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61.
The transport equations for the second-order velocity structure functions 〈(δu)2〉 and 〈(δq)2〉 are used as a scale-by-scale budget to quantify the effect of initial conditions at low Reynolds numbers, typical of grid
turbulence. The validity of these equations is first investigated via hot-wire measurements of velocity and transverse vorticity
fluctuations. The transport equation for 〈(δq)2〉 is shown to be balanced at all scales, while anisotropy of the large scales leads to a significant imbalance in the equation
for 〈(δu)2〉. The effect of using similarity to evaluate the transport equation is rigorously tested. This approach has the desirable
benefit of requiring less extensive measurements to calculate the inhomogeneous term of the transport equation. The similarity
form of the 〈(δq)2〉 equation produces nearly identical results as those obtained without the similarity assumption. In the case of the 〈(δu)2〉 equation, the similarity method forces a balance at large separation, although the imbalance due to large scale anisotropy
remains. The initial conditions of the turbulence at constant R
M
≃ 10,400 (28≤ R
λ≤ 55) are changed by using three grids of different geometries. Initial conditions affect the shape and magnitude of the second-
and third-order structure functions, as well as the anisotropy of the large scales. The effect of initial conditions on the
scale-by-scale budget is restricted to the inhomogeneous term of the transport equations, while the dissipation term remains
unaffected despite the low R
λ. Scales as small as λ are affected by the changes in initial conditions. 相似文献
62.
Barco-Bonilla N Romero-González R Plaza-Bolaños P Fernández-Moreno JL Frenich AG Vidal JL 《Analytica chimica acta》2011,693(1-2):62-71
The objective of this study was the optimization and comparison of two extraction methods for the determination of polycyclic aromatic hydrocarbons (PAHs) in wastewater (WW). A distribution study of the target compounds between the aqueous phase and the suspended particulate matter (SPM) has been performed in order to establish whether the analysis of both phases is necessary. In this sense, the feasibility of stir bar sorptive extraction (SBSE) and solid-phase extraction (SPE) for the determination of 24 PAHs in WW samples has been evaluated. The results demonstrated the suitability of SBSE to perform a comprehensive analysis of liquid samples containing high amounts of SPM, such as in the determination of PAHs in WWs. A gas chromatography triple quadrupole mass spectrometry (GC-QqQ-MS/MS) method has been also optimized for the separation and detection of the target compounds, avoiding the co-elution of some groups of isomers, such as benzo[b], [j] and [k] fluoranthenes and indene[1,2,3-cd]pyrene/dibenz[a,h]anthracene. For that purpose, a specific capillary column developed for PAH determination was used. The SBSE procedure was validated and adequate parameters (such as recovery, linearity, precision, limits of detection and quantification) were obtained. Finally, the validated method was applied to the analysis of real samples collected from an experimental WW treatment plant, detecting some PAHs at concentrations in the range 0.007-0.022 μg L(-1). 相似文献
63.
Multi-component, regio-selective aldol addition of β-ketoesters to aldehydes: scope and applications
More V Di Mola A Croce G Tedesco C Petronzi C Peduto A De Caprariis P Filosa R Massa A 《Organic & biomolecular chemistry》2011,9(24):8483-8488
Simple and effective multi-component one-pot aldol addition/protection reactions of β-ketoesters to a series of aldehydes in the presence Me(3)SiCl and i-Pr(2)EtN have been described. The analysis of the scope of the reaction revealed a dramatic dependence of the reactivity on the substrates used. Thus the effect of a catalytic amount of DMF and different reaction conditions was widely investigated. Further transformations of the aldol adducts were particularly useful to give valuable diols and compounds with quaternary stereocenters, while X-ray structural analysis gave also important stereochemical information about this challenging reaction. 相似文献
64.
Sola A Otón F Espinosa A Tárraga A Molina P 《Dalton transactions (Cambridge, England : 2003)》2011,40(46):12548-12559
Aldimine 4 bearing a 2-quinolyl group was prepared by aza-Wittig reaction between the triphenyliminophosphorane derived from the 1,1'-diazidoferrocene and 2-formylquinoline. However, aldimine 5, bearing a pyrene ring, was prepared using the most reactive tributyliminophosphorane derivative and the corresponding 1-formylpyrene. On the other hand, formation of aldimine 8 involves a tandem process, Staudinger reaction/intramolecular aza-Wittig reaction, by using directly 1,1'-diazidoferrocene and 2-(diphenylphosphonyl)benzaldehyde. Aldimine 4 behaves as chemosensor molecule for Ni(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+) cations through two different channels: electrochemical (ΔE(1/2) = 222-361 mV) and chromogenic (Δλ = 122-153 nm), which can be used for the "naked eye" detection of these metal cations. Aldimine 5 behaves as a highly selective redox (in CH(3)CN) and fluorescent (in CH(3)Cl-DMF) probe for Hg(2+) metal cations even in the presence of a large excess of the other metal cations tested. Aldimine 8 displays electrochemical affinity (ΔE(1/2) = 60-288 mV) to Li(+), Ca(2+), Mg(2+), Zn(2+) and Pb(2+) metal cations, with the phosphorus oxide functionality as a binding site. From the (1)H NMR titration data as well as DFT calculations, different tentative binding modes have been established, for these structurally related ferrocenyl derivatives. 相似文献
65.
Three online solid phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method examples are presented where two different types of chromatographic columns or solvent systems were coupled to meet specific analytical objectives: (i) SPE of target analytes by restricted access media from high ionic strength urine matrix was coupled with reversed phase LC-MS/MS conditions accommodating high ionization potentials of the analytes (urinary bisphenol A and other phenolic derivatives); (ii) strong cation exchange SPE of analytes of diverse polarity and pK(a) was coupled with reversed phase LC-MS/MS analysis (urinary atrazine metabolites); (iii) pre-concentration of low pg per sample analytes by weak anion exchange SPE was hyphenated with ion pair LC-MS analysis (intracellular nucleotide triphosphate analogs). With these examples we suggest a conductive generic work flow for the development of online SPE-LC-MS methods and show how advanced commercial LC devices and software allow for the design of complex yet highly versatile analytical separation systems suited to the unique physicochemical properties of the target analytes. 相似文献
66.
Mussardo P Corda E González-Ruiz V Rajesh J Girotti S Martín MA Olives AI 《Analytical and bioanalytical chemistry》2011,400(2):321-327
The interaction between DNA and several newly synthesized derivatives of the natural anticancer compound luotonin A has been
studied. The results from our work reveal an effective and selective alkaloid/double-stranded DNA (ds-DNA) interaction. In
the presence of increasing amounts of ds-DNA, a noticeable fluorescence quenching of the luotonin A derivatives under study
was observed. However, this effect did not take place when single-stranded DNA (ss-DNA) was employed. The association constant
alkaloids/ds-DNA was calculated by quantitation of such a quenching effect. The influence of other quenchers, namely Co2+ and Br− on the native fluorescence of luotonin A and derivatives was also studied, and a remarkable quenching effect was observed
for both ions. We have also investigated how by binding DNA the alkaloids could get protected from the external Co2+ and Br− quenchers. The Stern–Volmer constants (K
SV) for Co2+ and Br− quenching effect on the studied alkaloids were considerably reduced (10–50%) after incubation of the compounds in the presence
of DNA with regard to the K
SV values in absence of DNA. An increase in the fluorescence anisotropy values of luotonins was also produced only in the presence
of ds-DNA but not in the case of ss-DNA. To better characterize the nature of that interaction, viscosimetry assays and ethidium
bromide displacement studies were conducted. With regard to DNA reference solutions, the viscosity of solutions containing
DNA and luotonin A derivatives was reduced or not significantly increased. It was also observed that the studied compounds
were unable to displace the intercalating agent ethidium bromide. All of these results, together with the obtained association
constants values (K
ass = 2.2 × 102 – 1.3 × 103), support that neither covalent nor intercalating interactions luotonin A derivatives/ds-DNA are produced, leading to the
conclusion that these alkaloids bind ds-DNA through the minor groove. The specific changes in the fluorescence behavior of
luotonin A and derivatives distinguishing between ss-DNA and ds-DNA binding, lead us to propose these compounds as attractive
turn-off probes to detect DNA hybridization. 相似文献
67.
Garrido Frenich A Romero-González R Martínez Vidal JL Martínez Ocaña R Baquero Feria P 《Analytical and bioanalytical chemistry》2011,399(6):2043-2059
This work compares two miniaturised sample preparation methods, solid phase microextraction (SPME) and hollow fiber liquid
phase microextraction (HF-LPME), in combination with gas chromatography coupled to tandem mass spectrometry with a triple
quadrupole analyzer for the determination of 77 pesticides in drinking water. In the case of SPME, extraction temperature
and time were optimized by experimental design, although other parameters, as desorption time, pH, and ionic strength, were
also evaluated. The extraction and desorption solvents [octanol/dihexyl ether (75:25, v/v) and cyclohexane, respectively],
as well as the extraction and desorption time, ionic strength, and pH, were studied for the HF-LPME procedure. Under the optimal
conditions, recoveries (70.2–113.5% for SPME and 70.0–119.5% for HF-LPME), intra-day precision (2.1–19.4% for SPME and 4.3–22.5%
for HF-LPME), inter-day precision (5.2–21.5% for SPME and 8.4–27.3% for HF-LPME), and limits of detection, between 0.1 and
28.8 ng/L for SPME and 0.2 and 47.1 ng/L for HF-LPME and overall uncertainty (9.6–25.2% for SPME and 13.3–27.5% for HF-LPME)
were established for both extraction procedures. Finally, the proposed methods were successfully applied to the analysis of
41 drinking water samples, and similar results were obtained with both extraction approaches. 相似文献
68.
The extensive use of bisphenol A (BPA) in the manufacture of consumer products results in widespread human exposure to the
chemical. In the body, BPA undergoes first-pass metabolism to form BPA glucuronide, considered to be a major BPA byproduct.
Concentrations of total (free plus conjugated) urinary species of BPA are used to assess human exposure to BPA. However, because
BPA can be present in numerous consumer and household products, potential contamination with parent BPA during collection
and handling may pose a challenge when measuring BPA in such biological samples as blood or urine. In this study we investigated
the in-vitro phase I metabolism of BPA in rat and human liver microsomes by using on-line solid-phase extraction–high-performance
liquid chromatography–tandem mass spectrometry to identify phase I metabolites (e.g., BPA oxidation products) that could be
used as potential alternative biomarkers of BPA exposure. We unambiguously identified 5-hydroxy BPA (BPA catechol) as an in-vitro
oxidative metabolite of BPA, but human microsomes oxidized only about 10% of BPA to BPA catechol. We evaluated the usefulness
of BPA catechol as a potential biomarker of human exposure to BPA by measuring total concentrations of BPA catechol and BPA
in 20 urine samples. We detected BPA catechol at much lower concentrations and frequency than those of BPA. Furthermore, we
found that free BPA catechol was rather unstable in urine, which highlights the importance of sampling techniques to adequate
interpretation of biomonitoring data. Together, these findings suggest that BPA catechol may not be a suitable biomarker of
environmental exposure to BPA, but could be used to confirm BPA exposure in special populations or in situations when urine
specimens were potentially contaminated with BPA. 相似文献
69.
A series of bimetallic N-heterocyclic carbene (NHC) ruthenium(II) complexes were synthesized, which comprise two [RuCl(2)(cymene)(NHC)] units that are interlinked via the NHC nitrogens by alkyl chains of different length. Electrochemical characterization revealed two mutually dependent oxidation processes for the complex with a methylene linker, indicating moderate intramolecular electronic coupling of the two metal centers (class II system). The degree of coupling decreases rapidly upon increasing the number of CH(2) units in the linker and provides essentially decoupled class I species when propylene or butylene linkers are used. Electrochemical analyses combined with structural investigations suggest a through-bond electronic coupling. Replacement of the alkyl linker with a p-phenylene group afforded cyclometalated complexes, which were considerably less stable. The electronic coupling in the methylene-linked complex and the relatively robust NHC-ruthenium bond may provide access to species that are switchable on the molecular scale. 相似文献
70.
Rangel TB Assreuy AM Pires Ade F Carvalho AU Benevides RG Simões Rda C Silva HC Bezerra MJ Nascimento AS Nascimento KS Nagano CS Sampaio AH Delatorre P Rocha BA Fernandes PM Cavada BS 《Molecules (Basel, Switzerland)》2011,16(6):5087-5103
DwL, a lectin extracted from the seeds of Dioclea wilsonii, is a metalloprotein with strong agglutinating activity against rabbit and ABO erythrocytes, inhibited by glucose and mannose. DwL was purified by affinity chromatography on a Sephadex G-50 column and ion exchange chromatography on a HiTrap SP XL column. SDS-PAGE revealed three electrophoretic bands corresponding to the α (25,634 ± 2 Da), β (12,873 ± 2 Da) and γ (12,779 ± 2 Da) chains. Protein sequencing was done by Tandem Mass Spectrometry. The primary sequence featured 237 amino acids and was highly homologous to other reported Diocleinae lectins. A complete X-ray dataset was collected at 2.0 ? for X-Man-complexed DWL crystals produced by the vapor diffusion method. The crystals were orthorhombic and belonged to the space group I222, with the unit-cell parameters a = 59.6, b = 67.9 and c = 109.0 ?. DWL differed in potency from other ConA-like lectins and was found to induce neutrophil migration in rats, making it particularly useful in structural/functional studies of this class of proteins. 相似文献