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31.
32.
An analysis of surface potential nonlinearity (ψ0) at metal oxide/electrolyte interfaces is presented. By using grand canonical Monte Carlo simulations of a simple lattice model of an interface, we show that a correlation exists between ionic strength, as well as surface site densities, and the non-Nernstian response of a metal-oxide electrode. We propose two approaches to deal with the ψ0-nonlinearity: one based on perturbative expansion of the Gibbs free energy and another based on the assumption of the pH dependence of surface potential slope. The theoretical analysis based on our new potential form gives excellent performance in extreme pH regions, where classical formulae for ψ0 are unjustified. The new formula is general and independent of any underlying assumptions. For this reason, it can be directly applied to experimental surface potential measurements, including those for individual surfaces of single crystals, as we present for data reported by Kallay and Preo?anin [6]. 相似文献
33.
Adsorption of electrolyte ions on metal oxides significantly affects the interfacial charge distribution. The general procedure for the prediction of surface charge on oxides in salt solutions was given by Sverjensky for the 2-pK Triple Layer Model (2-pK TLM) (Sverjensky, Geochim. Cosmochim. Acta 69:225–257, 2005). Based on his parameters values and by assuming parameters transferability (Piasecki, J. Colloid Interface Sci. 302:389–395, 2006) we have predicted the adsorption constants for three monovalent ions (Rb+, F?, Br?) for eight oxides within the framework of the 1-pK Triple Layer Model (1-pK TLM). The obtained parameters values along with the previously reported ones (Piasecki, J. Colloid Interface Sci. 302:389–395, 2006) allowed us to compare the adsorption affinities of alkali metal cations and halide anions, and construct the following Hofmeister series for the cations (Cs+≈ Rb+≈ K+< Na+< Li+) and for the anions (F?? Cl?≈ Br?< I?) for investigated oxides. The same lyotropic series was predicted by the 2-pK TLM. It indicates that Hofmeister series is invariable during parameter transfer between surface complexation models. 相似文献
34.
Lou DW Saito Y Zarzycki PK Ogawa M Jinno K 《Analytical and bioanalytical chemistry》2006,385(1):96-104
An improved high-performance liquid chromatographic method for separation of a number of ginsenosides has been developed.
The influence of temperature (from 0 to 25°C) on the retention and separation of the ginsenosides was studied by applying
a binary mobile phase (acetonitrile/water, 82:18 v/v) and a diol column (LiChrospher 100 Diol). The column temperature is
one of the more important parameters for the retention and separation of the components investigated. Selected thermodynamic
parameters, including changes of enthalpy (ΔH°) and entropy (ΔS°), were estimated from linear van’t Hoff plots, and possible retention mechanisms were discussed. Moreover, the best separation
conditions were selected based on optimization criteria including maximum retention time (t
R max), minimum resolution (R
s
min), and relative resolution product (r). Temperature regions close to 14°C offered the highest selectivity and almost equal distribution of the ginsenosides peaks
across the chromatogram. Under such isocratic conditions, excellent separation of chromatographic standards and selected ginseng
samples was achieved in less than 16 min. 相似文献
35.
Nebeluk Robert Zarzycki Krzysztof Seredyński Dawid Chaber Patryk Figat Maksym Domański Paweł D. Zieliński Cezary 《Nonlinear dynamics》2023,111(9):8383-8395
Nonlinear Dynamics - Moving-object tracking using a pan–tilt camera setup is quite a well-known task in robotics. However, the presented research addresses specific properties of the tracked... 相似文献
36.
Kowalski P Chmielewska A Konieczna L Oledzka I Zarzycki PK Lamparczyk H 《Biomedical chromatography : BMC》2004,18(5):311-317
A simple and robust analytical method for rapid separation and sensitive quantification of baclofen in human plasma by capillary electrophoresis technique was developed. Electrophoretic separation was optimized and successfully performed using simple sodium tetraborate aqueous solution. Observed detection limit in biological material was 10 ng. Using UV detection at 200 nm excellent linearity (r = 0.999) was observed over the concentration range from 0.025 to 1.0 microg mL(-1). The described method has been validated and applied to the quantitative determination of baclofen in human plasma. The bioavailability of Baclofen (Polpharma) and Lioresal (Novartis) in 18 healthy volunteers was investigated. The results indicate bioequivalence of the reference and Baclofen preparations. 相似文献
37.
The first results obtained by small-angle neutron scattering (SANS) study of sub-liquidus immiscibility of glasses are presented. Measurements were performed on the neutron small-angle scattering spectrometer of the Institut Laue-Langevin (Grenoble, France). The glass studied was 0.88 (SiO2), 0.12 (Na2O) from SiO2Na2O system which presents a well-known miscibility gap already explored by small-angle X-ray scattering (SAXS) method. Absolute values of the neutron scattering cross section as a function of scattering vector were obtained for this glass quenched and heat treated at 560°C for various lengths of time. It is shown that the ANS method can be used to follow phase separation kinetics and the comparison with SAXS results can in principle be used to separate the effects of density and concentration fluctuations in this system. 相似文献
38.
39.
In this paper, an improved total antioxidant potential (TAP) estimation using high-performance liquid chromatographic (HPLC) assay with fluorometric detection has been described. The principle of this method is based on the hydroxyl radicals generated in the Fenton-like reaction and subsequently detected using hydroxyterephthalic acid (HTPA), which is a reaction product of hydroxyl radicals and terephthalic acid (TPA), working as a sensing compound. HTPA quantity in the samples was measured by fluorescence detector working at excitation and emission wavelengths equal to 312 and 428 nm, respectively. A number of key experimental conditions including the influence of the reaction (incubation) time on the surface areas of HTPA peaks, concentration of Fe(II) ions as well as the influence of concentration of TPA on the surface area of the chromatographic peak of HTPA were optimized to the characteristic feature of TAP measurements. The elaborated assay has been used to evaluate TAP values of selected low-molecular mass compounds like pyrogallol, tryptamine, and n-alcohols (methanol, ethanol, and n-propanol) as well as chlorogenic and ascorbic acids and benzoic acid derivatives, which are commonly present in the food samples. 相似文献
40.
Paweł K. Zarzycki Elżbieta WłodarczykMichał J. Baran 《Journal of chromatography. A》2009,1216(44):7602-7611
In the present work we optimised the separation of battery of key UV non-transparent low-molecular-mass compounds having possible endocrine disrupting compounds (EDCs) activity or which may be used as the endocrine effect biomarkers. Simple optimization strategy was based on strong temperature effect that is driven by electrostatic interactions between macrocyclic mobile phase additives like cyclodextrins and eluted components of interest under C18 stationary phase and acetonitrile/water mobile phase conditions. Particularly, the effect of temperature involving native β-cyclodextrin and its hydroxypropyl derivative to improve separation of number of natural (d-equilenin, equilin, estetrol, estriol, estrone, 17β-estradiol, 17α-hydroxyprogesterone, 20α-hydroxyprogesterone, cortisol, cortisone, progesterone, testosterone, tetrahydrocortisol and tetrahydrocortisone) and artificial steroids (ethynylestradiol, norgestrel isomers, medroxyprogesterone, mestranol, methyltestosterone, norethindrone, 17α-estradiol) as well as non-steroidal compounds (diethylstilbesterol, bisphenol A, 4-tert-butylphenol, dimethyl phthalate, dibutyl phthalate and dioctyl phthalate) was investigated. It has been found that successful isocratic separation of 27 chemicals can be achieved using acetonitrile/water eluents modified with β-cyclodextrin or hydroxypropyl-β-cyclodextrin at concentration of 10 mM and temperature of 47 °C. Separation protocol is simple, reliable, direct and non-radioactive and may be easily adapted for rapid separation and quantification of wide range of given steroids and related EDCs in environmental samples, particularly those that are characterised by unstable biological matrix and components of interest load. 相似文献