全文获取类型
收费全文 | 282篇 |
免费 | 13篇 |
国内免费 | 3篇 |
专业分类
化学 | 178篇 |
力学 | 7篇 |
数学 | 74篇 |
物理学 | 39篇 |
出版年
2023年 | 1篇 |
2022年 | 4篇 |
2021年 | 6篇 |
2020年 | 3篇 |
2019年 | 2篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 7篇 |
2015年 | 5篇 |
2014年 | 9篇 |
2013年 | 11篇 |
2012年 | 18篇 |
2011年 | 25篇 |
2010年 | 14篇 |
2009年 | 8篇 |
2008年 | 14篇 |
2007年 | 29篇 |
2006年 | 13篇 |
2005年 | 13篇 |
2004年 | 15篇 |
2003年 | 10篇 |
2002年 | 17篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 7篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 7篇 |
1995年 | 2篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1992年 | 4篇 |
1991年 | 5篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1976年 | 1篇 |
1965年 | 2篇 |
1962年 | 1篇 |
1930年 | 1篇 |
排序方式: 共有298条查询结果,搜索用时 31 毫秒
11.
Abstract Methyl-substituted psoralens (4'-(hydroxymethyl)-4,5',8-trimethylpsoralen and 4,5',8-trimethylpsoralen) are found to yield an ene product as well as the expected [2+2] cycloaddition product from photochemical reaction with simple olefins. As determined by absorbance, liquid chromatography-mass spectrometry and nuclear magnetic resonance, both products are formed at the pyrone side of the respective psoralen. The product distribution is dependent on olefin concentration as well as the nature of the olefin. In deoxygenated solutions, cyclic olefins form as much as 50% ene product, while unsubstituted straight-chain olefins form as little as 3%. In oxygenated solutions, the product distribution is strongly affected by singlet oxygen. 相似文献
12.
13.
Shawna Grosskopf Kathy Hayes Lori Taylor William L Weber 《The Journal of the Operational Research Society》2017,68(4):377-389
We use data envelopment analysis to model the educational production function, and then explore how a shift to weighted student funding using the student weights embedded in the Texas School Finance Formula would alter the allocation of inputs and potential outputs. School outputs are measured as value-added reading and math scores on standard achievement tests. We find that if school districts allocated their resources efficiently, then they would not allocate their resources to campuses according to the funding model weights. Policies that promote greater efficiency would also enhance equity in educational outcomes. 相似文献
14.
Donald E. Kiely Kathy Semk-gray James M. Riordan 《Journal of carbohydrate chemistry》2013,32(2):191-211
Abstract N,N'-Diacetyl-tri-O-acetylxylaramide (8) and N,N'-diacetyl-tri-O-acetylribaramide (20) were directly converted to the nitrogen heterocycle 6-acetamido-2,6-diacetyloxy-aza-1,4-cyclohexadlen-3-one (9) with sodium acetate in acetic anhydride. Treatment of tri-O-acetylxylaramide (7) or tri-O-acetylribaramide (19) with the same solvent-base combination gave the highly crystalline 2,3,5,6-tetraacetyloxypyridlne (30) as the principal product. Mechanistic considerations for the formation of these nitrogen heterocycles are presented. 相似文献
15.
Lieven Van Meulebroek Julie Vanden Bussche Kathy Steppe Lynn Vanhaecke 《Analytical and bioanalytical chemistry》2014,406(11):2613-2626
In this study, a generic extraction protocol and full-scan high-resolution Orbitrap-mass spectrometry (MS) detection method were developed, enabling the metabolomic screening for carotenoids in tomato fruit tissue. To this end, the carotenoids lutein, zeaxanthin, α-carotene, β-carotene, and lycopene (representing both xanthofylls and carotenes) were considered. The extraction procedure was optimized by means of a D-optimal design and consisted of a liquid–liquid extraction with methanol/tert-butyl methyl ether (1:1, v/v). The considered compounds were detected by a single-stage ExactiveTM mass spectrometer, operating at a mass resolution of 100,000 full width at half maximum. The validation study demonstrated excellent performance in terms of linearity (R 2?>?0.99), repeatability (CV?≤?10.6 %), within-laboratory reproducibility (CV?≤?12.2 %), and mean corrected recovery (ranging from 85 to 106 %). Additionally, a comparative evaluation towards well-established detection techniques, i.e., tandem mass spectrometry (MS/MS) and ultraviolet-visible spectroscopy (UV–VIS) photodiode array, indicated superior performance of high-resolution Orbitrap-MS with regard to specificity/selectivity and sensitivity (with limits of detection ranging from 1.0 to 3.8 pg μL?1). As a result, it may be concluded that high-resolution Orbitrap-MS is a suited alternative for UV–VIS or MS/MS in analyzing carotenoids and may offer significant value in carotenoid research because of the metabolomic screening possibilities. Figure
Development and validation of a full-scan high-resolution Orbitrap-MS method for the analysis of carotenoids in tomato fruit tissue. Validation enclosed comparison with MS/MS and UV-VIS PDA 相似文献
16.
Chimera Spectrum Diagnostics for Peptides Using Two-Dimensional Partial Covariance Mass Spectrometry
Taran Driver Nikhil Bachhawat Leszek J. Frasinski Jonathan P. Marangos Vitali Averbukh Marina Edelson-Averbukh 《Molecules (Basel, Switzerland)》2021,26(12)
The rate of successful identification of peptide sequences by tandem mass spectrometry (MS/MS) is adversely affected by the common occurrence of co-isolation and co-fragmentation of two or more isobaric or isomeric parent ions. This results in so-called `chimera spectra’, which feature peaks of the fragment ions from more than a single precursor ion. The totality of the fragment ion peaks in chimera spectra cannot be assigned to a single peptide sequence, which contradicts a fundamental assumption of the standard automated MS/MS spectra analysis tools, such as protein database search engines. This calls for a diagnostic method able to identify chimera spectra to single out the cases where this assumption is not valid. Here, we demonstrate that, within the recently developed two-dimensional partial covariance mass spectrometry (2D-PC-MS), it is possible to reliably identify chimera spectra directly from the two-dimensional fragment ion spectrum, irrespective of whether the co-isolated peptide ions are isobaric up to a finite mass accuracy or isomeric. We introduce ‘3-57 chimera tag’ technique for chimera spectrum diagnostics based on 2D-PC-MS and perform numerical simulations to examine its efficiency. We experimentally demonstrate the detection of a mixture of two isomeric parent ions, even under conditions when one isomeric peptide is at one five-hundredth of the molar concentration of the second isomer. 相似文献
17.
Synthesis and Properties of Semiconducting Bispyrrolothiophenes for Organic Field‐Effect Transistors
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Crystalann Jones Dr. Damien Boudinet Dr. Yu Xia Mitch Denti Adita Das Dr. Antonio Facchetti Prof. Dr. Tom G. Driver 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5938-5945
A series of new highly soluble bispyrrolothiophenes were synthesized from vinyl azides by using transition‐metal‐catalyzed C?H‐bond functionalization. In addition to modifying the substituents present on the end‐pyrrolothiophene moieties, the arene linker in between the two units was also varied. The solution‐state properties and field‐effect‐transistor (FET) electrical behavior of these bispyrrolothiophenes was compared. Our investigations identified that the optical properties and oxidation potential of our compounds were dominated by the pyrrolothiophene unit with a λmax value of approximately 400 nm and oxidation at approximately 1 V. FET devices constructed with thin films of these bispyrrolothiophenes were also fabricated by means of thin‐film solution processing. One of these compounds, a bispyrrolothiophene linked with benzothiodiazole, exhibits a mobility of approximately 0.3 cm2 V?1 s?1 and the Ion/Ioff value is greater than 106. 相似文献
18.
Nicewonger R Fowke A Nguyen K Ditto L Caserta J Harris M Baldino CM 《Molecular diversity》2003,7(2-4):247-252
A microwave-assisted method is described for monoacylating 7-amino-5-aryl-6-cyanopyrido[2,3-d]pyrimidines using excess acid chlorides in pyridine. A diacylated intermediate is effectively deacylated to the product amide by a macroporous-Tris resin. A small library of 17 amides was prepared to validate the method. The integration of commercial microwave technology into the ArQule chemistry platform is also discussed. 相似文献
19.
S.M. Driver 《Surface science》2007,601(2):510-517
We have used a novel fibre-optic low-energy electron diffraction (FO-LEED) instrument, capable of low flux measurements that minimise electron beam damage to surface overlayers, to study methanethiolate (CH3-S-) structural phases formed on Cu{1 1 1} at temperatures between 110 and 300 K. Three structural phases were seen: a (√3 × √3)R30° phase that forms at 110-140 K; a (4 × 4) phase which was observed transiently at 110 K; and a pseudo-{1 0 0} reconstructed phase which forms at room temperature. We discuss these in the context of previous studies of this system, and demonstrate the ability of the FO-LEED instrument to record high-quality LEED patterns and intensity data from a strongly beam-sensitive surface. 相似文献
20.
We introduce a class of non-commutative Heisenberg-like infinite-dimensional Lie groups based on an abstract Wiener space. The Ricci curvature tensor for these groups is computed and shown to be bounded. Brownian motion and the corresponding heat kernel measures, {νt}t>0, are also studied. We show that these heat kernel measures admit: (1) Gaussian like upper bounds, (2) Cameron-Martin type quasi-invariance results, (3) good Lp-bounds on the corresponding Radon-Nikodym derivatives, (4) integration by parts formulas, and (5) logarithmic Sobolev inequalities. The last three results heavily rely on the boundedness of the Ricci tensor. 相似文献