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排序方式: 共有502条查询结果,搜索用时 18 毫秒
21.
Dr. Akos Banyasz Dr. Thomas Gustavsson Dr. Delphine Onidas Dr. Pascale Changenet‐Barret Dr. Dimitra Markovitsi Dr. Roberto Improta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(11):3762-3774
The singlet excited states of adenine oligomers, model systems widely used for the understanding of the interaction of ultraviolet radiation with DNA, are investigated by fluorescence spectroscopy and time‐dependent (TD) DFT calculations. Fluorescence decays, fluorescence anisotropy decays, and time‐resolved fluorescence spectra are recorded from the femtosecond to the nanosecond timescales for single strand (dA)20 in aqueous solution. These experimental observations and, in particular, the comparison of the fluorescence behavior upon UVC and UVA excitation allow the identification of various types of electronic transitions with different energy and polarization. Calculations performed for up to five stacked 9‐methyladenines, taking into account the solvent, show that different excited states are responsible for the absorption in the UVC and UVA spectral domains. Independently of the number of bases, bright excitons may evolve toward two types of excited dimers having π–π* or charge‐transfer character, each one distinguished by its own geometry and spectroscopic signature. According to the picture arising from the joint experimental and theoretical investigation, UVC‐induced fluorescence contains contribution from 1) exciton states with a different degree of localization, decaying within a few ps, 2) “neutral” excited dimers decaying on the sub‐nanosecond timescale, being the dominant species, and 3) charge‐transfer states decaying on the nanosecond timescale. The majority of the photons emitted upon UVA excitation are related to charge‐transfer states. 相似文献
22.
Fourmigué M Reinheimer EW Assaf A Jeannin O Saad A Auban-Senzier P Alemany P Rodríguez-Fortea A Canadell E 《Inorganic chemistry》2011,50(9):4171-4181
An efficient synthetic procedure for the preparation of unsymmetrically substituted tetrathiafulvalene (TTF) donors has been used to obtain the trimethylene-tetrathiafulvalene (tTTF) donor with high purity. Good quality crystals of the two (tTTF)(2)X (X = Br, I) salts have been obtained by electrocrystallization. The two salts are isomorphous and contain tTTF layers which are built from (tTTF)(2) dimeric units. Both systems are low-dimensional antiferromagnets with the highest Ne?el temperatures for TTF based radical cation salts: ≈ 35 K (Br salt) and ≈43 K (I salt). The resistivity is found to substantially decrease with pressure although both salts still have activated conductivity at 25 kbar. First-principles Density Functional Theory (DFT) calculations have been used to investigate the relative strength of the three different types of magnetic interactions in the tTTF layers as well as the potential magnetic ground states. These calculations successfully predict the nature of the ground state and suggest a possible correlation between structural details and Ne?el temperatures for the bromine and iodine salts. Remarkably, the calculated antiferromagnetic ground state can be predicted from the nesting properties of the Fermi surface for the hypothetical Pauli paramagnetic metallic state. 相似文献
23.
Andrea Ventrella Raffaella Verrone Francesco Longobardi Angela Agostiano Vincenzo Lippolis Michelangelo Pascale Chris M. Maragos Michael Appell Lucia Catucci 《Journal of inclusion phenomena and macrocyclic chemistry》2013,75(3-4):285-292
T-2 and HT-2 toxins are mycotoxins produced by several Fusarium species that are commonly found in various cereal grains, including oats, barley, wheat and maize. Intake estimates indicate that the presence of these mycotoxins in the diet can be of concern for public health. In this work, the inclusion processes occurring between fluorescent anthracene-derivatives of T-2 and HT-2 toxins and different cyclodextrin (CD) molecules were investigated in aqueous solutions by means of UV–Vis absorption, fluorescence emission and dynamic light scattering. Binding constant values and chemico-physical parameters were calculated. It was found that β-CDs give stronger inclusion reactions with both T-2 and HT-2 derivatives, as stated by important emission intensity increments. Such interactions were found to be fundamentally enthalpy-driven. Among β-CDs, the effect of the methylation at hydroxyl groups was tested: as a result, the di-methyl form of β-CD was found to induce the best fluorescence intensity enhancements. 相似文献
24.
Guy Bouchoux Yannik Hoppiiliard Pascale Jaudon 《Journal of mass spectrometry : JMS》1987,22(2):98-102
Dissociative ionization of 1,2-epoxy n-alkanes gives rise to abundant [C4H7O]+ ions of structure [CH3OCHCHCH2]+. This conclusion is drawn from metastable ion analysis and from collisional activation spectra. This fragmentation involves the C? C ring opening and a 1,4-H migration leading to the corresponding enol ether [CH3OCHCHCH2R]+. precursor of [CH3OCHCHCH2]+ fragment. The same isomerization scheme applies to 1,2-epoxy methyl substituted alkanes and 2,3-epoxy n-alkanes. 相似文献
25.
26.
Hunter CA Jones PS Tiger P Tomas S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(23):5435-5446
Chemical double-mutant cycles have been used to quantify intermolecular functional-group interactions in H-bonded zipper complexes in chloroform. If the same interaction is measured in zippers of different overall stability, the double-mutant cycles can be combined to produce a triple-mutant box. This construct quantifies cooperativity between the functional group interaction of interest and the other interactions that are used to change the overall stability of the complexes. The sum of two edge-to-face aromatic interactions (-2.9 +/- 0.5 kJ mol-1) is shown to be insensitive to changes of up to 13.7 +/- 0.2 kJ mol-1 in the overall stability of the complex. In principle, enthalpic cooperative effects caused by entropy-enthalpy compensation could perturb the measurement of intermolecular interactions when using the double-mutant cycle approach, but these experiments show that, for this system, the magnitude of the effect lies within the error of the measurements. 相似文献
27.
Cyril T. Langlois Tetsuo Oikawa Pascale Bayle-Guillemaud Christian Ricolleau 《Journal of nanoparticle research》2008,10(6):997-1007
CuAg core–shell nanoparticles are synthesized by ultra-high vacuum thermal evaporation. We show on this system how the Energy-Filtered
Transmission Electron Microscopy (EFTEM) technique allows one to improve the characterization by precisely pointing out the
formation of core–shell arrangements in bimetallic nanoparticle assemblies. A criterion to measure the shell thickness from
EFTEM images on unique core–shell nanoparticles is defined, that can be used for core–shell nanoparticles of any sizes, with
shell thicknesses over 1 nm. It is based on the intensity variation along a line drawn across a core–shell nanoparticle on
a EFTEM image. This criterion has been validated by a close comparison of the shell thickness measurements performed in this
work and the ones obtained by acoustic micro-Raman spectroscopy. Using this criterion, we report a strong correlation between
the size of the Cu cores and the formation of the core–shell arrangements in the nanoparticle assembly studied in this work.
The influence of the Cu core shape is also evidenced. The characterisation of such systems using High Resolution TEM (HRTEM)
is also discussed. 相似文献
28.
A study of the microbiological reduction of different α-halogenoketones (4-chloro-3-octanone, 4-chloro-5-nonanone, 5-bromo-4-nonanone and 5-chloro-4-nonanone) with several strains of microorganism showed great difficulty in reducing ketone functions located in the middle of carbon chains. However, by choosing the appropriate microorganism, several enantiomerically pure diastereoisomers of the corresponding halohydrins have been obtained and were transformed into chiral epoxides. 相似文献
29.
Key words The rheological properties of rat arteries were studied in vitro. Using intact arterial segments undergoing large deformations in longitudinal and circumferential direction, both the stress-strain relationship and the corresponding histological changes with deformation are presented. Correlations between the mechanical properties and the histological structure are discussed. 相似文献
30.
Nitrosation of thiols and thioethers in the gas phase: A combined theoretical and experimental study
Gerbaux P Wantier P Flammang R 《Journal of the American Society for Mass Spectrometry》2004,15(3):344-355
Recent studies have demonstrated the biological importance of the interaction of nitric oxide with proteins such as cytochrome-c or hemoglobin. In particular, the possibility that the nitrosonium cation, NO(+), could reversibly bind to sulfide atom type was proposed. At pH values of biological relevance, nitrosation was proposed to occur through the action of NO(+) carriers such as nitrosothiols or nitrosamines. In this context, the gas phase chemistry of protonated nitrosothiols is studied in the present work by a combination of mass spectrometry and computational methods. 相似文献