全文获取类型
收费全文 | 398篇 |
免费 | 16篇 |
国内免费 | 1篇 |
专业分类
化学 | 324篇 |
力学 | 3篇 |
数学 | 28篇 |
物理学 | 60篇 |
出版年
2023年 | 7篇 |
2022年 | 3篇 |
2021年 | 15篇 |
2020年 | 7篇 |
2019年 | 4篇 |
2018年 | 7篇 |
2017年 | 2篇 |
2016年 | 17篇 |
2015年 | 8篇 |
2014年 | 14篇 |
2013年 | 16篇 |
2012年 | 29篇 |
2011年 | 22篇 |
2010年 | 15篇 |
2009年 | 17篇 |
2008年 | 34篇 |
2007年 | 28篇 |
2006年 | 22篇 |
2005年 | 26篇 |
2004年 | 31篇 |
2003年 | 23篇 |
2002年 | 23篇 |
2001年 | 11篇 |
2000年 | 8篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1988年 | 2篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1983年 | 1篇 |
1981年 | 2篇 |
排序方式: 共有415条查询结果,搜索用时 31 毫秒
1.
2.
Polo F Antonello S Formaggio F Toniolo C Maran F 《Journal of the American Chemical Society》2005,127(2):492-493
The rate constant of intramolecular electron transfer through oligopeptides based on the alpha-aminoisobutyric acid residue was determined as a function of the peptide length and found to depend weakly on the donor-acceptor separation. By measuring the electron-transfer activation energy and estimating the energy gap between donor and bridge, we were able to discard the electron hopping mechanism. 相似文献
3.
Scrimin P Tecilla P Tonellato U Veronese A Crisma M Formaggio F Toniolo C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(12):2753-2763
Three copies of peptide sequences from the peptaibol family, known to affect the permeability of the lipid bilayer of membranes, were connected to tris(2-aminoethyl)amine (TREN), a tripodal metal ion ligand, to prepare functional peptides capable of modifying the permeability of liposomal membranes. Some of the resulting tripodal polypeptide derivatives are very effective in promoting carboxyfluorescein (CF) leakage from CF-loaded unilamellar vesicles composed of a 70:30 phosphatidylcholine/cholesterol blend. The activity of these novel compounds was shown to be tunable upon metal ion coordination of the TREN subunit; the tripodal apopeptide was far more effective than its ZnII complex. Leakage experiments showed that a minimum number of five amino acids per peptide chain is required to form active systems. A mechanism is proposed in which the ZnII ion changes the conformation of the template from extended to globular and thus acts as an allosteric regulator of the activity of the systems. Molecular modeling studies indicate that when the three peptide chains are connected to the template in the extended conformation, the resulting tripodal polypeptide is able to span across the membrane, thus allowing the formation of permeable channels made of a cluster of molecules. The same change of conformation induces, to some extent, fusion of the membranes of different liposomes. 相似文献
4.
Verardo G Pagani E Geatti P Martinuzzi P 《Analytical and bioanalytical chemistry》2003,376(5):659-667
The composition of the surface waxes of three apple ( Malus domestica L.) cultivars ("Florina", "Golden B" and "Ozark Gold") has been studied by means of spectroscopic and GC–MS analysis of the class-fractionated mixture of components. Odd n -alkanes, mainly C27 and C29 molecules, are prevalent in the saturated fraction. Small concentrations of alkenes were also found; the C28:1 component is strongly (72%) in excess over the other 1-alkenes. Straight-chain esters (mainly of palmitic acid) of saturated primary alcohols (C18–C30) were also detected; whereas the acyl moiety is made up essentially of an even number of carbons, the alcohol counterpart does not exhibit this characteristic. Aldehydes are present (C20–C30) with the homologue patterns C26–C30 most strongly represented. Straight-chain free secondary alcohols characterize the waxes of "Florina" and "Ozark Gold"; the hydroxy function is located far from the extremity of the carbon framework. Outstanding is the presence of three alcohols with 29 carbon centres. These alcohols are accompanied by free straight-chain primary alcohols, mainly with even-numbered carbon chains in the range C26–C30. Free fatty acids are present; all of have a framework of even-numbered carbon chains mainly in the range C16–C20. C18:1 (oleic acid) is well represented. 相似文献
5.
Antonello S Formaggio F Moretto A Toniolo C Maran F 《Journal of the American Chemical Society》2001,123(39):9577-9584
The electron transfer to peresters was studied by electrochemical means in N,N-dimethylformamide. The reduction was carried out by three independent methods: (i) heterogeneously, by using glassy carbon electrodes, (ii) homogeneously, by using electrogenerated radical anions as the donors, and (iii) intramolecularly, by using purposely synthesized donor-spacer-acceptor (D-Sp-A) systems. Convolution analysis of the heterogeneous data led to results in excellent agreement with the dissociative electron transfer theory. The homogeneous redox catalysis data also confirmed the reduction mechanism. The cyclic voltammetries of the D-Sp-A molecules could be simulated, leading to determination of the corresponding intramolecular dissociative rate constants. Analysis of the results showed that, regardless of the way by which the acceptor is reduced, the investigated dissociative electron transfers are strongly nonadiabatic and, particularly, that the experimental rates are several orders of magnitude smaller than the adiabatic limit. A possible mechanism responsible for the observed behavior is discussed. 相似文献
6.
Gaetano Alberghina Maria Emanuela Amato Francesco Agatino Bottino Antonino Corsaro Salvatore Fisichella 《Journal of heterocyclic chemistry》1986,23(6):1747-1752
The 1H-nmr data of some (Z)-α-(p-substituted-phenyl)-β-(2-furyl), -(2-pyrrolyl), and -(N-methyl-2-pyrrolyl)-acrylonitriles have been investigated to indicate the preferred conformation and to establish the conformational preferences of the β-heterocyclic ring. The ultraviolet spectra have been discussed in order to obtain information about the chromophores responsible for the absorption. The infrared spectra have been analyzed for the identification of the main absorption frequencies of cyano and ethylenic groups and to assign the characteristic absorption bands to specific normal vibrations of the heteroaromatic nuclei. 相似文献
7.
Atmospheric bulk deposition of major and trace elements was measured at Venice from November 1995 to October 1997. Collection was carried out using polyethylene bulk passive samplers, samples being collected bi-weekly. In order to highlight the contribution of the atmosphere to water chemistry and particle budgets in the Lagoon of Venice, the geochemical composition (Si, Al, Ca, Mg, K, Na, Mn, Cr, Zn, Pb, Cd, Cu, As) of dissolved and insoluble bulk fractions was determined by AAS + ICP mass spectrometry. Great sample variability was found, with almost two orders of magnitude between maximum and minimum values for several metals. All fluxes in 1995/96 were 30% lower than in 1996/97, ranging from -3% (Ca) to -57% (Li), except for Zn, Cd and As. On the contrary, the solubility of all elements decreased during 1996/97. Partitioning between soluble and insoluble phases shows that Al, Cr, Fe and Si are mainly in the insoluble form, whereas for As, Ca, Cu, Mg, Na, Ni, K, Pb and Zn the dissolved fraction represents 50-90% of total input. The amount of particle load affects partitioning between dissolved and particulate, especially for Al and Pb. Seasonal variability was evident. The lowest pH values (approximately 5.2) were recorded in winter, causing an increase of solubility for all metals except for As, which showed the highest solubility in summer. 相似文献
8.
Bazzicalupi C Bencini A Berni E Bianchi A Ciattini S Giorgi C Maoggi S Paoletti P Valtancoli B 《The Journal of organic chemistry》2002,67(25):9107-9110
The synthesis of three new tris-macrocycles, containing three [12]aneN(4) (L1), [12]aneN(3)O (L2), or [14]aneN(4) (L3) moieties appended to a tren unit, is reported. The crystal structure of the [(Na(ClO(4))(6)) subset L1(2)H(13)]Na(6)Cl(2)(ClO(4))(12) compound shows the anionic cluster [Na(ClO(4))(6)](5)(-) assembled inside the cavity defined by two bowl-shaped polyammonium receptors, held by multiple charge-charge and hydrogen bond interactions. 相似文献
9.
10.
Emanuela Emanuele Dimitra Markovitsi Philippe Millié Krystyna Zakrzewska 《Chemphyschem》2005,6(7):1387-1392
The singlet excited states of the model DNA duplex (dA)10.(dT)10 are studied. Calculations are performed in the exciton theory framework. Molecular dynamics calculations provide the duplex geometry. The dipolar coupling is determined using atomic transition charges. The monomer transition energies are simulated by Gaussian functions resembling the absorption bands of nucleosides in aqueous solutions. Most of the excited states are found to be delocalized over at least two bases and result from the mixing of different monomer states. Their properties are only weakly affected by conformational changes of the double helix. On average, the highest oscillator strength is carried by the upper eigenstates. The duplex absorption spectra are shifted a few nanometers to higher energies with respect to the spectra of noninteracting monomers. The states with larger spatial extent are located close to the maximum of the absorption spectrum. 相似文献