma. Ongoing advances in liquid chromatography tandem mass spectrometry (LC/MS/MS) have led to substantial decreases in detection limits for thyroid hormones and other biomolecules in complex matrices, including human plasma. Despite these advances, current analytical approaches do not allow for the measurement of native thyroid hormone in teleost fish plasma by mass spectrometry and continue to rely on immunoassay. In this study, we developed a new method that allows for the rapid extraction and simultaneous measurement of total T4 (TT4) and total T3 (TT3) in low volumes (50 μL) of fish plasma by LC/MS/MS. Methods were optimized initially in plasma from rainbow trout (Oncorhynchus mykiss) and applied to plasma from other teleost fishes, including fathead minnows (Pimephales promelas), mummichogs (Fundulus heteroclitus), sockeye salmon (Oncorhynchus nerka), and coho salmon (Oncorhynchus kisutch). Validation of method performance with T4- and T3-spiked rainbow trout plasma at 2 and 4 ng/mL produced mean recoveries ranging from 82 to 95 % and 97 to 105 %, respectively. Recovery of 13C12-T4 internal standard in plasma extractions was: 99?±?1.8 % in rainbow trout, 85?±?11 % in fathead minnow, 73?±?5.0 % in mummichog, 73?±?1.7 % in sockeye salmon, and 80?±?8.4 % in coho salmon. While absolute levels of thyroid hormones measured in identical plasma samples by LC/MS/MS and RIA varied depending on the assay used, T4/T3 ratios were generally consistent across both techniques. Less variability was measured among samples subjected to LC/MS/MS suggesting a more precise estimate of thyroid hormone homeostasis in the species targeted. Overall, a sensitive and reproducible method was established that takes advantage of LC/MS/MS techniques to rapidly measure TT4 and TT3 with negligible interferences in low volumes of plasma across a variety of teleost fishes. 相似文献
943.
Anna Laura Capriotti Chiara Cavaliere Patrizia Foglia Susy Piovesana Roberto Samperi Serena Stampachiacchiere Aldo Laganà 《Analytica chimica acta》2013
The nutritional and cancer-protective properties of the oil extracted mechanically from the ripe fruits of Olea europaea trees are attracting constantly more attention worldwide. The preparation of high-quality protein samples from plant tissues for proteomic analysis poses many challenging problems. In this study we employed a proteomic platform based on two different extraction methods, SDS and CHAPS based protocols, followed by two precipitation protocols, TCA/acetone and MeOH precipitation, in order to increase the final number of identified proteins. 相似文献
944.
Anna Laura Capriotti Giuseppe Caruso Chiara Cavaliere Susy Piovesana Roberto Samperi Aldo Laganà 《Analytica chimica acta》2013
Microparticles (MPs) are small fragments of apoptotic or activated cells that may contribute to pathological processes in many diseases. Platelet-derived MPs (PMPs) are the most abundant type of MPs in human blood. To characterize the proteins in PMPs we used a shotgun proteomics approach by nanoHPLC separation followed by MS analysis on an LTQ Orbitrap XL. PMPs were produced from isolated platelets stimulated with adenosine diphosphate (ADP). We developed an analytical platform constituted by two different steps: in the first one we used a standard shotgun strategy; in the second one, to improve low-molecular weight, low-abundance-proteins identification, the samples were fractionated using hydrogel nanoparticles, an enrichment system based on a mixed mechanism of dimensional exclusion and colorant affinity. This was chosen to tackle a common issue with shotgun approaches, in which the low-abundance proteins are not detected when surveys are on a broad scale. By means of the entire analytical platform, we identified 603 proteins, 243 of which were not previously identified. A simple and straightforward procedure for the study of PMPs was provided, producing a tool for further understanding their biological and pathological roles, and a baseline for future studies aimed at discovering biomarkers involved in several diseases. 相似文献
945.
Stereoselective syntheses on a gram scale of (3Z,6E,8E)-, (3Z,6E,8Z)-and (3Z,6Z,8Z)-3,6,8-dodecatrien-1-ol, 8, 9 and 10, respectively, are described. A key step of the synthesis of 8 consisted of a copper-mediated coupling reaction between 4-(2-tetrahydropyranyloxy)-1-butynylmagnesium bromide (15) and the mesyl ester of (2E,4E)-2,4-octadien-1-ol (14). A similar copper-mediated reaction between 15 and the mesyl ester of (E)-2-octen-4-yn-1-ol (19) was used to construct the C-12 carbon skeleton of 9. On the other hand, the synthesis of 10 was based on a palladium-promoted reaction between (Z)-1-bromo-1-pentene (23) and the organozinc bromide derived from 3,6-heptadiyn-1-yl acetate (27). 相似文献
946.
947.
Maria Chiara Aversa Anna Barattucci Paola Bonaccorsi Placido Giannetto 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1203-1208
Abstract L-cysteine is a stimulating starting product for the generation of transient sulfenic acids that add to suitable acceptors, allowing formation of sulfoxides showing a biologically active residue. For instance, N-(tert-butoxycarbonyl)-L-cysteine methyl ester furnished in few steps (R)-2-tert-butoxycarbonylamino-2-methoxycarbonyl-ethanesulfenic acid, which was readily converted into (R,S S )-(2-tert-butoxycarbonylamino-2-methoxycarbonyl-ethylsulfinyl)ethene, the methyl ester of Boc-protected nor-alliin. 相似文献
948.
Tristan de Rond Pamela Peralta-Yahya Xiaoliang Cheng Trent R. Northen Jay D. Keasling 《Analytical and bioanalytical chemistry》2013,405(14):4969-4973
Mass spectrometry based technologies are promising as generalizable high-throughput assays for enzymatic activity. In one such technology, a specialized enzyme substrate probe is presented to a biological mixture potentially exhibiting enzymatic activity, followed by an in situ enrichment step using fluorous interactions and nanostructure-initiator mass spectrometry. This technology, known as Nimzyme, shows great potential but is limited by the need to synthesize custom substrate analogs. We describe a synthetic route that simplifies the production of these probes by fashioning their perfluorinated invariant portion as an alkylating agent. This way, a wide variety of compounds can be effectively transformed into enzyme activity probes. As a proof of principle, a chloramphenicol analog synthesized according to this methodology was used to detect chloramphenicol acetyltransferase activity in cell lysate. This verifies the validity of the synthetic strategy employed and constitutes the first reported application of Nimzyme to a non-carbohydrate-active enzyme. The simplified synthetic approach presented here may help advance the application of mass spectrometry to high-throughput enzyme activity determination. Figure
The Nimzyme high-throughput enzyme activity assay allows for the detection of enzyme activity in cell lysate. Fluorous interactions between a specialized substrate probe and a nanostructure-initiator mass spectrometry surface allow for in situ cleanup and the subsequent collection of unambiguous mass spectra. One of the main hurdles that prevents the widespread adoption of this technology is the need to chemically synthesize the required probes. Here, we present a simplified route to derive Nimzyme probes from a wide variety of biologically interesting substrates. 相似文献
949.
950.
Fabio Terzi Jonathan Pelliciari Chiara Zanardi Laura Pigani Antti Viinikanoja Jukka Lukkari Renato Seeber 《Analytical and bioanalytical chemistry》2013,405(11):3579-3586
A gold electrode partially coated by graphene multilayer is developed and tested with respect to high concentrations of hydrogen peroxide. The effective use of conventional electrode materials for the determination of such an analyte by anodic oxidation or cathodic reduction is prevented by the occurrence of adsorptions fouling the electrode surface. This prevents reliable and repeatable voltammetric curves for being recorded and serious problems arise in quantitative analysis via amperometry. The gold–graphene electrode is shown to be effective in quantitative evaluation, by cathodic reduction, of hydrogen peroxide at concentration levels that are of interest in an industrial. Acid, neutral, and basic pH values have been tested through correct adjustment of a Britton Robinson buffer. The experiments have been performed both by cyclic voltammetry and with amperometry at constant potential in unstirred solution. The latter technique has been employed in drawing a calibration linear plot. In particular, the performances of the developed electrode system have been compared with those of both pure gold and pure graphene electrode materials. The bi-component electrode was more sensitive; co-catalytic action by the combination of the two components is hypothesised. The system is stable over many potential cycles, as checked by surface-enhanced Raman spectra recorded over time. 相似文献