全文获取类型
收费全文 | 401篇 |
免费 | 16篇 |
国内免费 | 1篇 |
专业分类
化学 | 299篇 |
晶体学 | 2篇 |
力学 | 3篇 |
数学 | 27篇 |
物理学 | 87篇 |
出版年
2023年 | 5篇 |
2022年 | 3篇 |
2021年 | 12篇 |
2020年 | 14篇 |
2019年 | 6篇 |
2018年 | 15篇 |
2017年 | 9篇 |
2016年 | 17篇 |
2015年 | 10篇 |
2014年 | 17篇 |
2013年 | 20篇 |
2012年 | 19篇 |
2011年 | 30篇 |
2010年 | 17篇 |
2009年 | 15篇 |
2008年 | 20篇 |
2007年 | 28篇 |
2006年 | 12篇 |
2005年 | 13篇 |
2004年 | 19篇 |
2003年 | 10篇 |
2002年 | 18篇 |
2001年 | 13篇 |
2000年 | 11篇 |
1999年 | 8篇 |
1998年 | 8篇 |
1997年 | 4篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 7篇 |
1993年 | 4篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1990年 | 1篇 |
1987年 | 1篇 |
1985年 | 3篇 |
1983年 | 1篇 |
1981年 | 3篇 |
1980年 | 2篇 |
排序方式: 共有418条查询结果,搜索用时 453 毫秒
101.
Diogo P. Moraes Juliana S. F. Pereira Liange O. Diehl Márcia F. Mesko Valderi L. Dressler José Neri G. Paniz Guenter Knapp Érico M. M. Flores 《Analytical and bioanalytical chemistry》2010,397(2):563-570
In this work, three sample preparation methods were evaluated for further halogen determination in elastomers containing high
concentrations of carbon black. Samples of nitrile-butadiene rubber, styrene-butadiene rubber, and ethylene-propylene-diene
monomer elastomers were decomposed using oxygen flask combustion and microwave-induced combustion (MIC) for further Br and
Cl determination by ion chromatography (IC), inductively coupled plasma optical emission spectrometry (ICP OES), and inductively
coupled plasma mass spectrometry (ICP-MS). Extraction assisted by microwave radiation in closed vessels was also evaluated
using water or alkaline solution. Digestion by MIC was carried out using 50 mmol l−1 (NH4)2CO3 as the absorbing solution. The effect of the reflux step was also evaluated. Accuracy was evaluated using certified reference
materials with polymeric matrix composition and by comparison of results using neutron activation analysis. Agreement for
Br and Cl was better than 95% by MIC using 5 min of reflux, and no statistical difference was found using IC, ICP OES, and
ICP-MS for determination of both analytes. For MIC, the relative standard deviation (RSD) was lower than 5%. Using extraction
in closed vessels, a high amount of residues was observed, and recoveries were lower than 45% for both analytes. For oxygen
flask combustion, the agreement was similar using MIC but RSD was higher (20%). The residual carbon content, an important
parameter used to evaluate the digestion efficiency, was always below 1% for MIC. Using MIC, it was possible to digest elastomers
with high efficiency, resulting in a single solution suitable for halogen determination by different techniques. 相似文献
102.
103.
Rare earth element (REE) concentrations in United States Geological Survey (USGS) rock standards AGV-1, GSP-1, G-2 and PCC-1 were determined by isotope dilution mass spectrometry (IDMS), neutron activation and inductively coupled argon plasma atomic emission spectrometric techniques. The procedure involved acid digestion of samples in PTFE pressure bombs and group separation of REEs by an ion-exchange method. For IDMS an additional separation step using α-hydroxyisobutyric acid as an eluent was used in a cation-exchange column to split the REEs into subgroups. Comparison of the results with literature values showed that the IDMS values are the most precise and accurate. However, the precisions and the accuracies of the other techniques are acceptable. 相似文献
104.
Abstract— The mutational interactions between near-ultraviolet (near-UV, 334 nm, 365 nm) radiation and DNA damaging agents (far-UV (254 nm) and ethyl-methanesulphonate (EMS)) were studied in strains of Escherichia coli B/r trp thy with different susceptibilities to near-UV-induced growth delay (wild-type, rel and srd ). Far-UV induced reversion to tryptophan independence is reduced while forward mutation to streptomycin is enhanced by prior exposure of the rel+ srd+ strains to near-UV radiation. The observed interactions are reduced ( rel ) or absent ( srd ) in the two mutant strains as are the corresponding growth and macromolecular synthesis delays normally observed after near-UV treatment. Quantitatively, the degree of interaction induced by near-UV pre-treatment correlates closely with the degree of protein synthesis inhibition. We propose a mechanism for the contrasting interactions at the two genetic loci based on the different pathways by which pre-mutagenic lesions may be processed. The primary chromophore for the mutational interactions would appear to be 4-thiouracil-containing transfer RNA. 相似文献
105.
A flow injection potentiometric procedure for saccharin determination in dietary products is proposed. Saccharin is precipitated as mercurous saccharinate and the excess of the mercurous cation is potentiometrically measured using a silver wire coated with a mercury film as the working electrode. A filter unit is used to avoid contact between the precipitate and the electrode surface. With relocation in the flow manifold, the accumulated precipitate is removed on-line. Sucrose, glucose, aspartame, sodium cyclamate and sodium benzoate do not interfere when present in amounts similar to those observed in commercial products. Results are comparable with those obtained by UV-spectrophotometry and the correlation coefficient between methods is equal to 0.9930. A linear relationship between DeltaE (mV) and the logarithm of saccharin concentration was obtained in the saccharin concentration range 2 x 10(-3) - 1 x 10(-2)M. The sampling frequency is 60/hour and only 0.76 mg of Hg(2+)(2) is consumed in each determination. 相似文献
106.
De Oliveira MF Saczk AA Okumura LL Fernandes AP De Moraes M Stradiotto NR 《Analytical and bioanalytical chemistry》2004,380(1):135-140
A new, versatile, and simple method for quantitative analysis of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry is described. These metals can be quantified by direct dissolution of fuel ethanol in water and subsequent voltammetric measurement after the accumulation step. A maximum limit of 20% (v/v) ethanol in water solution was obtained for voltammetric measurements without loss of sensitivity for metal species. Chemical and operational optimum conditions were analyzed in this study; the values obtained were pH 2.9, a 4.7-m thickness mercury film, a 1,000-rpm rotation frequency of the working electrode, and a 600-s pre-concentration time. Voltammetric measurements were obtained using linear scan (LSV), differential pulse (DPV), and square wave (SWV) modes and detection limits were in the range 10–9–10–8 mol L–1 for these metal species. The proposed method was compared with a traditional analytical technique, flame atomic absorption spectrometry (FAAS), for quantification of these metal species in commercial fuel ethanol samples. 相似文献
107.
A new strategy for minimization of Cu(2+) and Pb(2+) interferences on the spectrophotometric determination of Cd(2+) by the Malachite green (MG)-iodide reaction using electrolytic deposition of interfering species and solid phase extraction of Cd(2+) in flow system is proposed. The electrolytic cell comprises two coiled Pt electrodes concentrically assembled. When the sample solution is electrolyzed in a mixed solution containing 5% (v/v) HNO(3), 0.1% (v/v) H(2)SO(4) and 0.5 M NaCl, Cu(2+) is deposited as Cu on the cathode, Pb(2+) is deposited as PbO(2) on the anode while Cd(2+) is kept in solution. After electrolysis, the remaining solution passes through an AG1-X8 resin (chloride form) packed minicolumn in which Cd(2+) is extracted as CdCl(4)(2-). Electrolyte compositions, flow rates, timing, applied current, and electrolysis time was investigated. With 60 s electrolysis time, 0.25 A applied current, Pb(2+) and Cu(2+) levels up to 50 and 250 mg l(-1), respectively, can be tolerated without interference. For 90 s resin loading time, a linear relationship between absorbance and analyte concentration in the 5.00-50.0 mug Cd l(-1) range (r(2)=0.9996) is obtained. A throughput of 20 samples per h is achieved, corresponding to about 0.7 mg MG and 500 mg KI and 5 ml sample consumed per determination. The detection limit is 0.23 mug Cd l(-1). The accuracy was checked for cadmium determination in standard reference materials, vegetables and tap water. Results were in agreement with certified values of standard reference materials and with those obtained by graphite furnace atomic absorption spectrometry at 95% confidence level. The R.S.D. for plant digests and water containing 13.0 mug Cd l(-1) was 3.85% (n=12). The recoveries of analyte spikes added to the water and vegetable samples ranged from 94 to 104%. 相似文献
108.
Teruel M de Moraes PR Xavier LA Riveros JM 《European journal of mass spectrometry (Chichester, England)》2003,9(4):279-285
Gas-phase [C, H(3), S](+) ions obtained by electron impact from (CH(3))(2)S at 14 eV undergo two distinct low-pressure ion-molecule reactions with the parent neutral: proton transfer and charge exchange. The kinetics of these reactions studied by Fourier transform ion cyclotron resonance (FT-ICR) techniques clearly suggests the [C, H(3), S](+) species to be a mixture of isomeric ions. While proton transfer is consistent with reagent ions displaying the CH(2)SH(+) connectivity, the observed charge exchange strongly argues for the presence of thiomethoxy cations, CH(3)S(+), predicted to be stable only in the triplet state. Charge exchange reactions are also observed in the reaction of these same [C, H(3), S](+) ions with benzene, toluene and phenetole. For these substrates, the CH(2)SH(+) ions can promote proton transfer and electrophilic methylene insertion in the aromatic ring with elimination of H(2)S. The results obtained for the different substrates suggest that the fraction of long-lived fraction of thiomethoxy cations obtained at 14 eV by electron ionization of dimethyl sulfide amounts to ~(22 -/+ 4)% of the [C, H(3), S](+) fragments. 相似文献
109.
Gas-phase reactions of four acylium ions and a thioacylium ion with three isomeric alpha-, beta- and gamma-hydroxy ketones are performed by pentaquadrupole mass spectrometric experiments. Novel structurally diagnostic reactions are observed, and found to correlate directly with interfunctional group separation. All five ions tested (CH(3)CO(+), CH(2)(double bond)CHCO(+), PhCO(+), (CH(3))(2)NCO(+) and (CH(3))(2)NCS(+)) react with the gamma-hydroxy ketone (5-hydroxy-2-pentanone) to form nearly exclusively a cyclic oxonium ion of m/z 85 that formally arises from hydroxy anion abstraction. With the beta-hydroxy ketone (4-hydroxy-2-pentanone), CH(2)(double bond)CHCO(+), PhCO(+) and (CH(3))(2)NCO(+) form adducts that undergo fast cyclization via intramolecular water displacement, yielding resonance-stabilized cyclic dioxinylium ions. With the alpha-hydroxy ketone (3-hydroxy-3-methyl-2-butanone), PhCO(+), (CH(3))(2)NCO(+) and (CH(3))(2)NCS(+) form stable adducts. Evidence that these adducts display cyclic structures is provided by the triple-stage mass spectra of the (CH(3))(2)NCS(+) adduct; it dissociates to (CH(3))(2)NCO(+) via a characteristic reaction-dissociation pathway that promotes sulfur-by-oxygen replacement. If cyclizations are assumed to occur with intramolecular anchimeric assistance, relationships between structure and reactivity are easily recognized. 相似文献
110.
Ilton L Alcantara Paulo S Roldan Gustavo R Castro Fabrício V Moraes Fábio A Silva Cilene C F Padilha Jorge D Oliveira Pedro M Padilha 《Analytical sciences》2004,20(7):1029-1032
A rapid and sensitive method was developed to determine trace levels of Cd2+ ions in an aqueous medium by flame atomic absorption spectrometry, using on-line preconcentration in a mini-column packed with 100 mg of 2-aminothiazol modified silica gel (SiAT). The Cd2+ ions were sorbed at pH 5.0. The preconcentrated Cd2+ ions were directly eluted from the column to the spectrometer's nebulizer-burner system using 100 microL of 2 mol L(-1) hydrochloric acid. A retention efficiency of over 95% was achieved. The enrichment factor (calculated as the ratio of slopes of the calibration graphs) obtained with preconcentrations in a mini-column packed with SiAT (A = -1.3 x 10(-3) + 1.8 x 10(-3)[Cd2+]) and without preconcentrations (A = 4 x 10(-5) + 3.5 x 10(-5)[Cd2+]), was 51 and the detection limit calculated was 0.38 microg L(-1). The preconcentration procedure was applied to determine trace levels of Cd in river water samples. The optimum preconcentration conditions are discussed herein. 相似文献