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.

Exploración estocástica de las superficies de energía potencial de dímeros cis-trans y trans-trans del ácido fórmico

Potential energy surface (PES) of cis-trans and trans-trans formic acid dimers were sampled using a stochastic method, and the geometries, energies, and vibrational frequencies were computed at B3LYP/6-311++G(3df,2p) level of theory. The results show that molar free energy of dimerization deviated up to 108.4% when basis set superposition error (BSSE) and zero-point energy (ZPE) were not considered. For cis-trans dimers, C=O and O - H bond weakened, whereas C - O bonds strengthened due to dimerization. Also, trans-trans FA dimers did not show a trend regarding strengthening or weakening of the C=O, O - H and C - O bonds.

LC-MS/MS method applied to preclinical pharmacokinetic investigation of olanzapine-loaded lipid-core nanocapsules

In spite of different methods reported in the literature to determine olanzapine in biological fluids, all of them used high volumes of plasma. Therefore, the purpose of this paper was to develop an LC-MS/MS method using small plasma volume (0.1 mL) to apply in a preclinical pharmacokinetic investigation. The method was linear over the concentration ranges of 10 - 1000 ng mL-1. Extraction recoveries, stability, and validation parameters were evaluated. Results were within the acceptable limits of international guidelines. A significant decrease in clearance led to a significant 2.26-times increase in AUC0 - 6h of olanzapine-loaded lipid-core nanocapsules compared with free-olanzapine.

Sínteses totais das enoquipodinas

Enokipodins comprises a family of sesquiterpenes isolated from the mushroom Flammulina velutipes. These substances are attractive synthetic targets due to either their biological potential or structural characteristics. Since their isolation, about a decade ago, a considerable number of successful total syntheses have been published. Both via a racemic or enantioselective approach, these studies describe original and creative synthetic routes, particularly concerning the methodology used for constructing the benzylic quaternary center of these natural products. In this brief review, we discuss the reported total synthesis of enokipodins, focusing on the strategy adopted for the quaternary stereogenic center.

Química entre a microcamada superficial oceânica e os aerossóis marinhos

The sea surface microlayer (SML), although poorly understood, is important in biogeochemical cycling and sea - air exchanges; it is a source or a sink for a range of pollutants. In this paper, an overview of sampling techniques and the role of SML in biogeochemical cycles and climate is presented. The chemical and biological nature of the ocean surface film and its interaction with atmospheric aerosols are discussed. Special attention is given to organic constituents, gel-like compounds, surfactants, halogenated compounds, and metals. Estimates of air - sea exchange fluxes-with focus on organic carbon, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls-are compiled. In addition, research gaps in the chemical composition of marine aerosols and their relationship with SML are described.

UV determination of epinephrine, uric acid, and acetaminophen in pharmaceutical formulations and some human body fluids using multivariate calibration

In this work, a spectrophotometric methodology was applied in order to determine epinephrine (EP), uric acid (UA), and acetaminophen (AC) in pharmaceutical formulations and spiked human serum, plasma, and urine by using a multivariate approach. Multivariate calibration methods such as partial least squares (PLS) methods and its derivates were used to obtain a model for simultaneous determination of EP, UA and AC with good figures of merit and mixture design was in the range of 1.8 - 35.3, 1.7 - 16.8, and 1.5 - 12.1 µg mL-1. The 2nd derivate PLS showed recoveries of 95.3 - 103.3, 93.3 - 104.0, and 94.0 - 105.5 µg mL-1 for EP, UA, and AC, respectively.

Simulação de sinais de RMN através das equações de Bloch

The aim of this paper was to present a simple and fast way of simulating Nuclear Magnetic Resonance signals using the Bloch equations. These phenomenological equations describe the classical behavior of macroscopic magnetization and are easily simulated using rotation matrices. Many NMR pulse sequences can be simulated with this formalism, allowing a quantitative description of the influence of many experimental parameters. Finally, the paper presents simulations of conventional sequences such as Single Pulse, Inversion Recovery, Spin Echo and CPMG.

A quimiometria nos cursos de graduação em química: proposta do uso da análise multivariada na determinação de pkª

An experiment was proposed applying the Chemometric approach of Multivariate Analysis for inclusion in undergraduate Chemistry courses to promote and expand the use of this analytical-statistical tool. The experiment entails the determination of the acid dissociation constant of dyes via UV-Vis electronic spectrophotometry. The dyes used show from simple equilibrium to very complex systems involving up to four protolytic species with high spectral overlap. The Chemometric methodology was more efficient than univariate methods. For use in classes, it is up to the teacher to decide which systems should be utilized given the time constraints and laboratory conditions.

Thermal behaviour of TEGMMA copolymers obtained by photopolymerization using iron complexes

Copolymers of methyl methacrylate (MMA) and triethyleneglycol dimethacrylate (TEGDMA) obtained by photoinitiated polymerization using Fe(III) complexes were submitted to thermogravimetry (TGA) under dynamic air atmosphere and N2, and differential scanning calorimetric analysis (DSC). Thermal events were observed only between 90 - 110 ºC. Glass transitions were observed at ca. 100 ºC, followed by an exothermic peak at 170 ºC. The exothermic peak was assigned to a thermal curing process due to the presence of unreacted vinyl groups of the monomers. DSC revealed to be a useful tool to evaluate the curing completeness in this kind of material, using small amounts of sample in relatively short time.

Relação cerebroplacentária e acidemia ao nascimento em gestações com insuficiência placentária detectada antes da 34ª semana de gestação

OBJETIVO: avaliar a hipótese de que a relação cerebroplacentária (RCP) fetal relaciona-se com acidemia no nascimento, em gestações complicadas pela insuficiência placentária detectada antes da 34ª semana de gestação. MÉTODOS: trata-se de coorte prospectiva de 55 pacientes entre a 26ª e a 34ª semanas de gestação, com diagnóstico de insuficiência placentária caracterizada pelo Doppler de artéria umbilical alterado (índice de pulsatilidade >p95). Para cada paciente foi realizada avaliação da vitalidade fetal pela doplervelocimetria de artéria umbilical, artéria cerebral média e ducto venoso, e pelo perfil biofísico fetal. Foi calculada a RCP pela razão entre os valores do índice de pulsatilidade da artéria umbilical e da artéria cerebral média, bem como o cálculo de seu z-score (número de desvios padrão que se afasta da média para a idade gestacional). A acidemia no nascimento foi caracterizada quando pH<7,2. RESULTADOS: das 55 pacientes, 29 (52,7%) apresentaram acidemia no nascimento. O grupo com acidemia, comparado ao grupo com pH>7,2, apresentou associação significativa com os valores da RCP (mediana 0,47 versus 0,58; p=0,009), índice de pulsatilidade da artéria umbilical (mediana 2,45 versus 1,93; p=0,003), índice de pulsatilidade para veias (IPV) do ducto venoso (mediana 1,08 versus 0,85; p=0,034) e perfil biofísico fetal suspeito ou alterado (37 versus 8%; p=0,031). A análise da RCP pelo seu z-score demonstrou tendência de maior afastamento negativo da média, mas sem atingir valor significativo (p=0,08). Foi constatada correlação significativa entre o pH no nascimento e a RCP (r=0,45; p<0,01), o z-score da RCP (r=0,27; p<0,05) e o IPV do ducto venoso (r=-0,35 p<0,01). CONCLUSÃO: A RCP associa-se à presença de acidemia no nascimento nas gestações com insuficiência placentária antes da 34ª semana, e esse parâmetro pode configurar potencial fator para avaliação da gravidade do comprometimento fetal.

Consumo dietético de gestantes e ganho ponderal materno após aconselhamento nutricional

OBJETIVOS: conhecer o consumo dietético de gestantes avaliando a ingestão de macronutrientes e micronutrientes, e verificar o ganho ponderal materno na gravidez. MÉTODOS: estudo retrospectivo do período de junho de 2002 a junho de 2008 com gestantes que receberam orientação nutricional durante pré-natal em hospital universitário, agrupadas de acordo com o estado nutricional antropométrico classificado pelo índice de massa corpórea (IMC) pré-gestacional. O consumo dietético foi analisado pelas informações de entrevista de frequência alimentar realizada na primeira avaliação da gestante no serviço de nutrição, para obter os dados do hábito alimentar, calculando-se a ingestão de macronutrientes e micronutrientes. As gestantes receberam aconselhamento nutricional, e foi analisado o ganho ponderal materno na gravidez. RESULTADOS: do total de 187 gestantes que receberam orientação nutricional, 23 (12,2%) eram de baixo peso, 84 (45,0%), eutróficas, 37 (19,8%) com sobrepeso, e 43 (23,0%), obesas. As gestantes de baixo peso apresentaram menor consumo de lípides quando comparadas ao grupo com eutrofia (101,4 versus 137,3 g; p=0,043). A média do consumo de ferro foi maior nas gestantes eutróficas (14,6 mg/d) quando comparadas às com sobrepeso (12,2 mg/d) ou obesidade (10,9 mg/d; p<0,001). A média da ingestão de folatos foi maior nas gestantes eutróficas quando comparadas às obesas (336,5 versus 234,5 µg/d; p=0,002). O ganho de peso excessivo, acima do recomendado, foi significativamente mais frequente (p=0,009) nas gestantes com sobrepeso (56,7%) e obesidade (39,5%) quando comparadas às com baixo peso (17,4%) e eutrofia (31,0%). CONCLUSÕES: o ganho ponderal materno acima do recomendado associou-se ao sobrepeso e à obesidade. O consumo dietético de gestantes difere conforme o estado nutricional antropométrico materno, com menor ingestão diária de ferro nas gestantes com sobrepeso e obesidade, e menor ingestão de folatos nas obesas, o que reforça a importância da suplementação vitamínica pré-natal.