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71.
The literature about direct solid sample analysis of the past 10–15 years using electrothermal atomic absorption spectrometry
has been reviewed. It was found that in the vast majority of publications aqueous standards were reported as having been used
for calibration after careful program optimization. This means the frequently expressed claim that certified reference materials
with a matrix composition and analyte content close to that of the sample have to be used for calibration in solid sample
analysis is not confirmed in the more recent literature. There are obviously limitations, and there are examples in the literature
where even calibration with certified reference materials did not lead to accurate results. In these cases the problem is
typically associated with spectral interferences that cannot be corrected properly by the systems available for conventional
line source atomic absorption spectrometry, including Zeeman-effect background correction. Using high-resolution continuum
source atomic absorption spectrometry, spectral interferences become visible owing to the display of the spectral environment
at both sides of the analytical line at high resolution, which makes program optimization straightforward. Any spectrally
continuous background absorption is eliminated automatically, and even rapidly changing background absorption does not cause
any artifacts, as measurement and correction of background absorption are truly simultaneous. Any kind of fine-structured
background can be eliminated by “subtracting” reference spectra using a least-squares algorithm. Aqueous standards are used
for calibration in all published applications of high-resolution continuum source atomic absorption spectrometry to direct
solid sample analysis.
This contribution is based on a presentation given at the Colloquium for Analytical Atomic Spectroscopy (CANAS ‘07) held March
18–21, 2007 in Constance, Germany. 相似文献
72.
Milhazes N Martins P Uriarte E Garrido J Calheiros R Marques MP Borges F 《Analytica chimica acta》2007,596(2):231-241
A complete physicochemical characterisation of MDMA and its synthetic precursors MDA, 3,4-methylenedioxybenzaldehyde (piperonal) and 3,4-methylenedioxy-β-methyl-β-nitrostyrene was carried out through voltammetric assays and Raman spectroscopy combined with theoretical (DFT) calculations. The former provided important analytical redox data, concluding that the oxidative mechanism of the N-demethylation of MDMA involves the removal of an electron from the amino-nitrogen atom, leading to the formation of a primary amine and an aldehyde. The vibrational spectroscopic experiments enable to afford a rapid and reliable detection of this type of compounds, since they yield characteristic spectral patterns that lead to an unequivocal identification.Moreover, the rational synthesis of the drug of abuse 3,4-methylenedioxymethamphetamine (MDMA or “ecstasy”) from one of its most relevant precursors 3,4-methylene-dioxyamphetamine (MDA), is reported. In addition, several approaches for the N-methylation of MDA, a limiting synthetic step, were attempted and the overall yields compared. 相似文献
73.
EP Sheretov VS Gurov MV Dubkov OV Korneeva 《Rapid communications in mass spectrometry : RCM》1999,13(16):1699-1702
In this article we compare the classical monopole mass filter of von Zahn and the monopole mass filter with a hyperbolic V-shaped electrode. The experimental results and those of computer simulation for both mass spectrometers are presented. We show that the replacement of a conventional 90 degrees V-shaped electrode by an electrode with a hyperbolic profile substantially improves the peak shape of any given mass, and increases the mass resolution by a factor of 3-4 and the abundance sensitivity by a factor of 100. The potential of high analytical performance combined with electroforming techniques for electrode manufacture indicate future practical uses of such instruments. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
74.
M.A. Continentino J.C. Fernandes R.B. Guimar aes H.A. Borges A. Sulpice J.-L. Tholence J.L. Siqueira J.B.M. da Cunha C.A. dos Santos 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,9(4):613-618
The system Cu2FeO2BO3 is an oxyborate belonging to the family of the ludwigites. In this paper we present AC susceptibility, magnetization measurements
and M?ssbauer spectroscopy on this material which allows for a complete characterization of its complex magnetic behavior.
We find an hierarchy of interactions which clearly defines three regimes with decreasing temperature. These are associated
with, the freezing of the Fe moments, the antiferromagnetic ordering of the Cu sub-lattice and finally the coupling between
both systems.
Received 25 September 1998 相似文献
75.
Ingrid M. Dittert Daniel L. G. Borges Bernhard Welz Adilson J. Curtius Helmut Becker-Ross 《Mikrochimica acta》2009,166(1-2):21-26
A DNA biosensor was constructed by immobilizing DNA on a glassy carbon (GC) electrode modified with multiwall carbon nanotubes (MWNTs) dispersed in Nafion (DNA/MWNTs/GCE). The DNA-modified electrode exhibited two well-defined oxidation peaks corresponding to the guanine and adenine residues of DNA, respectively. The effects of the adsorption potential, DNA concentration and quantity of MWNTs used for DNA immobilization were investigated, as were the effects of buffer, pH and scan rate on the voltammetric behavior of DNA. Phenol, m-cresol and catechol showed noticeable inhibition towards the response of the electrode due to their interactions with DNA. These findings were used to design biosensors with linear response to these phenolic pollutants. 相似文献
76.
Roberta E.S. Froes Waldomiro Borges Neto Nilton C. Silva José B.B. da Silva 《Microchemical Journal》2009,92(1):68-72
A 23 factorial design and a CCD (Central Composite Design) were employed to optimize the operational conditions for determining Al, Ba, Ca, Cd, Cr, Cu, K, Mg, Na, Ni, Pb, Sn and Zn in soft drink samples by inductively coupled plasma optical emission spectrometry (ICP OES). Satisfactory parameters of merit were obtained (Plasma stability, linearity, SBR, BEC, LOD and LOQ). The accuracy was evaluated by means of a recovery study. Thirty five soft drink samples were analyzed. The results obtained were used in an exploratory analysis, in which principal component analysis and cluster analysis were applied in order to differentiate the several soft drink classes. Adequate LOQ values were obtained for all elements (0.34 μg L− 1 for Ca to 88.7 μg L− 1 for Mg) and the recovery study results ranged between 80 and 100%. Cluster analysis revealed four sample classes characterized by flavor and other characteristics, such as being light, diet, low calorie or regular beverages. A model with 4 PCs was obtained by means of a principal component analysis, which explained 99.8% of the total variance. 相似文献
77.
Sibele R. Rosso Elton Franceschi Gustavo R. Borges Marcos L. Corazza J. Vladimir Oliveira Sandra R.S. Ferreira 《The Journal of chemical thermodynamics》2009,41(11):1254-1258
This work reports phase equilibrium measurements for the ternary systems linoleic (acid + CO2 + ethanol) and (linolenic acid + CO2 + ethanol). The fatty acids present in the ternary systems were selected based on composition of banana peel oil extracted by supercritical CO2 at 20 MPa and 313 K. The motivation of this research relies on the fact that these unsaturated fatty acids are recognized to play an important role in lowering blood pressure and serum cholesterol and because they are present in high concentrations in banana peel extract. Besides that, equilibrium data of these compounds are scarce in literature. The phase equilibrium experiments were performed using a high-pressure variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 19 MPa. For both systems, only vapour–liquid phase transitions were visually recorded for all data measured. 相似文献
78.
79.
The phenomenon known as non-enzymatic glycation is described as the reaction of reducing sugars with basic amino groups of proteins and nucleic acids, as well as with simple amines, without enzyme mediation. Non-enzymatic model glycation reactions that make use of low-molecular-weight compounds make an important contribution in the elucidation of glicated processes in vitro and in vivo. Four alpha-dicarbonyl compounds, aldehydic (glyoxal, methylglyoxal and phenylglyoxal) and ketonic (diacetyl), were reacted with the modified amino acid N(alpha)-acetyl-L-lysine (AcLys) in an attempt to establish structure/activity relationships for the reactivity of alpha-dicarbonyls with the amine compound. Electrospray ionization mass spectrometry (ESI-MS) combined with tandem mass spectrometry (MS/MS) and collision-induced dissociation (CID) was used to identify and characterize reagents, intermediates and reaction products. The formation of dicarbonyl-derived lysine dimers was observed exclusively. Especially, attention is drawn to alkyl- (asymmetrical dicarbonyl systems) and carboxyl- (glyoxal system) substituted imidazolium ions, at ring position 2.The main differences observed in the reactions studied were related to the reactivity with the diimine intermediate. This intermediate can react either with a non-hydrated dicarbonyl molecule at the aldehydic carbonyl, or with a mono-hydrated one at the ketonic carbonyl, particularly for asymmetrical dicarbonyls. For 2-carboxyl-substituted imidazolium ion (glyoxal reaction), besides the usual keto-enol rearrangement from the diol group, an alternative reaction pathway (proton abstraction) appears to contribute also for the imidazolium ring-closure process. Moreover, the formation of imidazolium ring structures can depend on several factors, namely, the presence (or absence) of electron donor substituents at the formed diol, the degree of stability of the new electrophile generated and/or the equilibrium concentration of the non- and mono-hydrated dicarbonyl forms in solution, the last being particularly important for asymmetrical dicarbonyls.The results reported reveal the complexity of reactivity as well as the diversity of imidazolium molecular structures. 相似文献
80.
The Schlieren effect is a consequence of light inflexions altering the spectrophotometric measurements that are due to the formation of optical artefacts such as mirror and lenses inside the flowing sample. It may influence signal-to-noise ratio, sample throughput and measurement repeatability in spectrophotometric flow-based procedures. It was critically examined, in order to provide guidelines for system design. Results demonstrate that the magnitude of the Schlieren effect is governed by the combined influence of two components. The first is related to loss of light by reflection at sharp liquid interfaces and prevails under poor mixing conditions. In this situation the transmitted light becomes more intense and somewhat erratic. The second is related to light refraction in regions with pronounced refractive index gradients, and prevails under good mixing conditions. It can lead to positive or negative modifications of the transmitted light, the direction being dependent on the relevance of these components. The importance of the solubility of the chemical species involved, the possibility of interactions with the inner wall of the tubing, and the feasibility of dual-wavelength spectrophotometry for compensating purposes are discussed. 相似文献