Biomimetic mineralization: encapsulation in calcium carbonate shells

Calcium carbonate biomineralization is a self-assembly process that has been studied to be applied in the biomedical field to encapsulate biomolecules. Advantages of engineering mineral capsules include improved drug loading efficiencies and protection against external environment. However, common production methods result in heterogeneous capsules and subject biomolecules to heat and vibration which cause irreversible damage. To overcome these issues, a microfluidic device was designed, manufactured and tested in terms of selectivity for water and oil to produce a W/O/W emulsion. During the development of this work there was one critical challenge: the selective functionalization in closed microfluidic channels. Wet chemical oxidation of PDMS with 1M NaOH, confirmed by FTIR, followed by adsorption of polyelectrolytes - PDADMAC/PSS - confirmed by UV-Vis and AFM results, render the surface of PDMS hydrophilic. UV-Vis spectroscopy also confirmed that this modification did not affect PDMS optical properties, making possible to monitor fluids and droplets. More important, with this approach PDMS remains hydrophilic over time. However, due to equipment constrains selectivity in microchannels was not achieved. Therefore, emulsion studies took place with conventional methods. Several systems were tried, with promising results achieved with CaCO3 in-situ precipitation, without the use of polymers or magnesium. This mineral stabilizes oil droplets in water, but not in air due to incomplete capsule formation.

The ceramic artifacts in archaeological black earth (terra preta) from lower Amazon region, Brazil: mineralogy

Several archaeological black earth (ABE) sites occur in the Amazon region. They contain fragments of ceramic artifacts, which are very important for the archaeological purpose. In order to improve the archaeological study in the region we carried out a detailed mineralogical and chemical study of the fragments of ceramic artifacts found in the two ABE sites of Cachoeira-Porteira, in the Lower Amazon Region. Their ceramics comprise the following tempers: cauixi, cariapé, sand, sand +feldspars, crushed ceramic and so on and are composed of quartz, clay equivalent material (mainly burned kaolinite), feldspars, hematite, goethite, maghemite, phosphates, anatase, and minerals of Mn and Ba. Cauixi and cariapé, siliceous organic compounds, were found too. The mineralogical composition and the morphology of their grains indicate a saprolite (clayey material rich on quartz) derived from fine-grained felsic igneous rocks or sedimentary rocks as source material for ceramic artifacts, where silica-rich components such cauixi, cariapé and/or sand (feldspar and rock fragments) were intentionally added to them. The high content of (Al,Fe)-phosphates, amorphous to low crystalline, must be product of the contact between the clayey matrix of pottery wall and the hot aqueous solution formed during the daily cooking of animal foods (main source of phosphor). The phosphate crystallization took place during the discharge of the potteries put together with waste of organic material from animal and vegetal origin, and leaving to the formation of the ABE-soil profile.

The ceramic artifacts in archaeological black earth (terra preta) from Lower Amazon Region, Brazil: chemistry and geochemical evolution

This paper carried out a chemical investigation of archaeological ceramic artifacts found in archaeological sites with Black Earth (ABE) in the Lower Amazon Region at Cachoeira-Porteira, State of Pará, Brazil. The ceramic artifacts, mostly of daily use, belong to Konduri culture (from 900 to 400 years BP). They are constituted of SiO2, Al2O3, Fe2O3, Na2O and P2O5; SiO2 and Al2O3 together add up to 80 % and indicate influence of acid rocks, transformed into clay minerals basically kaolinite. The relative high contents of P2O5 (2.37 % in average) come out as (Al,Fe)-phosphate, an uncommon fact in primitive red ceramics, but found in some roman and egyptian archaeological sites. The contents of the trace elements are similar or below the Earth's crust average. This chemical composition (except P2O5) detaches saprolite material derived acid igneous rocks or sedimentary ones as the main raw material of the ceramics. The contents of K, Na and Ca represent the feldspars and rock fragments possibly introduced into saprolitic groundmass, indicated by mineralogical studies. The presence of cauixi and cariapé as well as quartz sand was confirmed by optical microscope, SEM analyses and by the high silica contents of ceramic fragments. Phosphorus was possibly incorporated into groundmass during cooking of foods, and ABE soil profile formation developed on yellow Latosols. The raw materials and its tempers (cauixi, or cariapé, feldspar, crushed rocks, old ceramic artifacts and quartz fragments) are found close to the sites and therefore and certainly came from them.

Ferroelectric phase transitions studies in 0.5Ba(Zr0.2Ti0.8) O3-0.5(Ba0.7Ca0.3)TiO3 ceramics

The ferroelectric phase transitions in 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BCZT 50/50) ceramics,fabricatedbyasolidstatereaction,werestudiedbyusing X-Ray diffraction, Raman spectroscopy, and measuring electric polarization, dielectric permittivity and pyroelectric current. Xraydiffraction(XRD)confirmsthecoexistenceoftetragonal(T) andrhombohedral(R)phasesatroomtemperature.Thetemperature dependence of the Raman modes frequency reveals the existenceoftwophasetransitionscorrespondingtotherhombohedral – tetragonal, and tetragonal - cubic close to 30 and 100 °C, respectively. The temperature dependence of electric polarization,pyroelectriccurrent,anddielectricpermittivityfurther supports theferroelectric (tetragonal) toparaelectric (cubic) phasetransition.Moreover,thedielectricpermittivityrevealsthe diffuseness of the phase transition and is attributed to the compositional fluctuations of different polar micro-regions.

State of the art and open questions on cathode preparation based on carbon coated lithium iron phosphate

One important component with particular relevance in battery performance is the cathode, being one of the main responsible elements for cell capacity and cycle life. Carbon coated lithium iron phosphate, C-LiFePO4, active material is one of the most promising cathode materials for the next generation of large scale lithium ion battery applications and strong research efforts are being devoted to it, due to its excellent characteristics, including high capacity, ~170 mAh/g, and safety. This review summarizes the main developments on C-LiFePO4 based cathode film preparation and performance. The effect of the binder, conductive additive, relationship between active material-binder-conductive additive and drying step, in the electrode film fabrication and performance is presented and discussed. Finally, after the presentation of the cell types fabricated with C-LiFePO4 active material and their performance, some conclusions and guidelines for further investigations are outlined.

Chemical and physical attributes and calcium, magnesium, potassium, and phosphorus in the soil of murundu fields in Brazil

Fields of murundus (FM) are wetlands that provide numerous ecosystem services. The objectives of this study were to evaluate the chemical [organic carbon (OC), P, K+, Ca2+, Mg2+, Al3+ and H+Al] and physical [texture and bulk density (Bd)] soil attributes and calculate the organic matter (OM) and nutrient stock (P, Ca, Mg, and K) in soils of FM located in the Guapore River basin in Mato Grosso. Thirty-six sampling points were selected, and soil samples were collected from two environments: the murundu and plain area surrounding (PAS). At each sampling point, mini trenches of 0.5 × 0.5 × 0.4 m were opened and disturbed and undisturbed soil samples were collected at depths of 0-0.1, 0.1-0.2, and 0.2-0.4 m. In the Principal Component Analysis the variables H+Al (49%) and OM (4%) were associated with the F1 component and sand content (47%) with the F2 component. The FM had lower pH values and higher concentrations of K+, P, and H+Al than PAS at all depths (p < 0.05). Additionally, FM stocked up to 433, 360, 205, and 11 kg ha-1 of Ca, Mg, K, and P, respectively, for up to a depth of 0.2 m. The murundu stored two times more K and three times more P than that in the PAS. Our results show that the FM has high sand content and Bd greater than 1.5 Mg m-3, high acidity, low OC content, and low nutrient concentrations. Thus, special care must be taken to preserve FM such that human intervention does not trigger environmental imbalances.

Importancia del Ca2+ en la fisiología espermática: modulación de su actividad por progesterona y proteínas del plasma seminal. Importance of calcium in sperm physiology: its regulation by progesterone and proteins from the seminal plasma.

El objetivo general del proyecto es estudiar el efecto de la progesterona y de algunas proteínas del plasma seminal sobre la actividad del Ca2+ en diferentes procesos fisiológicos que ocurren en el espermatozoide, los cuales están estrechamente relacionados con la capacidad fertilizante de esta célula. La progesterona, principal esteroide secretado por las células del cumulus oophorus, ejerce su efecto a través de un receptor no-genómico provocando aumento en el calcio intracelular de los espermatozoides y, consecuentemente, promoviendo la capacitación, la respuesta quimiotáctica y la exocitosis acrosomal. Pese a estas observaciones, los mecanismos a través de los cuales la progesterona estimula fenómenos tan diversos en el espermatozoide son aún desconocidos. Tampoco se conoce con exactitud el papel funcional y los mecanismos de acción de algunas proteínas del plasma seminal que interaccionan y se unen a los espermatozoides, con alta especificidad, durante la eyaculación. Por lo tanto, resulta altamente interesante profundizar los estudios sobre las propiedades funcionales de las proteínas caltrin (calcium transport inhibitor) y ß-microseminoprotein (MSP) del plasma seminal de mamíferos, las cuales responden a las características mencionadas. Los estudios hasta ahora realizados han dado cuenta de que caltrin inhibe la incorporación de Ca2+ extracelular, previene la exocitosis acrosomal espontánea y promueve la unión espermatozoide-zona pelúcida. También hay datos preliminares que sugieren un efecto inhibitorio sobre la movilidad hiperactivada de los espermatozoides. Respecto a MSP, sólo se sabe que inhibe la exocitosis acrosomal espontánea y que su contenido, en el plasma seminal, guarda una relación inversa con la fertilidad. Por todo lo expuesto, se propone estudiar los mecanismos de acción de la progesterona y las proteínas caltrin y MSP sobre los procesos fisiológicos antes indicados. Para ello, se estudiarán las variaciones de Ca2+ intracelular en espermatozoides individuales sometidos a diferentes tratamientos (gradientes de progesterona, capacitación en presencia y ausencia de caltrin y/o MSP, etc.), usando video microscopía de fluorescencia y análisis computarizado de imágenes. También se examinará la influencia de estas moléculas sobre la interacción de gametas y la fertilización.

Metabolismo de fosfolípidos, señal de calcio y sus implicancias en la diferenciación de Trypanosoma cruzi. Phospholipids metabolism, calcium signal and its implications in the differentiation of Trypanosoma cruzi.

Trypanosoma cruzi es un protozoo primitivo agente causal de la enfermedad de Chagas. La transmisión de esta enfermedad depende tanto del desarrollo y de la diferenciación del microorganismo en el intestino del vector. Las diferentes formas del parásito se han adaptado a una serie de condiciones impuestas por los distintos ambientes en donde debió habitar. Esta capacidad de sobrevivir a medios externos tan variados está dada por la diversidad en las vías de transducción de señales en el parásito. T. cruzi se multiplica y diferencia (metaciclogénesis) en el recto de los triatominos. A este nivel, los parásitos se enfrentan a un incremento en la osmolaridad causado por un elevado contenido de NaCl en la orina. En nuestro laboratorio se observó que diferentes estímulos son capaces de producir incrementos en los niveles de IP3 y de Ca2+ intracelular, consecuencia de la activación del ciclo del inositol fosfato, y activación de fosfolipasa D (PLD) y fosfatidilinositol 3 quinasa (PI3K). En un medio carente de Na+ los epimastigotes estimulados con carbacol, mostraron una señal de calcio disminuida mientras que la acumulación de IP3 no se modificó. Además, esta señal se incrementó en presencia de PMA, activador de proteína quinasa C, mientras que la acumulación de IP3 se anuló completamente. Estos resultados indujeron a pensar en un mecanismo alternativo y/o paralelo a IP3 en la liberación de Ca2+, en el cual la presencia de un intercambiador Na+/H+ favorecería la liberación del ion desde organelas acídicas. Es conocido que la señal de calcio es requerida para la metaciclogénesis, y que esta señal es independiente del Ca2+ extracelular (Lammel y col. 1996, Marchesini y col., 2002). De este modo se propone que "los epimastigotes de T. cruzi utilizan como elementos conservados a lo largo de la evolución a los elementos del ciclo del inositol fosfato, uno de los sistemas de transducción de señales más antiguo, para responder a estímulos que inducen la diferenciación del parásito". Por lo tanto, para el desarrollo de este proyecto se propone determinar la presencia de un RcIP3 en epimastigotes y conocer su compromiso en la liberación de Ca2+ desde reservorios intracelulares. Además, establecer si un intercambiador Na+/H+ en membrana de acidocalcisomas estaría relacionado con la señal de calcio intracelular y su posible regulación por proteina quinasa C y A (PKC y PKA, respectivamente). Por otro lado, para dilucidar la implicancia de estos mecanismos en el proceso de metaciclogénesis, se propone estudiar la activación del intercambiador Na+/H+ y la señal de calcio en condiciones de hiperosmolaridad, tal como ocurre en el recto del triatomino. Ademas, ya que el proceso de diferenciación involucra una reorganización de los microtubulos del citoesqueleto se pretende estudiar el compromiso del metabolismo de fosfolípidos y tubulina en procesos que contribuyen a la inducción de la metaciclogenesis. El alcance de los objetivos mencionados ayudará a dilucidar la presencia de componentes tales como RcIP3 y el intercambiador Na+/H+ involucrados en la señalización del ion bivalente. Por otro lado, se espera demostrar que los isotipos de tubulina encontrados en T. cruzi cambien en cantidad relativa y nivel de expresión cuando los epimastigotes sean estimulados con posibles inductores de la diferenciación. Además, se espera observar simultáneamente un aumento en la actividad de dos enzimas relacionadas con la reorganización de microtúbulos: PI-3K y PLD. En tal caso, y para comprobar su implicancia en el proceso, se espera que la inhibición de tales enzimas sea capaz de revertir el efecto producido por los estímulos. Como la PLC se expresa principalmente en las forma epimastigotes mas que en los tripomastigotes (forma infectiva), la señal de Ca2+ inducida por IP3 se relacionaría con la capacidad del parásito para responder a ciertos cambios de pH y osmolaridad que enfrenta el microorganismo en el tracto digestivo del insecto vector.

The production of vermicompost from dairy sludge and its value as a plant growth medium

Dairy sludge generated at Glanbia Ingredients Ltd., Kilkenny has up until now been landspread. This study investigated the feasibility of using earthworms to vermicompost the sludge as an alternative method of treatment. It was found that high levels of ammonia in the sludge led to earthworm fatality but that by manually aerating the sludge the ammonia could be volatilised or by adding zeolite the ammonia could be absorbed, thus solving the problem. In a medium scale trial, the earthworm species Dendrobaena veneta and Eisenia fetida dominated the polyculture. Earthworms grew and generated cocoons during vermicomposting. During vermicomposting no leachate was generated. Nutrient changes took place during vermicomposting. There were high levels of nitrate, increased calcium and sulphate in the vermicomposted dairy sludge. The amount of magnesium, potassium and chloride did not change, while phosphate was undetectable after vermicomposting. The levels of nitrate and phosphate were good indicators of the extent of vermicomposting. The vermicomposted dairy sludge provided improved growth and yields of radishes and barley compared to the dairy sludge and control. Compared to the vermicompost, the dairy sludge provided heavier ryegrass yields and more marigolds with larger flower diameters. Generally, it is the amount of phosphate in dairy sludge that dictates how much can be applied as a fertiliser on land. Vermicomposting reduced the amount of phosphate to an undetectable level but on the other hand created a problem of high nitrate levels. In a pot trial with grass grown in vermicompost the nitrate leached from the vermicompost. In field conditions the leaching of nitrate might occur and could cause an increased risk of contamination of groundwater and watercourses.

Avaliação da capacidade de fixação de fósforo pelo solo

Phosphate "fixation" is the convertion of soluble into insoluble phosphate in the soil. There are many factors conditioning phosphate fixation by soil such as reactions originating less soluble compounds (phosphates of iron, aluminum, calcium, magnesium, etc.), PO4-3 adsorption by the colloidal fraction of soils, PO4-3 absorption by the soil microflora, etc. Certain soils of the state of São Paulo (Brazil) are relatively rich in both iron and aluminum oxides. PO4-3 fixation, using P31 and P32 has been verified by researchers, specially with "Terra Roxa". The known methods for fixation evaluation are conventional as this depends on phosphate solution concentration, pH, time of contact between soil and solution, relation of sample weight to solution volume, shaking time, etc. In this experiment, the following conventional method was used: 4 g of soil were shaken for 15 minutes at 30-40 rpm, in 300 ml Erlenmeyer flask in a Wagner shaking machine, together with 100 ml of 0,03 normal phosphate solution (being 0,01 normal as PO4-3 contributed by H8PO4 and 0,02 normal as PO4-3 from KH2PO4). After shaking it was set aside for 24 hours and then filtered. Phosphate was determined in a suitable aliquot of both the original solution (blank) and the soil extract, by the vanadomolibidic-phosphoric acid method. From phosphate concentration in the blank minus phosphate concentration in the soil stract the rate of fixation by 100 g of soil was calculated. The data obtained show that "Terra Roxa" and "Terra Roxa Misturada" have a fairly high PO4-3 fixation capacity, varying from 10 to 24 milliequivalents of PO4-3 per 100 g of soil.

Mathematical model to analyze the heat transfer in tunnel kilns for burning of ceramics

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2013

Processing and properties of alumina reinforced mullite ceramics

Magdeburg, Univ., Fak. für Maschinenbau, Diss., 2013

Método do EDTA na determinação do cálcio e magnésio "trocável" do solo

This paper describes the determination of exchangeable calcium and magnesium in soil by using ethylenediamine tetracetic acid, after the separation of the principals interferents (iron, aluminum, manganese and phosphate) by using both ammonium hidroxide and ammonium sulfide in only one operation. In order to compare the chelometric and the permanganometric methods for determining exchangeable calcium, five replications of nine soils were analysed by both methods. The accuracy of the determination of exchangeable magnesium in soil was evalueted by means of the recovered magnesium, when the proposed method was applied. The data obtained in both studies allowed to conclude that the technique proposed is good and the accuracy is satisfactory.

Factors affecting phosphate fixation in soils of the state of São Paulo

A laboratory experiment was carried out to study the effects of chemical and physical characteristics of the soil on the phosphate fixing capacity. One hundred samples collected from various localities were at first characterized chemically and their particlesize distribution determined. They were then tested as to their phosphate fixing capacities. The results obtained were statistically analysed by means of both simple linear and multiple correlation. The following conclusions could be drawn: 1. simple linear regression analysis indicated that % C, exchangeable Al+3, CEC, % clay, pH and % sand were the soil characteristics which significantly affected phosphate fixing capacity of São Paulo State soils; 2. multiple linear regression analysis indicated that % C, exchangeable Mg(+2)9 exchangeable- Al+3 and % clay were the soil characteristics which significantly affected the phosphate fixing capacity of São Paulo State soils; 3. the phosphate phonomena fixing as they occur in the soils of the São Paulo State can be best described by the following equation: Y = -2,266 - 3,484 + 3,514 + 5,559 + 1,005 %C Mg+2 Al+3 % clay exchangeable exchangeable 4. phosphate fixation in the soil is affected by the combined effects of both soil chemical and physical characteristics.