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81.
Nicols Veiga Natalia Alvarez Eduardo E. Castellano Javier Ellena Gianella Facchin María H. Torre 《Molecules (Basel, Switzerland)》2021,26(21)
In a search for new antitumoral agents, a series of homoleptic copper(II) complexes with amino acids and dipeptides, as well as heteroleptic complexes containing both dipeptides and 1,10-phenanthroline, were studied. Furthermore, a single-crystal structure containing alanyl-leucinato ([Cu3(AlaLeu)3(H2O)3(CO3)]·PF6·H2O), which is the first homotrinuclear carbonato-bridged copper(II) complex with a dipeptide moiety, is presented. To assess possible antitumor action mechanisms, we focused on the comparative analysis of pro- and antioxidant behaviors. Pro-oxidant activity, in which the reactive oxygen species (ROS) formed by the reaction of the complexes with H2O2 produce oxidative damage to 2-deoxy-d-ribose, was evaluated using the TBARS method. Additionally, the antioxidant action was quantified through the superoxide dismutase (SOD)-like activity, using a protocol based on the inhibitory effect of SOD on the reduction of nitrobluetetrazolium (NBT) by the superoxide anion generated by the xanthine/xanthine oxidase system. Our findings show that Cu–amino acid complexes are strong ROS producers and moderate SOD mimics. Conversely, Cu–dipeptide–phen complexes are good SOD mimics but poor ROS producers. The activity of Cu–dipeptide complexes was strongly dependent on the dipeptide. A DFT computational analysis revealed that complexes with high SOD-like activity tend to display a large dipole moment and condensed-to-copper charge, softness and LUMO contribution. Moreover, good ROS producers have higher global hardness and copper electrophilicity, lower copper softness and flexible and freely accessible coordination polyhedra. 相似文献
82.
83.
Patricia A. M. Williams Evelina G. Ferrer Karina A. Pasquevich Enrique J. Baran Zulema Chaia Eduardo E. Castellano Oscar E. Piro 《无机化学与普通化学杂志》2000,626(12):2509-2514
The crystal structure of the complexes [Cu(sac)2(bzim)2(H2O)] ( 1 ) and [Cu(sac)2(bzim)(H2O)(EtOH)] · 2 EtOH ( 2 ) (sac = saccharinate anion; bzim = benzimidazole; EtOH = ethanol) was determined by single crystal X‐ray diffractometry. Complex 1 crystallizes in the monoclinic C2/c space group with Z = 8 whereas complex 2 belongs to the triclinic P1 space group with Z = 2. Room temperature magnetic susceptibilities as well as electronic and IR spectra of both complexes were discussed. Their thermal behaviour was investigated by means of TG and DTA methods. 相似文献
84.
Ronald K. Castellano Colin Nuckolls S. Holger Eichhorn Malcolm R. Wood Andrew J. Lovinger Julius Rebek Jr. 《Angewandte Chemie (International ed. in English)》1999,38(17):2603-2606
When outfitted with long alkyl chains , polycaps, capsules along a polymer chain, spontaneously organize themselves into a two-dimensional liquid crystalline phase. Further organization results from shearing or pulling the liquid crystalline samples, producing three-dimensional assemblies of micrometer-wide, infinitely long fibers (see schematic representation). 相似文献
85.
86.
Emanuele Pugliese Claudio Castellano Matteo Marsili Luciano Pietronero 《The European Physical Journal B - Condensed Matter and Complex Systems》2009,67(3):319-327
We introduce and study a model of an interacting population of agents who collaborate in groups which compete for limited
resources. Groups are formed by random matching agents and their worth is determined by the sum of the efforts deployed by
agents in group formation. Agents, on their side, have to share their effort between contributing to their group’s chances
to outcompete other groups and resource sharing among partners, when the group is successful. A simple implementation of this
strategic interaction gives rise to static and evolutionary properties with a very rich phenomenology. A robust emerging feature
is the separation of the population between agents who invest mainly in the success of their group and agents who concentrate
in getting the largest share of their group’s profits. 相似文献
87.
Sabrina Castellano Marisabella Santoriello Pietro Campiglia Giovanna Cardillo Alessia Bertamino Isabel Gomez-Monterrey Ettore Novellino Gianluca Sbardella 《Tetrahedron letters》2009,50(49):6869-6871
An inexpensive and regioselective approach to dihydrothieno[3,2-g]quinoline-4,9-dione is reported. A combination of a mild version of Skraup reaction with a sequential substitution/Michael addition allowed the selective preparation in acceptable yield of a pharmacologically important quinone derivative, previously obtained only in trace and together with the other regioisomer. 相似文献
88.
Susana H. Tarulli Oscar V. Quinzani Prof. Dr. Sandra D. Mandolesi Jorge A. Guida Gustavo A. Echeverría Oscar E. Piro Eduardo E. Castellano 《无机化学与普通化学杂志》2009,635(11):1604-1612
A series of palladium(II) thiosaccharinates with triphenylphosphane (PPh3), bis(diphenylphosphanyl)methane (dppm), and bis(diphenylphosphanyl)ethane (dppe) have been prepared and characterized. From mixtures of thiosaccharin, Htsac, and palladium(II) acetylacetonate, Pd(acac)2, the palladium(II) thiosaccharinate, Pd(tsac)2 (tsac: thiosaccharinate anion) ( 1 ) was prepared. The reaction of 1 with PPh3, dppm, and dppe leads to the mononuclear species Pd(tsac)2(PPh3)2 · MeCN ( 2 ), [Pd(tsac)2(dppm)] ( 3 ), Pd(tsac)2(dppm)2 ( 4 ), and [Pd(tsac)2(dppe)] · MeCN ( 5 ). Compounds 2 , 4 , and 5 have been prepared also by the reaction of Pd(acac)2 with the corresponding phosphane and Htsac. All the new complexes have been characterized by chemical analysis, UV/Vis, IR, and Raman spectroscopy. Some of them have been also characterized by NMR spectroscopy. The crystalline structures of complexes 3 , and 5 have been studied by X‐ray diffraction techniques. Complex 3 crystallizes in the monoclinic space group P21/n with a = 16.3537(2), b = 13.3981(3), c = 35.2277(7) Å, β = 91.284(1)°, and Z = 8 molecules per unit cell, and complex 5 in P21/n with a = 10.6445(8), b = 26.412(3), c = 15.781(2) Å, β = 107.996(7)°, and Z = 4. In compounds 3 and 5 , the palladium ions are in a distorted square planar environment. They are closely related, having two sulfur atoms of two thiosaccharinate anions, and two phosphorus atoms of one molecule of dppm or dppe, respectively, bonded to the PdII atom. The molecular structure of complex 3 is the first reported for a mononuclear PdII‐dppm‐thionate system. 相似文献
89.
Eliana M.A. Valle Benedicto A.V. Lima Antonio G. Ferreira Fbio B. do Nascimento Victor M. Deflon Izaura C.N. Digenes Ulrich Abram Javier Ellena Eduardo E. Castellano Alzir A. Batista 《Polyhedron》2009,28(16):3473-3478
The reaction of cis-[RuCl2(P–P)(N–N)] type complexes (P–P = 1,4-bis(diphenylphosphino)butane or (1,1′-diphenylphosphino)ferrocene; N–N = 2,2′-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P–P)(N–N)]+ species. Upon characterization of the isolated compounds by elemental analysis, 31P{1H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good π acceptor, coordinates trans to the nitrogen atom. A 31P{1H} NMR experiment following the reaction of the precursor cis-[RuCl2(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N–N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF6 species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex. 相似文献
90.
The role of electrostatics is studied in the adsorption of cationic proteins to zwitterionic phosphatidylcholine (PC) and anionic PC/phosphatidylglycerol (PG) mixed small unilamellar vesicles (SUVs). For model proteins the interaction is monitored vs. PG content at low ionic strength. The adsorption of lysozyme and myoglobin (isoelectric point, pI 7-11) is investigated in SUVs, along with changes of the fluorescence emission spectra of the cationic proteins, via their adsorption on SUVs. In the Gouy-Chapman formalism, the activity coefficient goes with the square of charge number. Deviations from the ideal model could indicate the asymmetric location of the anionic phospholipid in the bilayer inner leaflet, in mixed zwitterionic/anionic SUVs for both lysozyme- and myoglobin-PC/PG systems, in agreement with experiments and molecular dynamics simulations. Fitted effective SUV charge stays constant. Effective—formal difference increases 0.417 e.u. Effective protein charge increases as PC/PG < PC being greater for myoglobin. The molar free energies of the protein in aqueous and lipid phases increase as PC < PC/PG. Both free-energy changes are greater for myoglobin. Effective interfacial charge stays constant for anionic PC/PG SUVs being greater for myoglobin. 相似文献