全文获取类型
收费全文 | 135篇 |
免费 | 3篇 |
专业分类
化学 | 104篇 |
晶体学 | 1篇 |
数学 | 5篇 |
物理学 | 28篇 |
出版年
2022年 | 5篇 |
2021年 | 5篇 |
2020年 | 2篇 |
2019年 | 2篇 |
2018年 | 1篇 |
2016年 | 3篇 |
2015年 | 3篇 |
2014年 | 5篇 |
2013年 | 11篇 |
2012年 | 3篇 |
2011年 | 8篇 |
2010年 | 3篇 |
2009年 | 4篇 |
2008年 | 7篇 |
2007年 | 7篇 |
2006年 | 10篇 |
2005年 | 13篇 |
2004年 | 2篇 |
2003年 | 10篇 |
2002年 | 6篇 |
2001年 | 3篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1996年 | 3篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有138条查询结果,搜索用时 15 毫秒
71.
Alicia MaestroRafael Pedrosa Alfonso Pérez-EncaboJuan J. Pérez-Rueda 《Tetrahedron》2012,68(45):9293-9300
Perhydro-1,3-benzoxazines derived from (−)-8-amino menthol behave as masked aldehydes and chiral templates in diastereoselective intramolecular Pauson-Khand reactions with norbornene and norbornadiene. The regioselectivity is excellent for unsubstituted or methyl-substituted acetylenes and moderate with phenyl-substituted alkynes. The stereoselection is very poor or moderate depending also on the substitution pattern of both the triple bond and the perhydrobenzoxazine nucleus. The hydrolysis of the cycloadducts leads to 2- or 3-formyl-cyclopentenone derivatives. 相似文献
72.
Gonçalves B Hidalgo C Pedrosa MA Orozco RO Sánchez E Silva C 《Physical review letters》2006,96(14):145001
Radial profiles of the parallel-radial Reynolds stress component, proportional to the cross correlation between parallel and radial fluctuating velocities, have been measured in the plasma boundary region of the TJ-II stellarator. Experimental results show the existence of significant parallel turbulent forces at plasma densities above the threshold value to trigger perpendicular sheared flows. This finding provides the first experimental evidence of the role of parallel turbulence forces on edge momentum redistribution in fusion devices. 相似文献
73.
Regio- and diastereoselective methoxyselenenylation of cinnamylamines attached to a chiral perhydrobenzoxazine occurs in high yields by reaction with benzeneselenenyl chloride in dichloromethane-methanol. The diastereoselection is dependent on the temperature of the reaction and the structure of the substituent at C-2 and can be rationalized by accepting a 1,4-asymmetric induction process after coordination of the selenium to the nitrogen atom of the allylamine system. 相似文献
74.
Hortal AR Martínez-Haya B Lobato MD Pedrosa JM Lago S 《Journal of mass spectrometry : JMS》2006,41(7):960-968
Molecular weight distributions (MWD) of asphaltenes and their aggregates have been investigated in laser desorption ionization (LDI) mass spectrometric experiments. A systematic investigation of the dependence of the measured MWD on the asphaltene sample density and on the laser pulse energy allows the assignment of most probable molecular weights within 300-500 amu and average molecular weights of 800-1000 amu for the monomeric asphaltenes, as well as for the estimation of the contribution from asphaltene clusters in typical LDI measurements. The results serve to reconcile the existing controversy between earlier mass spectrometric characterizations of asphaltenes based on laser desorption techniques by different groups. Furthermore, the MWD measurements performed on particularly dense samples yield an additional differentiated broad band peaking around 9000-10,000 amu and extending over 20,000 amu, not observed previously in LDI experiments, thereby revealing a strong propensity of the asphaltenes to form clusters with specific aggregation numbers, which is in qualitative agreement with previous theoretical predictions and with the interpretation of measurements performed with other techniques. 相似文献
75.
Condensation of (−)-8-benzylaminomenthol with o-phthaldehyde lead to the chiral perhydro-1,3-benzoxazine 2 as single diastereoisomer. That compound reacted with different organometallics leading to 3 in excellent de. Hydrolysis of carbinols, followed by oxidation of the intermediates allowed for the synthesis of enantiopure phthalides. 相似文献
76.
Water treatment has become a source of concern as new pollutants and higher volumes of waste water must be treated. Emerging biological approaches, namely the use of bioreactors, for cleaning processes have been introduced. The use of bioreactors requires the development of efficient monitoring tools, preferably with real-time measurements. In this work, a couple of flow injection systems were developed and optimized for the potentiometric determination of fluoride to monitor a rotating biological contactor (RBC) bioreactor and a sequencing batch reactor (SBR) with off-line and on-line sampling. Both the RBC and the SBR bioreactors were set up for the biodegradation of the halogenated organic compound 2-fluorophenol and, as fluoride was a degradation byproduct, the process was monitored by following up its concentration.The described flow injection potentiometric methods enabled the fluoride determination within the required quantification range 0.10-100 mM. The possible interferences from the growth medium were minimized in-line. The determination rate was 78 h−1 for the off-line monitoring of RBC and 50−1 h for the on-line monitoring of the SBR, with a sample consumption of 0.500 mL and 0.133 mL per determination, respectively. Furthermore, the overall reagent consumption was quite low. The accuracy of the system was evaluated by comparison with a batch procedure. The SBR efficiency was monitored both on-line by the flow system and off-line by HPLC, for comparison purposes. 相似文献
77.
Lopes-Costa T Gámez F Lago S Pedrosa JM 《Journal of colloid and interface science》2011,354(2):733-738
In this work, surface properties of octadecylamine (ODA) monolayers in the presence of different concentrations of calf thymus DNA in the aqueous subphase covering a range of 2-8μM have been investigated. The increase of DNA concentration is accompanied by a marked increment in the expansion of the corresponding isotherms. In addition, there is a change in the profile of the isotherms ranging from an abrupt liquid-solid transition for the lipid monolayer on pure water to a slow condensation of the monolayer in a liquid state when DNA is added to the subphase, demonstrating the effective adsorption of the polynucleotide to the long chain amine monolayer. Additional phase transitions appear in the isotherms upon addition of sufficient amount of DNA, revealing the existence of specific processes such as folding or squeezing out of the DNA. This system is, however, highly reversible during compression-expansion cycles due to the strong interaction between the two components. These results are also supported by Brewster Angle Microscopy (BAM) images showing significant changes in the morphology of the film. Integral reflectivity of the BAM microscope has been used to study both isotherms themselves and the kinetic process of DNA inclusion into the lipid-like ODA monolayer. This parameter has been proven to be very effective for quantification of the monolayer processes showing high consistency with the compressibility and kinetics results. 相似文献
78.
Angel Alberola Celia Andres Alfonso González Ortega Rafael Pedrosa Martina Vicente 《合成通讯》2013,43(10):1161-1165
Cyanogen bromide reacts with β-aminoenones, in very mild conditions, leading to α-bromo-β-aminoenones with excellent yields. 相似文献
79.
80.
Celso Alves Joana Silva Susete Pinteus Eva Alonso Rebeca Alvario Adriana Duarte Diorge Marmitt Mrcia Inês Goettert Helena Gaspar Amparo Alfonso Maria C. Alpoim Luis M. Botana Rui Pedrosa 《Molecules (Basel, Switzerland)》2021,26(5)
Marine natural products have exhibited uncommon chemical structures with relevant antitumor properties highlighting their potential to inspire the development of new anticancer agents. The goal of this work was to study the antitumor activities of the brominated diterpene sphaerodactylomelol, a rare example of the dactylomelane family. Cytotoxicity (10–100 µM; 24 h) was evaluated on tumor cells (A549, CACO-2, HCT-15, MCF-7, NCI-H226, PC-3, SH-SY5Y, SK-ML-28) and the effects estimated by MTT assay. Hydrogen peroxide (H2O2) levels and apoptosis biomarkers (membrane translocation of phosphatidylserine, depolarization of mitochondrial membrane potential, Caspase-9 activity, and DNA condensation and/or fragmentation) were studied in the breast adenocarcinoma cellular model (MCF-7) and its genotoxicity on mouse fibroblasts (L929). Sphaerodactylomelol displayed an IC50 range between 33.04 and 89.41 µM without selective activity for a specific tumor tissue. The cells’ viability decrease was accompanied by an increase on H2O2 production, a depolarization of mitochondrial membrane potential and an increase of Caspase-9 activity and DNA fragmentation. However, the DNA damage studies in L929 non-malignant cell line suggested that this compound is not genotoxic for normal fibroblasts. Overall, the results suggest that the cytotoxicity of sphaerodactylomelol seems to be mediated by an increase of H2O2 levels and downstream apoptosis. 相似文献