Dinâmica não-linear e reagente limitante: um exemplo de bifurcação transcrítica

The nonlinear analysis of a general mixed second order reaction was performed, aiming to explore some basic tools concerning the mathematics of nonlinear differential equations. Concepts of stability around fixed points based on linear stability analysis are introduced, together with phase plane and integral curves. The main focus is the chemical relationship between changes of limiting reagent and transcritical bifurcation, and the investigation underlying the conclusion.

Determination of sulfate in the wet-process of phosphoric acid by reverse flow injection

An improved method based on reverse flow injection is proposed for determining sulfate concentration in the wet-process of phosphoric acid (WPA). The effect of reagent composition, flow rate, temperature, acid concentration, length of the reaction coil, and linear response range on the flow system is discussed in detail. Optimal conditions are established for determining sulfate in the WPA samples. Baseline drift is avoided by a periodic washing step with EDTA in an alkaline medium. A linear response is observed within a range of 20 - 360 mg L-1, given by the equation A = 0.0020C (mg L-1) + 0.0300, R² = 0.9991. The detection limit of the proposed method for sulfate analysis is 3 mg L-1, and the relative standard deviation (n = 12) of sulfate absorbance peak is less than 1.60%. This method has a rate of up to 29 samples per hour, and the results compare well with those obtained with gravimetric method.

Estudo do teste de Scott via técnicas espectroscópicas: um método alternativo para diferenciar cloridrato de cocaína e seus adulterantes

Cocaine is usually seized mixed with a wide variety of adulterants such as benzocaine, lidocaine, caffeine, and procaine. The forensic identification of cocaine in these street drug mixtures is normally performed using colorimetric testing kits, but these tests may suffer from interferences, producing false-positive results. Here, we describe the use of analytical techniques including attenuated total reflection Fourier transform infrared (ATR-FTIR) and ultraviolet-visible (UV-VIS) spectroscopies to distinguish between cocaine and other adulterants (lidocaine, promethazine, powdered milk and yeast) that yield positive results on the Scott test using the thiocyanate cobalt reagent. A further 13 substances were also analyzed using the Scott test.

Determination of Mn2+ ion by solution scanometry as a new, simple and inexpensive method

In this research, scanometry was used as a new, simple, fast and inexpensive method for a colorimetric determination of Mn2+ ion in water samples and thermocouple wire through the use of periodate reagent in an acidic medium. The results showed the oxidization of colorless Mn2+ ion by periodate and the formation of a purplish MnO4- ion. The system had a linear range of 1.0 to 70.0 µg mL-1 Mn2+ ion with a detection limit of 0.314 µg mL-1 and a relative standard deviation of 2.77% for G color value. This method has the capability to determine low levels of Mn2+ ion in thermocouple wire and water samples.

MÉTODO DE SÍNTESE DE AZIDAS AROMÁTICAS USANDO VINAGRE

The present paper describes a simple and low-cost procedure for preparation of aryl azides from anilines using vinegar as an unusual solvent/reagent. We observed the sequence of diazotation followed by diazo displacement with sodium azide can be carried out in aqueous solution of acetic acid

A FACTORIAL DESIGN APPLIED TO THE STUDY OF CHROMIUM TOXICITY ON THE GLUTATHIONE LEVELS OF Brachiaria brizantha AND Brachiaria ruziziensis SEEDLINGS

Chromium toxicity affects redox reactions within plant cells, generating detrimental reactive oxygen species. Glutathione is an antioxidant peptide and also a substrate for the production of phytochelatins, which are chelating peptides reported to mitigate Cr3+ toxicity in plants. In this study, Brachiaria brizantha (B. brizantha) and Brachiaria ruziziensis (B. ruziziensis) seedlings were evaluated for physiological responses and glutathione production following the addition of zero or 5 mg L-1 Cr3+ to the nutrient solution. Glutathione levels were determined by colorimetric analysis at 412 nm using 5,5'-dithio-bis(2-nitrobenzoic acid) as a chromophore reagent and recovery with glutathione reductase (with evaluations at days 10 and 20 of continuous growth). The assessments were carried out in a completely randomized design with 2 authentic replications, and arranged in a 23 factorial. Cr3+ caused an average increase of 0.76 mg g-1 in the initial glutathione content. However, by day 20 there was an average reduction of 3.63 mg g-1. Chromium-affected physiological detrimental responses, albeit detected in both species, were less-pronounced in B. ruziziensis, along with a much higher level of glutathione. This study indicates that B. ruziziensis has a greater tolerance for chromium toxicity than B. brizantha, and that glutathione is likely to be involved in the mitigation of chromium stress in B. ruziziensis.

DERIVATIZACIÓN Y CARACTERIZACIÓN ESPECTROSCÓPICA DE UN BIOPOLÍMERO A BASE DE L -LISINA CON ANÁLOGOS DE LA D-BIOTINA: CO -POLI(L-LISINA)-GRAFT -(ε-N-[X-D -BIOTINIL]-L-LISINA)

We report the single-step derivatization reaction of a biopolymer based onL -lysine with D -biotin analogs:Co -poly(L -lysine)-graft-(ε-N -[X-D-biotinyl]-L -lysine) (PLL-X-Biotin). The valeric acid carboxylate of D -biotin is activated to an NHS ester for direct modification of amine groups in proteins and other macromolecules. NHS esters react by nucleophilic attack of an amine in the carbonyl group, releasing the NHS group, and forming a stable amide linkage. NHS-X-Biotin is the simplest biotinylation reagent commercially available. In contrast withD -biotin, it has a longer spacer arm off the valeric acid side chain allowing better binding potential for avidin or streptavidin probes. Derivatization of poly(L -lysine) (PLL) with NHS-X-Biotin led to a copolymer PLL-X-Biotin. UV-Visible, IR-FT and 1H NMR characteristics derived from synthesis are briefly discussed.

A NOVEL METHOD FOR THE DETERMINATION OF TRACE THORIUM BY DISPERSIVE LIQUID-LIQUID MICROEXTRACTION BASED ON SOLIDIFICATION OF FLOATING ORGANIC DROP

In this study, dispersive liquid-liquid microextraction based on the solidification of floating organic droplets was used for the preconcentration and determination of thorium in the water samples. In this method, acetone and 1-undecanol were used as disperser and extraction solvents, respectively, and the ligand 1-(2-thenoyl)-3,3,3-trifluoracetone reagent (TTA) and Aliquat 336 was used as a chelating agent and an ion-paring reagent, for the extraction of thorium, respectively. Inductively coupled plasma-optical emission spectrometry was applied for the quantitation of the analyte after preconcentration. The effect of various factors, such as the extraction and disperser solvent, sample pH, concentration of TTA and concentration of aliquat336 were investigated. Under the optimum conditions, the calibration graph was linear within the thorium content range of 1.0-250 µg L-1 with a detection limit of 0.2 µg L-1. The method was also successfully applied for the determination of thorium in the different water samples.

Amphoteric behavior of di-2-pyridyl ketone benzoylhydrazone in ethanol-water mixtures

The ligand di-2-pyridyl ketone benzoylhydrazone (DPKBH) is widely used for the determination of transition metal ions in environmental samples. Due to its low solubility in water it is used in aqueous-ethanol (1:1) solvent and for higher sensitivity the pH must be properly adjusted. The properties of DPKBH solutions must be known at different ethanol-water percentages in order to achieve higher sensitivity and/or selectivity for metal analysis. The acid-base behavior of this reagent in aqueous-ethanol solvent and the dissociation/ionization constants (pK1 and pK2) of DPKBH have been determined in different aqueous-ethanol solvent mixtures (10, 20, 30 and 50 % V/V of ethanol) from potentiometric titrations at 25.0 ± 0.1° C. As the amount of ethanol increases from 10 to 30% the pK1 and pK2 values increased, but they decreased in 50% of the organic solvent. The results are correlated with the medium composition and its effects.

Spectrophotometric determination of diclofenac in pharmaceutical preparations assisted by microwave oven

In this work, an effective and low-cost method for the determination of sodium or potassium diclofenac is proposed in its pure form and in their pharmaceutical preparations. The method is based on the reaction between diclofenac and tetrachloro-p-benzoquinone (p-chloranil), in methanol medium. This reaction was accelerated by irradiating of reactional mixture with microwave energy (1100 W) during 27 seconds, producing a charge transfer complex with a maximum absorption at 535 nm. The optimal reaction conditions values such as reagent concentration, heating time and stability of the reaction product were determined. Beer's law is obeyed in a concentration range from of 1.25x10-4 to 2.00x10-3 mol l-1 with a correlation coefficient of 0.9993 and molar absorptivity of 0.49 x10³ l mol-1 cm-1. The limit of detection (LOD) was 1.35x10-5 mol l-1 and the limit of quantification (LOQ) was 4.49x10-5 mol l-1. In the presence of the common excipients, such as glucose, lactose, talc, starch, magnesium stearate, sodium sulphite, titanium dioxide, polyethyleneglycol, polyvinylpirrolidone, mannitol and benzilic alcohol no interferences were observed. The analytical results obtained by applying the proposed method compare very favorably with those given by the United States Pharmacopeia standard procedure. Recoveries of diclofenac from various pharmaceutical preparations were within 95.9% to 103.3%, with standard deviations ranging from 0.2% to 1.8%.

Sensitive bromatometric assay methods for finasteride in pharmaceuticals

Three sensitive spectrophotometric methods are presented for the determination of finasteride in bulk and in tablets. The methods rely on the use of bromate-bromide reagent and three dyes namely, methyl orange, indigocarmine and thymol blue as reagents. They involve the addition of a measured excess of bromate-bromide reagent to finasteride in acid medium, and after the bromination reaction is judged to be complete, the unreacted bromine is determined by reacting with a fixed amount of either methylorange and measuring the absorbance at 520 nm (method A) or indigocarmine and measuring the absorbance at 610 nm (method B) or thymol blue and measuring the absorbance at 550 nm (method C). In all the methods, the amount of insitu generated bromine reacted corresponds to the amount of finasteride. The absorbance measured at the respective wavelength is found increase linearly with the concentration of finasteride. Beer's law is obeyed in the ranges 0.25- 2.0, 0.5-6.0 and 1-12 µg mL-1 for method A, method B and method C, respectively. The calculated molar absorptivity values are 5.7x10(4), 3.12x10(4) and 1.77x10(4) L mol-1 cm-1 respectively, for method A, method B and method C, and the corresponding Sandell sensitivity values are 0.0065, 0.012 and 0.021 µg cm-2. The limits of detection (LOD) and quantification (LOQ) are also reported for all the methods. Accuracy and, intra-day and inter-day precisions of the methods were established according to the current ICH guidelines. The methods were successfully applied to the determination of finasteride in commercially available tablets and the results were found to closely agree with the label claim. The results of the methods were statistically compared with those of a reference method by applying Student's t-test and F-test. The accuracy and reliability of the methods were further confirmed by performing recovery tests via standard addition procedure.

Direct determination of calcium in milk by atomic absorption spectrometry using flow-injection analysis

A flow-injection system with sample and reagent addition by the synchronous merging zones approach for calcium determination in milk by flame AAS is proposed. Main parameters were optimized using a factorial design with central point. The optimum conditions were 2.5% (m/v) for La concentration, 8 mL min-1 for the carrier flow-rate, 20 cm for coiled reactor and 250 ìL for sample volume. Different sample preparation procedures were evaluated such as dilution in water or acid and microwave-assisted decomposition using concentrated or diluted acids. The optimized flow system was applied to determine Ca in eleven commercial milk samples and two standard reference materials diluted in water. Similar calcium levels were encountered comparing the results obtained by the proposed method (dilution in water) with those obtained using microwave-oven digestion. Results obtained in two standard reference materials were in agreement at 95% confidence level with those certified. Recoveries of spiked samples were in the 93% - 116% range. Relative standard deviation (n = 12) was < 5.4% and the sample throughput was 150 measurements per hour, corresponding to a consumption of 250 µL of sample and 6.25 mg La per determination.

Spectrophotometric determination of arsenic in soil samples using 2-(5-bromo-2-pyridylazo)-5-di-ethylaminophenol (Br-PADAP)

In this paper, a new, simple and sensitive method for arsenic determination in soil is proposed. This is based on the reduction of silver (I) and iron (III) ions by arsine followed by a complexation reaction of iron (II) with the spectrophotometric reagent Br-PADAP 2-(5-bromo-2-pyridylazo)-5-di-ethylaminophenol. Arsenic determination with a Sandell's sensitivity of 3.1 10-4 cm-2, linear range from 0.1 µg ml-1 to 2.0 µg ml-1 (r560 = 0.9995), molar absorptivity of 2.45 10(5) l mol-1 cm-1 and a concentration detection limit of 1.4 ng ml-1 (3s) were obtained using a 10 ml sample volume. Selectivity was increased with the use of EDTA as a masking agent. The proposed method was applied for arsenic determination in the presence of several ions amounts in digested soil samples. The results revealed that antimony (III), mercury (II), germanium (IV), platinum (IV) interferes at all analyzed proportions. The interferences can be easily removed by the use of EDTA. Precision and accuracy obtained were satisfactory with a R.S.D. < 5 %. Recovery of arsenic in soil samples varied from 95.55 to 102.70 % with a mean of 99.63 %. These results demonstrated that the proposed method is applicable for arsenic analysis in different soil samples.

Flow-batch analyser for preparation of calibration standard mixtures in simultaneous multicomponent spectrometric analysis

The application of multivariate calibration techniques to multicomponent analysis by UV-VIS molecular absorption spectrometry is a powerful tool for simultaneous determination of several chemical species. However, when this methodology is accomplished manually, it is slow and laborious, consumes high amounts of reagents and samples, is susceptible to contaminations and presents a high operational cost. To overcome these drawbacks, a flow-batch analyser is proposed in this work. This analyser was developed for automatic preparation of standard calibration and test (or validation) mixtures. It was applied to the simultaneous determination of Cu2+, Mn2+ and Zn2+ in polyvitaminic and polymineral pharmaceutical formulations, using 4-(2-piridilazo) resorcinol as reagent and a UV-VIS spectrophotometer with a photodiode array detector. The results obtained with the proposed system are in good agreement with those obtained by flame atomic absorption spectrometry, which was employed as reference method. With the proposed analyser, the preparation of calibration and test mixtures can be accomplished about four hours, while the manual procedure requires at least two days. Moreover, it consumes smaller amounts of reagents and samples than the manual procedure. After the preparation of calibration and test mixtures, 60 samples h-1 can be carried out with the proposed flow-batch analyser.

Titrimetric and spectrophotometric assay of bupropion hydrochloride in pharmaceuticals using mercury(II) nitrate

Two simple, rapid and accurate methods for the determination of bupropion hydrochloride (BUP) in pure and in pharmaceutical preparations are described. Both methods are based on the measurement of the chloride of its hydrochloride. In the titrimetric method, the chloride content of bupropion hydrochloride is determined by titrating with mercury(II)nitrate using diphenylcarbazone-bromophenol blue as indicator. Titrimetric method is applicable over a range 2-20 mg of BUP and the reaction stoichiometry is found to be 2:1 (BUP: Hg(NO3)2). The spectrophotometric method involves the addition of a measured excess of mercury(II) nitrate reagent in formate buffer to the drug, and after ensuring the reaction had gone to completion, the unreacted mercury(II) is treated with a fixed amount of diphenylcarbazone, and absorbance measured at 515 nm. The absorbance is found to decrease linearly with increasing concentration of BUP and the calibration curve is linear over 1.0-15.0 µg mL-1 BUP. The proposed methods were successfully applied to the determination of BUP in commercially available dosage forms with good accuracy and precision, and without detectable interference by excipients. The accuracy was further ascertained by placebo blank and synthetic mixture analyses and also by recovery experiments via standard-addition procedure.