全文获取类型
收费全文 | 243篇 |
免费 | 5篇 |
国内免费 | 1篇 |
专业分类
化学 | 150篇 |
力学 | 3篇 |
数学 | 28篇 |
物理学 | 68篇 |
出版年
2021年 | 7篇 |
2020年 | 4篇 |
2019年 | 4篇 |
2018年 | 4篇 |
2017年 | 3篇 |
2016年 | 6篇 |
2015年 | 9篇 |
2014年 | 7篇 |
2013年 | 13篇 |
2012年 | 12篇 |
2011年 | 19篇 |
2010年 | 17篇 |
2009年 | 18篇 |
2008年 | 14篇 |
2007年 | 11篇 |
2006年 | 17篇 |
2005年 | 14篇 |
2004年 | 12篇 |
2003年 | 9篇 |
2002年 | 9篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有249条查询结果,搜索用时 250 毫秒
21.
Allylation reactions of racemic and optically pure 4-oxoazetidine-2-carbaldehydes were investigated both under anhydrous conditions and in aqueous media. Different Lewis acid or metal mediators showed varied diastereoselectivities on product formation during allylation reactions of the above aldehydes with allyltrimethylsilane, allyltributylstannane, or allyl bromide. Under standard reaction conditions, tin(IV) chloride-promoted addition of allyltrimethylsilane to 4-oxoazetidine-2-carbaldehydes provided the highest diastereoselectivity and the best yield. Boron trifluoride-diethyl ether-promoted reaction of allyltributylstannane provided slightly lower diastereoselectivity with the same facial preference. Indium-promoted allylation showed a reverse diastereofacial preference, although the observed selectivity is not synthetically useful. The mesylates of these homoallylic alcohols were used for the stereoselective preparation of cis-4-butadienyl-2-azetidinones. Interestingly, mesylates having an extra alkene or alkyne tether at position 1 or 3 of the beta-lactam ring, on heating in a sealed tube with equimolecular amounts of DBU in toluene, yielded fused tricyclic 2-azetidinones through a tandem one-pot elimination-intramolecular Diels-Alder reaction. 相似文献
22.
Krug C da Rosa EB de Almeida RM Morais J Baumvol IJ Salgado TD Stedile FC 《Physical review letters》2000,85(19):4120-4123
Ultrathin films of Al2O3 deposited on Si were submitted to rapid thermal annealing in vacuum or in oxygen atmosphere, in the temperature range from 600 to 800 degrees C. Nuclear reaction profiling with subnanometric depth resolution evidenced mobility of O, Al, and Si species, and angle-resolved x-ray photoelectron spectroscopy revealed the formation of Si-Al-O compounds in near-surface regions, under oxidizing atmosphere at and above 700 degrees C. Under vacuum annealing all species remained essentially immobile. A model is presented based on diffusion-reaction equations capable of explaining the mobilities and reproducing the obtained profiles. 相似文献
23.
An action for eleven-dimensional standard supergravity genuinely invariant under the D'Auria–Fré group is proposed. The construction of the action is carried out through a generalization of the Stelle–West–Grignani–Nardelli formalism. The action is genuinely invariant under this group without the need to impose auxiliary conditions such as a torsion-free condition. 相似文献
24.
Francisco J. Salgado Sara Vázquez Amparo Pérez-Díaz Pilar Arias 《Analytica chimica acta》2010,658(1):18-3648
Serum is a typical sample for non-invasive studies in clinical research. Its proteome characterization is challenging, since requires extensive protein depletion. Methods used nowadays for removal of high-abundance proteins are expensive or show quite often a low loading capacity, which has strong repercussions on the number of samples and replicates per analysis.In order to deplete immunoglobulins (Igs) and albumin (HSA) from 1 mL serum samples, we have developed a protocol based on a combination of thiophilic chromatography, not previously used in clinical proteomics, and a HSA-specific resin. Ig/HSA-depleted samples, immunoglobulinome and albuminone were analyzed by 2-DE. Thiophilic chromatography, coupled with HSA-depletion, allows a good 2-DE resolution as well as the visualization of new spots. Moreover, it yields enough protein to evaluate technical variability and facilitate subsequent protein identification. To validate the protocol, we carried out a preliminary comparative study between triplicate Igs/HSA-depleted serum samples from healthy control individuals and recently diagnosed/untreated rheumatoid arthritis (RA) patients. RA patients showed several acute phase proteins, as well as additional serum proteins, differentially and significantly regulated.Therefore, thiophilic chromatography can be used as an efficient and economical method in 2-DE to deplete immunoglobulins from large human serum samples before a more extensive fractioning. 相似文献
25.
26.
Norma A. Cortez‐Lemus Rodolfo Salgado‐Rodríguez Angel Licea‐Claveríe 《Journal of polymer science. Part A, Polymer chemistry》2010,48(14):3033-3051
The design, synthesis, and use of two new, stable, functionalized chain transfer agents (CTA's) containing OH and amine end groups for the RAFT polymerization is reported: 2‐hydroxyethoxy‐carbonylphenylmethyl dithiobenzoate and 2‐(2‐(tert‐butoxycarbonyl)ethylamino)‐2‐oxo‐1‐phenylethyl benzodithioate, respectively. The RAFT polymerization of n‐hexyl acrylate (HA) using those CTA's, were compared to several other functionalized dithiobenzoate esters reported in the literature containing COOH and Ester groups. The performances of the dithiobenzoates were compared in terms of kinetics and molecular weight distribution control. Good control in polymerization of n‐hexyl acrylate with a linear increase of Mn with conversion mantaining polydispersity indices (PDI) below 1.1 was obtained by use of the new functionalized CTA's developed and also by use of some other CTA's tested, to produce well‐defined linear polymers with one specific chain‐end functionality: ? OH, ? COOH or Amine. Using a postpolymerization reaction with functionalized azocompounds in a 5 to 1 ratio, α,ω‐telechelic polymers, with ? OH or ? COOH as functional group at the second end were obtained. By using this synthetic strategy α,ω‐homotelechelic and heterotelechelic polymers were readily prepared. The chemical availability of functional end‐groups in the telechelics was demonstrated by reaction with methacrylic anhydride. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3033–3051, 2010 相似文献
27.
Antonio Salgado Carmen Varela Ana María García Collazo Paolo Pevarello 《Magnetic resonance in chemistry : MRC》2010,48(8):614-622
The condensation of malonoaldehyde derivatives with either a 3‐amino‐[1,2,4]‐triazole or a 3,5‐diamino‐[1,2,4]‐triazole precursor was studied. In agreement with previous reports, two different bicycles, namely, bearing the regioisomeric [1,2,4]triazolo[1,5‐a]pyrimidine ( 1 ) or[1,2,4] triazolo [4,3‐a]pyrimidine ( 2 ) structural surrogates, could be obtained. We found that, depending on the triazole precursor, only one regioisomer resulted, either of the 1 or 2 series. We also observed that these two structural surrogates could be unambiguously differentiated by indirectly measuring their 15N chemical shifts by 1H? 15N HMBC experiments. The occasional conversion of [1,2,4]triazolo[4,3‐a]pyrimidines to the [1,2,4]triazolo[1,5‐a]pyrimidine counterparts could be unequivocally determined by 15N NMR data. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
28.
Chirped fibre Bragg grating based multiplexer and demultiplexer for DWDM applications 总被引:1,自引:0,他引:1
R. Romero O. Frazo F. Floreani L. Zhang P.V.S. Marques H.M. Salgado 《Optics and Lasers in Engineering》2005,43(9):987-994
A multiplexer/demultiplexer for 100 GHz channel spacing based on chirped fibre Bragg gratings with different bandwidths and optical circulators is presented. The spectral characteristics, specifications and operation of these passive devices are described, showing its potential use in dense wavelength division multiplexing (DWDM) applications. 相似文献
29.
M. Melo O. Frazão A.L.J. Teixeira L.A. Gomes J.R. Ferreira da Rocha H.M. Salgado 《Applied physics. B, Lasers and optics》2003,77(1):139-142
In this paper, we present a continuous-wave tunable fibre ring laser operating in the L-band. A bi-directional pumped L-band erbium-doped fibre amplifier provides gain to the loop. Tunability is achieved by bending a single-mode fibre taper using a micrometer drive, controlling in this way the spectral cavity losses. Laser emission is achieved between 1587 and 1606 nm, and low variation of the output laser power is observed over all the tuning range. PACS 42.55.Wd; 42.60.Da 相似文献
30.
Vega ED Lomsadze K Chankvetadze L Salgado A Scriba GK Calvo E López JA Crego AL Marina ML Chankvetadze B 《Electrophoresis》2011,32(19):2640-2647
The enantiomer migration order (EMO) of ephedrine was investigated in the presence of various CDs in CE. The molecular mechanisms of chiral recognition were followed for the ephedrine complexes with native α- and β-CD and heptakis(2,3-di-O-acetyl-6-O-sulfo)-β-CD (HDAS-β-CD) by CE, NMR spectroscopy and high-resolution MS. Minor structural differences were observed between the complexes of ephedrine with α- and β-CD although the migration order of enantiomers was opposite when these two CDs were applied as chiral selectors in CE. The EMO was also opposite between β-CD and HDAS-β-CD. Significant structural differences were observed between ephedrine complexes with the native CDs and HDAS-β-CD. The latter CD was advantageous as chiral CE selector not only due to its opposite electrophoretic mobility compared with that of the cationic chiral analyte, but also primarily due to its enhanced chiral recognition ability towards the enantiomers of ephedrine. 相似文献