全文获取类型
收费全文 | 7056篇 |
免费 | 1502篇 |
国内免费 | 508篇 |
专业分类
化学 | 2023篇 |
晶体学 | 26篇 |
力学 | 1765篇 |
综合类 | 126篇 |
数学 | 1072篇 |
物理学 | 4054篇 |
出版年
2024年 | 15篇 |
2023年 | 85篇 |
2022年 | 204篇 |
2021年 | 242篇 |
2020年 | 217篇 |
2019年 | 205篇 |
2018年 | 227篇 |
2017年 | 330篇 |
2016年 | 381篇 |
2015年 | 296篇 |
2014年 | 483篇 |
2013年 | 526篇 |
2012年 | 487篇 |
2011年 | 486篇 |
2010年 | 358篇 |
2009年 | 414篇 |
2008年 | 461篇 |
2007年 | 418篇 |
2006年 | 353篇 |
2005年 | 347篇 |
2004年 | 291篇 |
2003年 | 280篇 |
2002年 | 242篇 |
2001年 | 227篇 |
2000年 | 201篇 |
1999年 | 180篇 |
1998年 | 147篇 |
1997年 | 123篇 |
1996年 | 126篇 |
1995年 | 109篇 |
1994年 | 86篇 |
1993年 | 77篇 |
1992年 | 78篇 |
1991年 | 54篇 |
1990年 | 42篇 |
1989年 | 36篇 |
1988年 | 27篇 |
1987年 | 33篇 |
1986年 | 26篇 |
1985年 | 27篇 |
1984年 | 29篇 |
1983年 | 12篇 |
1982年 | 22篇 |
1981年 | 11篇 |
1980年 | 10篇 |
1979年 | 14篇 |
1978年 | 3篇 |
1977年 | 7篇 |
1971年 | 2篇 |
1957年 | 4篇 |
排序方式: 共有9066条查询结果,搜索用时 31 毫秒
41.
Vitamin E represents a group of lipophilic phenolic compounds, including α-tocopherol, β-tocopherol, γ-tocopherol, and δ-tocopherol, and α-tocotrienol, β-tocotrienol, γ-tocotrienol, and δ-tocotrienol isomers. Different forms of vitamin E have been proven to exhibit varying biological activities. However, due to their structural similarities, the separation of vitamin E isomers is a challenging task. Therefore, it is crucial to establish an efficient method for isolating individual isomers. In this study, co-current countercurrent chromatography was employed to isolate vitamin E isomers from commercial capsules using a n-heptane-methanol-water (10:9.5:0.5, v/v) solvent system. The partition coefficients of the main constituents in the capsules ranged from 0.94 to 6.23, requiring over 450 min for a complete separation. To improve separation efficiency, a co-current elution mode was implemented and the flow rates of the two liquid phases as well as sample amount were examined. The results suggested that increasing the flow rate of the stationary phase and sample size could result in more effective separation, shorter separation time, and higher yield. It proved that co-current countercurrent chromatography was an effective method for the separation of vitamin E isomers. 相似文献
42.
Qin Wang Yong Jiang Nina Wei Jindong Li Mei Zhang Linwei Chen 《Journal of separation science》2023,46(24):2300518
43.
44.
设计合成了一种新的C3对称性含膦三足体衍生物N',N',N'-三(亚磷酸三乙酯)缩氨三乙酸(L)及其Eu(Ⅲ)配合物.用1H NMR、13C NMR、红外光谱、元素分析、差热-热重及紫外光谱对其组成和结构进行分析和表征.结果表明,三足体衍生物与稀土苦味酸盐(Eu(pic)3·6H2O)形成了1:1配合物Eu(pic)3L.综合运用紫外-可见吸收光谱法、荧光光谱法和循环伏安法研究了Eu(pic)3L与小牛胸腺DNA之间的结合模式,结果表明,配合物Eu(pic)3L与DNA之间以嵌插形式发生相互作用.将该配合物作为杂交探针,对其在DNA电化学传感器方面的应用进行了探讨.结果发现,该配合物在修饰单链DNA的电极检测作用下,无明显的电化学信号响应,而当将其用于检测杂交双链DNA时,出现了明显信号,并且该配合物的DNA传感器对互补序列、错配序列及非互补序列都有良好的选择作用. 相似文献
45.
46.
Identification strategies for flame retardants employing time‐of‐flight mass spectrometric detectors along with spectral and spectra‐less databases 下载免费PDF全文
Alin C. Ionas Ana Ballesteros Gómez Pim E. G. Leonards Adrian Covaci 《Journal of mass spectrometry : JMS》2015,50(8):1031-1038
In the past, the preferred strategy for the identification of unknown compounds was to search in an appropriate mass spectral database for spectra obtained using either electron ionisation (GC‐MS analyses) or collision‐induced dissociation (LC‐MS/MS analyses). Recently, an increase has been seen in the use of accurate mass instruments and spectra‐less databases, based on monoisotopic accurate mass alone. In this article, we describe a systematic workflow for the screening and identification of new flame retardants. This approach utilises LC‐quadrupole‐time‐of‐flight MS and spectra‐less databases based only on monoisotopic accurate mass for the identification of ‘unknowns’. An in‐house database was built, and the input parameters used in the data analysis process were optimised for flame retardant chemicals, so that it can be easily transferred to other laboratories. The procedure was successfully applied to dust, foam and textiles from car interiors and indoor consumer products. The developed method was demonstrated for the main new flame retardant present in Antiblaze V6 and for the three unreported reaction by‐products/impurities present in the same technical mixture. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
47.
48.
Patients are usually exposed to multiple drugs, and metabolite profiling of each drug in complex biological matrices is a big challenge. This study presented a new application of an improved high resolution mass spectrometry (HRMS)-based data-mining tools in tandem to fast and comprehensive metabolite identification of combination drugs in human. The model drug combination was metronidazole-pantoprazole-clarithromycin (MET-PAN-CLAR), which is widely used in clinic to treat ulcers caused by Helicobacter pylori. First, mass defect filter (MDF), as a targeted data processing tool, was able to recover all relevant metabolites of MET-PAN-CLAR in human plasma and urine from the full-scan MS dataset when appropriate MDF templates for each drug were defined. Second, the accurate mass-based background subtraction (BS), as an untargeted data-mining tool, worked effectively except for several trace metabolites, which were buried in the remaining background signals. Third, an integrated strategy, i.e., untargeted BS followed by improved MDF, was effective for metabolite identification of MET-PAN-CLAR. Most metabolites except for trace ones were found in the first step of BS-processed datasets, and the results led to the setup of appropriate metabolite MDF template for the subsequent MDF data processing. Trace metabolites were further recovered by MDF, which used both common MDF templates and the novel metabolite-based MDF templates. As a result, a total of 44 metabolites or related components were found for MET-PAN-CLAR in human plasma and urine using the integrated strategy. New metabolic pathways such as N-glucuronidation of PAN and dehydrogenation of CLAR were found. This study demonstrated that the combination of accurate mass-based multiple data-mining techniques in tandem, i.e., untargeted background subtraction followed by targeted mass defect filtering, can be a valuable tool for rapid metabolite profiling of combination drugs in vivo. 相似文献
49.
Kessarin Ngamdee Theerapong Puangmali Thawatchai Tuntulani Wittaya Ngeontae 《Analytica chimica acta》2015
A new chemical sensor based on the measuring of circular dichroism signal (CD) was fabricated from cysteamine capped cadmium sulfide quantum dots (Cys-CdS QDs). The chiral-thiol molecules, d-penicillamine (DPA) and l-penicillamine (LPA), were used to evaluate potentials of this sensor. Basically, DPA and LPA provide very low CD signals. However, the CD signals of DPA and LPA can be enhanced in the presence of Cys-CdS QDs. The CD spectra of DPA and LPA exhibited a mirror image profile. Parameters affecting the determination of DPA and LPA were thoroughly investigated in details. Under the optimized condition, the CD signals of DPA and LPA displayed a linear relationship with the concentrations of both enantiomers, ranging from 1 to 35 μM. Detection limits of this sensor were 0.49 and 0.74 μM for DPA and LPA, respectively. To demonstrate a potential application of this sensor, the proposed sensor was used to determine DPA and LPA in real urine samples. It was confirmed that the proposed detection technique was reliable and could be utilized in a broad range of applications. 相似文献
50.
In this article, we present a Python‐based library of high quality semi‐global potential energy surfaces for 50 polyatomic molecules with up to six atoms. We anticipate that these surfaces will find widespread application in the testing of new potential energy surface construction algorithms and nuclear ro‐vibrational structure theories. To this end, we provide the ability to generate the energy derivatives required for Taylor series expansions to sixth order about any point on the potential energy surface in a range of common coordinate systems, including curvilinear internal, Cartesian, and normal mode coordinates. The PyPES package, along with FORTRAN, C, MATLAB and Mathematica wrappers, is available at http://sourceforge.net/projects/pypes-lib . © 2015 Wiley Periodicals, Inc. 相似文献