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181.
182.
Andr Cogne Afonso G. Guimaraes Jean Martin Robert Nardin Jean-Bernard Robert Wojciech J. Stec 《Magnetic resonance in chemistry : MRC》1974,6(12):629-635
The 1H NMR spectra of several 1,3,2-dioxaphosphorinanes bearing an extracyclic P? N bond have been analysed. The 3J(POCH) couplings are strongly dependent upon the orientation of the bond around the phosphorus atom. Depending upon the nature of the bonds attached to the nitrogen atom, the dioxaphosphorinane ring may adopt either a fixed chair conformation with the P? N bond in the axial or equatorial orientation, or it may be in equilibrium between two chair conformations where the P? N bond is alternately axial or equatorial. The equilibrium is fast on the NMR time scale. 相似文献
183.
HPLC-fractionated (p)- and (p)-phosphoramidites underwent tetrazole-catalyzed coupling to support-bound nucleosides to give intermediary phosphates with epimerization at phosphorus, as shown by conversion to epimerized mixtures of dinucleoside phosphorothioates. 相似文献
184.
Cis- and trans-2-hydroxy-2-thiono-4-methyl-1,3,2-dioxaphosphorinanes are cleanly transformed by means of [18O]- DMSO into corresponding 2-([18O]-oxo)-derivatives with ca 90% inversion of configuration at phosphorus atom. 相似文献
185.
Grochala W 《Chemical communications (Cambridge, England)》2005,(18):2330-2332
Using theoretical calculations we predict a novel family of compounds, which might serve for hydrogen storage, and for chemical vapour deposition of titanium carbide coatings. 相似文献
186.
Wojciech P. Oziminski Tadeusz M. Krygowski 《Journal of Physical Organic Chemistry》2010,23(6):551-556
The geometries, natural charges, and resonance structures of 11 monosubstituted benzene derivatives were analyzed at the B3LYP/6‐311++G(d,p) and HF/6‐311++G(d, p) levels of theory. The following angular substituents were chosen: OCH3, CH2CH3, OH, SH, NHCH3, NHNH2, N?O, CH?CH2, N?CH2, N?NH, and CHO. The analysis of resonance structures was performed by using two different methodologies: harmonic oscillator stabilization energies (HOSE) and natural resonance theory (NRT). Also, the natural bond orbital (NBO) donor–acceptor stabilization energies for different resonance structures were calculated. We found that for all the substituents, the purely geometric resonance stabilization parameter (HOSE) is linearly correlated with quantum chemically derived resonance structure weight (NRT) of a given structure. Also, the calculations provide qualitative support for the earlier assumption of a through space angular group induced bond alternation (AGIBA) effect. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
187.
Benfatto M Della Longa S Hatada K Hayakawa K Gawelda W Bressler C Chergui M 《The journal of physical chemistry. B》2006,110(29):14035-14039
A full multiple theoretical model (MXAN) is applied to fit picosecond difference X-ray absorption spectra at the ruthenium L(3) edge upon photoexcitation of aqueous [RuII(bpy)3]2+. We show that fitting difference spectra allows an increase in sensitivity, such that slight structural changes can be retrieved, which are not detected in fitting full spectra. The Ru-N bond distances of the excited complex in the (3)MLCT state are in good agreement with recently published values. The implementation of the present approach to L-edge spectra and its high sensitivity opens opportunities for its extension to a large class of experiments where difference X-ray absorption spectra are recorded. 相似文献
188.
Hebda M Stochel G Szaciłowski K Macyk W 《The journal of physical chemistry. B》2006,110(31):15275-15283
Switching of photocurrent direction in semiconducting systems upon changes of the electrode potential or incident light wavelength was realized by a series of photoelectrodes covered with titania modified with pentacyanoferrate complexes, [Fe(CN)(5)L](n)(-) (L = NH(3), thiodiethanol, thiodipropanol). These materials were characterized by optical spectroscopy and electrochemistry. The structure of the surface complexes was modeled using simple quantum-chemical models. The electrodes described in this paper enable control of the photocurrent direction by two stimuli: Changing the wavelength or the photoelectrode potential easily switches the direction of photocurrent. The materials are different from those of similar characteristics studied by other authors: They are not composites comprising of two types of semiconductors but rather engineered uniform materials. The photocurrent switching phenomenon is an intrinsic feature resulting from a specific electronic structure of the surface-modified semiconductor. 相似文献
189.
Blazewicz J Glover F Kasprzak M Markiewicz WT Oğuz C Rebholz-Schuhmann D Swiercz A 《Computational Biology and Chemistry》2006,30(5):313-320
DNA sequencing by hybridization (SBH) induces errors in the biochemical experiment. Some of them are random and disappear when the experiment is repeated. Others are systematic, involving repetitions in the probes of the target sequence. A good method for solving SBH problems must deal with both types of errors. In this work we propose a new hybrid genetic algorithm for isothermic and standard sequencing that incorporates the concept of structured combinations. The algorithm is then compared with other methods designed for handling errors that arise in standard and isothermic SBH approaches. DNA sequences used for testing are taken from GenBank. The set of instances for testing was divided into two groups. The first group consisted of sequences containing positive and negative errors in the spectrum, at a rate of up to 20%, excluding errors coming from repetitions. The second group consisted of sequences containing repeated oligonucleotides, and containing additional errors up to 5% added into the spectra. Our new method outperforms the best alternative procedures for both data sets. Moreover, the method produces solutions exhibiting extremely high degree of similarity to the target sequences in the cases without repetitions, which is an important outcome for biologists. The spectra prepared from the sequences taken from GenBank are available on our website http://bio.cs.put.poznan.pl/. 相似文献
190.
Grochala W 《Physical chemistry chemical physics : PCCP》2006,8(11):1340-1345
Prompted by catalysis of CO2 electroreduction by a tetraazamacrocyclic Ni(i)(cyclam) complex (cyclam = 1,4,8,11-tetraazacyclotetradecane), we examine theoretically the possibility of H2 reduction by this molecule. We show that the process 2 Ni(i) + H2 --> 2 [Ni(ii)(H-)] is thermodynamically facile, and that H2 could be reduced by a binuclear Ni(i) complex in two concerted 1e- processes. Our calculations also indicate that hydride complexes of Ni(iii)(cyclam) are significantly unstable thermodynamically and therefore they are unlikely to serve as intermediates in process of H2 evolution from water. 相似文献