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.

Diclofenac plasma protein binding: PK-PD modelling in cardiac patients submitted to cardiopulmonary bypass

Twenty-four surgical patients of both sexes without cardiac, hepatic, renal or endocrine dysfunctions were divided into two groups: 10 cardiac surgical patients submitted to myocardial revascularization and cardiopulmonary bypass (CPB), 3 females and 7 males aged 65 ± 11 years, 74 ± 16 kg body weight, 166 ± 9 cm height and 1.80 ± 0.21 m2 body surface area (BSA), and control, 14 surgical patients not submitted to CPB, 11 female and 3 males aged 41 ± 14 years, 66 ± 14 kg body weight, 159 ± 9 cm height and 1.65 ± 0.16 m2 BSA (mean ± SD). Sodium diclofenac (1 mg/kg, im Voltaren 75® twice a day) was administered to patients in the Recovery Unit 48 h after surgery. Venous blood samples were collected during a period of 0-12 h and analgesia was measured by the visual analogue scale (VAS) during the same period. Plasma diclofenac levels were measured by high performance liquid chromatography. A two-compartment open model was applied to obtain the plasma decay curve and to estimate kinetic parameters. Plasma diclofenac protein binding decreased whereas free plasma diclofenac levels were increased five-fold in CPB patients. Data obtained for analgesia reported as the maximum effect (EMAX) were: 25% VAS (CPB) vs 10% VAS (control), P<0.05, median measured by the visual analogue scale where 100% is equivalent to the highest level of pain. To correlate the effect versus plasma diclofenac levels, the EMAX sigmoid model was applied. A prolongation of the mean residence time for maximum effect (MRTEMAX) was observed without any change in lag-time in CPB in spite of the reduced analgesia reported for these patients, during the time-dose interval. In conclusion, the extent of plasma diclofenac protein binding was influenced by CPB with clinically relevant kinetic-dynamic consequences

pH titration of native and unfolded ß-trypsin: evaluation of the D D G0 titration and the carboxyl pK values

The stabilizing free energy of ß-trypsin was determined by hydrogen ion titration. In the pH range from 3.0 to 7.0, the change in free energy difference for the stabilization of the native protein relative to the unfolded one (D D G0 titration) was 9.51 ± 0.06 kcal/mol. An isoelectric point of 10.0 was determined, allowing us to calculate the Tanford and Kirkwood electrostatic factor w. This factor presented a nonlinear behavior and indicated more than one type of titratable carboxyl groups in ß-trypsin. In fact, one class of carboxyl group with a pK = 3.91 ± 0.01 and another one with a pK = 4.63 ± 0.03 were also found by hydrogen ion titration of the protein in the folded state

Estudos sobre a alimentação mineral do cafeeiro: XII. efeito da adubação na composição mineral das fôlhas

Leaf samples from coffee plants under three different fertilizations, namely NPK, NP and PK, were collected for chemical analysis. It was found that the contents of N, K, Ca, Mg and S in the first, second, third and fourth pair of leaves were the same from the statistical point of view. On the onder hand, there was a significant effect of the position of the leaf in the branch on the P content, which was higher in the first pair. With the exception of the P level ,the four pairs of leaves are chemically uniform. Nevertheless it is not considered as convenient to mix all kinds of leaves into one sample, since the composition may vary a great deal when sampling is done some other time, such as the period of fruit growing. It is recommended therefore that either the third or the fourth pair leaves should be collected for routine work in foliar diagnosis.

Aspectos do melhoramento genético do gado canchim

Neste trabalho estimou-se o coeficiente de herdabilidade do peso aos 18 meses de idade do gado Canchim, que e o bimestiço 5/8 Charolês-Zebu, bem como avaliaram-se os reprodutores pela estimação dos efeitos de touros e vacas, em função de sua descendencia. Os estudos se basearam em 252 pesos aos 18 meses de animais oriundos de 15 touros e 94 vacas. Foram feitos ajustes para sexo, estação do ano e numero de ordem da parição da vaca. O ajuste foi feito com auxílio do modelo matemático y ijkr = m + + si + e j + pk + e ijkr, onde s i (i = 1 , 2) = efeito do sexo, e j (j =1, 2, 3, 4) = efeito da estação do ano, Pk (k = 1,2,3,4,5) = efeito da parição. Com os dados ajustados y ijkr> obtidos pela formula y ijkr = Yijkr - si - êj - pk, foi feita a análise da variância seguindo-se o modelo de blocos incompletos, conforme PIMENTEL GOMES (1967, 1968, 1970), onde touros eram considerados como blocos e vacas como tratamentos. Os resultados obtidos foram: Com as estimativas dos componentes de variancia E, D, S, foram calculados os coeficientes de herdabilidade pelas formulas resultados foram: Tambera se estimaram os efeitos de touros e vacas o que permitiu apontar os melhores reprodutores do rebanho.

Influência da calagem, adubação fosfatada e micronutrientes na nodulação natural do feijoeiro (Phaseolus vulgaris L.)

Um experimento foi montado em casa de vegetação para testar os efeitos do fósforo (150 ppm), adubação básica (150 ppm P2O5,50 ppm K2O e micronutrientes) e calagem (1 ton CaC0(3)/ha) na nodulação natural do feijoeiro (cultivar Carioca) em 4 diferentes solos: Mediterrâneo, Podzolizado e dois outros de Terra Roxa Estruturada. O peso dos nódulos aumentou em dois solos (Mediterrâneo e Podzolizado), devido à adição de fósforo e em Terra Roxa Estruturada devido ao fósforo mais calagem. A adubação completa (PK + micronutrientes) foi a que proporcionou maior desenvolvimento das plantas, mesmo em ausência de calagem, indicando efeito de micronutrientes e potássio nos solos estudados. No entanto, nos solos de Terra Roxa, a adição de fósforo foi suficiente para o aumento do peso da parte aérea e teor de N total das plantas. O N total aumentou em plantas que receberam adubação completa. A adição de fósforo contribuiu para uma melhor nodulação natural (peso e numero de nódulos).

Presence of Wolbachia endosymbionts in microfilariae of Wuchereria bancrofti (Spirurida: Onchocercidae) from different geographical regions in India

In view of the recent discovery of rickettsial endosymbionts, Wolbachia in lymphatic filarial parasites, Wuchereria bancrofti and Brugia malayi and subsequently of their vital role in the survival and development of the latter, antibiotics such as tetracycline are being suggested for the treatment of lymphatic filariasis, by way of eliminating the endosymbiont. But, it is essential to assess their presence in parasites from areas endemic for lymphatic filariasis before such a new control tool is employed. In the present communication, we report the detection of Wolbachia endosymbionts in microfilariae of W. bancrofti parasites collected from geographically distant locations of India, such as Pondicherry (Union Territory), Calicut (Kerala), Jagadalpur (Madhya Pradesh), Thirukoilur (TamilNadu), Chinnanergunam (TamilNadu), Rajahmundry (Andhra Pradesh), and Varanasi (Uttar Pradesh), using Wolbachia specific 16S rDNA polymerase chain reaction.

Effect of food on immature development, consumption rate, and relative growth rate of Toxorhynchites splendens (Diptera: Culicidae), a predator of container breeding mosquitoes

Food utilization by the larvae of Toxorhynchites splendens (Wiedemann) was studied in the laboratory by offering larvae of Aedes aegypti Linnaeus, Anopheles stephensi (Liston), and Culex quinquefasciatus (Say). Quantitative analyses of data indicated that immature development was significantly faster with increase in food availability. The regression analysis showed that the degrees of the relationship between immature duration (Id) and food availability were higher when offered early instars of prey (first and second instars) than late instars. Consumption rate (Cr) of the predator increased with increase in food availability and this relationship was highly significant when larvae of An. stephensi were offered as food. Consumption rate to food level decreased with increase in the age class of the prey. There was a significant negative correlation between Id and Cr. This aspect helps to increase population turnover of T. splendens in a shorter period when the prey is abundant. Conversely, the predator compensated the loss in daily food intake at low food level by extending Id thereby attains the minimum threshold pupal weight for adult emergence. There was an increase in the relative growth rate (RGR) of the predator when An. stephensi was offered as prey and this was related to the high protein content of the prey per body weight. There was a positive correlation between Cr and RGR. This adaptive life characteristic strategy of this predator is useful for mass-rearing for large scale field release programmes in the control of container breeding mosquitoes is discussed.

Efficiency of diagnostic biomarkers among colonic schistosomiasis Egyptian patients

The schistosomal parasite plays a critical role in the development of malignant lesions in different organs. The pathogenesis of cancer is currently under intense investigation to identify reliable prognostic indices for disease detection. The objective of this paper is to evaluate certain biochemical parameters as diagnostic tools to efficiently differentiate between colonic carcinoma and colonic carcinoma associated with schistosomal infection among Egyptian patients. The parameters under investigation are interleukin 2 (IL-2), tumour necrosis factor alpha (TNF-α), carcinoembryonic antigen (CEA) levels, tissue telomerase, pyruvate kinase (PK), glucose-6-phosphate dehydrogenase (G-6-PD) and lactate dehydrogenase (LDH) enzyme activities. The results revealed a significant elevation in the level of the tumour markers IL-2, TNF-α and CEA as well as the activities of LDH, telomerase and G-6-PD among non-bilharzial and bilharzial colonic cancer groups, with a more potent effect in bilharzial infection-associated colonic cancer. A significant inhibition in PK activity was recorded in the same manner as compared to normal tissues. The efficacy of this biomarker was also evaluated through detecting sensitivity, specificity, negative and positive predictive values. In conclusion, schistosomal colonic carcinoma patients displayed more drastic changes in all parameters under investigation. The combination of the selected parameters succeeded in serving as biomarkers to differentiate between the two malignant types.

Rendimentos de culturas e alterações químicas do solo tratado com resíduos de curtume e crômio hexavalente

O presente trabalho foi elaborado com o objetivo de avaliar o rendimento das culturas do trigo, alface e rabanete e as alterações químicas de um Latossolo resultantes da adição de resíduos de curtume e de crômio hexavalente. Microparcelas, constituídas por recipientes com 60 L de solo e mantidas em casa de vegetação, receberam os seguintes tratamentos: testemunha; calcário + NPK; lodo do decantador primário + PK; resíduo de rebaixadeira de couro + calcário + NPK; aparas de couro + calcário + NPK; Cr6+ + calcário + NPK ; Cr6+ + calcário + esterco bovino; calcário + esterco bovino. O lodo continha 8,5 g kg-1 de Cr e foi aplicado em dose correspondente a 8,8 t ha-1. O resíduo de rebaixadeira possuía 17,1 g kg-1 Cr e as aparas de couro, 19,4 g kg-1 Cr. Esses resíduos foram aplicados nas doses correspondentes a 4,4 e 3,8 t ha-1. As doses de Cr6+ (K2Cr2O7) e esterco bovino foram de 100 mg kg-1 e 20 t ha-1, respectivamente. A aplicação de lodo elevou o pH do solo de 5,1 para 5,8; os teores de N, de 1,26 para 1,51 g kg-1, e os teores de Ca, de 4,1 para 5,9 cmol c dm-3, proporcionando rendimentos das três culturas equivalentes aos obtidos com a aplicação de calcário + NPK. Os teores de crômio no solo e nas partes vegetativas das culturas nos tratamentos com aplicação dos resíduos de curtume variaram, respectivamente, de 40,7 a 71,2 e de 0,08 a 2,71 mg kg-1, sendo considerados normais. A adição de resíduo de rebaixadeira de couro ou das aparas de couro não reduziu os rendimentos das culturas e não alterou os teores de Cr do solo e das plantas. A adição de Cr6+ provocou um efeito tóxico nas plantas, sendo responsável pela diminuição do rendimento da cultura do trigo em 91 % e da cultura da alface em 86 %, quando comparadas ao tratamento Calcário + NPK. Este efeito foi diminuído com a adição de agentes redutores como o esterco bovino.

Extratores de silício disponível em escórias e fertilizantes

Os métodos para quantificar o silício (Si) disponível em fertilizantes e escórias não têm sido confiáveis até o momento. Neste estudo, determinou-se o Si extraído de diversas fontes, utilizando como extratores: Na2CO3 + NH4NO3, variando concentração, tempo de agitação e de reação; água; HCl 0,5 mol dm-3; Na2CO3 a 50 g dm-3; ácido cítrico a 50 g dm-3; ácido acético 0,5 mol dm-3; resina trocadora de cátions (Amberlite IRC-50, pK 6,1), além do método da coluna de lixiviação. Paralelamente, desenvolveu-se um experimento em casa de vegetação, com arroz irrigado, com aplicação de 125 kg ha-1 de Si total, proveniente de 12 fontes. O tempo de agitação mostrou não ser fundamental na determinação do Si, embora o resultado de três horas tenha sido superior estatisticamente aos demais. As concentrações de 10 + 16 g dm-3 e 30 + 48 g dm-3 de Na2CO3 + NH4NO3 mostraram-se as mais promissoras na extração de Si; por isso a menor concentração (10 + 16 g dm-3) foi escolhida para avaliar as fontes quanto ao tempo de repouso. Durante o período de repouso, verificou-se que todas as fontes apresentaram aumento na liberação de Si ao longo do tempo, tendo o período de 5 a 9 dias apresentado melhor correlação entre o Si extraído pelo arroz e o Si recuperado na análise das várias fontes. A extração com Na2CO3 + NH4NO3 dos fertilizantes com Si pode representar, com um bom grau de confiabilidade, o potencial de liberação deste elemento no solo e aproveitamento pelas plantas. As fontes mais eficientes na liberação de Si para o arroz foram a Rhodia, seguida da Wollastonita, enquanto as fontes MB-4 e escórias de alto-forno foram as que menos liberaram Si. Os extratores ácidos demonstraram ser mais eficientes na extração de Si das escórias de alto-forno e pouco eficientes com a Wollastonita. A água foi o extrator com a menor taxa de recuperação de Si das fontes testadas. Os extratores que apresentaram melhores correlações entre o Si recuperado e o Si extraído pela cultura do arroz foram a resina Amberlite e o Na2CO3 10 g dm-3 + NH4NO3 16 g dm-3, seguidos pela coluna de lixiviação.

Recovery of degraded pasture in Rondônia: macronutrients and productivity of brachiaria brizantha

Pasture is the main form of land use in Amazonia. Over time the pasture grass loses vigor and yields decrease, indicating a certain degree of degeneration. The main causes of degradation are lack of pasture maintenance and subsequent weed infestation, the choice of regionally unsuitable forage species and excessive grazing. The main purpose of this study was to evaluate the impact of different recovery managements on soil chemical properties and grass yield of a degraded pasture in Rondônia. For this purpose, an experiment was installed in October 2001, consisting of five treatments: C = control; HA = harrowing + NPK + micronutrients; HE = Herbicide + NK + micronutrients; R = No-tillage rice + NPK + micronutrients; and S = No-tillage soybean + PK + micronutrients. The following N, P and K sources were used: ammonium sulfate for N, calcined phosphate for P and potassium chloride for K. The experiment was arranged in a randomized block design with four replications. The shoot dry matter yield of the grass was analyzed as of the 35th month of experimentation, in a dry and a rainy period. Phosphorus fertilization resulted in significant increases in Ca2+ and Mg2+ and increasing trend of P in the topsoil in the initial months of the experiment in treatments HA and S and increases in Ca2+ and P (trend) in the treatment R. The cumulative production of Brachiaria brizantha, from Sep/2004 to Mar/2005, was 30,025, 28,267 and 27,735 kg ha-1 shoot dry matter in the treatments HA, R and S, respectively. These values differed significantly from treatments C and HE, with 17,040 and 17,057 kg ha-1, respectively. It was concluded that phosphorus fertilization associated to pasture reform was effective to raise the dry matter yield of Brachiaria brizantha. Rice or soybean under no-tillage is recommended as a practice of pasture recovery, due to the residual effect of fertilization.

Crescimento e absorção de nutrientes pelo feijoeiro adubado com cama de aves e fertilizantes minerais

O feijoeiro é tradicionalmente cultivado em pequenas propriedades, onde é comum o uso de dejetos animais para adubação das culturas. Como é uma cultura de ciclo curto, os nutrientes precisam estar disponíveis logo após a germinação, o que nem sempre acontece quando a fertilização ocorre a partir de fertilizantes orgânicos. Neste trabalho, objetivou-se avaliar a eficiência de diferentes camas de aves em relação aos fertilizantes minerais na produção de matéria seca e na liberação de nutrientes para o feijoeiro, em casa de vegetação. O experimento foi conduzido em 2010, com amostras de um Latossolo Vermelho distroférrico com 16 g kg-1 de matéria orgânica, 1,9 e 84 mg dm-3 de P e K, respectivamente, e pH 6,0. Adotou-se delineamento experimental de blocos casualizados com 10 tratamentos e cinco repetições. As unidades experimentais foram constituídas por vasos com 14 dm³ de solo e cinco plantas de feijão, do cultivar BRS Requinte, durante 60 dias. Os tratamentos consistiram de cinco camas de aves compostas pelos seguintes materiais: palha de milho, bagaço de cana-de-açúcar, palha de pastagem natural, areia ou acícula de Pinus, formulações de nutrientes (NPK, NP, PK e NK) e um testemunha, sem nenhum fertilizante. Os fertilizantes minerais com P proporcionaram maior produção de matéria seca da parte aérea (MSPA) e de raízes (MSRA) do feijoeiro do que as camas de aves, por causa da maior liberação para o solo de N e P disponíveis. Dentre as camas estudadas, aquela constituída por areia foi a que proporcionou os maiores valores de MSPA e de MSRA. As plantas fertilizadas com as camas de aves acumularam, em média, 58,6 % do N e 59,0 % do P, em relação às fertilizadas com os tratamentos que continham N e P minerais. A taxa de recuperação pelas plantas de N e K foi maior para os nutrientes aplicados na forma mineral do que na orgânica. As camas de aves podem ser utilizadas como fertilizantes para a cultura do feijoeiro desde que sejam suplementadas com N e P minerais.

Aplicação de métodos quimiométricos na especiação de Cr(VI) em solução aquosa

The equilibria, the spectra and the identities of the species of Cr(VI) that are present in aqueous solution have long been an active subject of discussion in the literature. In this paper, three different chemometric methodologies are applied to sets of UV/Visible spectra of aqueous Cr(VI) solutions, in order to solve a chemical system where there is no available information concerning the composition of the samples nor spectral information about the pure species. Imbrie Q-mode factor analysis, followed by varimax rotation and Imbrie oblique projection, were used to estimate the composition of Cr(VI) equilibrium solutions and, by combining these results with the k-matrix method, to obtain the pure spectra of the species. Evolving factor analysis and self modeling curve resolution were used to confirm the number of the species and the resolution of the system, respectively. Sets of 3.3×10-4 and 3.3×10-5 mol L-1 Cr(VI) solutions, respectively, were analyzed in the pH range from 1 to 12. Two factors were identified, which were related to the chromate ion (CrO4(2-)) and bichromate ion (HCrO4-). The pK of the equilibrium was estimated as 5.8.

Ternary surface complex: coadsorption of Cu(II), Zn(II), Cd(II) and nitrilotris(methylenephosphonic) acid onto boehmite

This work studies the effect of NTMP (nitrilotris(methylenephosphonic acid)) on the adsorption of Cu(II), Zn(II), and Cd(II) onto boehmite in the pH range 5-9.5. The data were analyzed using the 2-pK constant capacitance model (CCM) assuming ternary surface complex formation. Under stoichiometric conditions, NTMP is more effective for removing Cu(II) than Zn(II) from solution and the contribution of ternary surface complexes are important to model the adsorption of both metals. Under nonstoichiometric conditions and high surface loading with a Me(II)/NTMP ratio of 1:5, Cu(II) and Zn(II) adsorption is significantly suppressed. In the case of Cd(II) the free metal adsorption is the most dominant species.