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71.
This paper describes how the nonpolar polymer polyisobutylene (PIB) can be used as a handle to prepare PIB-bound NHC ligands that are soluble in monophasic mixtures of mixed solvents but phase separable when such solvent systems are perturbed to be biphasic. The results here show that such PIB-bound NHC ligands can be used to synthesize useful palladium catalysts. In this paper, both PIB-bound analogs of an N,N′-bis(2,6-diisopropylphenyl) heterocyclic carbene and simpler N,N′-dialkyl heterocyclic carbene ligand were prepared and were successfully used to form palladium cross-coupling catalysts. The reactivity, recycling and reusability of these catalysts has been examined.  相似文献   
72.
A ruthenium cyclic biscarbene complex reacted with a H(2)O molecule under mild conditions to produce η(5)-oxapentadienyl complex, that proved to be the intermediate in the catalytic hydrative cyclization of a diyne.  相似文献   
73.
74.
Poly(2-methoxyethyl acrylate) (PMEA) exhibits excellent blood compatibility. To understand why such a surface functionality exists, the surface of PMEA should be characterized in detail, structurally and dynamically, under not only ambient conditions, but also in water. However, a thin film of PMEA supported on a solid substrate can be easily broken, namely it is dewetted. Our strategy to overcome this difficulty is to mix PMEA with poly(methyl methacrylate) (PMMA). Differential scanning calorimetry and cloud point measurements revealed that the PMEA/PMMA blend has a phase diagram with a lower critical solution temperature. The blend surface was also characterized by X-ray photoelectron spectroscopy in conjunction with microscopic observations. Although PMEA is preferentially segregated over PMMA at the blend surface due to its lower surface free energy, the extent of segregation in the as-prepared films was not sufficient to cover the surface. Annealing the blend film at an appropriate temperature, higher than the glass transition temperature and lower than the phase-separation temperature of the blend, enabled us to prepare a stable and flat surface that was perfectly covered with PMEA.  相似文献   
75.
X-ray absorption near edge structure (XANES) measurements at the C, N, and Fe K absorption edges were performed for iron(III)-tetraphenylporphyrin (FeTPP), iron(III)-tetrakis(p-carboxyphenyl)porphyrin (FeTCPP), and iron(III)-tetrakis(p-sulfonatophenyl)porphyrin (FeTSPP). The spectral shapes differ in the Fe K XANES, but not in C and N K XANES among FeTPP, FeTCPP, and FeTSPP. Crosschecks of XANES data for C, N, and Fe K absorption edges in combination with discrete variational (DV)-Xalpha molecular orbital (MO) calculations indicate that each p-electron-withdrawing group on four meso-phenyl substitutes in an Fe(III)-porphyrin complex brings about a unique electron state through the complex because of the electron-withdrawal strength, itself. Consequently, they affect the positive charge of the center Fe(III) ion.  相似文献   
76.
This study investigated the protonation of nitrogen atoms in porphyrins with meso-phenyl p-substituted by an electron-withdrawing group using N 1s X-ray photoelectron spectroscopy (XPS), the N K X-ray absorption near-edge structure (XANES), and the discrete variational (DV)-Xalpha molecular orbital (MO) method. Both tetraphenylporphyrin (TPP) and tetrakis(p-sulfonatophenyl)porphyrin (TSPP) have a single structure: the former has two protonated and two non-protonated N atoms in the porphine ring; the latter has four protonated N atoms in the porphine ring. In contrast, a combination of XPS, XANES, and DV-Xalpha MO calculations shows that tetrakis(p-carboxyphenyl)porphyrin (TCPP) has a dual structure: one structure has two protonated and two non-protonated N atoms; the other has four protonated N atoms. Furthermore, this result was also considered based on the protonation constants of N atoms in the porphyrins. The correlation between the strength of electron-withdrawing groups and protonation to N atoms in porphyrins can be described using the spectral patterns of the N 1s XPS and N K XANES spectra.  相似文献   
77.
Nitrogen atomic-layer-doped and uniformly doped GaAs were grown by MOVPE using dimethylhydrazine on a (001) plane. They showed several sharp photoluminescence lines with a full width at half maximum less than 1 meV at 8 K. Compared with uniformly doped GaAs, the photoluminescence intensity of the nitrogen-related line at the longest wavelength is enhanced in nitrogen atomic-layer-doped GaAs, suggesting that it is easier to form nitrogen pairs during atomic layer doping. To investigate the sharp nitrogen-related lines, we also grew GaAs with double atomic-layer-doped planes and varied the distance between the two planes. When the two planes are brought close to 1 nm, two new lines, NNC and NND, appear between the two nitrogen-related lines, NNA and NNB, observed in a single nitrogen atomic-layer-doped GaAs. The NNC and NND lines are also observed in uniformly doped GaAs. Therefore, NNA and NNB originate from excitons bound to pairs of nitrogen atoms, both of which are in the (001) plane, while NNC and NND originate from those bound to pairs of nitrogen atoms, of which pairing directions are not included in the (001) plane. From the photoluminescence characteristics, distances between nitrogen atoms of a pair are estimated for each line.  相似文献   
78.
Perfluorocarboxylic acids and their anions (PFCAs), such as perfluorooctanate (C7F15C(O)O?), have been generally recognized to be global pollutants and are believed to persist in the environment. Kinetic data for reactions of sulfate anion radicals (SO4?) with PFCAs are needed to evaluate the residence times of PFCAs in the environment, but no kinetic data have been reported, except for the rate constant for the reaction of SO4? with trifluoroacetate (CF3C(O)O?) (k1). In this study, using the fact that PFCAs react with SO4? to form shorter chain PFCAs, we determined rates relative to k1 of the reactions of photolytically generated SO4? with two short‐chain PFCAs, pentafluoropropionate (C2F5C(O)O?; k2) and heptafluorobutyrate (C3F7C(O)O?; k3), along with conversion ratios for conversion of C2F5C(O)O? into CF3C(O)O? (α) and conversion of C3F7C(O)O? into C2F5C(O)O? (β) and CF3C(O)O? (γ) at 298 K. Values of k1, k2, or k3 might change over the course of reaction with increasing ionic strength. Nevertheless, if the values of k1/k2, k2/k3, α, β, and γ remain almost constant during the reaction, a simple equation involving relative rates, such as k1/k2, can be used to relate the concentrations of C3F7C(O)O?, C2F5C(O)O?, and CF3C(O)O?. We compared the relative rates, such as k1/k2, and the conversion ratios determined from various experimental runs with different initial conditions to check whether relative rates and conversion ratios remained almost constant during each experimental run. The values of k1/k2, k2/k3, α, β, and γ seemed to remain almost constant, which facilitated determination of k2/k1 = 0.89 ± 0.07, k3/k1 = 0.84 ± 0.08, α = 0.88 ± 0.05, β = 0.75 ± 0.05, and γ = 0.17 ± 0.02. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 276–288, 2007  相似文献   
79.
The chemical species of carrier-free technetium, which were extractable into a TTA-benzene solution on reduction of96TcO 4 either with NaBH4 or concentrated HCl, were studied by means of silica gel chromatography. Elution peaks ascribed to the formation of Tc/tta/4 and Tc/tta/3 type complexes were observed. The latter complex was also synthesized by recoil effect of Ru/, p/Tc reactions in -irradiated Ru/tta/3.  相似文献   
80.
In order to produce routinely carrier-free96Tc and111In, their simultaneous production was examined by means of the stacked foil method. Both niobium and silver foils were arranged on the target holder so as the desired nuclear reactions took place effectively. Simultaneous irradiation of the target with 35 MeV -particles produced effectively111In and96Tc by the109Ag(, 2n)111In and93Nb(, n)96Tc reactions, respectively. Sufficient amounts of radioactivities for tracer uses are obtained by the irradiation at 5 A current for 2 hrs. In addition, carrier-free96TcO4 in a perchloric acid solution could be prepared by the combined use of precipitation and anion-exchange methods. Separation of carrier-free111In from the silver matrix was done by means of solvent extraction using acetylacetone as a chelating agent.  相似文献   
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