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151.
Serra B Zhang J Morales MD Guzmán-Vázquez de Prada A Reviejo AJ Pingarrón JM 《Talanta》2008,75(4):1134-1139
The rapid detection of catalase-positive and catalase-negative bacteria in complex culture media has been accomplished by monitoring of hydrogen peroxide consumption or generation with a graphite-Teflon-peroxidase-ferrocene composite electrode. Escherichia coli and Streptococcus pneumoniae have been used as model catalase-positive and catalase-negative bacteria, respectively. Hydrogen peroxide evolution was amperometrically measured at 0.00 V. Experimental conditions, including the working solution composition, the incubation time and the hydrogen peroxide concentration, were optimized. The reusability of the biosensor was improved by placing a nylon membrane on the bioelectrode surface to prevent fouling caused by the bacterial medium. The developed methodology allowed the detection of E. coli and S. pneumoniae at concentration levels of approximately 2x10(6) and 2x10(5) cfu/mL, in assays taking 10 and 15 min, respectively, without any pre-concentration step or pre-enrichment procedure. 相似文献
152.
Cid-Samamed A García-Río L Fernández-Gándara D Mejuto JC Morales J Pérez-Lorenzo M 《Journal of colloid and interface science》2008,318(2):525-529
A study was carried out on the influence of the n-alkyl acid addition on the electric percolation of AOT/iso-octane/water microemulsions ([AOT] = 0.5 M and W= [H(2)O]/[AOT] = 22.2). The observed influence has been explained taking into account the organic nature of these molecules and, hence, their capacity of disturbing the structure of the AOT-film. For these reasons, relationships with their molecular structure (chain length) were analysed. 相似文献
153.
Pita M Abad JM Vaz-Dominguez C Briones C Mateo-Martí E Martín-Gago JA Morales Mdel P Fernández VM 《Journal of colloid and interface science》2008,321(2):484-492
Controlled synthesis of cobalt ferrite superparamagnetic nanoparticles covered with a gold shell has been achieved by an affinity and trap strategy. Magnetic nanoparticles are functionalized with a mixture of amino and thiol groups that facilitate the electrostatic attraction and further chemisorption of gold nanoparticles, respectively. Using these nanoparticles as seeds, a complete coating shell is achieved by gold salt-iterative reduction leading to monodisperse water-soluble gold-covered magnetic nanoparticles, with an average diameter ranging from 21 to 29 nm. These constitute a versatile platform for immobilization of biomolecules via thiol chemistry, which is exemplified by the immobilization of peptide nucleic acid (PNA) oligomers that specifically hybridize with complementary DNA molecules in solution. Hybridation with DNA probes has been measured using Rhodamine 6G fluorescence marker and the detection of a single nucleotide mutation has been achieved. These results suggest the PNA-nanoparticles application as a biosensor for DNA genotyping avoiding commonly time-consuming procedures employed. 相似文献
154.
Hanna Morales Hernández Qiwei Sun Matthew Rosati Prof. Rebecca L. M. Gieseking Prof. Christopher J. Johnson 《Angewandte Chemie (International ed. in English)》2023,62(35):e202307723
The role of hydrogen atoms as surface ligands on metal nanoclusters is of profound importance but remains difficult to directly study. While hydrogen atoms often appear to be incorporated formally as hydrides, evidence suggests that they donate electrons to the cluster's delocalized superatomic orbitals and may consequently behave as acidic protons that play key roles in synthetic or catalytic mechanisms. Here we directly test this assertion for the prototypical Au9(PPh3)8H2+ nanocluster, formed by addition of a hydride to the well-characterized Au9(PPh3)83+. Using gas-phase infrared spectroscopy, we were able to unambiguously isolate Au9(PPh3)8H2+ and Au9(PPh3)8D2+, revealing an Au−H stretching mode at 1528 cm−1 that shifts to 1038 cm−1 upon deuteration. This shift is greater than the maximum expected for a typical harmonic potential, suggesting a potential governing cluster-H bonding that has some square-well character consistent with the hydrogen nucleus behaving as a metal atom in the cluster core. Complexing this cluster with very weak bases reveals a redshift of 37 cm−1 in the Au−H vibration, consistent with those typically seen for moderately acidic groups in gas phase molecules and providing an estimate of the acidity of Au9(PPh3)8H2+, at least with regard to its surface reactivity. 相似文献
155.
Alexis Morales Jochem Struppe Enrique Meléndez 《Journal of inclusion phenomena and macrocyclic chemistry》2008,60(3-4):263-270
The possible inclusion complexes of Cp2NbCl2 into α-, β-, and γ-CD hosts have been investigated. The existence of a true inclusion complex in the solid state was confirmed
by a combination of thermogravimetric analysis, FTIR, PXRD, and 13C CP-MAS NMR spectroscopies. The solid-state results demonstrated that α-cyclodextrin does not form inclusion complexes with
Cp2NbCl2 whereas β- and γ-cyclodextrins do form such complexes. PXRD, NMR, and thermal analysis showed that the organometallic molecules
of Cp2NbCl2OH are included in the cavities of β- and γ-cyclodextrins, possibly adopting a symmetrical conformation in the complex, with
each glucose unit in a similar environment. In solution, 1H NMR experiments suggest that niobocene has a shallow penetration on the β-CD leading to upfield shift on H-3 signal with
a minor perturbation on the H-5 proton while for γ-CD, both H-3 and H-5 are shifted upfield substantially. This suggests that
niobocene penetrates deeper into the γ-CD cavity than in the β-CD cavity, as a result of the cavity size.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
156.
Huang Y Khartulyari S Morales ME Stanislawska-Sachadyn A Von Feldt JM Whitehead AS Blair IA 《Rapid communications in mass spectrometry : RCM》2008,22(16):2403-2412
Red blood cell (RBC) folate levels are established at the time of erythropoiesis and therefore provide a surrogate biomarker for the average folate status of an individual over the preceding four months. Folates are present as folylpolyglutamates, highly polar molecules that cannot be secreted from the RBCs, and must be converted into their monoglutamate forms prior to analysis. This was accomplished using an individual's plasma pteroylpolyglutamate hydrolase by lysing the RBCs in whole blood at pH 5 in the presence of ascorbic acid. Quantitative conversion of formylated tetrahydrofolate derivatives into the stable 5,10-methenyltetrahydrofolate (5,10-MTHF) form was conducted at pH 1.5 in the presence of [(13)C(5)]-5-formyltetrahydrofolate. The resulting [(13)C(5)]-5,10-MTHF was then used as an internal standard for the formylated forms of tetrahydrofolate that had been converted into 5,10-MTHF as well any 5,10-MTHF that had been present in the original sample. A stable isotope dilution liquid chromatography-multiple reaction monitoring/mass spectrometry method was validated and then used for the accurate and precise quantification of RBC folic acid, 5-methyltetrahydrofolate (5-MTHF), tetrahydrofolate (THF), and 5,10-MTHF. The method was sensitive and robust and was used to assess the relationship between different methylenetetrahydrofolate reductase (MTHFR) 677C>T genotypes and RBC folate phenotypes. Four distinct RBC folate phenotypes could be identified. These were classified according to the relative amounts of individual RBC folates as type I (5-MTHF >95%; THF <5%; 5,10-MTHF <5%), type II (5-MTHF <95%; THF 5% to 20%; 5,10-MTHF <5%), type III (5-MTHF >55%; THF >20%; 5,10-MTHF >5%), and type IV (5-MTHF <55%; THF >20%; 5,10-MTHF >5%). 相似文献
157.
Polymer monoliths are promising materials for sample preparation due to their high porosity, pH stability, and simple preparation. The use of melamine formaldehyde foams has been reported as an effective support to prepare highly robust silica and polymer monoliths. Herein, divinylbenzene monoliths based on a 50:50 (%, w/w) crosslinker/porogen ratio have been nested within a melamine-formaldehyde sponge, resulting in monoliths with a surface area higher than 400 m2/g. The extraction performance of these monoliths was evaluated for the extraction of endocrine-disrupting bisphenols from aqueous solutions. We evaluated for the first time the versatility of sponge-nested polymer monoliths by comparing three different extraction modes (vortex mixing, magnetic stirring, and orbital shaking). Vortex mixing showed a comparable recovery of bisphenols (39%–81%) in a shorter extraction time (30 min, instead of 2 h). In addition, the robustness of the sponge-nested polymer monoliths was demonstrated for the first time by reshaping a larger monolithic cube (0.125 cm3) into four smaller pieces (4 × 0.03125 cm3) leading to a 16%–21% increase in extraction efficiency. This effect was attributed to an increase in the effective contact area with the sample, obtaining a higher analyte extraction capacity. 相似文献
158.
In this work, a characterization of reagent chromophere 5-(4-sulphophenylazo)-8-aminoquinoline [SPA] by IR and 1H RMN was carried out and a pKa value of 3.55 ± 0.03 was found as well. An 1:2 stoichiometry for the Cu(II)-SPA complex was determined at pH 9 by Job and molar ratio methods. A value of 1.4 × 1014 for the stability constant was also found. Based on the formation of this complex a new method for the copper determination in presence of gold and silver was developed by derivative spectrophotometry using a previous preconcentration on solid phase. In this method, the analytical measures were executed directly in the solid phase containing the complex. The Cu(II) reacts with the reagent chromophere SPA previously retained in the anionic exchange DEAE Sephadex A25. In this determination, the first derivative at 605 nm was used. The quantification range was between (3.2 ± 0.3 × 10−1) × 10−8 and (94.4 ± 0.9) × 10−8 mol L−1 (3.2 ± 0.3 × 10−1) × 10−8 , and (94.4 ± 0.9) × 10−8 mol L−1. The repeatability expressed as RSD was between 1.1 and 2.0%. The method was applied successfully for the copper determination in mineral residuals and natural water samples. The results were consistent with those provided by ICP-mass spectrometry. 相似文献
159.
Cuesta L Huertos MA Morales D Pérez J Riera L Riera V Miguel D Menéndez-Velazquez A García-Granda S 《Inorganic chemistry》2007,46(7):2836-2845
Complexes [Re(ONCMe2)(CO)3(bipy)] (1) and [Re(ONCMe2)(CO)3(phen)] (2), synthesized by reaction of the respective triflato precursors [Re(OTf)(CO)3(N-N)] (N-N = bipy, phen) with KONCMe2, feature O-bonded monodentate oximato ligands. Compound [Re(CO)3(phen)(HONCMe2)]BAr'4 (3), with a monodentate N-bonded oxime ligand, was prepared by reaction of [Re(OTf)(CO)3(phen)], HONCMe2, and NaBAr'4. Deprotonation of 3 afforded 2. The oximato complexes reacted with p-tolylisocyanate, p-tolylisothiocyanate, maleic anhydride, and tetracyanoethylene, affording the products of the insertion of the electrophile into the Re-O bond, compounds 4-7. One representative of each type of compound was fully characterized, including single-crystal X-ray diffraction. The reactions of 1 and 2 with dimethylacetylenedicarboxylate were found to involve first an insertion as the ones mentioned above but followed by incorporation of water, loss of acetone, and formation of the charge-separated neutral amido complexes 9 and 10. The structure of 9 and 10 was determined by X-ray diffraction, and key features of their electronic distribution were studied using a topological analysis of the electron density as obtained from the Fourier map. 相似文献
160.
C. A. Morales M. J. Pacifico E. R. Pujals 《Proceedings of the American Mathematical Society》1999,127(11):3393-3401
We construct a class of vector fields on 3-manifolds containing the hyperbolic ones and the geometric Lorenz attractor. Conversely, we shall prove that nonhyperbolic systems in this class resemble the Lorenz attractor: they have Lorenz-like singularities accumulated by periodic orbits and they cannot be approximated by flows with nonhyperbolic critical elements.