Reactive processing methods for functionalisation of polymers and in-situ compatibilisation of poly(ethylene terephthalate)-based blends

One of the main objectives of this study was to functionalise various rubbers (i.e. ethylene propylene copolymer (EP), ethylene propylene diene terpolymer (EPDM), and natural rubber (NR)) using functional monomers, maleic anhydride (MA) and glycidyl methacrylate (GMA), via reactive processing routes. The functionalisation of the rubber was carried out via different reactive processing methods in an internal mixer. GMA was free-radically grafted onto EP and EPDM in the melt state in the absence and presence of a comonomer, trimethylolpropane triacrylate (TRlS). To optinuse the grafting conditions and the compositions, the effects of various paranleters on the grafting yields and the extent of side reactions were investigated. Precipitation method and Soxhlet extraction method was established to purifY the GMA modified rubbers and the grafting degree was determined by FTIR and titration. It was found that without TRlS the grafting degree of GMA increased with increasing peroxide concentration. However, grafting was low and the homopolymerisation of GMA and crosslinking of the polymers were identified as the main side reactions competing with the desired grafting reaction for EP and EPDM, respectively. The use of the tri-functional comonomer, TRlS, was shown to greatly enhance the GMA grafting and reduce the side reactions in terms of the higher GMA grafting degree, less alteration of the rheological properties of the polymer substrates and very little formation of polyGMA. The grafting mechanisms were investigated. MA was grafted onto NR using both thermal initiation and peroxide initiation. The results showed clearly that the reaction of MA with NR could be thermally initiated above 140°C in the absence of peroxide. At a preferable temperature of 200°C, the grafting degree was increased with increasing MA concentration. The grafting reaction could also be initiated with peroxide. It was found that 2,5-dimethyl-2,5-bis(ter-butylproxy) hexane (TIOI) was a suitable peroxide to initiate the reaction efficiently above I50°C. The second objective of the work was to utilize the functionalised rubbers in a second step to achieve an in-situ compatibilisation of blends based on poly(ethylene terephthalate) (PET), in particular, with GMA-grafted-EP and -EPDM and the reactive blending was carried out in an internal mixer. The effects of GMA grafting degree, viscosities of GMAgrafted- EP and -EPDM and the presence of polyGMA in the rubber samples on the compatibilisation of PET blends in terms of morphology, dynamical mechanical properties and tensile properties were investigated. It was found that the GMA modified rubbers were very efficient in compatibilising the PET blends and this was supported by the much finer morphology and the better tensile properties. The evidence obtained from the analysis of the PET blends strongly supports the existence of the copolymers through the interfacial reactions between the grafted epoxy group in the GMA modified rubber and the terminal groups of PET in the blends.

Chemical and physical methods of enhancing the percutaneous absorption of antimicrobial agents

Contrary to previously held beliefs, it is now known that bacteria exist not only on the surface of the skin but they are also distributed at varying depths beneath the skin surface. Hence, in order to sterilise the skin, antimicrobial agents are required to penetrate across the skin and eliminate the bacteria residing at all depths. Chlorhexidine is an antimicrobial agent with the widest use for skin sterilisation. However, due to its poor permeation rate across the skin, sterilisation of the skin cannot be achieved and, therefore, the remaining bacteria can act as a source of infection during an operation or insertion of catheters. The underlying theme of this study is to enhance the permeation of this antimicrobial agent in the skin by employing chemical (enhancers and supersaturated systems) or physical (iontophoresis) techniques. The hydrochloride salt of chlorhexidine (CHX), a poorly soluble salt, was used throughout this study. The effect of ionisation on in vitro permeation rate across the excised human epidennis was investigated using Franz-type diffusion cells. Saturated solutions of CHX were used as donor and the variable studied was vehicle pH. Permeation rate was increased with increasing vehicle pH. The pH effect was not related to the level of ionisation of the drug. The effect of donor vehicle was also studied using saturated solutions of CHX in 10% and 20% ethanol as the donor solutions. Permeation of CHX was enhanced by increasing the concentration of ethanol which could be due to the higher concentration of CHX in the donor phase and the effect of ethanol itself on the membrane. The interplay between drug diffusion and enhancer pretreatment of the epidennis was studied. Pretreatment of the membrane with 10% Azone/PG demonstrated the highest diffusion rate followed by 10% olcic acid/PG pretreatment compared to other pretreatment regimens (ethanol, dimethyl sulfoxide (DMSO), propylene glycol (PG), sodium dodecyl sulphate (SDS) and dodecyl trimethyl ammonium bromide (DT AB). Differential Scanning Calorimetry (DSC) was also employed to study the mode of action of these enhancers. The potential of supersaturated solutions in enhancing percutaneous absorption of CHX was investigated. Various anti-nucleating polymers were screened in order to establish the most effective agent. Polyvinylpyrrolidone (PVP, K30) was found to be a better candidate than its lower molecular weight counterpart (K25) and hydroxypropyl methyleellulose (HPMC). The permeation studies showed an increase in diffusion rate by increasing the degree of saturation. Iontophoresis is a physical means of transdemal drug delivery enhancement that causes an increased penetration of molecules into or through the skin by the application of an electric field. This technique was employed in conjunction with chemical enhancers to assess the effect on CHX permeation across the human epidermis. An improved transport of CHX, which was pH dependant was observed upon application of the current. Combined use of iontophoresis and chemical enhancers further increased the CHX transport indicating a synergistic effect. Pretreatment of the membrane with 10% Azone/PG demonstrated the greatest effect.

Concepts and methods of quantitative assessment of risk to groundwater resources

This work presents a two-dimensional approach of risk assessment method based on the quantification of the probability of the occurrence of contaminant source terms, as well as the assessment of the resultant impacts. The risk is calculated using Monte Carlo simulation methods whereby synthetic contaminant source terms were generated to the same distribution as historically occurring pollution events or a priori potential probability distribution. The spatial and temporal distributions of the generated contaminant concentrations at pre-defined monitoring points within the aquifer were then simulated from repeated realisations using integrated mathematical models. The number of times when user defined ranges of concentration magnitudes were exceeded is quantified as risk. The utilities of the method were demonstrated using hypothetical scenarios, and the risk of pollution from a number of sources all occurring by chance together was evaluated. The results are presented in the form of charts and spatial maps. The generated risk maps show the risk of pollution at each observation borehole, as well as the trends within the study area. This capability to generate synthetic pollution events from numerous potential sources of pollution based on historical frequency of their occurrence proved to be a great asset to the method, and a large benefit over the contemporary methods.

Headspace analysis of smokeless powders: Development of mass calibration methods using microdrop printing for chromatographic and ion mobility spectrometric detection

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03–0.8 ng for the GC-MS and between 0.03–2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.

Headspace Analysis of Smokeless Powders: Development of Mass Calibration Methods using Microdrop Printing for Chromatographic and Ion Mobility Spectrometric Detection

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03 - 0.8 ng for the GC-MS and between 0.03 - 2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.

Analysis methods for meso- and macroporous silicon etching baths

Analysis methods for electrochemical etching baths consisting of various concentrations of hydrofluoric acid (HF) and an additional organic surface wetting agent are presented. These electrolytes are used for the formation of meso- and macroporous silicon. Monitoring the etching bath composition requires at least one method each for the determination of the HF concentration and the organic content of the bath. However, it is a precondition that the analysis equipment withstands the aggressive HF. Titration and a fluoride ion-selective electrode are used for the determination of the HF and a cuvette test method for the analysis of the organic content, respectively. The most suitable analysis method is identified depending on the components in the electrolyte with the focus on capability of resistance against the aggressive HF.

Concentration of human pollution tracers with ionic liquids

The main objective of the present thesis consists on the development of an analytical preconcentration technology for the concomitant extraction and concentration of human pollution tracers from wastewater streams. Due to the outstanding tunable properties of ionic liquids (ILs), aqueous biphasic systems (ABS) composed of ILs can provide higher and more selective extraction efficiencies for a wide range of compounds, being thus a promising alternative to the volatile and hazardous organic solvents (VOCs) typically used. For that purpose, IL-based ABS were employed and adequately characterized as an one-step extraction and concentration technique. The applicability of IL-based ABS was verified by their potential to completely extract and concentrate two representative pharmaceutical pollution tracers, namely caffeine (CAF) and carbamazepine (CBZ), from wastewaters. The low concentration of these persistent pollutants (usually found in μg·dm-3 and ng·dm-3 levels, respectively) by conventional analytical equipment does not permit a proper detection and quantification without a previous concentration step. Preconcentration methods commonly applied are costly, timeconsuming, with irregular recoveries and make use of VOCs. In this work, the ABS composed of the IL tetrabutylammonium chloride ([N4444]Cl) and the salt potassium citrate (K3[C6H5O7]) was investigated while demonstrating to be able to completely extract and concentrate CAF and CBZ, in a single-step, overcoming thus the detection limit of the applied analytical equipment. Finally, the hydrotropic effect responsible for the ability of IL-based ABS to extract and concentrate a wide variety of compounds was also investigated. It was shown that the IL rules the hydrotropic mechanism in the solubility of CAF in aqueous solutions, with an increase in solubility up to 4-fold. Moreover, the proper selection of the IL enables the design of the system that leads to a more enhanced solubility of a given solute in the IL-rich phase, while allowing a better extraction and concentration. IL-based ABS are a promising and more versatile technique, and are straightforwardly envisaged as selective extraction and concentration routes of target micropollutants from wastewater matrices.

Effects of Ageratum Conyzoides on Semen Characteristics and Sperm Morphology in Rats Exposed to Sodium Arsenite

Arsenite is a major environmental toxicant that is well known to cause reproductive injury. The sperm protective potential of Ageratum conyzoides Linn in arsenic-treated rats was carried out in this study taking advantage of the antioxidant constituents and its androgenic activities. Twenty-four male albino rats aged 16 weeks, weighing 225 to 228g were used. They were grouped into 4(A-Da) with each group containing 6 rats. Group A was orally treated with 100mg/kg ethanol leaf extract of Ageratum conyzoides L., daily for 14 days, group B (single oral dose of sodium arsenite 2.5 mg/kg body weight), C (Ageratum conyzoides extract daily for 14 days and sodium arsenite (SA) given on the 14th day) and group D (Propylene glycol as negative control). It was observed that group B had a more lower (p<0.05) percentage motility (26.7±6.67%) when compared across the groups while group A had a significantly higher (p<0.05) mean value (63.3±3.33%). The sperm motility of rats in group D was significantly higher (p<0.05) than groups B and C. This implies that A. conyzoides extract had no adverse effect on the sperm motility of the rats and also ameliorates the adverse effect of arsenite on sperm motility. The mean value obtained for sperm liveability, semen volume and Sperm concentration followed a similar pattern although, the differences were not significant (p>0.05) for semen volume and the Sperm concentration of rats across the groups. The total sperm abnormality obtained across the groups ranges between 10.44 and 14.27% with group B treated with sodium arsenite (SA) having the highest value when compared with groups A and D, although, the differences were not significant (P>0.05). The study concluded that ethanol leaf extract of Ageratum conyzoides has no negative effect on sperm motility, liveability characteristics and morphology and also protected spermatozoa against arsenic reproductive toxicity in wistar strain albino rats..

The effects of acute administration of Chinese aphrodisiacs sold in Blantyre City on sperm characteristics and fertility profile in guinea pigs

Background Chinese aphrodisiacs have become popular remedy for sexual dysfunction and improvement of libido in men in Malawi. However, selling of these drugs seems not to be well regulated. Probably the aphrodisiacs that are currently on the market have unknown efficacy, potency and safety profiles. The aim of this study was to assess the efficacy of imported Chinese aphrodisiacs using guinea pigs as a model. Materials and Methods Two types of drugs were purchased from vendors in Blantyre City. Tonic tea, which was purported to improve erectile function and libido, and sperm multiplier tablets which were claimed to increase the sperm count. The tonic tea was prepared by soaking one tea bag in 100ml boiling water. The tea was cooled and administered to eight male experimental animals in varying doses. Each animal was introduced into a separate cage with a female guinea pig. Sexual behaviour such as mounting, sniffing behind the female were observed and recorded. Each sperm multiplier tablet was dissolved in distilled water and administered to the experimental animals in the morning and evening for seven days. At the end of the treatment, the experimental and control animals were sacrificed, their semen collected and analysed sperm motility, concentration and morphology. Results For the tonic tea, there were no statistical differences between the experimental and the control animals in terms of the number of mountings and sniffing behind the female. The sperm multiplier drug showed statistically significant differences between the experimental and the control animals in terms of the sperm motility (78.24 ± 1.35 vs. 86.54 ± 1.88, p< 0.05), and concentration (54.28 ± 1.24 vs. 67.59 ± 2.12, p<0.05). Conclusion The tonic tea did not show any efficacy in improving erection and libido. The sperm multiplier tablets, purported to increase sperm production, significantly increased the sperm motility, sperm concentration in the treated animals.

Evaluation of faecal sampling methods for the analysis of Giardia sp. in companion animals

Dissertação de Mestrado Integrado em Medicina Veterinária

Effect of supraphysiological dose of Nandrolone Decanoate on the testis and testosterone concentration in mature and immature male rats: A time course study

Background: Most studies on anabolic-androgenic steroids abuse have been done in adult rats, but few data are available to immature. Objective: This study was conducted to assay the effect of Nandrolone Decanoate (ND) on the testis and testosterone concentration in male immature rats compare with mature ones in short and long time. Materials and Methods: 40 mature rats were divided into 4 groups: group A (short term) and group B (long-term) received 10 mg/kg/day ND interaperitoneally for 35 and 70 days, respectively. Group C (control) without any treatment, and group D (vehicle) received dimethyl sulfoxide (DMSO) solution in two periods 35 and 70 days. 40 immature rats were divided into 4 groups same as mature ones. After surgery body weight, testis size, histomorphometry of testis, and serum testosterone level were evaluated. Results: Our results showed that ND decreased the number of Leydig cells in group B (39.9 ±. 919), group A (43.4 ±. 120), and long term (40.6 ±. 299) immature rats, which could result in a reduction of testosterone concentration significantly in all experimental groups except short term mature group. Number of sertoli cells, testis size, and diameter of seminiferous tubules decreased in the long-term immature group. Eventually, the number of sperm was decreased in mature and immature groups, but a severe depletion of sperm was occurred in both mature and immature in long time in comparison to the control group (p< 0.05). Conclusion: This time course study showed that supraphysiological dose of ND may negatively affect the number of Leydig cells, sperm cell, and testosterone concentration of immature rats in the same matter of mature rats. However, the number of sertoli cell, testis size, and seminferous diameter were decreased only in the long immature rats.

Stress Concentration Factor and Fatigue Life Evaluation in offshore tubular KT-Joints

In the last few decades, offshore field has grown fast especially after the notable development of technologies, explorations of oil and gas in deep water and the high concern of offshore companies in renewable energy mainly Wind Energy. Fatigue damage was noticed as one of the main problems causing failure of offshore structures. The purpose of this research is to focus on the evaluation of Stress Concentration Factor and its influence on Fatigue Life for 2 tubular KT-Joints in offshore Jacket structure using different calculation methods. The work is done by using analytical calculations, mainly Efthymiou’s formulations, and numerical solutions, FEM analysis, using ABAQUS software. As for the analytical formulations, the calculations were done according to the geometrical parameters of each method using excel sheets. As for the numerical model, 2 different types of tubular KT-Joints are present where for each model 5 shell element type, 3 solid element type and 3 solid-with-weld element type models were built on ABAQUS. Meshing was assigned according to International Institute of Welding (IIW) recommendations, 5 types of mesh element, to evaluate the Hot-spot stresses. 23 different types of unitary loading conditions were assigned, 9 axial, 7 in-plane bending moment and 7 out-plane bending moment loads. The extraction of Hot-spot stresses and the evaluation of the Stress Concentration Factor were done using PYTHON scripting and MATLAB. Then, the fatigue damage evaluation for a critical KT tubular joint based on Simplified Fatigue Damage Rule and Local Approaches (Strain Damage Parameter and Stress Damage Parameter) methods were calculated according to the maximum Stress Concentration Factor conducted from DNV and FEA methods. In conclusion, this research helped us to compare different results of Stress Concentration Factor and Fatigue Life using different methods and provided us with a general overview about what to study next in the future.

Molecular And Biochemical Characterization Of Caffeine Synthase And Purine Alkaloid Concentration In Guarana Fruit.

Guarana seeds have the highest caffeine concentration among plants accumulating purine alkaloids, but in contrast with coffee and tea, practically nothing is known about caffeine metabolism in this Amazonian plant. In this study, the levels of purine alkaloids in tissues of five guarana cultivars were determined. Theobromine was the main alkaloid that accumulated in leaves, stems, inflorescences and pericarps of fruit, while caffeine accumulated in the seeds and reached levels from 3.3% to 5.8%. In all tissues analysed, the alkaloid concentration, whether theobromine or caffeine, was higher in young/immature tissues, then decreasing with plant development/maturation. Caffeine synthase activity was highest in seeds of immature fruit. A nucleotide sequence (PcCS) was assembled with sequences retrieved from the EST database REALGENE using sequences of caffeine synthase from coffee and tea, whose expression was also highest in seeds from immature fruit. The PcCS has 1083bp and the protein sequence has greater similarity and identity with the caffeine synthase from cocoa (BTS1) and tea (TCS1). A recombinant PcCS allowed functional characterization of the enzyme as a bifunctional CS, able to catalyse the methylation of 7-methylxanthine to theobromine (3,7-dimethylxanthine), and theobromine to caffeine (1,3,7-trimethylxanthine), respectively. Among several substrates tested, PcCS showed higher affinity for theobromine, differing from all other caffeine synthases described so far, which have higher affinity for paraxanthine. When compared to previous knowledge on the protein structure of coffee caffeine synthase, the unique substrate affinity of PcCS is probably explained by the amino acid residues found in the active site of the predicted protein.

Assessment Of The Fixation Of Mandibular Symphysis Fractures Using Conical Cannulated Screws: Mechanical And Photoelastic Tests.

The aim of this study was to use mechanical and photoelastic tests to compare the performance of cannulated screws with other fixation methods in mandibular symphysis fractures. Ten polyurethane mandibles were allocated to each group and fixed as follows: group PRP, 2 perpendicular miniplates; group PLL, 1 miniplate and 1 plate, parallel; and group CS, 2 cannulated screws. Vertical linear loading tests were performed. The differences between mean values were analyzed with the Tukey test. The photoelastic test was carried out using a polariscope. The results revealed differences between the CS and PRP groups at 1, 3, 5, and 10 millimeters of displacement. The photoelastic test confirmed higher stress concentration in all groups close to the mandibular base, whereas the CS group showed it throughout the region assessed. Conical cannulated screws performed well in mechanical and photoelastic tests.