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61.
In this paper we deal with the flow of natural convection between two vertical planes with horizontal temperature gradient. We show that periodic steady flow occur when Rayleigh number increases. Critical values are obtained numerically and a nonlinear analysis is presented according to Center manifold method. 相似文献
62.
Frédéric Daems Jean-Michel Romnee Catherine Rasse Éric Froidmont 《Analytical letters》2017,50(14):2189-2216
Many studies have been conducted on the impact of animal feed on isoflavones and their metabolite concentrations in bovine milk, but few studies have focused on the development and validation of analytical protocols for quantifying these compounds in biological matrices other than milk and plants. The purpose of this study was to develop a method that would enable four isoflavones and equol in cows’ feces and digestive fluids to be quantified simultaneously. The method is based on aglycones released by methanolic ultrasound-assisted extraction, followed by enzymatic hydrolysis and high-performance liquid chromatography tandem–mass spectrometry analysis. The sample preparation was optimized using the Box–Behnken design. The selected extraction conditions were 80°C, 10?min, and 50% methanol for digestive fluids and 70°C, 35?min, and 60% methanol for feces. For hydrolysis, the selected conditions were 37°C, 1?h, and a pH of 6 for both matrices. The analytical method showed a good linear regression model ranging from 5 to 125?ng?mL?1. Both inter- and intraday accuracy (≤8.5 and ≤12.3%) and precision (≤11.1 and ≤15.2%) were suitable. No matrix effects were found. There was good repeatability and extract stability for at least 4 days of storage at???20 and 6°C. All recoveries were in the acceptable range of 70–120% for both matrices, except for biochanin A in feces, where the value was approximately 43%. This sensitive and reliable method will be useful for monitoring the passage of isoflavones and equol in the digestive system of ruminants. 相似文献
63.
Sylvain Dulaurent Christian Moesch Pierre Marquet Jean-Michel Gaulier Gérard Lachâtre 《Analytical and bioanalytical chemistry》2010,396(6):2235-2249
In clinical or forensic toxicology, general unknown screening procedures are used to identify as many xenobiotics as possible,
belonging to numerous chemical classes. We present here a general unknown screening procedure based on liquid chromatography
coupled with use of a single linear ion trap mass spectrometer, and focus on the identification of pesticides and/or metabolites
in whole blood. After solid-phase extraction (SPE), the compounds of interest were separated using a reversed-phase column
and identified by the mass spectrometer operated first in the full-scan mass spectrometry (MS) mode, in the positive and negative
polarities, followed by MS2 and MS3 scanning of ions selected in data-dependent acquisition. The total scan time was 2.45 s. Two mass spectral libraries (MS2 and MS3), each of 450 spectra, were created for the 320 pesticides and metabolites detected after injection of pure solutions. Robustness
of the spectra and matrix effects were studied and were satisfactory for the present application. Detection limits for the
320 compounds were studied by extracting 1 mL spiked blood at concentrations between 10 μg/L and 10 mg/L. If necessary, it
was possible to decrease the detection limits of some compounds by 10–100-fold by scanning MS2 in only one polarity, owing to a shorter total scan time. However, at the same time, the detection specificity decreased
as no confirmation could be recorded in the following MS3 scan and no information could be registered in the other polarity. So, in these rare cases, confirmation by another method
was required. 相似文献
64.
Jean-Michel Henlin Hans Rink Erich Spieser Gerhard Baschang 《Helvetica chimica acta》1992,75(2):589-603
Starting from 3-(benzyloxy)cyclobutane-1,1-dimethanol, 3-thyminyl- and 3-adenylcyclobutane-1,1-dimethanol were synthesized by direct introduction of the heterocycles (Scheme 1). The mono-O-substituted methoxytrityl derivatives were separately converted to octameric phosphodiesters on an aminomethyl-polystyrene carrier by the phosphotriester method. These oligomers of carba-nucleosides were prepared in order to study their annealing behaviour towards ribo- and deoxyribo-nucleic acids as well as their potential for homologous hybridization. 相似文献
65.
Tunable distributed feedback lasing output based on reflection grating configuration instead of the traditional transmission one was realized from rhodamine 6G (R6G)-doped ethanol and 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl)-4H-pyran-(DCM)-doped methanol. Pure gain coupling and additional index coupling were obtained in R6G-doped ethanol and DCM-doped methanol, respectively. The tuning, which was found to be independent of the refractive index of the lasing media, went through the entire stimulated emission band for the two cases. Dual-peak lasing emission indicative of the existence of an index grating was observed in DCM-doped methanol. The interval between the two peaks increased with pump energy. 相似文献
66.
The authors study the large time asymptotics of a solution of the Fisher-KPP reaction-diffusion equation,with an initial condition that is a compact perturbation of a step function.A well-known result of Bramson states that,in the reference frame moving as 2t-(3/2) log t+x∞,the solution of the equation converges as t-→ +o∞ to a translate of the traveling wave corresponding to the minimal speed c* =2.The constant x∞ depends on the initial condition u(0,x).The proof is elaborate,and based on probabilistic arguments.The purpose of this paper is to provide a simple proof based on PDE arguments. 相似文献
67.
Valentin Goujard Jean-Michel Tatibouët Catherine Batiot-Dupeyrat 《Plasma Chemistry and Plasma Processing》2011,31(2):315-325
The carbon dioxide reforming of methane to synthesis gas was investigated in a dielectric barrier discharge reactor at room
temperature. The influence of dilution of reactants by helium was studied. We showed that, at a fixed contact time, the conversions
of CH4 and CO2 increase when the amount of helium in the gas mixture increases. This result is attributed to the “penning ionization” phenomenon,
which corresponds to an energy transfer from excited He to molecules in ground state (CH4, CO2). The selectivity to products is affected by the dilution factor. As soon as helium is present in a large amount the formation
of products resulting from recombination of methyl radicals (such as C2, C3 and C4) is less favourable due to the lowest probability of collisions to proceed. A kinetic model is proposed based on the assumption
that the reactant molecules CH4 or CO2 are attacked by active species produced by the plasma discharges, and the production of this active species are function
of the plasma power. This model which takes into account the dilution by helium fits particularly well the experimental data
we obtained. 相似文献
68.
Bisson J Poupard P Pawlus AD Pons A Darriet P Mérillon JM Waffo-Téguo P 《Journal of chromatography. A》2011,1218(36):6079-6084
The phytochemical study of the root extract of the stilbenoid-rich Vitis riparia × Vitis berlandieri grapevine was carried out by centrifugal partition chromatography (CPC). For this reason, we developed a new elution mode we named back-step, which allowed us to obtain cleaner fractions and a more efficient separation process when used in conjunction with a classical elution approach. Three hydroxystilbenes: (E)-resveratrol, (E)-?-viniferin and (E)-vitisin C, with greater than 90% purity were thus obtained through such process, with minimal sample handling and purification steps. Online coupling of CPC to ESI mass spectrometry was used for optimization of the separation parameters and to facilitate the characterization of the stilbenoids. This study details the first phytochemical investigation of stilbenoids from the hybrid species together with a new elution mode able to widen the range of ARIZONA biphasic systems. 相似文献
69.
Taking pyridine as a prototypal example of biologically important nitrogen bases involved in proton-coupled electron transfers, it is shown with the example of the photochemically triggered oxidation of phenol by Ru(III)(bpy)(3) that this proton acceptor partakes in a concerted pathway whose kinetic characteristics can be extracted from the overall kinetic response. The treatment of these data, implemented by the results of a parallel study carried out in heavy water, allowed the determination of the intrinsic kinetic characteristics of this proton acceptor. Comparison of the reorganization energies and of the pre-exponential factors previously derived for hydrogen phosphate and water (in water) as proton acceptors suggests that, in the case of pyridine, the proton charge is delocalized over a primary shell of water molecules firmly bound to the pyridinium cation. 相似文献
70.
Chen P El Ojaimi M Gros CP Richard P Barbe JM Guilard R Shen J Kadish KM 《Inorganic chemistry》2011,50(8):3479-3489
A series of homobimetallic manganese cofacial porphyrin-corrole dyads were synthesized and investigated as to their electrochemistry, spectroelectrochemistry, and ligand binding properties in nonaqueous media. Four dyads were investigated, each of which contained a Mn(III) corrole linked in a face-to-face arrangement with a Mn(III) porphyrin. The main difference between compounds in the series is the type of spacer, 9,9-dimethylxanthene, anthracene, dibenzofuran, or diphenylether, which determines the distance and interaction between the metallomacrocycles. Each redox process of the porphyrin-corrole dyads was assigned on the basis of spectroscopic and electrochemical data and by comparison with reactions and properties of the monocorrole and the monoporphyrin which were examined under the same solution conditions. The Mn(III) porphyrin part of the dyad undergoes two major one-electron reductions in pyridine and benzonitrile, the first of which involves a Mn(III)/Mn(II) process and the second the addition of an electron to the conjugated π-ring system of the macrocycle. The Mn(III) corrole part of the dyads also exhibits two major redox processes, one involving Mn(III)/Mn(II) and the other Mn(III) to Mn(IV) under the same solution conditions. The potentials and reversibility of each electron transfer reaction were shown to depend upon the solvent, type of spacer separating the two macrocycles, and the presence or absence of axial ligation, the latter of which was investigated in detail for the case of acetate ion which was found to bind within the cavity of the dyad to both manganese centers, both before and after the stepwise electroreduction to the Mn(II) forms of the two macrocycles. An intramolecular chloride ion exchange between the porphyrin part of the dyads which contain Mn(III)Cl and the singly oxidized corrole in the dyad is observed after the Mn(III)/Mn(IV) reaction of the corrole, suggesting that chloride is coordinated inside the cavity in the neutral compound. 相似文献