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71.
Aubert T Ledneva AY Grasset F Kimoto K Naumov NG Molard Y Saito N Haneda H Cordier S 《Langmuir : the ACS journal of surfaces and colloids》2010,26(23):18512-18518
Metal atom clusters constitute very promising candidates as luminophores for applications in biotechnology because they are nanosized entities offering robust luminescence in the near-infrared field (NIR). However, they cannot be used as prepared for biological applications because of potential toxic effects and quenching of the clusters' luminescence in aqueous media, and they therefore need to be dispersed in a biocompatible matrix. We describe herein the encapsulation of octahedral rhenium clusters, denoted as A(4)[Re(6)Q(8)L(6)] (A = Cs or K, Q = S or Se, and L = OH or CN), in silica nanoparticles by a water-in-oil microemulsion process, paying particular attention to the clusters' stability. The obtained A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles are 30 nm in size with good monodispersity and a perfectly spherical shape, as shown by scanning electron microscopy (SEM). The presence of cluster units inside the silica matrix was evidenced by scanning transmission electron microscopy in annular dark-field mode (ADF-STEM). From the point of view of their optical properties, the A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles show red and NIR emission under UV excitation, even when dispersed in water. The evolution of the structural and luminescence properties of clusters before and after encapsulation was followed by Raman and photoluminescence spectroscopy. 相似文献
72.
Hisao Yamashige Shuji Matsuo Tsutomu Kurisaki Rupert C C Perera Hisanobu Wakita 《Analytical sciences》2005,21(3):309-314
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
73.
Hisao Yamashige Shuji Matsuo Tsutomu Kurisaki Rupert C C Perera Hisanobu Wakita 《Analytical sciences》2005,21(6):635-639
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
74.
Photoluminescence characteristics of nitrogen atomic-layer-doped GaAs grown by MOVPE 总被引:1,自引:0,他引:1
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
75.
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
76.
Sound attenuattion constants are calculated for the one-dimensional ferro- and antiferromagnetic systems at finite temperatures. Their frequency dependences, in both cases, turn out to be , where ωc is a “cut-off” frequency related to the three-dimensional anisotropic interactions. 相似文献
77.
78.
POSSIBLE ROLE OF METALLOTHIONEIN IN THE CELLULAR DEFENSE MECHANISM AGAINST UVB IRRADIATION IN NEONATAL HUMAN SKIN FIBROBLASTS 总被引:1,自引:0,他引:1
Shizuko Kobayashi Yumiko Hirota Junko Sayato-Suzuki Makoto Takehana Hisao Nishimura Noriko Nishimura Chiharu Tohyama 《Photochemistry and photobiology》1994,59(6):650-656
Abstract: The role of metallothionein (MT) in protecting skin cells against UVB irradiation was investigated. Fibroblast strains from normal adult (HS-K) and neonatal (NB1RGB) human skins as well as keratinocyte strains from human skin (SV40-HSK) and newborn Balb/c mouse skin (Pam 212) were exposed to UVB irradiation.
The sensitivity of HS-K and NB1RGB cells to UVB irradiation was similar; those of SV40-HSK and Pam 212 cells were two- and six-fold as sensitive to UVB irradiation as HS-K cells, respectively. The HS-K cells contained the greatest cellular reduced form of glutathione (GSH) levels compared to the three other skin cells: the levels were 13-, 7- and 6-fold of those in NB1RGB, SV40-HSK and Pam 212 cells, respectively. These results indicated that the sensitivity of skin cells to UVB irradiation was not always associated with their endogenous GSH levels. In particular, despite the fact that NB1RGB cells contained a relatively small amount of GSH, they were less sensitive to UVB irradiation.
NB1RGB cells contained 4–30 times more MT than those in other skin cells examined. The sulfhydryl residues of MT molecules in the NB1RGB cells were estimated to be mostly unoccupied by metals, suggesting they act in a similar way to those of GSH. Moreover, NB1RGB cells in which the MT content was elevated by dexamethasone (1 μ M ) or Zn2+ (7 μg/mL) treatment were more resistant to UVB irradiation than nontreated ones.
These results suggest that, at least in neonatal human skin fibroblasts, MT may play a role in protection against UVB irradiation. 相似文献
The sensitivity of HS-K and NB1RGB cells to UVB irradiation was similar; those of SV40-HSK and Pam 212 cells were two- and six-fold as sensitive to UVB irradiation as HS-K cells, respectively. The HS-K cells contained the greatest cellular reduced form of glutathione (GSH) levels compared to the three other skin cells: the levels were 13-, 7- and 6-fold of those in NB1RGB, SV40-HSK and Pam 212 cells, respectively. These results indicated that the sensitivity of skin cells to UVB irradiation was not always associated with their endogenous GSH levels. In particular, despite the fact that NB1RGB cells contained a relatively small amount of GSH, they were less sensitive to UVB irradiation.
NB1RGB cells contained 4–30 times more MT than those in other skin cells examined. The sulfhydryl residues of MT molecules in the NB1RGB cells were estimated to be mostly unoccupied by metals, suggesting they act in a similar way to those of GSH. Moreover, NB1RGB cells in which the MT content was elevated by dexamethasone (1 μ M ) or Zn
These results suggest that, at least in neonatal human skin fibroblasts, MT may play a role in protection against UVB irradiation. 相似文献
79.
80.