Critical behavior of self-avoiding walks on fractals

Using a new graph counting technique suitable for self-similar fractals, exact 18th-order series expansions for SAWs on some Sierpinski carpets are generated. From them, the critical fugacityx _c and critical exponents _SAW and _SAW are obtained. The results show a linear dependence of the critical fugacity with the average number of bonds per site of the lattices studied. We find for some carpets with low lacunarity that _SAW<0.75, thus violating the relation _SAW(fractal) > _SAW (d) for SAWs on the fractals which are embedded in ad-dimensional Euclidean space.     

A new approach for the sequential injection spectrophotometric determination of the total antioxidant activity

A sequential injection system based on the ABTS (2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulphonic-acid) methodology was developed. The proposed method, incorporating a mixing chamber in the side port of the selection valve, was evaluated to measure the total antioxidant activity of several beverages and foods.The ABTS⁺ is generated by oxidation of ABTS with potassium persulfate and is reduced in presence of hydrogen-donating antioxidants converting into a colourless product. The applicability of the developed method was tested by measurement of the antioxidant activity of pure compounds as well as by analysing complex food and beverage samples. The antioxidant activity was presented as l(+) ascorbic acid equivalence. The values obtained by this methodology were not significantly different from the results obtained by the original spectrophotometric ABTS assay. For most of the studied antioxidants, antioxidant activity varied with pH and dilution. The proposed SIA system is suitable for screening direct or diluted total antioxidant activity of pure compounds or food samples.     

Protonation of acyl anion equivalents generated from acylphosphonates: nonhydride access to the aldehyde oxidation state from the carboxylic acid oxidation state

Acylphosphonates, which are easily available from carboxylic acids, are potent acyl anion precursors and undergo cyanide ion promoted phosphonate-phosphate rearrangement to provide the corresponding acyl anion equivalents as reactive intermediates. The protonation of these acyl anion equivalents furnished cyanohydrin O-phosphates in good yields. For the high yield formation of cyanohydrin O-phosphates from arylphosphonates THF should be used and from alkylphosphonates DME was used.     

Developing a sequential injection-square wave voltammetry (SI-SWV) method for determination of atrazine using a hanging mercury drop electrode

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 i_p = (−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.     

A downsized flow set up based on multicommutation for the sequential photometric determination of iron(II)/iron(III) and nitrite/nitrate in surface water

In this work, a downsized flow set up designed based on multicommutation concept for photometric determination of iron(II)/iron(III) and nitrite/nitrate is surface water is described. The flow system network comprised a set of three-way solenoid valves, reaction coil and a double-channel flow cell, which were nested in order to obtain a compact and small-size instrument. To accomplish the downsizing requirement light source (LED) and radiation detection (phototransistor) were coupled to the flow cell. In order to demonstrated the effectiveness of the system, the photometer methods based on Griess reaction and 1-10-phenantroline for nitrite and iron(II) determination, respectively, were selected. Under computer control the set up provided facilities to handle four reagent solutions employing a single pumping channel, thus permitting also the determination of nitrate and iron(III) after its reduction to nitrite and to iron(II), respectively. The overall system performance was demonstrated working several days running standard solution, no significant variation of base line, linear response range and slop (less than 1%) were observed. The usefulness of the downsized system was ascertained by analyzing a set of surface water. Aiming to access the accuracy sample were also analyzed employing reference procedures and no significant difference at 95% confidence level were observed for the four analytes. Other profitable features such as analytical throughput of 40 determination per hour; relative standard deviation of 1%; linear response range between 50 and 300 μg l⁻¹ for nitrite and nitrate, 0.5-6.0 mg l⁻¹ iron(II) and iron(III); low reagent consumption 75 μg for nitrate/nitrite and 0.6 mg for iron(II)/iron(III) per determination; and 2.4 ml waste generation per determination were also achieved.     

Kinetics and Mechanism of Ni(II) Chelation in Model and Real Solutions of Xylem Sap of Quercus ilex

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, k_f (M^?1 s^?1) of Ni(II) complexes with citrate and oxalate were evaluated that compare with the values from Eigen mechanism.