Iontophoresis for modulation of cardiac drug delivery in dogs.

Cardiac arrhythmias are a frequent cause of death and morbidity. Conventional antiarrhythmia therapy involving oral or intravenous medication is often ineffective and complicated by drug-associated side effects. Previous studies from our laboratory have demonstrated the advantages of cardiac drug-polymer implants for enhanced efficacy for cardiac arrhythmia therapy compared with conventional administration. However, these studies were based on systems that deliver drugs at a fixed release rate. Modulation of the drug delivery rate has the advantage of regulating the amount of the drug delivered depending upon the disease state of the patient. We hypothesized that iontophoresis could be used to modulate cardiac drug delivery. In this study, we report our investigations of a cardiac drug implant in dogs that is capable of iontophoretic modulation of the administration of the antiarrhythmic agent sotalol. We used a heterogeneous cation-exchange membrane (HCM) as an electrically sensitive and highly efficient rate-limiting barrier on the cardiac-contacting surface of the implant. Thus, electric current is passed only through the HCM and not the myocardium. The iontophoretic cardiac implant demonstrated in vitro drug release rates that were responsive to current modulation. In vivo results in dogs have confirmed that iontophoresis resulted in regional coronary enhancement of sotalol levels with current-responsive increases in drug concentrations. We also observed acute current-dependent changes in ventricular effective refractory periods reflecting sotalol-induced refractoriness due to regional drug administration. In 30-day dog experiments, iontophoretic cardiac implants demonstrated robust sustained function and reproducible modulation of drug delivery kinetics.

Fatores abióticos condicionantes da distribuição de espécies arbóreas em quatro formações florestais do Estado de São Paulo

No estudo das comunidades florestais, estabelecer a importância relativa dos fatores que definem a composição e a distribuição das espécies é um desafio. Em termos de gradientes ambientais o estudo das respostas das espécies arbóreas são essenciais para a compreensão dos processos ecológicos e decisões de conservação. Neste sentido, para contribuir com a elucidação dos processos ecológicos nas principais formações florestais do Estado de São Paulo (Floresta Ombrófila Densa de Terras Baixas, Floresta Ombrófila Densa Submontana, Floresta Estacional Semidecidual e Savana Florestada) este trabalho objetivou responder as seguintes questões: (I) a composição florística e a abundância das espécies arbóreas, em cada unidade fitogeográfica, variam conforme o gradiente edáfico e topográfico?; (II) características do solo e topografia podem influenciar na previsibilidade de ocorrência de espécies arbóreas de ampla distribuição em diferentes tipos vegetacionais? (III) existe relação entre o padrão de distribuição espacial de espécies arbóreas e os parâmetros do solo e topografia? O trabalho foi realizado em parcelas alocadas em unidades de conservação (UC) que apresentaram trechos representativos, em termos de conservação e tamanho, das quatro principais formações florestais presentes no Estado de São Paulo. Em cada UC foram contabilizados os indivíduos arbóreos (CAP ≥ 15 cm), topografia, dados de textura e atributos químicos dos solos em uma parcela de 10,24 ha, subdividida em 256 subparcelas. Análises de correspodência canônica foram aplicadas para estabelecer a correspondência entre a abundância das espécies e o gradiente ambiental (solo e topografia). O método TWINSPAN modificado foi aplicado ao diagrama de ordenação da CCA para avaliar a influência das variáveis ambientais (solo e topografia) na composição de espécies. Árvores de regressão \"ampliadas\" (BRT) foram ajustadas para a predição da ocorrência das espécies segundo as variáveis de solo e topografia. O índice de Getis-Ord (G) foi utilizado para determinar a autocorrelação espacial das variáveis ambientais utilizadas nos modelos de predição da ocorrência das espécies. Nas unidades fitogeográficas analisadas, a correspondência entre o gradiente ambiental (solo e topografia) e a abundância das espécies foi significativa, especialmente na Savana Florestada onde observou-se a maior relação. O solo e a topografia também se relacionaram com a semelhança na composição florística das subparcelas, com exceção da Floresta Estacional Semicidual (EEC). As principais variáveis de solo e topografia relacionadas a flora em cada UC foram: (1) Na Floresta Ombrófila Densa de Terras Baixas (PEIC) - teor de alumínio na camada profunda (Al (80-100 cm)) que pode refletir os teor de Al na superfície, acidez do solo (pH(H2O) (5-25 cm)) e altitude, que delimitou as áreas alagadas; (2) Na Floresta Ombrófila Densa Submontana (PECB) - altitude, fator que, devido ao relevo acidentado, influencia a temperatura e incidência de sol no sub-bosque; (3) Na Savana Florestada (EEA) - fertilidade, tolerância ao alumínio e acidez do solo. Nos modelos de predição BRT, as variáveis químicas dos solos foram mais importantes do que a textura, devido à pequena variação deste atributo no solo nas áreas amostradas. Dentre as variáveis químicas dos solos, a capacidade de troca catiônica foi utilizada para prever a ocorrência das espécies nas quatro formações florestais, sendo particularmente importante na camada mais profunda do solo da Floresta Ombrófila Densa de Terras Baixas (PEIC). Quanto à topografia, a altitude foi inserida na maioria dos modelos e apresentou diferentes influências sobre as áreas de estudo. De modo geral, para presença das espécies de ampla distribuição observou-se uma mesma tendência quando à associação com os atributos dos solos, porém com amplitudes dos descritores edáficos que variaram de acordo com a área de estudo. A ocorrência de Guapira opposita e Syagrus romanzoffiana, cujo padrão variou conforme a escala, foi explicada por variáveis com padrões espaciais agregados que somaram entre 30% e 50% de importância relativa no modelo BRT. A presença de A. anthelmia, cujo padrão também apresentou certo nível de agregação, foi associada apenas a uma variável com padrão agregado, a altitude (21%), que pode ter exercido grande influência na distribuição da espécie ao delimitar áreas alagadas. T. guianensis se associou a variáveis ambientais preditoras com padrão espacial agregado que somaram cerca de 70% de importância relativa, o que deve ter sido suficiente para estabelecer o padrão agregado em todas as escalas. No entanto, a influência dos fatores ambientais no padrão de distribuição da espécie não depende apenas do ótimo ambiental da espécie, mas um resultado da interação espécie-ambiente. Concluiu-se que: (I) características edáficas e topográficas explicaram uma pequena parcela da composição florística, em cada unidade fitogeográfica, embora a ocorrência de algumas espécies tenha se associado ao gradiente edáfico e topográfico; (II) a partir de características dos solos e da topografia foi possível prever a presença de espécies arbóreas, que apresentaram particularidades em relação a sua associação com o solo de cada fitofisionomia; (III) a partir de associações descritivas o solo e a topografia influenciam o padrão de distribuição espacial das espécies, na proporção em que contribuem para a presença das mesmas.

Ethylene vinyl acetate/nanoclay-based pigment composites: Morphology, rheology, and mechanical, thermal, and colorimetric properties

In this study, a new type of nanopigment, obtained from a nanoclay (NC) and a dye, was synthesized in the laboratory, and these nanopigments were used to color an ethylene vinyl acetate (EVA) copolymer. Several of these nanoclay-based pigments (NCPs) were obtained through variations in the cation exchange capacity (CEC) percentage of the NC exchanged with the dye and also including an ammonium salt. Composites of EVA and different amounts of the as-synthesized nanopigments were prepared in a melt-intercalation process. Then, the morphological, mechanical, thermal, rheological, and colorimetric properties of the samples were assessed. The EVA/NCP composites developed much better color properties than the samples containing only the dye, especially when both the dye and the ammonium salt were exchanged with NC. Their other properties were similar to those of more conventional EVA/NC composites.

Linear low-density polyethylene colored with a nanoclay-based pigment: Morphology and mechanical, thermal, and colorimetric properties

In this study, a novel kind of hybrid pigment based on nanoclays and dyes was synthesized and characterized. These nanoclay-based pigments (NCPs) were prepared at the laboratory with sodium montmorillonite nanoclay (NC) and methylene blue (MB). The cation-exchange capacity of NC exchanged with MB was varied to obtain a wide color gamut. The synthesized nanopigments were thoroughly characterized. The NCPs were melt-mixed with linear low-density polyethylene (PE) with an internal mixer. Furthermore, samples with conventional colorants were prepared in the same way. Then, the properties (mechanical, thermal, and colorimetric) of the mixtures were assessed. The PE–NCP samples developed better color properties than those containing conventional colorants and used as references, and their other properties were maintained or improved, even at lower contents of dye compared to that with the conventional colorants.

Constraining porewater chemistry in a 250m thick argillaceous rock sequence

The geochemistry of an argillaceous rock sequence from a deep borehole in NE-Switzerland was investigated. The focus was to constrain the porewater chemistry in low permeability Jurassic rocks comprising the Liassic, the Opalinus Clay formation, the 'Brown Dogger' unit and the Effingen Member (Malm). A multi-method approach including mineralogical analysis, aqueous and Ni-ethylenediamine extraction, squeezing tests and pCO(2) measurements as well as geochemical modelling was applied for this purpose. A consistent dataset was obtained with regard to the main solutes in the porewaters. A fairly constant anion-accessible porosity of similar to 50% of the total porosity was deduced for all analysed samples which displayed variable clay-mineral contents. Sulphate concentrations were shown to be constrained by a sulphate-bearing phase, presumably by celestite or a Sr-Ba sulphate. Application of a simple equilibrium model, including cation exchange reactions, calcite and celestite equilibrium showed good agreement with squeezing data, indicating the suitability of the modelling approach to simulate porewater chemistry in the studied argillaceous rocks. The modelling highlighted the importance of correct determination of the exchangeable cation population. The analysis corroborates that squeezing of the studied rocks is a viable and efficient way to sample porewater.

Chemical and isotopic compositions of pore fluids from ODP Sites 169-1034 and 169-1037

We have analysed the concentrations of Li, K, Rb, Cs, and B, and the isotopic ratios of Li and B of a suite of pore fluids recovered from ODP Sites 1037 (Leg 169; Escanaba Trough) and 1034 (Leg 169S; Saanich Inlet). In addition, we have analysed dissolved K, Rb, and Cs concentrations for estuarine mixing of the Ganges-Brahmaputra river system. Together, these data sets have been used to assess the role of sediments in the marine geochemical cycles of the alkali elements and boron. Uptake onto clay minerals during estuarine mixing removes 20-30% of the riverine input of dissolved Cs and Rb to the oceans. Prior to this study, the only other recognised sink of Rb and Cs was uptake during low-temperature alteration of the oceanic crust. Even with this additional sink there is an excess of inputs over outputs in their modern oceanic mass balance. Pore fluid data show that Li and Rb are transferred into marine sediments during early diagenesis. However, modeling of the Li isotope systematics of the pore fluids from Site 1037 shows that seawater Li taken up during marine sedimentation can be readily returned to solution in the presence of less hydrated cations, such as NH4+. This process also appears to result in high concentrations of pore fluid Cs (relative to local seawater) due to expulsion of adsorbed Cs from cation exchange sites. Flux calculations based on pore fluid data for a series of ODP sites indicate that early diagenesis of clay sediments removes around 8% of the modern riverine input of dissolved Li. Although NH4+-rich fluids do result in a flux of Cs to the oceans, on the global scale this input only augments the modern riverine Cs flux by ~3%. Nevertheless, this may have implications for the fate of radioactive Cs in the natural environment and waste repositories.

Characteristics of soil profiles from the Ouémé Upper Catchment (HVO), Térou, Benin

Soil degradation threatens agricultural production and food security in Sub-Saharan Africa. In the coming decades, soil degradation, in particular soil erosion, will become worse through the expansion of agriculture into savannah and forest and changes in climate. This study aims to improve the understanding of how land use and climate change affect the hydrological cycle and soil erosion rates at the catchment scale. We used the semi-distributed, time-continuous erosion model SWAT (Soil Water Assessment Tool) to quantify runoff processes and sheet and rill erosion in the Upper Ouémé River catchment (14500 km**2, Central Benin) for the period 1998-2005. We could then evaluate a range of land use and climate change scenarios with the SWAT model for the period 2001-2050 using spatial data from the land use model CLUE-S and the regional climate model REMO. Field investigations were performed to parameterise a soil map, to measure suspended sediment concentrations for model calibration and validation and to characterise erosion forms, degraded agricultural fields and soil conservation practices. Modelling results reveal current "hotspots" of soil erosion in the north-western, eastern and north-eastern parts of the Upper Ouémé catchment. As a consequence of rapid expansion of agricultural areas triggered by high population growth (partially caused by migration) and resulting increases in surface runoff and topsoil erosion, the mean sediment yield in the Upper Ouémé River outlet is expected to increase by 42 to 95% by 2025, depending on the land use scenario. In contrast, changes in climate variables led to decreases in sediment yield of 5 to 14% in 2001-2025 and 17 to 24% in 2026-2050. Combined scenarios showed the dominance of land use change leading to changes in mean sediment yield of -2 to +31% in 2001-2025. Scenario results vary considerably within the catchment. Current "hotspots" of soil erosion will aggravate, and a new "hotspot" will appear in the southern part of the catchment. Although only small parts of the Upper Ouémé catchment belong to the most degraded zones in the country, sustainable soil and plant management practices should be promoted in the entire catchment. The results of this study can support planning of soil conservation activities in Benin.

Synthesis and characterization of cobalt(III) complexes with sinambic amplector ligands

The synthesis of the hexadentate ligand 5,6-dimethyl-2,2,9,9-tetra(methyleneamine)-4,7-dithiadecane (1,2-Me(2)EtN(4)S(2)amp) is reported. The diastereiosomers were separated as cobalt(III) complexes using cation exchange chromatography. The rac and mesa isomers were characterized by NMR (C-13, H-1, Co-59), ESI-MS, UV-Vis spectroscopy and cyclic voltammetry. Single crystals of [Co(rac-1,2-Me(2)EtN(4)S(2)amp)] Cl-2(ClO4) (.) 2H(2)O were characterized by X-ray diffraction. The low-temperature (11 K) absorption spectra of the complexes have been measured in Nafion films and from the observed positions of both spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(2g) bands, octahedral ligand-field parameters (10Dq, B and C) were determined. These results, in conjunction with the Co-59 NMR data, are used to further explore the relationship between the Co-59 magnetogyric ratio (gamma(Co)) and the product of the nephelauxetic ratio and the wavelength of the (1)A(1g) --> T-1(1g) transition (beta(DeltaE)(-1)) for complexes of mixed donor nitrogen-thioether ligands. (C) 2004 Elsevier Ltd. All rights reserved.

A pore-forming haemolysin from the hookworm, Ancylostoma caninum

Hookworms feed on blood, but the mechanism by which they lyse ingested erythrocytes is unknown. Here we show that Ancylostoma caninum, the common dog hookworm, expresses a detergent soluble, haemolytic factor. Activity was identified in both adult and larval stages, was heat-stable and unaffected by the addition of protease inhibitors, metal ions, chelators and reducing agents. Trypsin ablated lysis indicating that the haemolysin is a protein. A closely migrating doublet of hookworm proteins with apparent molecular weights of 60-65 kDa bound to the erythrocyte membrane after lysis of cells using both unlabeled and biotinylated detergent-solubilised hookworm extracts. In addition, separation of detergent-soluble parasite extracts using strong cation-exchange chromatography, resulted in purification of 60-65 kDa proteins with trypsin-sensitive haemolytic activity. Erythrocytes lysed with particulate, buffer-insoluble worm extracts were observed using scanning electron microscopy and appeared as red cell ghosts with approximately 100 nm diameter pores formed in the cell membranes. Red blood cell ghosts remained visible indicating that lysis was likely caused by pore formation and followed by osmotic disruption of the cell. (C) 2004 Australian Society for Parasitology Inc. Published by Elsevier Ltd. All rights reserved.

The effect of ionic strength variation and anion competition on the development of nitrate accumulations in variable charge subsoils

The leaching of N fertilisers has led to the formation of nitrate (NO3) accumulations in deep subsoils (>5 m depth) of the Johnstone River catchment. This paper outlines the chemical mechanism by which these NO3 accumulations are formed and maintained. This was achieved via a series of column experiments designed to investigate NO3 leaching in relation to the soil charge chemistry and the competition of anions for exchange sites. The presence of variable charge minerals has led to the formation positive surface charge within these profiles. An increase in the soil solution ionic strength accompanying the fertiliser leaching front acts to increase the positive (and negative) charge density, thus providing adsorption sites for NO3. A decrease in the soil solution ionic strength occurs after the fertiliser pulse moves past a point in the profile, due to dilution with incoming rainwater. Nitrate is then released from the exchange back into the soil solution, thus buffering the decrease in the soil solution ionic strength. Since NO3 was adsorbed throughout the profile in this experiment it does not effectively explain the situation occurring in the field. Previous observations of the sulfate (SO4) profile distribution indicated that large SO4 accumulations in the upper profile may influence the NO3 distribution through competition for adsorption sites. A subsequent experiment investigating the effect of SO4 additions on NO3 leaching showed that NO3 adsorption was minimal in the upper profile. Adsorption of NO3 did occur, though only in the region of the profile where SO4 occupancy was low, i.e. in the lower profile. Therefore, the formation of the NO3 accumulations is dependent on the variable charge mineralogy, the variation of charge density with soil solution ionic strength, and the effects of SO4 competition for adsorption sites.

Characterisation and environmental application of an Australian natural zeolite for basic dye removal from aqueous solution

An Australian natural zeolite was collected, characterised and employed for basic dye adsorption in aqueous solution. The natural zeolite is mainly composed of clinoptiloite, quartz and mordenite and has cation-exchange capacity of 120 meq/100 g. The natural zeolite presents higher adsorption capacity for methylene blue than rhodamine B with the maximal adsorption capacity of 2.8 x 10(-5) and 7.9 x 10(-5) Mot/g at 50 degrees C for rhodamine B and methylene blue, respectively. Kinetic studies indicated that the adsorption followed the pseudo second-order kinetics and could be described as two-stage diffusion process. The adsorption isotherm could be fitted by the Langmuir and Freundlich models. Thermodynamic calculations showed that the adsorption is endothermic process with Delta H degrees at 2.0 and 8.7 kJ/mol for rhodamine B and methylene blue. It has also found that the regenerated zeolites by high-temperature calcination and Fenton oxidation showed similar adsorption capacity but lower than the fresh sample. Only 60% capacity could be recovered by the two regeneration techniques. (c) 2006 Elsevier B.V. All rights reserved.

Isomeric distribution and catalyzed isomerization of cobalt(III) complexes with pentadentate macrocyclic ligands. Importance of hydrogen bonding

We have investigated the isomeric distribution and rearrangement of complexes of the type [CoXLn](2+,3+) (where X = Cl-, OH-, H2O, and L-n represents a pentadentate 13-, 14-, and 15-membered tetraaza or diaza-dithia (N-4 or N2S2) macrocycle bearing a pendant primary amine). The preparative procedures for chloro complexes produced almost exclusively kinetically preferred cis isomers (where the pendant primary amine is cis to the chloro ligand) that can be separated by careful cation-exchange chromatography. For L-13 and L-14 the so-called cis-V isomer is isolated as the kinetic product, and for L-15 the cis-VI form (an N-based diastereomer) is the preferred, while for the L-14(S) complex both cis-V and trans-I forms are obtained. All these complexes rearrange to form stable trans isomers in which the pendent primary amine is trans to the monodentate aqua or hydroxo ligand, depending on pH and the workup procedure. In total 11 different complexes have been studied. From these, two different trans isomers of [CoCIL14S](2+) have been characterized crystallographically for the first time in addition to a new structure of cis-V-[CoCIL14S](2+); all were isolated as their chloride perchlorate salts. Two additional isomers have been identified and characterized by NMR as reaction intermediates. The remaining seven forms correspond to the complexes already known, produced in preparative procedures. The kinetic, thermal, and baric activation parameters for all the isomerization reactions have been determined and involve large activation enthalpies and positive volumes of activation. Activation entropies indicate a very important degree of hydrogen bonding in the reactivity of the complexes, confirmed by density functional theory studies on the stability of the different isomeric forms. The isomerization processes are not simple and even some unstable intermediates have been detected and characterized as part of the above-mentioned 11 forms of the complexes. A common reaction mechanism for the isomerization reactions has been proposed for all the complexes derived from the observed kinetic and solution behavior.

Using multivariate analysis to predict the behaviour of soils under effluent irrigation

Onsite wastewater treatment systems aim to assimilate domestic effluent into the environment. Unfortunately failure of such systems is common and inadequate effluent treatment can have serious environmental implications. The capacity of a particular soil to treat wastewater will change over time. The physical properties influence the rate of effluent movement through the soil and its chemical properties dictate the ability to renovate effluent. A research project was undertaken to determine the role that physical and chemical soil properties play in predicting the long-term behaviour of soil under effluent irrigation and to determine if they have a potential function as early indicators of adverse effects of effluent irrigation on treatment sustainability. Principal Component Analysis (PCA) and Cluster Analysis grouped the soils independently of their soil classifications and allowed us to distinguish the most suitable soils for sustainable long term effluent irrigation and determine the most influential soil parameters to characterise them. Multivariate analysis allowed a clear distinction between soils based on the cation exchange capacities. This in turn correlated well with the soil mineralogy. Mixed mineralogy soils in particular sodium or magnesium dominant soils are the most susceptible to dispersion under effluent irrigation. The soil Exchangeable Sodium Percentage (ESP) was identified as a crucial parameter and was highly correlated with percentage clay, electrical conductivity, exchangeable sodium, exchangeable magnesium and low Ca:Mg ratios (less than 0.5).

Adsorption study for removal of basic red dye using bentonite

Colored wastewater poses a challenge to the conventional wastewater treatment techniques. Solid-liquid phase adsorption has been found to be effective for the removal of dyes from effluent. In this paper, the ability of bentonite as an adsorbent for the removal of a commercial dye, Basic Red 2 (BR2), from an aqueous solution has been investigated under various experimental conditions. The adsorption kinetics was shown to be pseudo-second-order. It was found that bentonite had high adsorption capacity for BR2 due to cation exchange. The adsorption equilibrium data can be fitted well by the Langmuir adsorption isotherm model. The effect of the experimental parameters, such as temperature, salt, and pH was investigated through a number of batch adsorption experiments. It was found that the removal of dye increased with the increase in solution pH. However, the change of temperature (15-45 degrees C) and the addition of sodium chloride were found to have little effect on the adsorption process. The results show that electrostatic interactions are not dominant in the interaction between BR2 and bentonite. It was found that the adsorption was a rapid process with 80-90% of the dye removed within the first 2-3 min. Bentonite as an adsorbent is promising for color removal from wastewater.

Measurement of exchangeable cations in saline soils

The measurement of exchangeable cations in saline soils is limited by the difficulty in accurately separating soluble cations from exchangeable cations. A method is examined for saline soils in which exchangeable cations are calculated as the total extractable cations minus the concentration of soil solution (soluble) cations. In addition, a further two standard methods were investigated, one which assumes the total soil extractable cations are exchangeable, the other utilises a pretreatment to remove soluble salts prior to measurement of the remaining (exchangeable) cations. After equilibration with a range of sodium adsorption ratio (SAR) solutions at various ionic strengths, the exchangeable cation concentrations of two soils (Dermosol and Vertosol) were determined by these methods and compared to known values. The assumption that exchangeable cations can be estimated as the total soil extractable cations, although valid at low ionic strength, resulted in an overestimation of exchangeable Na and Ca concentrations at higher ionic strengths due to the presence of soluble salts. Pretreatment with ethanol and glycerol was found to effectively remove soluble salts thus allowing the accurate measurement of the effective cation exchange capacity (ECEC), however, dilution associated with the pretreatment process decreased concentrations of exchangeable Ca while simultaneously increasing exchangeable Na. Using the proposed method, good correlations were found between known and measured concentrations of exchangeable Na (Dermosol: y=0.873x and Vertosol: y=0.960x) and Ca (Dermosol: y=0.906x, and Vertosol: y=1.05x). Therefore, for soils with an ionic strength of approximately 50 mM (ECse 4 dS m-1) or greater (in which exchangeable cation concentrations are overestimated by assuming the total soil cations are exchangeable), concentrations can be calculated as difference between total extractable cations and soluble cations.