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941.
CA Kluba A Bauman IE Valverde S Vomstein TL Mindt 《Organic & biomolecular chemistry》2012,10(37):7594-7602
Radiolabeled regulatory peptides are useful tools in nuclear medicine for the diagnosis (imaging) and therapy of cancer. The specificity of the peptides towards GPC receptors, which are overexpressed by cancer cells, and their favorable pharmacokinetic profile make them ideal vectors to transport conjugated radionuclides to tumors and metastases. However, after internalization of the radiopeptide into cancer cells and tumors, a rapid washout of a substantial fraction of the delivered radioactivity is often observed. This phenomenon may represent a limitation of radiopeptides for clinical applications. Here, we report the synthesis, radiolabeling, stability, and in vitro evaluation of a novel, dual-targeting peptide radioconjugate designed to enhance the cellular retention of radioactivity. The described trifunctional conjugate is comprised of a Tc-99m SPECT reporter probe, a cell membrane receptor-specific peptide, and a second targeting entity directed towards mitochondria. While the specificity of the first generation of dual-targeting conjugates towards its extracellular target was demonstrated, intracellular targeting could not be confirmed probably due to non-specific binding or hindered passage through the membrane of the organelle. The work presented describes a novel approach with potential to improve the efficacy of radiopharmaceuticals by enhancing the intracellular retention of radioactivity. 相似文献
942.
Bruna S. Santos Sandra C.C. Nunes Alberto A.C.C. Pais Teresa M.V.D. Pinho e Melo 《Tetrahedron》2012,68(19):3729-3737
Chiral spiro-β-lactam derivatives have been prepared via stereoselective 1,3-dipolar cycloaddition of 6-diazopenicillanates. Using dipolarophiles such as acrylonitrile, acrylates or methyl vinyl ketone spiro-2-pyrazoline-β-lactams were obtained, whereas the cycloaddition with N-substituted-maleimides afforded spiro-1-pyrazoline-β-lactams. 6-Diazopenicillanates also reacted with electron-deficient alkynes to give the corresponding spiro-3H-pyrazole-β-lactam as single product. The observed stereoselectivity can be explained considering that the major product results from the addition to the less sterically hindered α-side of the β-lactam. Microwave-induced denitrogenation of spiro-1-pyrazoline-β-lactams allowed the stereoselective synthesis of novel spirocyclopropyl-β-lactams. The rationalization of the observed selectivity was supported by electronic structure calculations. 相似文献
943.
Boucetta H Podor R Stievano L Ravaux J Carrier X Casale S Gossé S Monteiro A Schuller S 《Inorganic chemistry》2012,51(6):3478-3489
Ruthenium, a fission product arising from the reprocessing of spent uranium oxide (UOX) fuel, crystallizes in the form of acicular RuO(2) particles in high-level waste containment glass matrices. These particles are responsible for significant modifications in the physicochemical behavior of the glass in the liquid state, and their formation mechanisms are a subject of investigation. The chemical reactions responsible for the crystallization of RuO(2) particles with acicular or polyhedral shape in simplified radioactive waste containment glass are described. In situ high-temperature environmental scanning electron microscopy (ESEM) is used to follow changes in morphology and composition of the ruthenium compounds formed by reactions at high temperature between a simplified RuO(2)-NaNO(3) precursor and a sodium borosilicate glass (SiO(2)-B(2)O(3)-Na(2)O). The key parameter in the formation of acicular or polyhedral RuO(2) crystals is the chemistry of the ruthenium compound under oxidized conditions (Ru(IV), Ru(V)). The precipitation of needle-shaped RuO(2) crystals in the melt might be associated with the formation of an intermediate Ru compound (Na(3)Ru(V)O(4)) before dissolution in the melt, allowing Ru concentration gradients. The formation of polyhedral crystals is the result of the direct incorporation of RuO(2) crystals in the melt followed by an Ostwald ripening mechanism. 相似文献
944.
de Boer SY Gloaguen Y Reek JN Lutz M van der Vlugt JI 《Dalton transactions (Cambridge, England : 2003)》2012,41(37):11276-11283
The first examples of reactivity at the backbone of a bidentate PN-ligand L1H relevant to N-H activation are described, leading to novel Pd(II) and Cu(I) amido complexes. Activation of the PN-ligand backbone led to selective dearomatization of the pyridyl ring structure. In the case of Pd(II), the intermediate could be efficiently stabilized using PMe(3). Selective N-H bond cleavage of e.g. trifluorosulfonylamide resulted in facile formation of mononuclear metal-amido species 2 and 4, which have been crystallographically characterized. Hydrogen-bonding dimerization is observed in these solid state structures. The results obtained with these structurally versatile and reactive scaffolds likely open up new avenues in cooperative catalysis. 相似文献
945.
Farooq Ali Shah Saqib Ali Saira Shahzadi Corrado Rizzoli Sandra Ianelli 《Journal of chemical crystallography》2011,41(9):1249-1253
Abstract
Reaction of di-n-butyltin oxide with 4,5-dimethoxy-2-nitrobenzoic acid yields the title compound which crystallizes as the usual dicarboxylatotetraorganodistannoxane dimer. Experimental details for the preparation and the structural characterization (by FTIR, NMR and single crystal XRD) are provided. The IR data shows that ligand acts in the bidentate manner. The crystal structure analysis of the compound reveals the presence of a centrosymmetric planar Sn2O2 unit connected to exocyclic Sn atom via two bidentate bridging carboxylate ligands. The remaining two carboxylate ligands are coordinated to the exocyclic Sn atom in the monodentate manner. 相似文献946.
Iwaki M Andrianambinintsoa S Rich P Breton J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(7):1523-1533
Chemically induced Fourier transform infrared difference spectra associated with redox transitions of several primary electron donors and acceptors in photosynthetic reaction centers (RCs) have been compared with the light-induced FTIR difference spectra involving the same cofactors. The RCs are deposited on an attenuated total reflection (ATR) prism and form a film that is enclosed in a flow cell. Redox transitions in the film of RCs can be repetitively induced either by perfusion of buffers poised at different redox potentials or by illumination. The perfusion-induced ATR-FTIR difference spectra for the oxidation of the primary electron donor P in the RCs of the purple bacteria Rb. sphaeroides and Rp. viridis and P700 in the photosystem 1 of Synechocystis 6803, as well as the Q(A)/Q(A) transition of the quinone acceptor (Q(A)) in Rb. sphaeroides RCs are reported for the first time. They are compared with the light-induced ATR-FTIR difference spectra P+Q(A)/PQ(A) for the RCs of Rb. sphaeroides and P700+/P700 for photosystem 1. It is shown that the perfusion-induced and light-induced ATR-FTIR difference spectra recorded on the same RC film display identical signal to noise ratios when they are measured under comparable conditions. The ATR-FTIR difference spectra are very similar to the equivalent FTIR difference spectra previously recorded upon photochemical or electrochemical excitation of these RCs in the more conventional transmission mode. The ATR-FTIR technique requires a smaller amount of sample compared with transmission FTIR and allows precise control of the aqueous environment of the RC films. 相似文献
947.
Paulo R. Olivato Sandra A. Guerrero Mario L.T. Hiu Janaina Mattos Simone Harms Marcos S.V. Schimidt 《光谱学快报》2013,46(6):1041-1056
The vco analysis of p-substituted α-phenoxy-acetones X-θ-O-CH2-C(O)-Me (1-6) indicates the existence of the cislgauche rotational isomerism. The nearly constant increase in the cislgauche population ratios for the whole series, on going from carbon tetrachloride to acetonitrile, and the small sensitivity of the carbonyl frequency shifts (Δvc) for the cis rotamer, on going from electron-attracting to electron-donating substituents, are interpreted as an interplay of the Field (F) and the Inductive (-I) Effects, which originates an almost constant carbonyl bond order, and suggests that the cis rotamers have almost the same energy in the whole series. The decrease in the cislgauche population ratios, in all solvents, and the deshielding effects on the carbonyl carbon atom, and on the methylene carbon atom in a weaker extent, observed in the 13C NMR spectra, on going from electron-attracting to electron-donating substituents, are discussed in terms of φ*CO/nO orbital and Arδ+ -Oδ- — Cδ+ =Oδ- Coulombic interactions, which stabilize the gauche rotamers of the investigated compounds. 相似文献
948.
Roberto Cesareo Angel D. Bustamante Julio S. Fabian Sandra Del Pilar Zambrano Walter Alva Luis Z. Chero Maria C. Del Carmen Espinoza Rosendo R. Rodriguez Marco F. Seclen Fidel V. Gutierrez Edgard B. Levano Juan A. Gonzales Marcia A. Rizzutto Enrico Poli Cristiane Calza Marcelino Dos Anjos Renato Pereira De Freitas Ricardo T. Lopes Carlos Elera Izumi Shimada Victor Curay Maria G. Castillo Giovanni E. Gigante Gabriel M. Ingo Fabio Lopes Ulla Holmquist David Diestra 《Applied Physics A: Materials Science & Processing》2013,113(4):889-903
Three types of alloys were recognized when analyzing pre-Columbian artifacts from the North of Peru: gold, silver, and copper alloys; gilded copper and silver; silvered copper; tumbaga, i.e., copper or silver enriched on gold at the surface by depletion gilding. In this paper, a method is described to differentiate gold alloys from gilded copper and from copper–gold tumbaga, and silver alloys from silvered copper and copper–silver tumbaga. This method is based on the use of energy-dispersive X-ray fluorescence, i.e., on a sophisticated analysis of XRF-spectra carrying out an accurate determination of Cu(K α /K β ), Ag(K α /K β ), Au(L α /L β ), and Au-L α /Cu-K α or Ag-K α /Cu-K α ratios. That implies a dedicated software for the quantitative determination of the area of X-ray peaks. This method was first checked by a relevant number of standard samples and then it was applied to pre-Columbian alloys from the North of Peru. 相似文献
949.
Sandra Mara Alves Jorge 《代数通讯》2013,41(6):2184-2198
950.
W. Frank Moore Greg Piepmeyer Sandra Spiroff Mark E. Walker 《Mathematische Zeitschrift》2013,273(3-4):907-920
We study H. Dao’s invariant ${\eta_c^R}$ of pairs of modules defined over a complete intersection ring R of codimension c having an isolated singularity. Our main result is that ${\eta_c^R}$ vanishes for all pairs of modules when R is a graded complete intersection ring of codimension c > 1 having an isolated singularity. A consequence of this result is that all pairs of modules over such a ring are c-Tor-rigid. 相似文献