Development and validation of a dissolution test for primaquine/polyethylene oxide matrix tablets

A simple, precise, specific, repeatable and discriminating dissolution test for primaquine (PQ) matrix tablets was developed and validated according to ICH and FDA guidelines. Two UV assaying methods were validated for determination of PQ released in 0.1 M hydrochloric acid and water media. Both methods were linear (R²>0.999), precise (R.S.D.<1.87%) and accurate (97.65-99.97%). Dissolution efficiency (69-88%) and equivalence of formulations (f2) was assessed in different media and apparatuses (basket/100 rpm and paddle/50 rpm) tested. Discriminating condition was 900 mL aqueous medium, basket at 100 rpm and sampling times at 1, 4 and 8 h. Repeatability (R.S.D.<2.71%) and intermediate precision (R.S.D.<2.06%) of dissolution method were satisfactory.

DFT study on low molecular weight α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene and α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene S-oxide bridged derivatives

The equilibrium geometries of α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene (DBDT) and α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene S-oxide (DBDTO) were studied at the DFT level of theory with a standard 6-311G* basis set. The molecular structures of the DBDT series were more planar than the corresponding DBDTO series, as revealed by dihedral angles. The UV-visible absorption calculated at TD-DFT/6-311G* showed two absorption peaks for all the molecules except C=S and C=O bridged molecules. In DBDTOs, C=S and C=O bridged molecules showed three and four absorption peaks, respectively. The DBDTOs had lower band gaps and longer wavelengths compared to the corresponding DBDTs.

Coprecipitation of trace amounts of silicon with aluminum hydroxide and the determination by flame atomic absorption spectrometry

A simple preconcentration method of silicon based on coprecipitation with aluminum hydroxide prior to its flame atomic absorption (FAAS) determination was established. The recovery values of analyte ion was higher than 95%. The parameters including types of hydroxide ion source for precipitation, acid type for dissolution step, amount of aluminum ion as collector, pH, temperature, standing and centrifuge time, and sample volume were optimized for the quantitative recovery of the analyte. The influences of matrix ions were also examined. The relative standard deviation was found to be 3.2%. The limit of detection was calculated as (0.1 mg L-1). The preconcentration factor is 100 for (200 mL) solution. The proposed method was successfully applied for the determination of silicon in some water and alloy samples.

Ni(II), Cu(II), AND Zn(II) COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z)-(3-METHYLPYRIDIN-2- YLEIMINO)METHYL)PHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II), Cu(II), and Zn(II) are described. All three compounds have the general formula [M(L)2(H2O)2], where L = deprotonated phenol in the Schiff base 2-((z)-(3-methylpyridin-2-yleimino)methyl)phenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD), and room temperature magnetic moments. The Cu(II) and Ni(II) complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II) sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature) showed a typical ΔMS = ± 1 transition. The complexes ([M(L)2(H2O)2]) were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.

The Regulation of Skeletal and Cardiac Muscle Blood Flow in Humans. Studies by positron emission tomography with special reference to exercise, adenosine and nitric oxide

Virtually every cell and organ in the human body is dependent on a proper oxygen supply. This is taken care of by the cardiovascular system that supplies tissues with oxygen precisely according to their metabolic needs. Physical exercise is one of the most demanding challenges the human circulatory system can face. During exercise skeletal muscle blood flow can easily increase some 20-fold and its proper distribution to and within muscles is of importance for optimal oxygen delivery. The local regulation of skeletal muscle blood flow during exercise remains little understood, but adenosine and nitric oxide may take part in this process. In addition to acute exercise, long-term vigorous physical conditioning also induces changes in the cardiovasculature, which leads to improved maximal physical performance. The changes are largely central, such as structural and functional changes in the heart. The function and reserve of the heart’s own vasculature can be studied by adenosine infusion, which according to animal studies evokes vasodilation via it’s a_2A receptors. This has, however, never been addressed in humans in vivo and also studies in endurance athletes have shown inconsistent results regarding the effects of sport training on myocardial blood flow. This study was performed on healthy young adults and endurance athletes and local skeletal and cardiac muscle blod flow was measured by positron emission tomography. In the heart, myocardial blood flow reserve and adenosine A_2A receptor density, and in skeletal muscle, oxygen extraction and consumption was also measured. The role of adenosine in the control of skeletal muscle blood flow during exercise, and its vasodilator effects, were addressed by infusing competitive inhibitors and adenosine into the femoral artery. The formation of skeletal muscle nitric oxide was also inhibited by a drug, with and without prostanoid blockade. As a result and conclusion, it can be said that skeletal muscle blood flow heterogeneity decreases with increasing exercise intensity most likely due to increased vascular unit recruitment, but exercise hyperemia is a very complex phenomenon that cannot be mimicked by pharmacological infusions, and no single regulator factor (e.g. adenosine or nitric oxide) accounts for a significant part of exercise-induced muscle hyperemia. However, in the present study it was observed for the first time in humans that nitric oxide is not only important regulator of the basal level of muscle blood flow, but also oxygen consumption, and together with prostanoids affects muscle blood flow and oxygen consumption during exercise. Finally, even vigorous endurance training does not seem to lead to supranormal myocardial blood flow reserve, and also other receptors than A_2A mediate the vasodilator effects of adenosine. In respect to cardiac work, atheletes heart seems to be luxuriously perfused at rest, which may result from reduced oxygen extraction or impaired efficiency due to pronouncedly enhanced myocardial mass developed to excel in strenuous exercise.

Silicon and rice disease management

The element silicon (Si) is not considered an essential nutrient for plant function. Nevertheless, Si is absorbed from soil in large amounts that are several fold higher than those of other essential macronutrients in certain plant species. Its beneficial effects have been reported in various situations, especially under biotic and abiotic stress conditions. The most significant effect of Si on plants, besides improving their fitness in nature and increasing agricultural productivity, is the restriction of parasitism. There has been a considerable amount of research showing the positive effect of Si in controlling diseases in important crops. Rice (Oryza sativa), in particular, is affected by the presence of Si, with diseases such as blast, brown spot and sheath blight becoming more severe on rice plants grown in Si-depleted soils. The hypothesis underlying the control of some diseases in both mono- and di-cots by Si has been confined to that of a mechanical barrier resulting from its polymerization in planta. However, some studies show that Si-mediated resistance against pathogens is associated with the accumulation of phenolics and phytoalexins as well as with the activation of some PR-genes. These findings strongly suggest that Si plays an active role in the resistance of some plants to diseases rather than forming a physical barrier that impedes penetration by fungal pathogens.

Preparation and electrochemical characterization of Pt nanoparticles dispersed on niobium oxide

Electrodes consisting of Pt nanoparticles dispersed on thin films of niobium oxide were prepared onto titanium substrates by a sol-gel method. The physical characterization of these electrodes was carried out by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. The mean size of the Pt particles was found to be 10.7 nm. The general aspects of the electrochemical behavior were studied by cyclic voltammetry in 1 mol L-1 HClO4 aqueous solution. The response of these electrodes in relation to the oxidation of formaldehyde and methanol in acidic media was also studied.

The Li+, Na+ and K+ ion exchange reaction process on the surface of mixed oxide SiO2/TiO2/Sb2O5 surface prepared by the sol-gel processing method

The porous mixed oxide SiO2/TiO2/Sb2O5 obtained by the sol-gel processing method presented a good ion exchange property and a high exchange capacity towards the Li+, Na+ and K+ ions. In the H+/M+ ion exchange process, the H+ / Na+ could be described as presenting an ideal character. The ion exchange equilibria of Li+ and K+ were quantitatively described with the help of the model of fixed tetradentate centers. The results of simulation evidence that for the H+ / Li+ exchange the usual situation takes place: the affinity of the material to the Li+ ions is decreased with increasing the degree of ion exchange. On the contrary, for K+ the effects of positive cooperativity, that facilitate the H+ / K+ exchange, were revealed.

Adsorption of hidrogen peroxide on the surface of silica - titania mixed oxide obtained by the sol-gel processing method

This work describes the sol-gel mixed oxide SiO2/TiO2 property, ST, as prepared, and submitted to heat treatment a 773 K, STC. SEM and EDS images show, within magnification used, a uniform distribution of the TiO2 particles in SiO2/TiO2 matrix. Both, ST and STC adsorb hydrogen peroxide on the surface and through EPR and UV-Vis diffuse reflectance spectra, it was possible to conclude that the species on the surface is the peroxide molecule attached to the Lewis acid site of titanium particle surface, alphaTi(H2O2)+. As the material is very porous, presumably the hydrogen peroxide molecule is confined in the matrix pores on the surface, a reason why the adsorbed species presents an exceptional long lived stability.

Model based study of a calcium oxide looping process for post-combustion carbon dioxide capture

Calcium oxide looping is a carbon dioxide sequestration technique that utilizes the partially reversible reaction between limestone and carbon dioxide in two interconnected fluidised beds, carbonator and calciner. Flue gases from a combustor are fed into the carbonator where calcium oxide reacts with carbon dioxide within the gases at a temperature of 650 ºC. Calcium oxide is transformed into calcium carbonate which is circulated into the regenerative calciner, where calcium carbonate is returned into calcium oxide and a stream of pure carbon dioxide at a higher temperature of 950 ºC. Calcium oxide looping has proved to have a low impact on the overall process efficiency and would be easily retrofitted into existing power plants. This master’s thesis is done in participation to an EU funded project CaOling as a part of the Lappeenranta University of Technology deliverable, reactor modelling and scale-up tools. Thesis concentrates in creating the first model frame and finding the physically relevant phenomena governing the process.

Lanthanum based high surface area perovskite-type oxide and application in CO and propane combustion

The perovskite-type oxides using transition metals present a promising potential as catalysts in total oxidation reaction. The present work investigates the effect of synthesis by oxidant co-precipitation on the catalytic activity of perovskite-type oxides LaBO3 (B= Co, Ni, Mn) in total oxidation of propane and CO. The perovskite-type oxides were characterized by means of X-ray diffraction, nitrogen adsorption (BET method), thermo gravimetric and differential thermal analysis (ATG-DTA) and X-ray photoelectron spectroscopy (XPS). Through a method involving the oxidant co-precipitation it's possible to obtain catalysts with different BET surface areas, of 33-44 m²/g, according the salts of metal used. The characterization results proved that catalysts have a perovskite phase as well as lanthanum oxide, except LaMnO3, that presents a cationic vacancies and generation for known oxygen excess. The results of catalytic test showed that all oxides have a specific catalytic activity for total oxidation of CO and propane even though the temperatures for total conversion change for each transition metal and substance to be oxidized.

Soluble tissue sugar content and leaf blast severity in response to the application of calcinated serpentinite as a silicon source in irrigated rice

A field experiment conducted with the irrigated rice cultivar BRS Formoso, to assess the efficiency of calcinated serpentinite as a silicon source on grain yield was utilized to study its effect on leaf blast severity and tissue sugar levels. The treatments consisted of five rates of calcinated serpentinite (0, 2, 4, 6, 8 Mg.ha-1) incorporated into the soil prior to planting. The leaf blast severity was reduced at the rate of 2.96% per ton of calcinated serpentinite. The total tissue sugar content decreased significantly as the rates of serpentinite applied increased (R² = 0.83). The relationship between the tissue sugar content and leaf blast severity was linear and positive (R² = 0.81). The decrease in leaf blast severity with increased rates of calcinated serpentinite was also linear (R²= 0.96) and can be ascribed to reduced sugar level.

Polymer surface modification by atomic layer deposition

Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.

Porous silicon optical filters in gas sensing applications

In this thesis, the gas sensing properties of porous silicon-based thin-film optical filters are explored. The effects of surface chemistry on the adsorption and desorption of various gases are studied in detail. Special emphasis is placed on investigating thermal carbonization as a stabilization method for optical sensing applications. Moreover, the possibility of utilizing the increased electrical conductivity of thermally carbonized porous silicon for implementing a multiparametric gas sensor, which would enable simultaneous monitoring of electrical and optical parameters, is investigated. In addition, different porous silicon-based optical filter-structures are prepared, and their properties in sensing applications are evaluated and compared. First and foremost, thermal carbonization is established as a viable method to stabilize porous silicon optical filters for chemical sensing applications. Furthermore, a multiparametric sensor, which can be used for increasing selectivity in gas sensing, is also demonstrated. Methods to improve spectral quality in multistopband mesoporous silicon rugate filters are studied, and structural effects to gas sorption kinetics are evaluated. Finally, the stability of thermally carbonized optical filters in basic environments is found to be superior in comparison to other surface chemistries currently available for porous silicon. The results presented in this thesis are of particular interest for developing novel reliable sensing systems based on porous silicon, e.g., label-free optical biosensors.

Specific surface charging of latex, clay and mineral oxide particles in aqueous, non-aqueous and mixed solvent systems

En djupare förståelse för växelverkan mellan partiklar i suspensioner är av betydelse för utvecklingen av en mängd olika industriella produkter och processer. Till exempel kan nämnas pigmentbaserade färger och bestrykning av papper. Genom att öka kontrollbarheten kan dessa lättare optimeras för att uppnå förbättrade produktegenskaper och/eller sänkta produktionskostnader. Av stor betydelse är även en förbättrad möjlighet att minska produktens miljöpåverkan. I avhandlingen studerades jonstyrkan och jonspecificiteten inverkan i olika akvatiska suspensioner innehållande olika elektrolyter. De partiklar som avhandlingen omfattade var metalloxider, leror samt latex. Jonstyrkan studerades från låga (c <10-3M) till och med höga (c> 10-1M) elektrolytkoncentrationer. Vid koncentrationer under 0.1 M var partikelladdningen styrd av pH och jonstyrkan. Vid högre elektrolytkoncentrationer påverkade även jonspecificiteten partikelladdningen. Jonspecificiteten arrangerades i fenomenologiska serier funna i litteraturen samt med Born modellen definierad i termodynamiken. Överraskande höga absoluta zeta-potential värden erhölls vid höga elektrolytkoncentrationer vilket visar att den elektrostatiska repulsionen har betydelse även vid dessa förhållanden. Vidare studerades titanoxidsuspensioners egenskaper i akvatiska, icke-akvatiska och blandade lösningssystem under varierande koncentration av oxal- och fosfatsyra. Vid lågt vatteninnehåll studerades även suspensioner med svavelsyra. Konduktiviteten i suspensioner med lågt vatteninnehåll ökade med tillsatt oxal- eller fosforsyra vilket är en omvänd effekt jämfört med svavelsyra eller akvatiska suspensioner. Den omvända effekten skiftade gradvis tillbaka med ökad vatteninnehåll. En analys av suspensionernas adsorption i höga etanolkoncentrationer gjordes med konduktiviteten, pH och zeta-potentialen. Viskositet studerades och applicerades framgångsrikt i viskositet/ytladdningsmodeller utvecklade för akvatiska suspensioner.