全文获取类型
收费全文 | 2336篇 |
免费 | 103篇 |
国内免费 | 9篇 |
专业分类
化学 | 1963篇 |
晶体学 | 12篇 |
力学 | 25篇 |
数学 | 221篇 |
物理学 | 227篇 |
出版年
2023年 | 24篇 |
2022年 | 45篇 |
2021年 | 68篇 |
2020年 | 48篇 |
2019年 | 59篇 |
2018年 | 40篇 |
2017年 | 37篇 |
2016年 | 81篇 |
2015年 | 85篇 |
2014年 | 82篇 |
2013年 | 116篇 |
2012年 | 150篇 |
2011年 | 201篇 |
2010年 | 119篇 |
2009年 | 109篇 |
2008年 | 152篇 |
2007年 | 153篇 |
2006年 | 115篇 |
2005年 | 121篇 |
2004年 | 101篇 |
2003年 | 93篇 |
2002年 | 74篇 |
2001年 | 37篇 |
2000年 | 20篇 |
1999年 | 34篇 |
1998年 | 17篇 |
1997年 | 13篇 |
1996年 | 23篇 |
1995年 | 23篇 |
1994年 | 21篇 |
1993年 | 15篇 |
1992年 | 11篇 |
1991年 | 13篇 |
1990年 | 19篇 |
1989年 | 15篇 |
1988年 | 10篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 15篇 |
1984年 | 9篇 |
1983年 | 5篇 |
1982年 | 12篇 |
1980年 | 8篇 |
1979年 | 12篇 |
1978年 | 9篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1970年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有2448条查询结果,搜索用时 15 毫秒
111.
112.
Simultaneous determination of pharmaceuticals and some of their metabolites in wastewaters by high performance liquid chromatography with 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)
The present work describes the development of a sensitive and reliable analytical method based on solid‐phase extraction followed by analysis using liquid chromatography with tandem mass spectrometry for the simultaneous determination of pharmaceuticals from antibiotics (fluoroquinolones, sulfonamides, and their N4‐acetyl metabolites, and trimethoprim as sulfonamides synergist) and anthelmintics groups. SPE was optimized using different cartridges (Strata‐X, Oasis HLB, Strata C18‐E, Isolute C18, SampliQ C8/Si‐SCX). The highest recovery was achieved using Strata X cartridge (>80%) with good reproducibility (RSDs < 5%) despite various physicochemical properties of the compounds. Investigated analytes were identified and quantitatively determined by liquid chromatography with tandem mass spectrometry using multiple reaction monitoring. The method was shown to be linear over the concentration range of 0.05–30 μg/L for febantel and albendazole, and 0.10–60 μg/L for all other pharmaceuticals. Correlation coefficients were >0.99 for all compounds except for sulfamethazine (0.98). In order to demonstrate the applicability of the developed method, wastewater from the veterinary industry was analyzed. Results evidenced the presence of febantel, praziquantel, albendazole, enrofloxacin, sulfamethazine, and sulfadiazine. 相似文献
113.
Ming Xu Sandrine Frelon Olivier Simon Ryszard Lobinski Sandra Mounicou 《Analytical and bioanalytical chemistry》2014,406(4):1063-1072
A non-denaturating isoelectric focusing (ND-IEF) gel electrophoresis protocol has been developed to study and identify uranium (U)–protein complexes with laser ablation–inductively coupled plasma mass spectrometry (LA-ICP MS) and electrospray ionization mass spectrometry (ESI-MS). The ND-IEF-LA-ICP MS methodology set-up was initiated using in vitro U–protein complex standards (i.e., U–bovine serum albumin and U–transferrin) allowing the assessment of U recovery to 64.4?±?0.4 %. This methodology enabled the quantification of U–protein complexes at 9.03?±?0.23, 15.27?±?0.36, and 177.31?±?25.51 nmol U L?1 in digestive gland cytosols of the crayfish, Procambarus clarkii, exposed respectively to 0, 0.12, and 2.5 μmol of waterborne depleted U L?1 during 10 days. ND-IEF-LA-ICP MS limit of detection was 19.3 pmol U L?1. Elemental ICP MS signals obtained both in ND-IEF electropherograms and in size exclusion chromatograms of in vivo U–protein complexes revealed interactions between U- and Fe- and Cu-proteins. Moreover, three proteins (hemocyanin, pseudohemocyanin-2, and arginine kinase) out of 42 were identified as potential uranium targets in waterborne-exposed crayfish cytosols by microbore reversed phase chromatography coupled to molecular mass spectrometry (µRPC-ESI-MS/MS) after ND-IEF separation. Figure
The paper presents the development of a non-denaturating protocol for the separation of uranium-protein complexes by isoelectric focusing gel electrophoresis (ND-IEF) before their quantitative detection by Laser Ablation coupled to Inductively Coupled Plasma Mass Spectrometry. Potential protein targets of uranium are subsequently identified by liquid chromatography - electrospray mass spectrometry 相似文献
114.
Mike De Vrieze Dieter Verzele Roman Szucs Pat Sandra Frédéric Lynen 《Analytical and bioanalytical chemistry》2014,406(25):6179-6188
Over the past decades, several in vitro methods have been tested for their ability to predict drug penetration across the blood-brain barrier. So far, in high-performance liquid chromatography, most attention has been paid to micellar liquid chromatography and immobilized artificial membrane (IAM) LC. IAMLC has been described as a viable approach, since the stationary phase emulates the lipid environment of a cell membrane. However, research in IAMLC has almost exclusively been limited to phosphatidylcholine (PC)-based stationary phases, even though PC is only one of the lipids present in cell membranes. In this article, sphingomyelin and cholester stationary phases have been tested for the first time towards their ability to predict drug penetration across the blood-brain barrier. Upon comparison with the PC stationary phase, the sphingomyelin- and cholester-based columns depict similar predictive performance. Combining data from the different stationary phases did not lead to improvements of the models. Figure
Schematic representation of how IAM-LC is used to predict drug penetration across the blood-brain barrier. 相似文献
115.
Jana ic
labur Marko Brajer Sandra Voa Ante Gali Sanja Radman Suzana Rimac-Brn
i Qiang Xia Zhenzhou Zhu Nabil Grimi Francisco J. Barba Nataa Hulak 《Molecules (Basel, Switzerland)》2021,26(7)
Spices are a popular food of plant origin, rich in various phytochemicals and recognized for their numerous properties. The aim of the study was to evaluate the antioxidant and antimicrobial activity, as well as the content of specialized metabolites, of aqueous extracts of three spice species––garlic (Allium sativum L.), ginger (Zingiber officinalle L.) and turmeric (Curcuma longa L.)––prepared by green extraction methods. Ultrasound treatment increased the chromaticity parameter b value of turmeric and ginger extracts, thus indicating a higher yellow color predominantly due to curcuminoids characteristic of these species. Ultrasound-assisted extraction significantly increased the content of total soluble solids, phenolic compounds, total carotenoids and vitamin C. The temperature of the system was also an important factor, with the highest (70 °C) conditions in ultrasound-assisted extraction having a positive effect on thermolabile compounds (vitamin C, phenolics, total carotenoids). For example, turmeric extract treated with ultrasound at 70 °C had up to a 67% higher vitamin C content and a 69.4% higher total carotenoid content compared to samples treated conventionally at the same temperature, while ginger extracts had up to 40% higher total phenols. All different concentrations of spice extracts were not sufficient for complete inhibition of pathogenic bacterial strains of Salmonella, L. monocytogenes and S. aureus; however, only garlic extracts had an effect on slowing down the growth and number of L. monocytogenes colonies. Spice extracts obtained by ultrasonic treatment contained a significantly higher level of bioactive compounds and antioxidant capacity, suggesting that the extracts obtained have significant nutritional potential and thus a significant possibility for phytotherapeutic uses. 相似文献
116.
Melanie Platzer Sandra Kiese Thomas Herfellner Ute Schweiggert-Weisz Oliver Miesbauer Peter Eisner 《Molecules (Basel, Switzerland)》2021,26(5)
Numerous assays were developed to measure the antioxidant activity, but each has limitations and the results obtained by different methods are not always comparable. Popular examples are the DPPH and ABTS assay. Our aim was to study similarities and differences of these two assay regarding the measured antioxidant potentials of 24 phenolic compounds using the same measurement and evaluation methods. This should allow conclusions to be drawn as to whether one of the assays is more suitable for measuring specific subgroups like phenolic acids, flavonols, flavanones, dihydrochalcones or flavanols. The assays showed common trends for the mean values of most of the subgroups. Some dihydrochalcones and flavanones did not react with the DPPH radical in contrast to the ABTS radical, leading to significant differences. Therefore, to determine the antioxidant potential of dihydrochalcone or flavanone-rich extracts, the ABTS assay should be preferred. We found that the results of the flavonoids in the DPPH assay were dependent on the Bors criteria, whereas the structure–activity relationship in the ABTS assay was not clear. For the phenolic acids, the results in the ABTS assay were only high for pyrogallol structures, while the DPPH assay was mainly determined by the number of OH groups. 相似文献
117.
Sandra Grebenteuch Clemens Kanzler Stefan Klaußnitzer Lothar W. Kroh Sascha Rohn 《Molecules (Basel, Switzerland)》2021,26(4)
Lipid oxidation and the resulting volatile organic compounds are the main reasons for a loss of food quality. In addition to typical compounds, such as alkanes, aldehydes and alcohols, methyl ketones like heptan-2-one, are repeatedly described as aroma-active substances in various foods. However, it is not yet clear from which precursors methyl ketones are formed and what influence amino compounds have on the formation mechanism. In this study, the formation of methyl ketones in selected food-relevant fats and oils, as well as in model systems with linoleic acid or pure secondary degradation products (alka-2,4-dienals, alken-2-als, hexanal, and 2-butyloct-2-enal), has been investigated. Elevated temperatures were chosen for simulating processing conditions such as baking, frying, or deep-frying. Up to seven methyl ketones in milk fat, vegetable oils, and selected model systems have been determined using static headspace gas chromatography-mass spectrometry (GC-MS). This study showed that methyl ketones are tertiary lipid oxidation products, as they are derived from secondary degradation products such as deca-2,4-dienal and oct-2-enal. The study further showed that the position of the double bond in the precursor compound determines the chain length of the methyl ketone and that amino compounds promote the formation of methyl ketones to a different degree. These compounds influence the profile of the products formed. As food naturally contains lipids as well as amino compounds, the proposed pathways are relevant for the formation of aroma-active methyl ketones in food. 相似文献
118.
Garcia S Chavez L Lowery TJ Han SI Wemmer DE Pines A 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,184(1):72-77
Hyperpolarized xenon associated with ligand derivatized cryptophane-A cages has been developed as a NMR based biosensor. To optimize the detection sensitivity we describe use of xenon exchange between the caged and bulk dissolved xenon as an effective signal amplifier. This approach, somewhat analogous to 'remote detection' described recently, uses the chemical exchange to repeatedly transfer spectroscopic information from caged to bulk xenon, effectively integrating the caged signal. After an optimized integration period, the signal is read out by observation of the bulk magnetization. The spectrum of the caged xenon is reconstructed through use of a variable evolution period before transfer and Fourier analysis of the bulk signal as a function of the evolution time. 相似文献
119.
Granwehr J Harel E Hilty C Garcia S Chavez L Pines A Sen PN Song YQ 《Magnetic resonance imaging》2007,25(4):449-452
Remote detection nuclear magnetic resonance and magnetic resonance imaging can be used to study fluid flow and dispersion in a porous medium from a purely Eulerian point of view (i.e., in a laboratory frame of reference). Information about fluid displacement is obtained on a macroscopic scale in a long-time regime, while local velocity distributions are averaged out. It is shown how these experiments can be described using the common flow propagator formalism and how experimental data can be analyzed to obtain effective porosity, flow velocity inside the porous medium, fluid dispersion and flow tracing of fluid. 相似文献
120.
In this brief review, an overview about recent efforts to simulate the spectroscopic signatures of chiral molecules is given with focus on real time propagation approaches to solve the time-dependent Schrödinger equation. In particular the simulation of electric circular dichroism spectra and vibrational Raman optical activity is discussed. In comparison to linear absorption spectra, where only the response of the electric dipole moment is necessary, the response of the magnetic dipole moment and electric quadrupole moment is more intricate. Issues such as gauge origin dependence, basis set dependence, non-local potentials and the dipole approximation are addressed. 相似文献