Estudo do coeficiente de partição octanol-água de bifenilas policloradas (PCBs) utilizando parâmetros topológicos

A model based on chemical structure was developed for the accurate prediction of octanol/water partition coefficient (K OW) of polychlorinated biphenyls (PCBs), which are molecules of environmental interest. Partial least squares (PLS) was used to build the regression model. Topological indices were used as molecular descriptors. Variable selection was performed by Hierarchical Cluster Analysis (HCA). In the modeling process, the experimental K OW measured for 30 PCBs by thin-layer chromatography - retention time (TLC-RT) has been used. The developed model (Q² = 0,990 and r² = 0,994) was used to estimate the log K OW values for the 179 PCB congeners whose K OW data have not yet been measured by TLC-RT method. The results showed that topological indices can be very useful to predict the K OW.

Extração no ponto nuvem de compostos orgânicos homólogos e isômeros

In this work, the feasibility of employing micelle-mediated extraction for selective separation of homologous or isomeric organic compounds is demonstrated. Firstly, the main parameters controlling extraction performances, such as surfactant concentration and temperature were varied. A Scheffé-type experimental design was demonstrated as a novel and useful method to characterize the various experimental factors. At each point selected in the two-phase domain and for a given solute, extraction percentage (E%), concentration ratio, phase volume ratio, and equilibrium partition coefficient (K C) were determined. The values of E% and K C decrease in the following order: phenol > 1-phenylethanol ~ 2-phenylethanol > benzyl alcohol.

Thermodynamic quantities of solvation and dilution for some acetanilide derivatives in octanol and water mutually saturateds

Based on published thermodynamic quantities for solution, partitioning and sublimation of acetanilide (ACN), acetaminophen (ACP) and Phenacetin (PNC), the thermodynamic quantities for drugs solvation in octanol-saturated water (W(ROH)) and water-saturated octanol (ROH(W)) as well as the drugs dilution in ROH(W) were calculated. The Gibbs energies of solvation were favourable in all cases. The respective enthalpies and entropies were negative indicating an enthalpy-driving for the solvation process in all cases. On the other hand, the Gibbs energies of dilution were favourable for ACP and PNC but unfavourable for ACN, whereas the respective enthalpies and entropies were negative for ACP and PNC but positive for ACN indicating enthalpy-driving for the dilution process in the case of the former drugs and entropy-driving for the latter. From the obtained values for the transfer processes, an interpretation based on solute-solvent interactions was developed.

Funciones termodinámicas relativas a la transferencia del ketoprófen desde el agua hasta algunos sistemas orgánicos

The thermodynamics of molal partitioning of ketoprofen (KTP) was studied in cyclohexane/buffer (CH/W), octanol/buffer (ROH/W), and dimyristoyl phosphatidylcholine (DMPC), dipalmitoyl phosphatidylcholine (DPPC), and egg lecithin (EGG/W) liposome systems. In all cases the partition coefficients (Kmo/w)were greater than unity; therefore the standard free energies of transfer were negative indicating affinity of KTP for organic media. The Kmo/w values were approximately seventy-fold higher in the ROH/W system compared with the CH/W system. On the other hand, the Kmo/w values were approximately ten or fifty-fold higher in the liposomes compared with the ROH/W system. In all cases, the standard enthalpies and entropies of transfer of KTP were positive indicating some degree of participation of the hydrophobic hydration on partitioning processes.

Fluxos de óxido nitroso na interface ar-mar na Baía de Guanabara

In Surface water concentrations of N2O were measured at 37 stations in Guanabara Bay and fluxes estimated across the air-sea interface. Concentrations averaged 8.2 ± 2.2 nmol L-1 and 90% of the stations showed supersaturation averaging 33%. N2O fluxes were estimated using a two-film model which is given by the product of the concentration difference across the film and the gas transfer coefficient (k w). Two parametrizations of k w were used which provided average fluxes of 0.3 and 3.0 µg N m-2 h-1. Flux measurements using floating chambers (not reported here) seem to agree with the upper limit of these estimates.

Malaria seroepidemiology: comparison between indirect fluorescent antibody test and enzyme immunoassay using bloodspot eluates

Blood sampling on filter paper is a current practice seroepidemiological studies by indirect fluorescent antibody test (IFAT). There is, however, scant comparative information about the use of bloodspot eluates for detection of malarial IgG antibodies simultaneously by IFAT and enzyme immunoassay (ELISA). Here we report data obtained by both serological methods done on 219 bloodspot eluate samples collected in a rural community in Brazilian Amazon Basin (Alto Paraíso, Ariquemes municipality) where malaria is endemic. Plasmodium falciparum and P. vivax thick smear antigens were used in the IFAT; a detergent-soluble P. falciparum antigen was prepared for ELISA. Substantial agreement of results (Kappa coefficient k = 0.686) was observed when P. falciparum antigen was used in both tests, and IFAT titers were found to be strongly correlated ELISA antibody units (Spearman correlation coeficient rs = 0.818, p < 0.0001). Only moderate agreement (k = 0.467) between IFAT with P. vivax antigen and ELISA with P. falciparum antigen was observed. Spearman correlation coefficient value between quantitative results (IFAT titers and ELISA antibody units) in this case was numerically lowe (rs = 0.540, p < 0.0001). Our results suggest that, with P. falciparum antigen, both IFAT and ELISA performed on bloodspot eluates are equivalent for seropidemiological purposes.

Determinação do coeficiente de distribuição (Kd) de benzo(a)pireno em solo por isotermas de sorção

Leaking of diesel oil from gas stations is frequent in Brazil. The presence of polycyclic aromatic hydrocarbons (PAHs), which are highly toxic is an indication of contamination by heavy hydrocarbons from diesel oil. Here were present the determination of the distribution coefficient (Kd) of benzo(a)pyrene (the most carcinogenic of the PAHs) in tropical soils using the sorption isotherm model. The sorption curves acquired for benzo(a)pyrene were of the S-type, probably due to the water/methanol experimental conditions. The sorption curves allowed calculation of the distribution coefficient (Kd). The experimental Kd values were lower than those calculated from literature Koc values (partition coefficient normalized by organic carbon), due mainly to the cosolvency effect and the percentage of organic matter and clay in soil.

Emprego de sílica gel organicamente modificada e impressa ionicamente para pré-concentração seletiva on-line de íons cobre

The present work purposes the preparation of a silica gel sorbent organically modified with 2-aminoethyl-3-aminobutylmethyldimethoxysilane (AAMDMS) and imprinted with Cu2+ ions by means surface imprinting technique and its use for selective on-line sorbent preconcentration of Cu2+ ions with further UV-VIS spectrophotometric determination by flow injection analysis. The Cu2+-imprinted silica gel, when compared with non imprinted silica gel and silica gel, showed from the binary mixture of Cu2+/Ni2+ relative selectivity coefficient (k') of 6.84 and 5.43 and 6.64 and 19.83 for the mixture Cu2+/Pb2+, thus demonstrating higher selectivity of Cu2+-imprinted silica gel towards Cu2+ ions. Under optimized condition, the on-line preconcentration method provided detection limit of 3.4 μg L-1 and linear range ranging from 30.0 up to 300.0 μg L-1 (r = 0.995). The accuracy of method was successfully assessed by analyzing different kind of spiked water samples with recovery values ranging from 92.2 up to 103.0%.

Caracterização físico-química do fármaco antichagásico benznidazol

Currently, benznidazole (BNZ) is a unique therapeutic alternative available in Brazil to treat Chagas disease. Despite its traditional medical use, little is known about the chemical nature of this drug. A detailed study of the physicochemical properties of BNZ was performed using multiple assays. Thermal, diffractometric, morphological and reological drug profiles were obtained. The partition coefficient and solubility results allowed this drug to be classified as a class IV drug according to the biopharmaceutical classification system. This information will be useful for the development of more effective BNZ formulations and for establishing the quality profile of BNZ.

Investigando cinza da casca do arroz como fase estacionária em cromatografia: uma proposta de aula experimental nos cursos de graduação

This article describes an experiment that involves the extraction and separation of the pigments of spinach extract by column chromatography using the silica obtained from rice husk ash as a stationary phase. The experimental procedure is very simple to apply in the chemistry laboratory, and allowed to illustrate some concepts of organic chemistry: structure of organic molecules, solubility, polarity, extraction, partition coefficient, adsorption and retention factor (Rf), as well as objectives and fundamentals of chromatographic methods. The experiment can be carried out in a 4 h period.

Estudio del coeficiente de reparto de ácidos carboxílicos grasos en sistemas modificados heptano/agua

The use of fatty acids (FAs) as amphiphiles is very important because they have a behaving similar to surfactants. The formulation for the preferential partition of these species was studied by varying the amount of salt at constant acid concentration. As the salt concentration increases, a Winsor I→III→II transition is observed for all the systems studied. Furthermore, the electrolyte concentration required to obtain the optimum formulation varies inversely with the chain length of the acid. The partition coefficient of the surfactant allows one to obtain thermodynamic information on the acid transfer process between the phases of the system.

Carcinogenicidade do carbendazim e seus metabólitos

The carcinogenic potential of carbendazim and its metabolites was analyzed using statistical treatment of electronic parameters obtained from DFT/ 6-311++G(d,p) and AM1 calculations. The carcinogen-DNA interaction is described in the framework of the theory of unsynchronized resonance of covalent bond as a process of electron transfer involving the HOMO and LUMO frontier orbitals. Through a Principal Component Analysis (PCA) of the electron affinity, carcinogen-DNA interaction energy, electrostatic attraction and cell membrane permeability (dipole moment m and partition coefficient LogP) evidence was obtained showing carbendazim displays carcinogenic activity. For the metabolites of carbendazim, no evidence was found in the literature of their carcinogenic activities. However, the electronic parameters for these metabolites exhibited similarity to known carcinogens, thereby showing the importance of the results obtained in this study for a policy based on the precautionary principle.

PARTIÇÃO DE PROTEÍNAS DE SORO DE LEITE EM SISTEMAS AQUOSOS BIFÁSICOS BASEADOS EM LÍQUIDOS IÔNICOS

In this work, we used an aqueous two-phase system (ATPS) consisting of the ionic liquid [C4mim][Cl] and the salt K2HPO4 to partition α-lactalbumin, β-lactoglobulin, and lactoferrin whey proteins. Extraction efficiency values above 87% indicate that the proteins primarily migrated to the ionic liquid-rich phase (top phase). Partition coefficient values ranged from 6.17 to 8.93 for a-lactalbumin, from 22.80 to 34.55 for β-lactoglobulin, and from 26.46 to 40.06 for lactoferrin. Therefore, the saline ATPS with the ionic liquid examined in this study can be considered to be a promising alternative for extracting whey proteins.

Magnetic, thermal and spectral characterization of 2,6-dimethoxybenzoates of Co(II), Ni(II) and Cu(II)

The complexes of 2,6-dimethoxybenzoic acid anion with ions of Co(II), Ni(II), and Cu(II) have been synthesized as polycrystalline solids, and characterized by elemental analysis, spectroscopy, magnetic studies, and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have following colours: pink for Co(II), green for Ni(II), and blue for Cu(II) compounds. The carboxylate group binds as monodentate, and bidentate bridging and chelating ligands. On heating in air to 1173 K the complexes decompose in four, three or two steps. At first, they dehydrate in one or two steps to anhydrous salts, that next decompose to oxides of the respective metals. The solubility of the investigated dimethoxybenzoates in water at 293 K is of the order of 10-2 mol/dm3. Their magnetic moments were determined in the temperature range of 76-303 K. The results reveal the compounds of Co(II) and Ni(II) to be high-spin complexes and that of Cu(II) to form dimer.

Magnetic, thermal and spectral behaviour of 3-chloro-2-nitrobenzoates of Co(II), Ni(II), and Cu(II)

Physico-chemical properties of 3-chloro-2-nitrobenzoates of Co(II), Ni(II) and Cu(II) were synthesized and studied. The complexes were obtained as mono- and dihydrates with a metal ion to ligand ratio of 1 : 2. All analysed 3-chloro-2-nitrobenzoates are polycrystalline compounds with colours depending on the central ions: pink for Co(II), green for Ni(II) and blue for Cu(II) complexes. Their thermal decomposition was studied in the range of 293 ­ 523 K, because it was found that on heating in air above 523 K 3-chloro-2-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step and anhydrous compounds are formed. The final products of their decomposition are the oxides of the respective transition metals. From the results it appears that during dehydration process no transformation of nitro group to nitrite takes place. The solubilities of analysed complexes in water at 293 K are of the order of 10-4 ­ 10-2 mol / dm³. The magnetic moment values of Co2+, Ni2+ and Cu2+ ions in 3-chloro-2-nitrobenzoates experimentally determined at 76 ­ 303 K change from 3.67µB to 4.61µB for Co(II) complex, from 2.15µB to 2.87µB for Ni(II) 3-chloro-2-nitrobenzoate and from 0.26µB to 1.39µB for Cu(II) complex. 3-Chloro-2-nitrobenzoates of Co(II) and Ni(II) follow the Curie-Weiss law. Complex of Cu(II) forms dimer.