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81.
An intelligent, automatic system based on an array of non-specific-response chemical sensors was developed. As a great amount of information is required for its correct modelling, we propose a system generating it itself. The sequential injection analysis (SIA) technique was chosen as it enables the processes of training, calibration, validation and operation to be automated simply. Detection was carried out using an array of potentiometric sensors based on PVC membranes of different selectivity. The diluted standard solutions needed for system learning and response modelling are automatically prepared from more concentrated standards. The electrodes used were characterised with respect to one and two analytes, by means of high-dimensionality calibrations, and the response surface of each was represented; this characterisation enabled an interference study of great practical utility. The combined response was modelled by means of artificial neural networks (ANNs), and thus it was possible to obtain an automated electronic tongue based on SIA. In order to identify the ANN which provided the best model of the electrode responses, some of the network's parameters were optimised and its usefulness in determining NH4+, K+ and Na+ ions in synthetic samples was then tested. Finally, it was used to determine these ions in commercial fertilisers, the obtained results being compared with reference methods. 相似文献
82.
Bernaus A Gaona X Ivask A Kahru A Valiente M 《Analytical and bioanalytical chemistry》2005,382(7):1541-1548
The present work studies the adsorption behaviour of mercury species on different soil components (montmorillonite, kaolinite and humic acid) spiked with CH3HgCl and CH3HgOH at different pH values, by using XAS techniques and bacterial mercury sensors in order to evaluate the availability of methyl mercury on soil components. The study details and discusses different aspects of the adsorption process, including sample preparation (with analysis of adsorbed methyl mercury by ICP-OES), the various adsorption conditions, and the characterization of spiked samples by XAS techniques performed at two synchrotron facilities (ESRF in Grenoble, France and HASYLAB in Hamburg, Germany), as well as bioavailability studies using mercury-specific sensor bacteria. Results show that XAS is a valuable qualitative technique that can be used to identify the bonding character of the Hg in mercury environment. The amount of methyl in mercury adsorbed to montmorillonite was pH-dependent while for all soil components studied, the bond character was not affected by pH. On the other hand, clays exhibited more ionic bonding character than humic acids did with methyl mercury. This interaction has a higher covalent character and so it is more stable for CH3HgOH than for CH3HgCl, due to the higher reactivity of the hydroxyl group arising from the possible formation of hydrogen bonds.The bioavailability of methyl mercury adsorbed to montmorillonite, kaolinite and humic acids was measured using recombinant luminescent sensor bacterium Escherichia coli MC1061 (pmerBRBSluc). In case of contact exposure (suspension assays), the results showed that the bioavailability was higher than it was for exposure to particle-free extracts prepared from these suspensions. The highest bioavailability of methyl mercury was found in suspensions of montmorillonite (about 50% of the total amount), while the bioavailabilities of kaolinite and humic acids were five times lower (about 10%). The behaviour of methyl mercury in the presence of montmorillonite could be explained by the more ionic bonding character of this system, in contrast to the more covalent bonding character observed for humic acids. Thus, XAS techniques seem to provide promising tools for investigating the mechanisms behind the observed bioavailabilities of metals in various environmental matrices, an important topic in environmental toxicology. 相似文献
83.
In this paper we show that the local time of the Brownian motion belongs to the Sobolev space
for any p2 and 0<<1/p. In order to prove this result we first discuss the smoothness and integrability properties of the composition of the Dirac function with a Wiener integral W(h), and we show that this composition belongs to
, for any >0 and p>1 such that +1/p>1. 相似文献
84.
The hydrolysis of p-F, p-Cl, and m-Cl phenyl trifluoracetates was studied in the presence of beta-cyclodextrin (beta-CD). The reactions are inhibited by beta-CD at pH 6 while they are catalyzed in alkaline solution. MM3 calculations reproduce some of the experimental results. The substrates form inclusion complexes with beta-CD which are of similar stability as those of the corresponding acetates; however, the association of the transition state is less favorable in these reactions than in those of the acetates, and consequently less stronger catalysis is observed. 相似文献
85.
Mas-Ballesté R Capdevila M Champkin PA Clegg W Coxall RA Lledós A Mégret C González-Duarte P 《Inorganic chemistry》2002,41(12):3218-3229
The nucleophilicity of the [Pt(2)S(2)] core in [[Ph(2)P(CH(2))(n)PPh(2)]Pt(mu-S)(2)Pt[Ph(2)P(CH(2))(n)PPh(2)]] (n = 3, dppp (1); n = 2, dppe (2)) metalloligands toward the CH(2)Cl(2) solvent has been thoroughly studied. Complex 1, which has been obtained and characterized by X-ray diffraction, is structurally related to 2 and consists of dinuclear molecules with a hinged [Pt(2)S(2)] central ring. The reaction of 1 and 2 with CH(2)Cl(2) has been followed by means of (31)P, (1)H, and (13)C NMR, electrospray ionization mass spectrometry, and X-ray data. Although both reactions proceed at different rates, the first steps are common and lead to a mixture of the corresponding mononuclear complexes [Pt[Ph(2)P(CH(2))(n)PPh(2)](S(2)CH(2))], n = 3 (7), 2 (8), and [Pt[Ph(2)P(CH(2))(n)PPh(2)]Cl(2)], n = 3 (9), 2 (10). Theoretical calculations give support to the proposed pathway for the disintegration process of the [Pt(2)S(2)] ring. Only in the case of 1, the reaction proceeds further yielding [Pt(2)(dppp)(2)[mu-(SCH(2)SCH(2)S)-S,S']]Cl(2) (11). To confirm the sequence of the reactions leading from 1 and 2 to the final products 9 and 11 or 8 and 10, respectively, complexes 7, 8, and 11 have been synthesized and structurally characterized. Additional experiments have allowed elucidation of the reaction mechanism involved from 7 to 11, and thus, the origin of the CH(2) groups that participate in the expansion of the (SCH(2)S)(2-) ligand in 7 to afford the bridging (SCH(2)SCH(2)S)(2-) ligand in 11 has been established. The X-ray structure of 11 is totally unprecedented and consists of a hinged [(dppp)Pt(mu-S)(2)Pt(dppp)] core capped by a CH(2)SCH(2) fragment. 相似文献
86.
E. Lachowicz B. R
a
ska F. Teixidor H. Meliani M. Barboiu N. Hovnanian 《Journal of membrane science》2002,210(2):279-290
The reactivity of new ligands described as S1, S5, S2O9 (in respect to character and amount of donors) towards metal ions was examined by extraction from HNO3 and HCl media. These ligands were next utilised as carriers for Ag and Pd transport through a supported liquid membrane (SLM). The effect of collecting a greater number of S donors in one molecule and the influence of type of donors (O–S versus S) on efficiency and selectivity of Ag and Pd(II) extraction and transport were examined.
The extraction of Ag from HNO3 solutions increased with increasing amount of S-donors in one molecule (S12O95). For palladium the sequence was different (S512O9). The transport of Ag through SLM impregnated with m-chlorotoluene solution of ionophore increased in the same order as in the case of extraction, whereas for Pd the row was different: S52O91. The highest fluxes of Ag and Pd transported from HNO3 equalled to 5.25×10−7 and 1.37×10−7 mol/m2 s, respectively. Palladium flux depended on stripping solution type (Na2S2O3
87.
Taoufik Hmidi Joan Mateu Joan Verdera 《Archive for Rational Mechanics and Analysis》2013,209(1):171-208
We show that the boundary of a rotating vortex patch (or V-state, in the terminology of Deem and Zabusky) is C ∞, provided the patch is close to the bifurcation circle in the Lipschitz norm. The rotating patch is also convex if it is close to the bifurcation circle in the C 2 norm. Our proof is based on Burbea’s approach to V-states. 相似文献
88.
γ-Carboxylation of β-diketones, 1, can be improved using samples containing 100% of ketoenol tautomers, 3, prepared by mild hydrolysis of the corresponding copper(II) complexes 2. Cyclization of the so formed 4-alkyl-3,5-dioxohexanoic acids, 4, affords 5-alkyl-4-hydroxy-6-methyl-2-pyrones, 5. 相似文献
89.
E. Yu. Mironova M. M. Ermilova M. N. Efimov L. M. Zemtsov N. V. Orekhova G. P. Karpacheva G. N. Bondarenko N. A. Zhilyaeva D. N. Muraviev A. B. Yaroslavtsev 《Russian Chemical Bulletin》2013,62(11):2317-2321
Physicochemical properties and catalytic performance of detonation nanodiamonds were studied. Original samples of nanodiamonds and nanodiamonds modified by hydrogen, oxygen, and nitric acid with hydrogen peroxide and infrared-treated were investigated. The catalyst structure and morphology were examined by transmission electron microscopy and IR spectroscopy. All the investigated catalysts were active in the steam reforming of ethanol. The correlation of catalytic properties with composition and structure of the described systems is discussed. The specific surface area of nanodiamonds is changed insignificantly upon modification. 相似文献
90.
J.A. Carrillo R.M. Colombo P. Gwiazda A. Ulikowska 《Journal of Differential Equations》2012,252(4):3245-3277
A well-posedness theory of measure valued solutions to balance laws is presented. Nonlinear semigroups are constructed by means of the operator splitting algorithm. This approach allows to separate the differential terms from the integral ones, leading to a significant simplification of the proofs. Continuous dependence with respect to parameters is also shown. The whole framework allows a unified approach to a variety of structured population models, providing to each of them the basic well posedness and stability results. 相似文献