全文获取类型
收费全文 | 287篇 |
免费 | 24篇 |
国内免费 | 2篇 |
专业分类
化学 | 222篇 |
晶体学 | 3篇 |
力学 | 1篇 |
数学 | 61篇 |
物理学 | 26篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 6篇 |
2020年 | 5篇 |
2019年 | 3篇 |
2018年 | 2篇 |
2016年 | 20篇 |
2015年 | 9篇 |
2014年 | 9篇 |
2013年 | 13篇 |
2012年 | 19篇 |
2011年 | 16篇 |
2010年 | 7篇 |
2009年 | 8篇 |
2008年 | 13篇 |
2007年 | 25篇 |
2006年 | 19篇 |
2005年 | 14篇 |
2004年 | 18篇 |
2003年 | 15篇 |
2002年 | 9篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 1篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1958年 | 1篇 |
排序方式: 共有313条查询结果,搜索用时 15 毫秒
51.
Andrews KW Schweitzer A Zhao C Holden JM Roseland JM Brandt M Dwyer JT Picciano MF Saldanha LG Fisher KD Yetley E Betz JM Douglass L 《Analytical and bioanalytical chemistry》2007,389(1):231-239
As part of a study initiating the development of an analytically validated Dietary Supplement Ingredient Database (DSID) in
the United States (US), a selection of dietary supplement products were analyzed for their caffeine content. Products sold
as tablets, caplets, or capsules and listing at least one caffeine-containing ingredient (including botanicals such as guarana,
yerba mate, kola nut, and green tea extract) on the label were selected for analysis based on market share information. Two
or three lots of each product were purchased and analyzed using high-pressure liquid chromatography (HPLC). Each analytical
run included one or two National Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs) and two
products in duplicate. Caffeine intake per serving and per day was calculated using the maximum recommendations on each product
label. Laboratory analysis for 53 products showed product means ranging from 1 to 829 mg caffeine/day. For products with a
label amount for comparison (n = 28), 89% (n = 25) of the products had analytically based caffeine levels/day of between −16% and +16% of the claimed levels. Lot-to-lot
variability (n = 2 or 3) for caffeine in most products (72%) was less than 10%. 相似文献
52.
Dwyer JT Holden J Andrews K Roseland J Zhao C Schweitzer A Perry CR Harnly J Wolf WR Picciano MF Fisher KD Saldanha LG Yetley EA Betz JM Coates PM Milner JA Whitted J Burt V Radimer K Wilger J Sharpless KE Hardy CJ 《Analytical and bioanalytical chemistry》2007,389(1):37-46
This article illustrates the importance of having analytical data on the vitamin and mineral contents of dietary supplements
in nutrition studies, and describes efforts to develop an analytically validated dietary supplement ingredient database (DSID)
by a consortium of federal agencies in the USA. Preliminary studies of multivitamin mineral supplements marketed in the USA
that were analyzed as candidates for the DSID are summarized. Challenges are summarized, possible future directions are outlined,
and some related programs at the Office of Dietary Supplements, National Institutes of Health are described. The DSID should
be helpful to researchers in assessing relationships between intakes of vitamins and minerals and health outcomes. 相似文献
53.
Sutherland F Gras R Luong J Cortes H Curvers J 《Journal of chromatographic science》2007,45(8):486-491
A novel analytical procedure has been developed for the analysis of ultra trace levels of 1,2-dichloroethane (EDC) in air using sample enrichment in combination with micromachined gas chromatography (GC) and differential mobility detection (DMD). When compared to other contemporary GC techniques, such as GC-flame ionization detection, GC-electron capture detection, or GC-electrolytic conductivity detection, the employment of a DMD in combination with a preconcentrator provided better sensitivity and markedly improved selectivity. The increase in sensitivity reduces false-negative results, while the improvement in selectivity decreases the potential for false-positive results. Using the technique described, a complete analysis can be conducted in less than 10 min, with a detection limit of 0.7 ppb (v/v) of EDC and a short term precision of less than 6%. A correlation coefficient of 0.9988 was obtained over an EDC concentration range from 0.7 ppb to 36.4 ppb (v/v). The analytical system also has an on-board microTCD in series with the DMD, allowing both detector outputs to be monitored simultaneously. With the pre-concentration technique, the microTCD can detect EDC as low as 15 ppb (v/v) with a substantially enhanced linear dynamic range in addition to providing a confirmation means for the presence of EDC at the level cited. 相似文献
54.
Jakubczyk D Barth C Kubas A Anastassacos F Koelsch P Fink K Schepers U Brenner-Weiß G Bräse S 《Analytical and bioanalytical chemistry》2012,403(2):473-482
N-Acyl-l-homoserine lactones (AHLs) are synthesized by Gram-negative bacteria. These quorum-sensing molecules play an important role
in the context of bacterial infection and biofilm formation. They also allow communication between microorganisms and eukaryotic
cells (inter-kingdom signalling). However, very little is known about the entire mechanism of those interactions. Precise
structural studies are required to analyse the different AHL isomers as only one form is biologically most active. Theoretical
studies combined with experimental infrared and Raman spectroscopic data are therefore undertaken to characterise the obtained
compounds. To mimic interactions between AHL and cell membranes, we studied the insertion of AHL in supported lipid bilayers,
using vibrational sum-frequency-generation spectroscopy. Deuterium-labelled AHLs were thus synthesized. Starting from readily
available deuterated fatty acids, a two-step procedure towards deuterated N-acyl-l-homoserine lactones with varying chain lengths is described. This included the acylation of Meldrum’s acid followed by amidation.
Additionally, the detailed analytical evaluation of the products is presented herein. 相似文献
55.
Fraser SJ Mulet X Martin L Praporski S Mechler A Hartley PG Polyzos A Separovic F 《Langmuir : the ACS journal of surfaces and colloids》2012,28(1):620-627
A strategy for tethering lipid liquid crystalline submicrometer particles (cubosomes) to a gold surface for the detection of proteins is reported. Time-resolved quartz crystal microbalance (QCM-D) was used to monitor the cubosome-protein interaction in real time. To achieve specific binding, cubosomes were prepared from the nonionic surfactant phytantriol, block-copolymer, Pluronic F-127, and a secondary biotinylated lipid, 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[biotinyl(polyethyleneglycol)-2000], which enabled attachment of the particles to a neutravidin (NAv)-alkanethiol monolayer at the gold surface of the QCM sensor chip. A second set of cubosomes was further functionalized with addition of the glycolipid (G(M1)) to facilitate a specific binding uptake of the protein, cholera toxin B subunit (CT(B)), from solution. QCM-D confirmed the specificity of the cubosome-NAv binding. The analysis of titration experiments, also performed with QCM, suggests that an optimal concentration of cubosomes is required for the efficient packing of the particles at the surface: high cubosome concentrations lead to chaotic cubosome binding onto the surface, sterically inhibiting surface attachment, or require significant reorganization to permit uniform cubosome coverage. The methodology enabled the straightforward preparation of a complex nanostructured edifice, which was then used to specifically capture analyte proteins (cholera toxin B subunit or free NAv) from solution, supporting the potential for development of this approach as a biosensing platform. 相似文献
56.
Cleaves HJ Michalkova Scott A Hill FC Leszczynski J Sahai N Hazen R 《Chemical Society reviews》2012,41(16):5502-5525
Life is believed to have originated on Earth ~4.4-3.5 Ga ago, via processes in which organic compounds supplied by the environment self-organized, in some geochemical environmental niches, into systems capable of replication with hereditary mutation. This process is generally supposed to have occurred in an aqueous environment and, likely, in the presence of minerals. Mineral surfaces present rich opportunities for heterogeneous catalysis and concentration which may have significantly altered and directed the process of prebiotic organic complexification leading to life. We review here general concepts in prebiotic mineral-organic interfacial processes, as well as recent advances in the study of mineral surface-organic interactions of potential relevance to understanding the origin of life. 相似文献
57.
Strain promoted cycloaddition is presented as a tool for RNA conjugation on the solid phase; RNA-cyclooctyne conjugates are prepared by cycloaddition to both azide (strain-promoted azide-alkyne cycloaddition, SPAAC) and nitrile oxide dipoles (strain-promoted nitrile oxide-alkyne cycloaddition, SPNOAC). The conjugation is compatible with 2'-OMe blocks and with 2'-O-TBDMS protection on the ribose moieties of the sugar. Nitrile oxide dipoles are found to be more reactive click partners than azides. The conjugation proceeds within 10 min in aqueous solvents, at room temperature without any metal catalyst and tolerates dipoles of varying steric bulk and electronic demands, including pyrenyl, coumarin and dabcyl derivatives. 相似文献
58.
The methanolysis of the Cu(II) complex of N-acetyl-N,N-bis(2-picolyl)amine (2) was investigated by a kinetic study as a function of pH in methanol at 25 °C and computationally by DFT calculations. The active species is the basic form of the complex (3(-)), or (1:Cu(II))((-)OCH(3))(HOCH(3))), and the rate constant for its solvolysis is k(max) = 1.5 × 10(-4) s(-1). The mechanism involves Cu(II) binding to the amide N lone pair, decoupling it from >N-C═O resonance, concomitant with Cu(II):((-)OCH(3)) delivery to the adjacent >N-C═O unit, followed by Cu(II)-assisted departure of the N,N-bis(2-picolyl)amide from a tetrahedral intermediate. 相似文献
59.
Charles Frances 《Comptes Rendus Mathematique》2003,336(9):751-756
In this Note, we show how to construct the conformal boundary of Margulis space–times when Γ is an affine Schottky group. To cite this article: C. Frances, C. R. Acad. Sci. Paris, Ser. I 336 (2003). 相似文献
60.
Thomas J. Barloon William T. C. Yuh Frances L. Chiang Simon C. S. Kao Yutaka Sato Mark Mehringer 《Magnetic resonance imaging》1989,7(6):635-642
A retrospective review of 21 patients with lesions involving the fourth ventricle was performed to determine the relative capability of computed tomography (CT) and MR for detection, characterization, localization, and diagnosis. Lesions involving the fourth ventricle included ependymoma (three), subependymoma (one), glioma (five), cysticercosis cyst (three), medulloblastoma (three), bleeding into the fourth ventricle (two), epidermoid cyst (two), “trapped” fourth ventricle (one), and lymphomatoid granuloma (one). Posterior fossa lesions that displaced but did not invade the fourth ventricle were excluded. Lesion detectability on CT was judged excellent in ten, good in 8, and fair or poor in 3. Detectability of lesions by MR was judged excellent in 16 and good in 5. There was complete agreement on lesion extension between CT and MR in 6 lesions, mild disagreement in 4, and moderate to significant disagreement in 11. Preoperatively, MR alone correctly diagnosed seven lesions, and CT alone correctly diagnosed three lesions. A review of the combined scans (after the correct diagnosis was given) showed both CT and MR were equal in the diagnosis of 14 lesions, MR better than CT in six, and CT better in one. There was complete agreement on both CT and MR with the surgical/pathologic findings in three lesions. Both studies proved disappointing in their ability to make the correct histologic diagnosis, probably because CT and MR characteristics may not always offer a definitive diagnosis and because of the wide spectrum of pathologic processes that may involve the fourth ventricle. 相似文献