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71.
Summary An X-ray diffraction method was used to study the structures of montmorillonites, the surfaces of which were covered to a systematically increasing extent with hexadecylpyridinium (HDP) cations. It was found that, depending on the degree of cover of the surface, the HDP cations form a mono- or bimolecular layer in the interlayer space. A detailed investigation was made of the selective sorption of binary mixtures on montmorillonite and on HDP-montmorillonites with different surface coverages. The adsorption excess isotherms were determined, as were the adsorption capacities from analysis of the isotherms, and also the equivalent specific surface areas.It was established that from benzene-n-heptane mixtures the benzene is adsorbed only on the external surface of montmorillonite, while in the case of organocomplexes it causes moderate disaggregation.From benzene, alcohols with different numbers of carbon atoms are also preferentially adsorbed on the internal surfaces of montmorillonite; with the rise in the number of carbon atoms, the extent of interlamellar adsorption decreases. In the case of HDP-montmorillonites in methanol-benzene mixtures, the adsorption capacity exhibits a monotonous increase with the degree of organopbility in the range under consideration. In the event of optimum organophility the disaggregation of the organocomplex is complete, and the equivalent specific surface area is 764-778 m2 · g–1. The swelling of the organocomplex, which can be characterized by X-ray diffraction measurement, is in close correlation with the interlamellar liquid adsorption. The results show modification of the surface of montmorillonite with HDP cations fundamentally determines the nature and extent of the selective liquid adsorption.
With 14 figures and 4 tables 相似文献
Zusammenfassung Die Struktur von mit Hexadecyl-pyridinium(HDP)-Kationen im systematisch gesteigerten Maße bedeckten Montmorilloniten wurde mit der Röntgendiffraktions-Methode untersucht. Es wurde festgestellt, daß die HDP-Kationen, von der Bedeckung der Oberfläche abhängend, im Schichtzwischenraum eine mono- bzw. bimolekulare Schicht bilden. Die selektive Sorption binärer Gemische wurde an Montmorilloniten und an HDP-Montmorilloniten verschiedener Bedeckung eingehend untersucht. Es wurden die Adsorptionsisothermen von Flüssigkeitsgemischen und aus deren Analyse die Adsorptionskapazitäten und die äquivalenten spezifischen Oberflächen bestimmt.Es wurde festgestellt, daß aus Benzol-n-Heptan-Gemischen das Benzol nur an der äußeren Montmorillonite-Oberfläche adsorbiert wird, während es bei Organokomplexen eine mäßige Desaggregation verursacht. Die Adsorption von Alkoholen verschiedener Kohlenstoffzahl aus Benzol erscheint auch an inneren Montmorillonit-Oberflächen bevorzugt; mit zunehmender Kohlenstoffzahl nimmt das Ausmaß der interlamellaren Adsorption ab. Bei HDP-Montmorilloniten zeigt die Adsorptionskapazität aus Methanol-Benzol-Gemischen mit zunehmender Organophilität im untersuchten Gebiet eine monotone Steigerung. Im Falle optimaler Organophilität ist die Desaggregation vollständig, die äquivalente spezifische Oberfläche beträgt 764-778 m2/g. Die durch Röntgenn-diffraktionsmessung charakterisierbare Quellung des Organokomplexes steht mit der interlamellaren Flüssig-keitsadsorption in engern Zusammenhang. Unsere Ergebnisse zeigen, daß Charakter und Ausmaß der selektiven Flüssigkeitsadsorption durch die Modifizierung der Montmorillonit-Oberfläche mit HDP-Kationen grundlegend verändert wird.
With 14 figures and 4 tables 相似文献
72.
A procedure for quantitative determination of acetylsalicylic acid and acetaminophen in pharmaceuticals by PLS (partial least squares) and PCR (principal component regression) treatment of FT (Fourier transform)-Raman spectroscopic data is proposed. The proposed method was tested on powdered samples. Three chemometric models were built: the first, for samples consisting of an active substance diluted by lactose, starch and talc; the second, in which a simple inorganic salt was applied as an internal standard and additions were not taken into account; and the third, in which a model was constructed for a commercial pharmaceutical, where all constituents of the tablet were known. By utilising selected spectral ranges and by changing the chemometric conditions it is possible to carry out fast and precise analysis of the active component content in medicines on the basis of the simplified chemometric models. The proposed method was tested on five commercial tablets. The results were compared with data obtained by intensity ratio and pharmacopoeial methods. To appraise the quality of the models, the relative standard error of predictions (RSEPs) were calculated for calibration and prediction data sets. These were 0.7-2.0% and 0.8-2.3%, respectively, for the different PLS models. Application of these models to the Raman spectra of commercial tablets containing acetylsalicylic acid gave RSEP values of 1.3-2.0% and a mean accuracy of 1.2-1.7% with a standard deviation of 0.6-1.2%. 相似文献
73.
Increased structural complexity leads to higher activity: peptides as efficient and versatile catalysts for asymmetric aldol reactions 总被引:3,自引:0,他引:3
[reaction: see text] Peptides containing a secondary amine and a carboxylic acid in a specific orientation to each other are presented as highly efficient catalysts for asymmetric aldol reactions: (1) their activity is considerably higher compared to that of proline, and (2) the enantioselectivity of the peptidic catalysts can be changed from (R)- to (S)-selectivity by simple modifications of the secondary structure. 相似文献
74.
Summary A new, highly sensitive and selective gas chromatography method, using radiochemical detection (GC-DR) was developed for the
selective determination of3H-labelled deramciclane and its N-desmethyl metabolite in dog plasma. Inter-day accuracy and precision, as well as system
suitability of the GC-RD method was investigated during the method validation. The calibration curve was proved to be linear
(r=0.9986) in a wide concentration range (13–1000 ngeqv mL−1)
The lower limit of quantitation (LLOQ) was 13.7 ngeqv mL−1, and the limit of the detection (LOD) was 1 ngeqv mL−1.
Using this new GC-RD method, plasma levels of3H-labelled deramciclane and its metabolite were determined in dogs, after the administration of a single 10 mg kg−1 oral dose. Pharmacokinetic curves and the calculated pharmacokinetic parameters were compared to those obtained using a previously
elaborated gas chromatography-nitrogen selective detection method (GC-NPD) and to those obtained by measuring the plasma level
of total radioactivity (liquid scintillation counting, LSC). Pharmacokinetic curves and the calculated pharmacokinetic parameters
obtained with the two different gas chromatography detection methods (NPD and RD) showed good correlation. Comparison of these
results to those acquired by total radioactivity measurement demonstrated that deramciclane was intensively metabolised. Moreover,
the biological half-life (t
1
2/β
) of the unknown metabolites proved to be more than a magnitude longer than the half-life of the parent compound or that of
N-desmethyl metabolite.
Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997. 相似文献
75.
Roman E. Enrique Castro W. Veronica Camus O. Margarita 《Journal of organometallic chemistry》1985,293(1):93-101
The reactions between the phosphine-organoiron [CpFeII-η6-C6Me5CH2PPh2]+ PF6? (1) and [RhCl(η4-diolefin)(μ-Cl)]2 in CH2Cl2 at reflux give the new heterobinuclear air-stable crystalline complexes [CpFeII-η6-C6Me5CH2)P(Ph)2Rh(η4-diene)Cl]PF6,(D'*-diene=cyclooctadiene (COD): 65%, 2; trimethylfluorobenzobicyclo[2.2.2]octadiene (Me3TFB): 48%, 3). Complexes 2 and 3 have been studied by 1H, 13C and 31P NMR spectroscopy and they are carbonylated (CO, 1 atm). Cyclic voltammetry experiments with addition of MeOH show electron transfer FeIRhI → FeIIRh0, the presence of a catalytic wave FeI/FeII and the possible formation of Rh hydrides. Under normal conditions 2 is a catalyst for hydrogenation of cyclohexene, but it is less efficient than the known mononuclear Rh1 analogues. 相似文献
76.
The macroradical decay in poly(methyl methacrylate) samples with different thermal histories was investigated in the temperature interval 20–100 °C using ESR spectroscopy and the second order kinetic model. The rate constants exhibit two different regimes with the transitions atT
tr=68±1°C which are independent of thermal treatment. ForT<T
tr andT>T
tr the rate constants as well as the corresponding activation parameters are sensitive to history because of different physical microstructures. The compensation law, i.e., the linear relation between lnk
o, eff andE
eff, was analyzed in terms of the so-called compensation quantitiesk
c andT
c and a proximity betweenT
c=T
tr andT
o=53±3 °C — Vogel temperature for -segmental dynamics was found. A comparison of kinetic and dynamic data suggests that the decay of terminal macroradicals in the low-temperature region is controlled by secondary relaxations and that the -mobility contributes to a more rapid decay at higher temperatures belowT
g. 相似文献
77.
R. Sz. Madarász 《Algebra Universalis》1995,34(2):179-184
Chris Brink, in his paper,Power Structures, describes the construction ofgeneralized quotient algebras. IfA is any algebra, the corresponding generalized quotient algebraA/R is defined for every value-preserving relation
. As we will see in the present paper, in order to make the corresponding operations on the setA/R well-defined, it is not enough forR to be value-preserving. The only redundancy in the definition of the usual quotient algebra is symmetry.Presented by G. Grätzer. 相似文献
78.
Consider equations of the form where q is in general a complex vector and the function F depends nontrivially both on q and on qy. We show that a family S of such equations can be investigated by the inverse scattering method. If an equation (*) belongs to S, the function F depends linearly on q and algebraically on qy. We show that the family S contains a subfamily in which each equation can be obtained from the two dimensional Toda lattice equations by a Bäcklund transformation. 相似文献
79.
57Fe Mössbauer study of amorphous and nanocrystalline Fe73.5Nb3Cu1Si13.5B9 after neutron irradiation
57Fe Mössbauer spectroscopy is used to study neutron irradiation induced changes in the short-range order of Fe73.5Nb3Cu1Si13.5B9 alloy. The samples are investigated in both amorphous and nanocrystalline states. Neutron irradiation leads to an increase of the standard deviation of a hyperfine field distribution (HFD), implying rearrangement of the atoms towards disordering. Simultaneously, changes in the average value of the hyperfine field and a net magnetic moment position occur as a consequence of a spin reorientation, atom mixing and microscopic stress centres which are introduced by neutron irradiation. 相似文献
80.
We generalize the well-known Baker's superstability result for exponential mappings with values in the field of complex numbers to the case of an arbitrary commutative complex semisimple Banach algebra. It was shown by Ger that the superstability phenomenon disappears if we formulate the stability question for exponential complex-valued functions in a more natural way. We improve his result by showing that the maximal possible distance of an -approximately exponential function to the set of all exponential functions tends to zero as tends to zero. In order to get this result we have to prove a stability theorem for real-valued functions additive modulo the set of all integers .