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71.
Luciana B.O. dos Santos 《Analytica chimica acta》2005,528(1):21-27
This paper describes the development of a sequential injection analysis method to automate the determination of atrazine by square wave voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. To perform these tasks, an 800 μL monosegment is formed, composed by 400 μL of sample and 400 μL of buffer/standard solution. To obtain an efficient homogenization, the sample solution is divided in five zones intercalated by four zones of the Britton-Robinson buffer (pH 2.0) in presence of appropriate concentration of NaNO3 and varying atrazine standard concentrations. This mixture zone is isolated from the carrier solution by two 100 μL air bubbles. After homogenization in an auxiliary reaction coil the mixture zone is injected toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode, at a flow rate of 50 μL s−1. After a suitable delay time, the potential is scanned from −0.5 to −1.2 V versus Ag/AgCl using a frequency of 300 Hz and pulse height of 25 mV. The linear dynamic range is observed for atrazine concentrations between 1.16 × 10−7 and 2.32 × 10−6 mol L−1, obeying the linear equation ip = (−6.91 ± 0.07) × 108[atrazine] + (4 ± 8), with r2 = 0.9996, for which the slope is given in nA L mol−1. The detection and quantification limits of the method are 2.1 × 10−8 and 7.0 × 10−8 mol L−1, respectively. The sampling frequency is 37 h−1, when the standard addition protocol is followed. This frequency can be increased to 42 h−1 if the protocol to obtain in-line calibration curve is used for quantification. The method was applied for determination of atrazine in spiked river water samples and its accuracy was evaluated by comparison with the batch standard addition approach, which revealed that there is no evidence of statistically significant differences between the two methods. 相似文献
72.
Santos E Schühle DT Jones H Schmickler W 《Langmuir : the ACS journal of surfaces and colloids》2005,21(14):6406-6421
The nonlinear optical properties of self-assembled monolayers obtained from bonding two different alpha-functionalized terthiophenes (alpha-T3) to (111) silver electrode surfaces have been investigated using second harmonic generation (SHG). The two (alpha-T3) compounds used were functionalized with alkane chains of different lengths (C8 and C4), and each was terminated with a thiol anchoring group. A nitrile group was attached to the terminal thiophene ring of the (alpha-T3) compound with the C4 chain. The orientation of the polarization of the incident beam was changed systematically and gradually between "p" and "s" orientation and the SH signal (isotropic and anisotropic contributions) analyzed in both directions ("P" and "S"). The symmetry of the system was reduced by the presence of the adlayers from C3v to C3. The dependence on the applied potential and the incident wavelength has also been studied. The relative magnitudes and phases of the various second-order tensor elements have been estimated and compared with the values for a bare surface. A resonance process in the (alpha-T3) pi moiety has been investigated, and from this, the effective "band-gap" energies of the organic semiconductor SAMs (i.e., the energy difference between the pi-pi bands) have been estimated. 相似文献
73.
Classification of white wine aromas with an electronic nose 总被引:3,自引:0,他引:3
This paper reports the use of a tin dioxide multisensor array based electronic nose for recognition of 29 typical aromas in white wine. Headspace technique has been used to extract aroma of the wine. Multivariate analysis, including principal component analysis (PCA) as well as probabilistic neural networks (PNNs), has been used to identify the main aroma added to the wine. The results showed that in spite of the strong influence of ethanol and other majority compounds of wine, the system could discriminate correctly the aromatic compounds added to the wine with a minimum accuracy of 97.2%. 相似文献
74.
M. J. L. Santos A. F. Rubira R. M. Pontes E. A. Basso E. M. Girotto 《Journal of Solid State Electrochemistry》2006,10(2):117-122
Much effort has been made to synthesize novel compounds and enhance the optical properties of poly(terthiophenes). The electrochromic
properties of poly(4,4′′-dimetoxy-3′-methyl-2′-5′,2′′-terthiophene) (PDMMT) and poly(4,4′′-dipentoxy-3′-methyl-2′-5′,2′′-terthiophene)
(PDPMT) have been studied focusing on the differences in the alkoxy-group length. Theoretical calculations were employed to
elucidate the structural and thermodynamic stability of the monomers and dimmers. The results showed that in this type of
thiophenes large alkoxy chains assist positive charge dispersion through hyperconjugative effect. Thus, PDPMT is thermodynamically
more stable than PDMMT in the oxidized state, leading to better electrochromic stability and optical memory. 相似文献
75.
L. L. M. Santos J. A. Osso S. G. Araujo 《Journal of Radioanalytical and Nuclear Chemistry》1995,200(3):227-232
The development of an automated water target for the production of18F is described. The system was fully fested and shown to be reliable and secure. The chemical separation of18F was carried out using an anionexchange resin and K2CO3 as eluent. The18F production yields were, on average, (4.81±0.42) MBq/Ah and the specific activity was higher than 6.623×105 MBq/mmol. Heat transfer measurements and calculations were made. 相似文献
76.
Margarida Maria Correia dos Santos Sheila Alves Maria de Lurdes Simões Gonçalves 《Electroanalysis》2007,19(22):2351-2361
The kinetics of formation and dissociation of Ni(II) complexes with oxalic and citric acids was studied by cyclic voltammetry in model solutions of xylem sap of Q. ilex (the dominant tree growing on serpentine soils of Northeast Portugal) using representative concentrations, pH and ionic strength. The role of magnesium on complex formation was analyzed from solutions where Mg is present at concentration levels found in the xylem sap of Q. ilex growing on both nonserpentine and serpentine soils. Kinetics studies were also done in diluted solutions of real xylem sap samples, spiked with increasing amounts of magnesium. The values obtained for the apparent rate constants were those anticipated by the proposed model. To test the validity of the methodology and mechanisms, formation rate constants, kf (M?1 s?1) of Ni(II) complexes with citrate and oxalate were evaluated that compare with the values from Eigen mechanism. 相似文献
77.
Preconcentration Systems Using Polyurethane Foam/Me-BDBD for Determination of Copper in Food Samples
Valfredo Azevedo Lemos Daniel Rodrigues Vieira Cleber Galvão Novaes Marcelo Eça Rocha Moacy Selis Santos Regina Terumi Yamaki 《Mikrochimica acta》2006,153(3-4):193-201
A new reagent, 6-[2′-(6′-methyl-benzothiazolylazo)]-1,2-dihydroxy-3,5-benzenedisulfonic acid (Me-BDBD), was synthesised and
used in on-line and off-line systems for copper preconcentration by solid-phase extraction. Spectrophotometry and Flame Atomic
Absorption Spectrometry (FAAS) were the detection techniques. Polyurethane foam loaded with Me-BDBD packed in a minicolumn
was used as sorbent in both systems. The spectral characteristics of Me-BDBD were investigated. The optimum pH values for
maximum sorption of the metal are between 7.0 and 8.5. Copper was desorbed with 0.05 and 0.50 mol L−1 hydrochloric acid solutions, for on-line and off-line systems, respectively. The effects of several foreign substances on
the adsorption of copper are reported. The enrichment factors obtained were 7 (on-line) and 26 (off-line) for the systems.
The proposed procedures allowed the determination of copper with detection limits of 3.4 and 1.4 μg L−1 (0.85 and 0.35 μg per gram of sample) for on-line and off-line systems, respectively. The precision of the procedures was
also calculated: 3.2 (on-line) and 1.9% (off-line). The validation of the procedures was carried out by analysis of certified
reference material. The copper contents in corn and rice flour and black tea samples were determined by applying the proposed
procedures. 相似文献
78.
The reaction between copper (II) and azide has been studied spectrophotometrically at four wavelengths, at 25 degrees , and ionic strength 4.00M (sodium perchlorate). The formation constants beta(2) and beta(3) found are 2.90 +/- 0.08 x 10(4) and 3.02 +/- 0.07 x 10(6) respectively. The results obtained from potentiometric measurements with a solid-state electrode disagree with those calculated from the spectrophotometric data. Causes of the discrepancy are discussed. 相似文献
79.
80.
Fluorescence of the single tryptophan of cutinase: temperature and pH effect on protein conformation and dynamics 总被引:1,自引:0,他引:1
Martinho JM Santos AM Fedorov A Baptista RP Taipa MA Cabral JM 《Photochemistry and photobiology》2003,78(1):15-22
The cutinase from Fusarium solani pisi is an enzyme with a single L-tryptophan (Trp) involved in a hydrogen bond with an alanine (Ala) residue and located close to a cystine formed by a disulfide bridge between two cysteine (Cys) residues. The Cys strongly quenches the fluorescence of Trp by both static and dynamic quenching mechanisms. The Trp fluorescence intensity increases by about fourfold on protein melting because of the disruption of the Ala-Trp hydrogen bond that releases the Trp from the vicinity of the cystine residue. The Trp forms charge-transfer complexes with the disulfide bridge, which is disrupted by UV light irradiation of the protein. This results in a 10-fold increase of the Trp fluorescence quantum yield because of the suppression of the static quenching by the cystine residue. The Trp fluorescence anisotropy decays are similar to those in other proteins and were interpreted in terms of the wobbling-in-cone model. The long relaxation time is attributed to the Brownian rotational correlation time of the protein as a whole below the protein-melting temperature and to protein-backbone dynamics above it. The short relaxation time is related to the local motion of the Trp, whose mobility increases on protein denaturation. 相似文献