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1.
M. Di Valentin A. Bisol G. Agostini G. Giacometti D. Carbonera 《Applied magnetic resonance》2006,30(3-4):555-576
A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C60, TTF-P-C60 and C-P-PF, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C60, versus fluorinated free-base porphyrin, PF), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C60 triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C60: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge. 相似文献
2.
Employing a cleavable carbohydrate–peptide linker, a new strategy for single-bead analysis of multivalent cyclic neoglycopeptides based on Edman degradation is described. Edman degradation of glycopeptides is hampered by the acid lability of the glycosidic bond and potential incompatibilities of phenylthiohydantoin (PTH) derivatives of glycosylated amino acids with PTH derivatives of the proteinogenic amino acids. To overcome this problem, carbohydrates are detached from the cyclopeptide templates before single-bead analysis, allowing for micro sequencing under routine conditions. With this strategy, application of multivalent cyclic neoglycopeptides in split-mix libraries with a subsequent screening process becomes possible for the first time. 相似文献
3.
Valentin Brimkov 《Discrete Applied Mathematics》2007,155(14):1812-1825
We consider the problem of computing the Lovász theta function for circulant graphs Cn,J of degree four with n vertices and chord length J, 2?J?n. We present an algorithm that takes O(J) operations if J is an odd number, and O(n/J) operations if J is even. On the considered class of graphs our algorithm strongly outperforms the known algorithms for theta function computation. We also provide explicit formulas for the important special cases J=2 and J=3. 相似文献
4.
A.D. Bykov V.N. Saveliev C. Camy-Peyret A. Valentin 《Journal of Molecular Spectroscopy》2004,224(2):164-175
Forty-seven N2 broadened water vapor line-widths have been measured in the 1845-2140 cm−1 spectral range with a Fourier Transform spectrometer in the 258-330 K temperature range at a spectral resolution of 0.005 cm−1 for the lines with upper state rotational quantum number up to 16. The measured exponents of the temperature dependence of the width exhibit a large range of values from 1.60 to −0.86. Theoretical calculations were made using a semi-empirical technique based on the Anderson theory. The calculated broadening coefficients as well as the temperature exponents for the half-width agree satisfactory with measured values. 相似文献
5.
Lyudmila Kondakova Victor Yanishpolskii Valentin Tertykh Tat'yana Buglova 《Analytical sciences》2007,23(1):97-101
Galactose oxidase from Fusarium graminearum IMV-1060 adsorbed on, and covalently bound to, silica carriers has been used for analytical determinations of D-galactose and galactose-containing sugars. Using a flowing oxygen electrode of the Clark-type, sensor system for enzymatic analysis of water solutions of galactose-containing carbohydrates was made. Measurements were taken both in the pulse and continuous modes of a substrate flowing through a column with an immobilized biocatalyst. The linear measurement ranges for galactose-containing carbohydrates concentrations were determined. 相似文献
6.
Some features of the propagation of one-soliton successions in the third order dispersion region are presented for the case where the phase difference between adjacent pulses is rads. We show that this considerably improves the stability of the pulses in the zero-dispersion region. Walk-off can be diminished by increasing the number of pulses in the succession. These features may help optimize the bandwidth of non-linear fibre communication links. 相似文献
7.
F. Benedetti S. Bozzini M. Forchiassin G. Nardin G. Pitacco C. Russo E. Valentin 《Journal of heterocyclic chemistry》1989,26(2):301-305
The heterocyclization reaction of arylsulfonylhydrazones from alkyl substituted 1,2-cyclohexanediones is sensitive to the steric requirements of the alkyl groups. A mechanism for the cyclization in acidic medium is also reported. 相似文献
8.
Valentin Herbez 《Tetrahedron letters》2005,46(40):6797-6799
Polyethylene glycol tert-octylphenyl ether and polyoxyethylenesorbitan trioleate are polydisperse macromolecular detergent molecules, containing a single hydroxyl function, which was transformed by 1,1-carbonyldiimidazole into imidazole-detergent conjugates with a carbamate linkage. 相似文献
9.
Lepère M Valentin A Henry A Camy-Peyret C Blanquet G Populaire JC Mantz AW 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(11):2413-2419
We studied the R(0) line profile in the CH4 v4 band from room temperature to 188 K with N2 as a perturber, to 100 K with O2 as perturber, and from room temperature to 15 K using He as a perturber. The N2 and O2 measurements were performed over a total pressure range of 15-110 mbar, and for the He measurements the maximum sample pressure at 15 K was 1.10 mbar. Broadening parameters were determined, taking into account the confinement narrowing (Dicke effect), and narrowing parameters, deduced from the soft or hard collision model, are compared with the dynamic friction coefficient calculated values. We also obtained preliminary values for the temperature dependence of the N2, O2 and He line broadening parameters for this transition. 相似文献
10.
Mladenov M Mirceski V Gjorgoski I Jordanoski B 《Bioelectrochemistry (Amsterdam, Netherlands)》2004,65(1):69-76
The electrode reaction of glutathione (GSH) at the hanging mercury drop electrode is studied by means of square-wave voltammetry (SWV). At potentials more positive than -0.350 V (vs. Ag/AgCl (3 mol/l KCl)) the oxidation of the mercury electrode in the presence of GSH leads to creation of a sparingly soluble mercury-GSH complex that deposits onto the electrode surface. Under cathodic potential scan, the deposited complex acts as a reducible reactant, giving raise to a well-defined cathodic stripping reversible SW voltammetric response. The electrode reaction can be described by the scheme: Hg(SG)(2(s))+e(-)+2H((aq))(+) = Hg((l))+2GSH((aq)). Thus, the electrode reaction provides information on both thermodynamics and kinetics of the chemical interactions of GSH with mercury. An experimental methodology for measuring the kinetics of the electrode reactions, based on the property known as "quasireversible maximum", is developed. The standard redox rate constant is 5.09, 5.75 and 5.22 cm s(-1) in a phosphate buffer at pH 5.6, 7.0 and 8.5, respectively, with a precision of +/-10%. The high rate of the electrode reaction reflects the strong affinity of GSH towards chemical interaction with mercury. The electrode reaction is particularly sensitive to the presence of heavy metal ions such as Cu(2+), Cd(2+), and Zn(2+.) The rate of the electrode reaction decreases significantly in the presence of these ions due to simultaneous interactions of GSH with the respective ion and mercury. 相似文献