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1.
Yumi ShimadaMakoto Nakamura Toshimasa SuzukaJunji Matsui Ryo TatsumiKen Tsutsumi Tsumoru MorimotoHideo Kurosawa Kiyomi Kakiuchi 《Tetrahedron letters》2003,44(7):1401-1403
A new method for the construction of the AB-ring core of Taxol was developed utilizing a new skeletal transformation protocol as a pivotal step. The acid-catalyzed rearrangement of the cyclopentenone-allene photoadduct gave a bridged seven-membered ketone, which was easily transformed, using the intramolecular Suzuki reaction and the oxidative cleavage of the vicinal diol, to the bicyclic diketone. 相似文献
2.
Hirotaka Okamoto Tadashi Inoue Kunihiro Osaki 《Journal of Polymer Science.Polymer Physics》1995,33(3):417-424
The complex Young's modulus, E*(ω), and the complex strain-optical coefficient, O*(ω), which is the ratio of the birefringence to the strain, were measured for polyisoprene (PIP) over a frequency range of 1 ~ 130 Hz and a temperature range of 22 ~ ?100°C. The imaginary part of O*, O″, was positive at low frequencies and negative at high frequencies. The real part, O′, was always positive and showed a maximum. The complicated behavior of O* could be understood by the assumption that E* = ER* + EG* and O* = CRER* + CGEG*, where ER* and EG* were complex quantities and CR and CG were constants. The CR value, equal to the ordinary stress-optical coefficient measured in the rubbery plateau zone, was 2.0 × 10?9 Pa?1. The CG value, defined as the ratio O″/E″ in the glassy zone, was ?1.1 × 10?11 Pa?1. The EG*, which was the major component of E* in the glassy zone, showed almost the same frequency dependence as that of polystyrene and polycarbonate. The ER*, which was dominant in the rubbery zone, was described well by the bead-spring theory. The temperature dependence of the EG* was stronger than that of the ER*. This difference caused the breakdown of the thermorheological simplicity for E* and O* around the glass-to-rubber transition zone. © 1995 John Wiley & Sons, Inc. 相似文献
3.
S. Osaki S. Sugihara Y. Takashima 《Journal of Radioanalytical and Nuclear Chemistry》1992,165(4):203-207
A gelling agent, N-lauroyl-L-glutamic-,-dibutylamide, was applied for liquid scintillation counting of inorganic32P and35S. The gel with toluene cocktail is transparent and rigid for a long time. Several grams of ammonium magnesium phosphate or barium sulfate can easily be measured without complicating procedures. 相似文献
4.
A method has been developed for highly sensitive determination of haloperidol in human serum involving a simple extraction procedure followed by gas chromatographic separation. Target components were separated from the extracting solvents with a Van den Berg type solventless sample injector before introduction Into a DB-1 capillary separation column. A surface ionization detector (SID), which has highly selective sensitivity for Substituted amines, was employed for quantitation using bromperidol as an internal standard. Chloroform proved to be the best extracting solvent, yielding a quantitative detection limit of 5 ng/ml (S/N = 2). Comparison of the response to target compounds obtained by the SID, FTD (flame thermionic detector), and FID (flame ionization detector) showed the SID to be superior. 相似文献
5.
K. Osaki T. Inoue T. Uematsu Y. Yamashita 《Journal of Polymer Science.Polymer Physics》2002,40(10):1038-1045
Linear viscoelasticity behavior is described with the sum of two terms for polystyrene solutions in tricresyl phosphate around the coil overlapping concentration (K. Osaki, T. Inoue, & T. Uematsu, J Polym Sci Part B: Polym Phys 2001, 39, 211). One is a Rouse–Zimm (RZ) term represented by the Zimm theory with arbitrarily chosen values of the hydrodynamic interaction parameter and the longest relaxation time (τRZ). The other (the L term) consists of a relaxation mode with a single relaxation time (τL > τRZ) and a high‐frequency limiting modulus proportional to the square of the concentration. In this study, we describe the viscosity (η) and first normal stress coefficient (Ψ1) in steady shear with simple formulas. The stress due to the L term is assumed to be given by a Kaye, Bernstein, Kearsley, and Zapas (K‐BKZ) equation with the damping function h(γ) = (1 + 0.2γ2)?1/2, where γ is the magnitude of shear. Contributions to η and Ψ1 from the RZ term are derived from the RZ model, in which the relaxation time in steady flow is given by τst = τ + (τRZ ? τ)/(1 + 0.35τRZ γ˙) instead of τRZ. Here, γ˙ is the rate of shear, and τ is the τRZ value at the infinite dilution limit. η and Ψ1 at various concentrations for two polystyrene samples (with molecular weights of 2890 and 8420 kg mol?1) are well described with parameters derived from dynamic viscoelasticity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1038–1045, 2002 相似文献
6.
Intramolecular vibrational energy redistributions of the O-H stretching (nuOH) vibration for the methanol monomer and its water complex, the methanol-water dimer, are investigated by using ab initio full-dimensional classical trajectory calculations. For the methanol monomer, in the high-energy regime of the 5nuOH overtone, the time dependence of the normal-mode energies indicates that energy flowed from the initial excited O-H stretching mode to the C-H stretching mode. This result confirms the experimental observation of energy redistribution between the O-H and C-H stretching vibrations [L. Lubich et al., Faraday Discuss. 102, 167 (1995)]. Furthermore, a lot of dynamical information in the time domain is contained in the power spectra, whose density is given by the Fourier transformation of the total momentum obtained from trajectory calculations. For the methanol-water hydrogen-bonded complex, at the high-energy level of the 5nuOH overtone, the calculated power spectrum shows considerable splitting and broadening, indicating significant energy redistribution through strong coupling between the O-H stretching vibration and other vibrations. It is thus clear that the A-H...B hydrogen-bond formation facilitates energy redistribution subsequent to the vibrational excitation of the hydrogen-bonded A-H stretching mode. 相似文献
7.
Yumi Arai Masayoshi Watanabe Kohei Sanui Naoya Ogata 《Journal of polymer science. Part A, Polymer chemistry》1985,23(12):3081-3093
Polycondensation methods greatly influence the molecular weight distribution of poly(hexamethylene sebacamide) (nylon 610) as determined by gel permeation chromatography (GPC). The ratio of weight average molecular weight to number average molecular weight (Mw/Mn) was used as a measure for estimating the molecular weight distribution. The Mw/Mn ratios of nylon 610 obtained from melt, solid phase, and high temperature polycondensation methods were 2 to 3.5, which were expected values for the most probable distribution. However, those for polymers obtained from the direct polycondensation in the presence of triphenylphosphine, interfacial polycondensation and low temperature polycondensation using an acid chloride varied over a wide range from 3.5 to 8.5. The effect of the kind of organic solvents in the interfacial method on the Mw/Mn ratios was especially large, and the molecular weight distribution could be controlled to some extent by selecting an appropriate solvent. 相似文献
8.
One-pot substitution of a C-H bond at the position next to the nitrogen atom of lactams with alkyl malonates proceeded effectively by dehydrogenation of lactams with N-tert-butylbenzenesulfinimidoyl chloride, followed by Mannich-type addition of alkyl malonates. 相似文献
9.
Annaraj J Suh Y Seo MS Kim SO Nam W 《Chemical communications (Cambridge, England)》2005,(36):4529-4531
A mononuclear nonheme ferric-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [(TMC)Fe(III)-O2]+, was prepared and used in mechanistic studies of aldehyde deformylation; a catalytic aldehyde deformylation by a nonheme iron(II) complex, [Fe(II)(TMC)]2+, and molecular oxygen is reported as well. 相似文献
10.
Clot O Akahori Y Moorlag C Leznoff DB Wolf MO Batchelor RJ Patrick BO Ishii M 《Inorganic chemistry》2003,42(8):2704-2713
The preparations of two new phosphinothiophene ligands, 3,3'-bis(diphenylphosphino)-2,2'-bithiophene (dppbt; 1) and 3,3' "-dihexyl-3',3' '-bis(diphenylphosphino)-2,5':2',2' ':5' ',2' "-quaterthiophene (hdppqt; 2) are reported. Oxidation of 1 gives 3,3'-bis(diphenylphosphine oxide)-2,2'-bithiophene (3), and the crystal structure of this compound was determined. Pd(II) and Au(I) complexes of these ligands have been synthesized and characterized. Crystal structures of [(dppbt)PdCl(2)] (1-Pd), [(hdppqt)PdCl(2)] (2-Pd), [(dppbt)(AuCl)(2)] (1-Au), and [(hdppqt)(AuCl)(2)] (2-Au) were obtained. [(dppbt)(AuCl)(2)] crystallized in two solid-state forms; crystals grown from CH(2)Cl(2)/Et(2)O show a gold-gold interaction of 3.3221(4) A, but from CH(2)Cl(2)/toluene, the molecule crystallizes as a toluene adduct (1-Au-tol) and does not show any gold-gold interaction. All the complexes were characterized via UV-vis spectroscopy and cyclic voltammetry, and the effect of the metal on the energy of the pi-pi transition and oxidation potential was determined. These data are correlated to the interannular torsion angles in the oligothienyl groups from the crystal structure studies. 相似文献