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461.
D. Mercuri G. Leone R. Barbucci R. Favaloro A. Facchini F. Signori S. Bronco F. Ciardelli 《Macromolecular Symposia》2008,266(1):74-80
Summary: Degeneration of intervertebral discs is the most common cause of back pain. The first phase of this degenerative process involves the nucleus pulposus. A rapid recovery of this structure can prevent further degradation of the annulus fibrosus. Guar Gum is an hydrophilic polysaccharide extracted from the seed endosperm of a plant. Through a cross-linking procedure a Guar hydrogel was synthesized. The Guar hydrogel could be injected by a syringe and it is a good candidate as a nucleus pulposus substitute. For the preparation of the artificial fibrosus annulus, commercially available polymer materials are tuned to achieve suitable mechanical properties. To achieve this peculiar behaviour, the main strategy investigated is the dispersion of hollow polymer micro spheres in a thermoplastic polymer matrix. Processing conditions and particle content are finely tuned to get the target mechanical behaviour. 相似文献
462.
Georg Wolfbauer Alan M. Bond Glen B. Deacon Douglas R. MacFarlane Leone Spiccia 《Journal of Electroanalytical Chemistry》2000,490(1-2)
The electrochemical reduction of the black dye photosensitizer [(H3-tctpy)RuII(NCS)3]− (H3-tctpy=2,2′:6′,2′′-terpyridine-4,4′,4′′-tricarboxylic acid) used in photovoltaic cells has been found to be a complex process when studied in dimethylformamide. At low temperatures, fast scan rates and at a glassy carbon electrode, the chemically reversible ligand based one-electron reduction process [(H3-tctpy)Ru(NCS)3]−+e−[(H3-tctpy√−)Ru(NCS)3]2− is detected. This process has a reversible half-wave potential (Er1/2) of −1585±20 mV versus Fc/Fc+ at 25°C. Under other conditions, a deprotonation reaction occurs upon reduction, which produces [(H3−x-tctpyx−)Ru(NCS)3](1+x)− and hydrogen gas. Mechanistic pathways giving rise to the final products are discussed. The Er1/2-value for the ligand based reductions of the deprotonated complex is 0.70 V more negative than for [(H3-tctpy)Ru(NCS)3]−. Consequently, data obtained from molecular orbital calculations are consistent with the reaction [(H3-tctpy)Ru(NCS)3]−+e−→[(H2-tctpy−)Ru(NCS)3]2−+1/2H2 yielding the monodeprotonated complex as the major product obtained after electrochemical reduction of [(H3-tctpy)Ru(NCS)3]−. The Er1/2-values for the metal based RuII/III process differ by 0.30 V when data obtained for the protonated and deprotonated forms of the black dye are compared. Electronic spectra obtained during the course of experiments in an optically transparent thin layer electrolysis configuration are consistent with the overall reaction scheme proposed on the basis of voltammetric measurements and molecular orbital calculations. Reduction studies on the free ligand, H3-tcpy, are consistent with results obtained with [(H3-tctpy)Ru(NCS)3]−. 相似文献
463.
Belousoff MJ Duriska MB Graham B Batten SR Moubaraki B Murray KS Spiccia L 《Inorganic chemistry》2006,45(9):3746-3755
Two new N-substituted derivatives of the 1,4,7-triazacyclononane (tacn) macrocycle, 1-benzyl-4,7-dimethyl-1,4,7-triazacyclononane (L2) and 1,4,7-tris(3-cyanobenzyl)-1,4,7-triazacyclononane (L3), have been prepared and, together with 1,4-dimethyl-1,4,7-triazacyclononane (L1), have been used to synthesize the corresponding hydroxo-bridged binuclear copper (II) complexes, [Cu2(mu-OH)2L2](ClO4)2.xH2O (1 L = L1, x = 0; 2 L = L2, x = 1; 3 L = L3, x = 2). The X-ray crystal structures of all three complexes reveal the presence of [Cu2(mu-OH)2]2+ cores capped by pairs of facially coordinating tacn ligands so that the Cu(II) centers reside in distorted square pyramidal coordination environments. Variable-temperature magnetic susceptibility measurements indicate weak antiferromagnetic coupling (J = -36.4 cm(-1)) between the Cu(II) centers in 1, while the centers in 2 and 3 have been shown to interact ferromagnetically (J = 11.2 and 49.3 cm(-1), respectively). The variation in the strength and sign of these interactions has been rationalized in terms of the differing geometries of the [Cu2(mu-OH)2]2+ cores. The ability of the Cu(II) complexes to cleave phosphate ester bonds has been probed using the model phosphate ester bis(4-nitrophenyl)phosphate (BNPP) at pH 7.4 and a temperature of 50 degrees C. The measured rate constant for 3 (3 x 10(-4) s(-1)) is significantly greater than those previously reported for the Cu(II) complexes of the fully alkylated tacn ligands, Me3tacn and iPr3tacn, which until now have been rated as the most effective tacn-based phosphate ester cleavage agents. 相似文献
464.
ABSTRACT Constitutive laws for elastic-plastic materials are derived by eliminating the transverse stress component on the basis of the plane-strain constraint. This leads to a fictitious hardening and temperature dependence of the loading function. For standard elastic-plastic materials the resulting laws are associated; however, the plastic strain state is represented by equivalent plastic-strain measures, which also account for transverse yielding. The new constitutive laws, together with the standard reduced form of the equilibrium and compatibility equations, permit the formulation of the plane-strain elastic-plastic analysis problem in terms of the in-plane stress components only. In the case of perfectly plastic materials, the subsequent plane-strain yield surfaces are contained within a domain bounded by a limit surface which represents the yield condition normally adopted in plane-strain limit analysis. 相似文献
465.
Norihiro Ikemoto Ross A. Miller Joseph F. Leone Benjamin Marcune Joseph D. Armstrong III 《Tetrahedron letters》2005,46(11):1867-1871
Two syntheses of the title compound 1 were developed based on different approaches for installing the oxazole ring moiety. Formation and dehydration of ketoamide was initially used and scaled up to afford 1 on several kilogram scale, then oxazolyl anion/iminium coupling reaction was developed for a more convergent approach. 相似文献
466.
Oliva R Leone M Falcigno L D'Auria G Dettin M Scarinci C Di Bello C Paolillo L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(6):1467-1473
The selective proteolytic activation of the HIV-1 envelope glycoprotein gp160 by furin and other precursor convertases (PCs) occurs at the carboxyl side of the sequence Arg508-Glu-Lys-Arg511 (site 1), in spite of the presence of another consensus sequence: Lys500-Ala-Lys-Arg503 (site 2). We report on the solution structural analysis of a 19-residue synthetic peptide, p498, which spans the two gp160-processing sites 1 and 2, and is properly digested by furin at site 1. A molecular model is obtained for p498, by means of molecular dynamics simulations, from NMR data collected in trifluoroethanol/water. The peptide N-terminal side presents a 9-residue helical segment, enclosing the processing site 2; the C-terminal segment can be described as a loop exposing the processing site 1. A hypothesis for the docking of p498 onto the catalytic domain of human furin, modeled by homology and fitting previous site-directed mutagenesis studies, is also presented. p498 site 1 is shown to have easy access to the furin catalytic site, unlike the nonphysiological site 2. Finally, on the basis of available data, we suggest a possible structural motif required for the gp160-PCs recognition. 相似文献
467.
R. Leone G. Odriozola L. Mussio A. Schmitt R. Hidalgo-Álvarez 《The European physical journal. E, Soft matter》2002,7(2):153-161
Coupled aggregation and sedimentation processes were studied by means of three-dimensional computer simulations. For this
purpose, a large prism with no periodic boundary conditions for the sedimentation direction was considered. Furthermore, three
equally sized and mutually excluded regions were defined inside the prism, a top, a middle and a bottom region. This allows
to study the time evolution of the cluster size distribution and the cluster structure separately for each region. The mass
distribution profile and the center-of-mass position were also accessed as a function of time. For the bottom region, the
effects of the sediment formation on the kinetics of growth and on the cluster structure were clearly observed. The obtained
results not only agree with the experimental data obtained by Allain et al. (C. Allain, M. Cloitre, M. Wafra, Phys. Rev. Lett. 74, 1478 (1995)) and with the simulations made by Gonzalez (A.E. Gonzalez, Phys. Rev. Lett. 86, 1243 (2001)), but also allow to gain further insight into the details.
Received 7 November 2001 相似文献
468.
Ronald E. Leone Paul von R. Schleyer 《Angewandte Chemie (International ed. in English)》1970,9(11):860-890
Carbonium ions are called “degenerate” when they rearrange through finite energy barriers to give products whose gross structures are identical with those of the starting ions. In such degenerate rearrangements (“automerizations”), individual atoms and groups become mixed but the overall structure is conserved. Automerizations can be observed by noting the dispersal of isotopic labels, the loss of optical activity, or the temperature dependence of NMR spectra. In certain cases, a combination of well-known rearrangement processes results in complete mixing of all atoms, C or H. The 2-norbornyl and 9-barbaralyl cations are examples of fully degenerate systems; conditions can be found where both give but single-line NMR spectra. 相似文献
469.
Energy transfer rates for the V → V processes: have been measured following excitation of specific levels with a tunable optical parametric oscillator. 相似文献
470.
Corradi Gianfranco Janssen Jacques Manca Raimondo 《Methodology and Computing in Applied Probability》2004,6(2):233-246
This paper presents the numerical solution of the process evolution equation of a homogeneous semi-Markov process (HSMP) with a general quadrature method. Furthermore, results that justify this approach proving that the numerical solution tends to the evolution equation of the continuous time HSMP are given. The results obtained generalize classical results on integral equation numerical solutions applying them to particular kinds of integral equation systems. A method for obtaining the discrete time HSMP is shown by applying a very particular quadrature formula for the discretization. Following that, the problem of obtaining the continuous time HSMP from the discrete one is considered. In addition, the discrete time HSMP in matrix form is presented and the fact that the solution of the evolution equation of this process always exists is proved. Afterwards, an algorithm for solving the discrete time HSMP is given. Finally, a simple application of the HSMP is given for a real data social security example. 相似文献