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111.
Tripathi SK Patel U Roy D Sunoj RB Singh HB Wolmershäuser G Butcher RJ 《The Journal of organic chemistry》2005,70(23):9237-9247
[Structure: see text]. The synthesis and characterization of a series of organochalcogen (Se, Te) compounds derived from benzyl alcohol 13 are described. The synthesis of the key precursor dichalcogenides 15, 22, and 29 was achieved by the ortho-lithiation route. Selenide 18 was obtained by the reaction of the dilithiated derivative 14 with Se(dtc)2. Oxidation of 15 and 22 with H2O2 afforded the corresponding cyclic ester derivatives 17 and 24, respectively. Oxidation of selenide 18 with H2O2 affords the spirocyclic compound 19. The presence of intramolecular interactions in dichalcogenides 15 and 22 has been proven by single-crystal X-ray studies. The cyclic compounds 17 and 19 have also been characterized by single-crystal X-ray studies. GP(X)-like antioxidant activity of selenium compounds has been evaluated by the coupled bioassay method. Density functional theory calculations at the mPW1PW91 level on ditelluride 22 have identified a fairly strong nonbonding interaction between the hydroxy oxygen and tellurium atom. The second-order perturbation energy obtained through NBO analysis conveys the involvement of n(O) --> sigma(Te-Te) orbital overlap in nonbonding interaction. Post wave function analysis with the Atoms in Molecules (AIM) method identified distinct bond critical point in 15 and 22 and also indicated that the nonbonding interaction is predominantly covalent. Comparison between diselenide 15 and ditelluride 22 using the extent of orbital interaction as well as the value of electron density at the bond critical points unequivocally established that a ditelluride could be a better acceptor in nonbonding interaction, when the hydroxy group acts as the donor. 相似文献
112.
The excess Gibb's free energy of mixing, GE, for ethyl iodide+toluene at 25°C have been obtained from the measured vapor pressuure data. The HE and GE values for ethyl iodide+toluene are positive throughout the ethyl iodide concentration range and GE>HE. The results have been analyzed in terms of Flory and ideal associated model theory of nonelectrolyte solutions. It has been observed that the ideal associated model approach which assumes the presence of AN and A2B molecular species describes well (within±10 J-mol–1 in the worst case) the general dependence of HE on XA (mole fraction of ethyl iodide) over the whole composition range for ethyl iodide+toluene mixtures. The equilibrium constants for A+A AB and 2A+BA2B reactions along with the enthalpies of formation of AB and A2B molecular species have been calculated. 相似文献
113.
S. P. Mishra /Miss/ Jyoti Singh 《Journal of Radioanalytical and Nuclear Chemistry》1986,105(2):107-116
Fractional precipitation techniques have been utilized to separate the lower valent and parent forms of56Mn in permanganate targets and an attempt is made to study a few aspects of chemical stabilization of recoil56Mn in permanganates. Ammonium permanganate, recoil behaviour of which has not been studied previously, is chosen as one of the targets along with the potassium permanganate for initial retention and also for isothermal annealing.56Mn initial retentions of about 12% and about 4% are obtained for potassium and ammonium permanganate, respectively, by activation from a Ra–Be neutron source. A usual trend for KMnO4 and the reduction of recoil fragments by ammonium ions in NH4MnO4 are seen through the isothermal annealing study. 相似文献
114.
The yellow complex of Pt(IV) with 1-pyridyl-4,4,6-trimethyl-1H,4H-pyrimidine-2-thiol (PyTPT) which has maximum absorbance at 430 nm, is studied for the spectrophotometric determination of the metal. Molar absorptivity is 5000 liters mol?1 cm?1 and Sandell's sensitivity is 0.039 μg/cm2. The determination of Pt(IV) (2.8–8.4 ppm) in the presence of diverse ions is described. 相似文献
115.
A visible light promoted, photoredox catalysed, green one-pot approach for the alkylation of amine substrates with sp2 carbon has been developed. This eosin Y based organic transformations, can behave as an effective direct hydrogen-atom transfer catalyst for coupling reaction. The proposed strategy includes simple procedure which can make adduct product with sp2 carbon. This eosin Y based photocatalytic hydrogen-atom transfer strategy may hold great potential for diverse functionalization of a wide range of native CH bonds in an economical and sustainable manner. 相似文献
116.
CNDO MO calculations are carried out for four acrylates, H2C=C (R1)-COO (R2) with R1=H, Me and R2=Me, Et for dipole moment determination using the Pople-Segal expression.7 Energy minimization for various conformers in each molecular system was achieved by the gradient method. Dipole moments for comparatively stable conformers of each of the molecules considered are reported. Theoretically calculated energy values are used to arrive at the equilibrium geometry and the corresponding dipole moments are compared with the experimental values in each system considered. 相似文献
117.
Kulwant Singh Kawaldeep Vijay Kumar 《Journal of Radioanalytical and Nuclear Chemistry》1998,231(1-2):45-50
The sum peak at 437 keV (356+81 keV) has been measured in various chemical and physico-chemical environments. The fact that
the intensity ratio of the sum peak to its single peak changes with the circumstances in which the radioactive source is placed
is used to observe the effect of the chemical environment on directional correlation coefficients of 351–81 keV cascade in133Ba−133Cs decay and to detect the variations in the electric field gradient in different barium compounds. The sum peak method has
been found to be useful in describing the chemical influences onG
22 parameters and hence in the study of electric field gradients. 相似文献
118.
Summary Thermodynamic effective fixed charge densities of mercuric phosphate and carbonate parchment supported membranes were evaluated by a number of methods particularly those ofTeorell-Meyer-Sievers, Altug andHair andKobatake et al. The value of the permselectivity was obtained for the two membranes based onKobatake et al. procedure. Membrane transport number was calculated using a modified Nernst relation and compared with the values determined by the TMS method. The theoretical predictions for membrane potential usingKobatake et al. equation are borne out quite satisfactorily by our experimental results for both membrane.
With 8 figures and 3 tables 相似文献
Zusammenfassung Es wurden die Dichte der fixierten Ladungen von Quecksilberphosphat und Quecksilberkarbonat-Niederschlagsmembranen nach den Methoden vonTorell-Meyer-Sievers, Altug undHair undKobatake bestimmt. Weiterhin wurden Durchlässigkeit und Transportzahlen ermittelt und mit Werten der TMS-Methode verglichen. Theoretische Voraussagen über das Membranpotential nach den Gleichungen vonKobatake stimmen mit den experimentellen Ergebnissen überein.
With 8 figures and 3 tables 相似文献
119.
The enthalpies of formation of the 2,2′-dipyridinium ion and the 2,2′-dipyridyl-iron(II) complex in methanol—water media at 25°C have been determined by caloriumetry. The entropy-changes have been calculated combining the enthalpy values with the corresponding free-energy changes previously reported. The role of solvents on the thermodynamic parameters has been discussed. 相似文献
120.
Vijay Kumar Kawaldeep K. Singh 《Journal of Radioanalytical and Nuclear Chemistry》1992,166(2):131-142
The sum peak method has been applied to electron capture probability changes to the 1086 keV level in the decay of152Eu in the different environments, e.g. ethylenediaminetetraacetic acid (EDTA), bovine serum albumin (BSA) and hydrochloric acid (HCl). An attempt is also made to determine the effect of chemical environment on the directional correlation coefficient of the 1409–122 keV - cascade in152Eu 152Sm decay. A change of G22 is found in the different chemical forms. 相似文献