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571.
Norma A. Cortez Gerardo Aguirre Miguel Parra-Hake Ratnasamy Somanathan 《Tetrahedron: Asymmetry》2013,24(20):1297-1302
The synthesis of (R)-tembamide and (R)-aegeline via asymmetric transfer hydrogenation involving enantioenriched monosulfonamide–RhCp1 complex in aqueous sodium formate as hydride donor is described. 相似文献
572.
Luis A. Bagatoll Tiziana Parasassi Gerardo D. Fidelio Enrico Gratton 《Photochemistry and photobiology》1999,70(4):557-564
Although 6-lauroyl-2-(N,N-dimethylamino)naphthalene (LAURDAN) is now widely used as a probe for lipid systems, most studies focus on the effect of the lipid environment on its emission properties but not on the excitation properties. The present study is intended to investigate the excitation properties of LAURDAN in diverse lipid environments. To this end, the fluorescence properties of LAURDAN were studied in synthetic ester and ether phosphatidylcholines and sphingomyelin vesicles below, at and above the corresponding lipid main phase-transition temperature. The excitation spectra of LAURDAN in these environments always show at least two well-resolved bands. In the different lipid vesicles the behavior of the red band in the LAURDAN excitation spectra is sensitive to the lipid chemical environment near the probe fluorescent moiety and to the packing of the different lipid phases (gel and liquid crystalline). We propose that the interaction between the LAURDAN dimethylamino group and the ester linkage of ester phospholipids is responsible for the strong stabilization of LAURDAN's red excitation band in the gel phase of ester phospholipid vesicles. We discuss the consequence of these proposed ground-state interactions on LAURDAN's emission generalized polarization function. In the context of variable excitation wavelengths, information concerning solvent dipolar relaxation through excitation generalized polarization function is also discussed. 相似文献
573.
574.
Ricard V. Solée Sergi Valverde Marti Rosas Casals Stuart A. Kauffman Doyne Farmer Niles Eldredge 《Complexity》2013,18(4):15-27
Technological evolution has been compared to biological evolution by many authors over the last two centuries. As a parallel experiment of innovation involving economic, historical, and social components, artifacts define a universe of evolving properties that displays episodes of diversification and extinction. Here, we critically review previous work comparing the two types of evolution. Like biological evolution, technological evolution is driven by descent with variation and selection, and includes tinkering, convergence, and contingency. At the same time, there are essential differences that make the two types of evolution quite distinct. Major distinctions are illustrated by current specific examples, including the evolution of cornets and the historical dynamics of information technologies. Due to their fast and rich development, the later provide a unique opportunity to study technological evolution at all scales with unprecedented resolution. Despite the presence of patterns suggesting convergent trends between man‐made systems end biological ones, they provide examples of planned design that have no equivalent with natural evolution. 相似文献
575.
Gerardo Canizal Guillermina Burillo Eduardo Muoz Roberto Gleason Takeshi Ogawa 《Journal of polymer science. Part A, Polymer chemistry》1994,32(16):3147-3151
The free radical polymerization of methyl methacrylate (MMA) in the presence of p,p′- disubstituted diphenylbutadiynes was studied. Both the rate and degree of polymerization are somewhat lowered by the presence of the diynes, but the propagating radicals were stabilized giving clear ESR signals of the interacted polyMMA radicals at the polymerization temperature of 70°C. The magnitude of the interaction depended on the electron density of the diynes; in the cases of diphenylbutadiyne and dimethoxycarbonyldiphenylbutadiyne, the intoraction was more enhanced showing ESR signals with smaller spectra widths and increasing the number of radicals with the polymerization time, while in the cases of electron donor-substituted diynes the interaction was weaker and the radical concentration remained constant during the polymerization. These systems are considered to be examples of the stabilization of transient radicals by the direct interaction of radicals with additives without formation or breaking of chemical bonds. No diacetylenic group was found in the polyMMA obtained. © 1994 John Wiley & Sons, Inc. 相似文献
576.
Chromatographia - A new method for the extraction of basic drugs from whole blood based on the use of a buffered protein precipitating reagent at pH9, to form NiWO4 in biological fluids and a... 相似文献
577.
Shin-Shyong Tseng Joseph W. Epstein Herbert J. Brabander Gerardo Francisco 《Journal of heterocyclic chemistry》1987,24(3):837-843
2-Aminobenzimidazoles were reacted with enaminones in acetic acid to give pyrimido[1,2-a]benzimidazoles. With a substituted enaminone only one regioisomer was obtained. Structural assignments based on nmr and uv spectroscopy are presented. Possible pathways leading to the products are discussed. 相似文献
578.
579.
Gerardo M. Ramos Tombo Hans Jakob Ammann Klaus Müller Camille Ganter 《Helvetica chimica acta》1983,66(1):50-59
The influence of steric compression on electronic structure in polycyclic olefinic alcohols and amines is studied by PE. spectroscopy. The unsubstituted alcohol 2 and amine 7 show PE.-spectroscopic properties that can be reconciled by postulating a predominance of intramolecularly H-bonded species in the gas phase. For the alkylated derivatives 5 and 9 , in which H-bonding is precluded, distinct, but only moderate lone-pair double-bond interactions are observed. 相似文献
580.
In a previous preliminary study, we found that a cyclic five-member ring beta-keto ester (lactone) reacts with one molecule of urea and two of aldehyde to give a new family of spiro heterobicyclic aliphatic rings in good yields with no traces of the expected dihydropyrimidine (Biginelli) products. The reaction is driven by a regiospecific condensation of two molecules of aldehyde with urea and beta-keto-gamma-lactone to afford only products harboring substitutions exclusively in a syn configuration (Byk, G.; Gottlieb, H. E.; Herscovici, J.; Mirkin, F. J. Comb. Chem. 2000, 2, 732-735). In the present work ((a) Presented in part at ISCT Combitech, October 15, 2002, Israel, and Eurocombi-2, Copenhagen 2003 (oral and poster presentation). (b) Also in American Peptide Society Symposium, Boston, 2003 (poster presentation). (c) Abstract in Biopolymers 2003, 71 (3), 354-355), we report a large and exciting extension of this new reaction utilizing parallel organic synthesis arrays, as demonstrated by the use of chiral beta-keto-gamma-lactams, derived from natural amino acids, instead of tetronic acid (beta-keto-gamma-lactone) and the potential of the spirobicyclic products for generating "libraries from libraries". Interestingly, we note an unusual and important anisotropy effect induced by perpendicular interactions between rigid pi systems and different groups placed at the alpha position of the obtained spirobicyclic system. Stereo/regioselectivity of the aldehyde condensation is driven by the nature of the substitutions on the starting beta-keto-gamma-lactam. Aromatic aldehydes can be used as starting reagents with good yields; however, when aliphatic aldehydes are used, the desired products are obtained in poor yields, as observed in the classical Biginelli reaction. The possible reasons for these poor yields are addressed and clarify, to some extent, the complexity of the Biginelli multicomponent reaction mechanism and, in particular, the mechanism of the present reaction. Finally, we have investigated and proposed a mechanism for this new reaction by intercepting several intermediates. 相似文献