Metacognitive presence in asynchronous online learning environments : self, mutual and hetero-regulation

Peer-reviewed

Tautomerism and Fragmentation of Biologically Active Hetero Atom (O, N)-Containing Acyclic and Cyclic Compounds Under Electron Ionization

In this thesis a total of 86 compounds containing the hetero atoms oxygen and nitrogen were studied under electron ionization mass spectrometry (EIMS). These compounds are biologically active and were synthesized by various research groups. The main attention of this study was paid on the fragmentations related to different tautomeric forms of 2- phenacylpyridines, 2-phenacylquinolines, 8-aryl-3,4-dioxo-2H,8H-6,7-dihydroimidazo- [2,1-c][1,2,4]triazines and aryl- and benzyl-substituted 2,3-dihydroimidazo[1,2-a]pyrimidine-5,7-(1H,6H)-diones. Also regio/stereospecific effects on fragmentations of pyrrolo- and isoindoloquinazolinones and naphthoxazine, naphthpyrrolo-oxazinone and naphthoxazino-benzoxazine derivatives were screened. Results were compared with NMR data, when available. The first part of thesis consists of theory and literature review of different types of tautomerism and fragmentation mechanisms in EIMS. The effects of tautomerism in biological systems are also briefly reviewed. In the second part of the thesis the own results of the author, based on six publications,are discussed. For 2-phenacylpyridines and 2-phenacylquinolines the correlation of different Hammett substituent constants to the relative abundances (RA) or total ion currents (% TIC) of selected ions were investigated. Although it was not possible to assign most of the ions formed unambiguously to the different tautomers, the linear fits of their RAs and % TICs can be related to changing contributions of different tautomeric forms. For dioxoimidazotriazines and imidazopyrimidinediones the effects of substituents were rather weak. The fragmentations were also found useful for obtaining structural information. Some stereoisomeric pairs of pyrrolo- and isoindoloquinazolines and regiomeric pairs of naphtoxazine derivatives showed clear differences in thir mass spectra. Some mechanisms are suggested for their fragmentations.

Extension of the impedance field method to the noise analysis of a semiconductor junction: Analytical approach

We present an analytical procedure to perform the local noise analysis of a semiconductor junction when both the drift and diffusive parts of the current are important. The method takes into account space-inhomogeneous and hot-carriers conditions in the framework of the drift-diffusion model, and it can be effectively applied to the local noise analysis of different devices: n+nn+ diodes, Schottky barrier diodes, field-effect transistors, etc., operating under strongly inhomogeneous distributions of the electric field and charge concentration

Extension of the impedance field method to the noise analysis of a semiconductor junction: Analytical approach

We present an analytical procedure to perform the local noise analysis of a semiconductor junction when both the drift and diffusive parts of the current are important. The method takes into account space-inhomogeneous and hot-carriers conditions in the framework of the drift-diffusion model, and it can be effectively applied to the local noise analysis of different devices: n+nn+ diodes, Schottky barrier diodes, field-effect transistors, etc., operating under strongly inhomogeneous distributions of the electric field and charge concentration

Highly selective transport of mercury(II) ion through a bulk liquid membrane

In this work carrier-facilitated transport of mercury(II) against its concentration gradient from aqueous 0.04 M hydrochloric acid solution across a liquid membrane containing isopropyl 2-[(isopropoxycarbothiolyl)disulfanyl]ethane thioate (IIDE) as the mobile carrier in chloroform has been investigated. Sodium thiocyanate solution (1.6 M) was the most efficient receiving phase agent among several aqueous reagents tested. Various parameters such as investigated. Under optimum conditions the transport of Hg(II) across the liquid membrane is more than 97% after 2.5 h. The carrier, IIDE, selectively and efficiently could able to transport Hg (II) ions in the presence of other associated metal ions in binary systems.

Simultaneous determination of gemifloxacin and diuretics in bulk, pharmaceutical dosage forms and human serum by RP-HPLC

An isocratic reversed phase high-performance liquid chromatographic (RP-HPLC) method has been developed for the simultaneous determination of gemifloxacin and diuretics (hydrochlorothiazide and furosemide) in bulk, dosage formulations and human serum at 232 nm. Chromatographic separation was achieved on Purospher Start C18 (250 mm x 4.6 mm, 5 µm) column using mobile phase, methanol: water: acetonitrile (70:25:5 v/v/v) adjusted to pH 3.0 via phosphoric acid 85% having flow rate of 0.8 mL min -1 at room temperature. Calibration curves were linear over range of 0.5-10 µg mL -1 with a correlation coefficient ± 0.999. LOD and LOQ were in the ranges of 0.75-2.56 µg mL -1. Intra and inter-run precision and accuracy results were 98.26 to 100.9.

Spectrophotometric and spectrofluorimetric determination of some drugs containing secondary amino group in bulk drug and dosage forms via derivatization with 7-Chloro-4-Nitrobenzofurazon

Sensitive and selective spectrophotometric and spectrofluorimetric methods have been developed for determination of some drugs such as Pramipexole, Nebivolol, Carvedilol, and Eletriptan, which commonly contain secondary amino group. The subject methods were developed via derivatization of the secondary amino groups with 7-Chloro-4-Nitrobenzofurazon in borate buffer where a yellow colored reaction product was obtained and measured spectrophotometrically or spectrofluorimetrically. Concentration ranges were found as 2.0 to 250 μg mL-1 and 0.1 to 3.0 μg mL-1, for spectrophotometric and spectrofluorimetric study, respectively. The described methods can be easily applied by the quality control laboratories in routine analyses of these drugs in pharmaceutical preparations.

Simple and sensitive spectrophotometric methods for the analysis of mesalamine in bulk and tablet dosage forms

Three simple, sensitive, economical and reproducible spectrophotometric methods (A, B and C) are described for determination of mesalamine in pure drug as well as in tablet dosage forms. Method A is based on the reduction of tungstate and/or molybdate in Folin Ciocalteu's reagent; method B describes the reaction between the diazotized drug and α-naphthol and method C is based on the reaction of the drug with vanillin, in acidic medium. Under optimum conditions, mesalamine could be quantified in the concentration ranges, 1-30, 1-15 and 2-30 µg mL-1 by method A, B and C, respectively. All the methods have been applied to the determination of mesalamine in tablet dosage forms. Results of analysis are validated statistically.

Theoretical investigations of the bulk modulus in the tetra-cubic transition of PbTiO3 material

Resulting from ion displacement in a solid under pressure, piezoelectricity is an electrical polarization that can be observed in perovskite-type electronic ceramics, such as PbTiO3, which present cubic and tetragonal symmetries at different pressures. The transition between these crystalline phases is determined theoretically through the bulk modulus from the relationship between material energy and volume. However, the change in the material molecular structure is responsible for the piezoelectric effect. In this study, density functional theory calculations using the Becke 3-Parameter-Lee-Yang-Parr hybrid functional were employed to investigate the structure and properties associated with the transition state of the tetragonal-cubic phase change in PbTiO3 material.

Current-phase relation in graphene Josephson junction

In this thesis, we present the results of high-frequency measurements on superconductor-graphene-superconductor junctions. We obtained the relation between the supercurrent through the junction and the superconducting phase. The relation allowed us to extract true critical current and to determine the transport regime of graphene in our SGS-junction samples at the Dirac point and away from it. An experimental temperature dependence of the current-phase relation is presented. We have calculated theoretical supercurrent-phase relation in the case of ballistic and diffusive junction. For the diffusive case, we have considered short and long limits where the coherence length is larger or smaller than the sample length, respectively.

Argentimetric assay of ranitidine in bulk drug and in dosage forms

Two simple, rapid and cost-effective methods based on titrimetric and spectrophotometric techniques are described for the assay of RNH in bulk drug and in dosage forms using silver nitrate, mercury(II)thiocyanate and iron(III)nitrate as reagents. In titrimetry, an aqueous solution of RNH is treated with measured excess of silver nitrate in HNO3 medium, followed by determination of unreacted silver nitrate by Volhard method using iron(III) alum indicator. Spectrophotometric method involve the addition a known excess of mercury(II)thiocyanate and iron(III)nitrate to RNH, followed by the measurement of the absorbance of iron(III)thiocyante complex at 470 nm. Titrimetric method is applicable over 4-30 mg range and the reaction stoichiometry is found to be 1:1 (RNH: AgNO3). In the spectrophotometric method, the absorbance is found to increase linearly with concentration of RNH which is corroborated by the correlation coefficient of 0.9959. The system obey Beer's law for 5-70 µg mL-1. The calculated apparent molar absorptivity and sandell sensitivity values are found to be 3.27 ´ 10³ L mol-1 cm-1, 0.107 µg cm-2 respectively. The limits of detection and quantification are also reported for the spectrophotometric method. Intra-day and inter-day precision and accuracy of the methods were evaluated as per ICH guidelines. The methods were successfully applied to the assay of RNH in formulations and the results were compared with those of a reference method by applying Student's t and F-tests. No interference was observed from common pharmaceutical excipients. The accuracy of the methods was further ascertained by performing recovery tests by standard addition method.

Simple and sensitive spectrophotometric methods for the determination of acebutolol hydrochloride in bulk sample and pharmaceutical preparations

A direct, extraction-free spectrophotometric method has been developed for the determination of acebutolol hydrochloride (ABH) in pharmaceutical preparations. The method is based on ion-pair complex formation between the drug and two acidic dyes (sulphonaphthalein) namely bromocresol green (BCG) and bromothymol blue (BTB). Conformity to Beer's law enabled the assay of the drug in the range of 0.5-13.8 µg mL-1 with BCG and 1.8-15.9 µg mL-1 with BTB. Compared with a reference method, the results obtained were of equal accuracy and precision. In addition, these methods were also found to be specific for the analysis of acebutolol hydrochloride in the presence of excipients, which are co-formulated in the drug.

Sensitive spectrophotometric determination of lamotrigine in bulk drug and pharmaceutical formulations using bromocresol green

Two new, simple, rapid and reproducible spectrophotometric methods have been developed for the determination of lamotrigine (LMT) both in pure form and in its tablets. The first method (method A) is based on the formation of a colored ion-pair complex (1:1 drug/dye) of LMT with bromocresol green (BCG) at pH 5.02±0.01 and extraction of the complex into dichloromethane followed by the measurement of the yellow ion-pair complex at 410 nm. In the second (method B), the drug-dye ion-pair complex was dissolved in ethanolic potassium hydroxide and the resulting base form of the dye was measured at 620 nm. Beer's law was obeyed in the concentration range of 1.5-15 µg mL-1 and 0.5-5.0 µg mL-1 for method A and method B, respectively, and the corresponding molar absorptivity values are 1.6932 x 10(4) and 3.748 x 10(4) L mol-1cm-1. The Sandell sensitivity values are 0.0151 and 0.0068 µg cm-2 for method A and method B, respectively. The stoichiometry of the ion-pair complex formed between the dug and dye (1:1) was determined by Job's continuous variations method and the stability constant of the complex was also calculated. The proposed methods were applied successfully for the determination of drug in commercial tablets.

Mössbauer spectra of iron oxides in the bulk and nanocrystalline states

Magnetic nanoparticles are very important in modern industry. These particles are used in many different spheres of life. Nanoparticles have unusual physical and chemical properties connected both with quantum dimensional effects and with the increased role of the surface atoms. Most clearly the difference between the properties of bulk materials and nanoparticles can be seen in the magnetic properties of these materials. The most typical magnetic properties of nanomaterials are superparamagnetism with the size of the cluster from 1 to 10 nm; single-domain magnetic state of nanoclusters and nanostructures up to 20 nm; magnetization processes connected with magnetic cluster ordering and with its forms and sizes; quantum magnetic tunneling effects when magnetization changes by jumps and giant magnetoresistance effects. For research of the magnetic properties of iron-containing nanostructures, it is convenient to apply Mӧssbauer spectroscopy. In this work a number of nano-sized samples of iron oxides were examined by Mössbauer spectroscopy. The Mössbauer spectra of nanoparticles with various sizes were obtained. Mössbauer spectra of iron oxide nanoparticles were compared with the spectra of bulk samples. It was shown how the spectra of iron oxide nanoparticles change depending on the particle sizes.