Introduction: Venous disease impairs the quality of life, necessitates time off work and causes venous ulcers. The focus of this thesis is to explore strategies to prevent chronic venous insufficiency (CVI) and venous ulceration. Aims 1. To identify a population at risk of developing venous ulcers 2. To study the pressure profile required by elastic stockings to halve transit venous time 3. To explore the role of compression following ankle fracture Methods: Data was collected from 231 patients with venous ulcers and age and sex matched 210 controls to identify risk factors for venous ulceration. Univariate and multivariate analysis of potential risk factors was undertaken to identify those that independently predict this risk. After identifying the population at risk, prophylactic strategies were developed. The effect of Engineered Compression Stockings (ECS) delivering 15mmHg, 25mmHg and 35mmHg pressure at the ankle on the calf venous transit time and volume was measured to determine the ideal pressure profile required to halve transit venous time, which should be appropriate for DVT prophylaxis. A dorsal foot vein was cannulated in 15 healthy volunteers with no venous disease. The transit time (secs) for ultrasound contrast from a foot vein to the popliteal vein was measured using duplex ultrasound. Calf volumes were recorded by water displacement. ECS delivering 25mmHg of pressure around the ankle were compared with no compression in a randomized controlled trial (RCT) in 90 patients within 72 hours of ankle fracture. Patients were randomised to either i) ECS and air-cast boot or ii) a liner and air-cast boot and were followed at 2, 4, 8, 12 weeks and 6 months. The primary outcome was functional recovery measured using the Olerud Molander Ankle Score (OMAS). Secondary outcomes were i) The American Orthopaedic Foot and Ankle Score (AOFAS), ii) SF12v2 Quality of Life score (QoL), iii) pain, and iv) frequency of DVT. Results The risk factors significantly associated with venous ulceration on multivariate analysis included a history of Deep Vein Thrombosis (DVT), phlebitis, hip replacement, poor mobility, weight/kg>100Kg, varicose veins (VV), family history of VV and weight (kg) between 75-100kg. A simple diagnostic scoring system was derived from this regression analysis with scores of . 3 predicting a 6.7% annual risk and of < 1 a 0.6% risk. Mean transit time without compression was 35, 32 and 33 secs while standing, sitting and lying. Transit time was consistently halved by ECS delivering 25mmHg to 14, 13 and 14 secs respectively (p<0.001). Mean leg volume whilst standing was reduced significantly from 3447ml with no ECS to 3259ml, 3161ml and 3067ml with ECS applying 15, 25 and 35mmHg respectively (p<0.001). ECS in ankle fracture patients reduced ankle swelling at all time points and significantly improved mean OMAS score at six months to 98 compared with 67 for the liner (p<0.001). AOFAS and SF12v2 scores were also significantly improved (p<0.001, p= 0.016). Of 86 patients with duplex imaging at four weeks, only five (12%) of the 43 ECS patients had a DVT compared with 10 (23%) of the 43 controls (p= 0.26). Conclusions: The risk score for venous ulcers will allow us to undertake RCTs on the prevention of leg ulceration. The pressure profile required to halve transit venous time is 25mmHg. The frequency of asymptomatic DVT following ankle fracture is sufficient to justify prophylaxis. Compression has a potential role in the management of ankle fractures by improving functional outcome and QoL. These studies facilitate research into the prevention of venous disease.

Metal nanoparticles have been widely used for many catalytic and electrocatalytic applications due to their larger surface area-to-volume ratios and higher densities of active sites compared to bulk materials. This has resulted in much interest in understanding the electrocatalytic behavior of metal nanoparticles with respect to their structure. However, most research on this topic has employed collections of nanoparticles. Due to difficulties in controlling and characterizing particle loading and interparticle distance in nanoparticle ensembles, single nanoparticles studies have recently become a topic of great interest. In this study, a soft nitriding technique was applied to chemical vapor-deposited carbon ultramicroelectrodes (UMEs) in order to immobilize ligand-free AuNPs onto the carbon substrate. The feasibility of this method is geared toward studying the properties of single AuNPs immobilized onto carbon nanoelectrodes. The ligand-free AuNPs immobilized onto the nitrided carbon UMEs were highly electrocatalytic toward methanol oxidation.

Metal-halide perovskites have attracted intense research endeavors because of their excellent optical and electronic properties. Different kinds of electronic and optoelectronic devices have been fabricated using perovskites. A feasible approach to utilize these properties in real device applications with improved performance and new functionalities is by fabricating heterostructures with extraneous materials. We have developed mixed-dimensional heterostructure systems using three-dimensional (3D) metal-halide perovskites and different types of different two-dimensional (2D) materials, including semimetal graphene, semiconducting phosphorus-doped graphitic-C3N4 sheets (PCN-S), and plasmonic Nb2CTx MXenes. First, selective growth of single-crystalline MAPbBr3 platelets on monolayer graphene by chemical vapor deposition (CVD) is achieved to prepare the MAPbBr3/graphene heterostructures. P-type doping from MAPbBr3 is observed in the monolayer graphene with a decreased work function of 272 meV under illumination. The photoresponse of the fabricated phototransistor heterostructure verifies the enhanced p-type character in graphene. Such kind of charge transfer can be used to improve device performance. Then, bulk-heterojunctions made of MAPbI3-xClx and PCN-S are prepared in solution. The matched band diagram and the midgap states in PCN-S present a convenient and efficient approach to reduce the dark current and increase the photocurrent of the as-fabricated photodetectors. As a result, the on/off ratio increases from 103 to 105, and the detectivity is up to 1013 Jones with an order of magnitude enhancement compared to the perovskite-only device. Last, plasmonic Nb2CTx MXenes and MAPbI3 heterostructures are prepared for photodiodes to broaden the detection band to near-infrared (NIR) lights. The use of the perovskite layer expanded the operation of the diode to the visible range while suppressing the dark current of the NIR-absorbing Nb2CTx layer. The fabricated photodiode reveals a detectivity of 0.25 A/W with a linear dynamic range of 96 dB in the visible region. In the NIR region, the device demonstrates an increased on/off ratio from less than 2 to near 103 and much faster response times of less than 30 ms. The improved performance is attributed to the passivation of the MAPbI3/Nb2CTx interface.

Atomic/plasma polymerization technology is widely used in various technical fields. This work is focused to use the PE-CVD technology in the field of formation of interphase and adhesive layers, which are developed into layered nanostructures. To ensure reproducible chemical and physical properties of the materials, the deposition process was monitored by mass spectrometry. Vapours of the pure tetravinylsilane, or a mixture of these vapours with oxygen, was used as a precursor for atomic polymerization, which results in the thin films with a large variability of properties. Physical and chemical properties were varied by the effective power delivered to the plasma discharge. The deposited films were analyzed from different perspectives using several methods (in situ spectroscopic ellipsometry, FTIR, nanoindentation, AFM). The removal of hydrogen atoms from the carbon-silicon network results in increased crosslinking of the material, which controls the mechanical and optical properties of the deposited layers. From the precisely defined a-CSi:H and a-CSiO:H materials, layered nanostructures composed of 3 and 7 individual layers was subsequently constructed. These nanostructures were analyzed by XPS and RBS to determine the atomic concentrations of carbon, silicon, oxygen and their binding states.

The thesis is focused on the study of properties of GaN nanocrystals and Ga structures on the surface of silicon and graphene substrate. In the theoretical part of this thesis, the basic properties of Ga/GaN and graphene are described, as well as their applications or connection of both structures together in different devices. The ability of metal nanoparticles to enhance not only photoluminescence, due to the interaction of the material with surface plasmons, is also shown in several examples. The experimental part of the work first deals with the production and characterization of graphene sheets prepared by Chemical Vapor Deposition. Ga/GaN growth on both types of substrates was performed in a UHV chamber using an effusion cell for Ga deposition and an atomic ion source for nitridation. Prepared structures were characterized using various methods (XPS, SEM, AFM, Raman spectroscopy or photoluminescence). In the last step, GaN nanocrystals were coated with Ga islands to study the photoluminescence enhancement.

This diploma thesis is focused on preparation and characterization of parylene C barrier properties. The layers were prepared by chemical vapour deposition (CVD). The interest in characterization of those layers is huge mainly because of their possible use in museology for the protection of the museum archives against the corrosion. Chlorinated dimer of para-xylylene was used as a precursor. Polypropylene foils, metal sheets and silica wafers were used as tested substrates for thin film preparation. Polypropylene foils were used for oxygen transmission rate measurements, metal sheets were used for corrosion tests and silica wafers were used for Fourier transform infrared spectroscopy (FTIR), confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM) and stylus profilometry.

abstract: Sn-based group IV materials such as Ge1-xSnx and Ge1-x-ySixSny alloys have great potential for developing Complementary Metal Oxide Semiconductor (CMOS) compatible devices on Si because of their tunable band structure and lattice constants by controlling Si and/or Sn contents. Growth of Ge1-xSnx binaries through Molecular Beam Epitaxy (MBE) started in the early 1980s, producing Ge1-xSnx epilayers with Sn concentrations varying from 0 to 100%. A Chemical Vapor Deposition (CVD) method was developed in the early 2000s for growing Ge1-xSnx alloys of device quality, by utilizing various chemical precursors. This method dominated the growth of Ge1-xSnx alloys rapidly because of the great crystal quality of Ge1-xSnx achieved. As the first practical ternary alloy completely based on group IV elements, Ge1-x-ySixSny decouples bandgap and lattice constant, becoming a prospective CMOS compatible alloy. At the same time, Ge1-x-ySixSny ternary system could serve as a thermally robust alternative to Ge1-ySny binaries given that it becomes a direct semiconductor at a Sn concentration of 6%-10%. Ge1-x-ySixSny growths by CVD is summarized in this thesis. With the Si/Sn ratio kept at ~3.7, the ternary alloy system is lattice matched to Ge, resulting a tunable direct bandgap of 0.8-1.2 eV. With Sn content higher than Si content, the ternary alloy system could have an indirect-to-direct transition, as observed for Ge1-xSnx binaries. This thesis summarizes the development of Ge1-xSnx and Ge1-x-ySixSny alloys through MBE and CVD in recent decades and introduces an innovative direct injection method for synthesizing Ge1-x-ySixSny ternary alloys with Sn contents varying from 5% to 12% and Si contents kept at 1%-2%. Grown directly on Si (100) substrates in a Gas-phase Molecular Epitaxy (GSME) reactor, both intrinsic and n-type doped Ge1-x-ySixSny with P with thicknesses of 250-760 nm have been achieved by deploying gas precursors Ge4H10, Si4H10, SnD4 and P(SiH3)3 at the unprecedented low growth temperatures of 190-220 °C. Compressive strain is reduced and crystallinity of the Ge1-x-ySixSny epilayer is improved after rapid thermal annealing (RTA) treatments. High Resolution X-ray Diffraction (HR-XRD), Rutherford Backscattering Spectrometry (RBS), cross-sectional Transmission Electron Microscope (XTEM) and Atomic Force Microscope (AFM) have been combined to characterize the structural properties of the Ge1-x-ySixSny samples, indicating good crystallinity and flat surfaces. / Dissertation/Thesis / Masters Thesis Chemistry 2019

Magister Pharmaceuticae - MPharm / Cardiovascular diseases (CVDs) such as ischaemic heart diseases, heart failure and stroke remain a major cause of death globally. Various deep-rooted factors influence CVD development; these include but are not limited to elevated blood lipids, high blood pressure, obesity and diabetes. A considerable number of proteins are involved directly and indirectly in the transport, maintenance and elimination of plasma lipids, including high and low-density lipoprotein cholesterol (HDL-C and LDL-C). There are several mechanisms involved in the removal of LDL particles from systemic circulation. One such mechanism is associated with the gene that encodes proprotein convertase subtilisin/kexin type 9 (PCSK9), which has become an exciting therapeutic target for the reduction of residual risk of CVDs. Currently, statins are the mainstay treatment to reduce LDL-C, and a need exists to further develop more effective LDL-C-lowering drugs that might supplement statins. This study was aimed at contributing to the generation of knowledge regarding the effect of niacin in reducing LDL levels through PCSK9 interaction.

Abstract: Cardiovascular disease (CVD) is the leading cause of death in the United States (US). One of the most important things primary care providers (PCP) can do to prevent CVD is using primary prevention treatments. In the practice where the project was implemented, a standardized process was not in place for identifying at-risk patients. Without this, there is no way to identify if providers were adequately assessing patients for atherosclerotic cardiovascular disease (ASCVD) risk by considering their risk-enhancing factors. One way to identify appropriate patients is by completing ASCVD risk calculation using the ASCVD Risk Estimator Plus from the American College of Cardiology and the American Heart Association. In addition, 2018 Guidelines for Cholesterol Management recommend ASCVD risk calculation on all patients 40-79. The use of this tool is free to both patients and providers through a website or mobile app. The calculator can be integrated into the Electronic Health Record (EHR) to improve ease of use however, that does not come standard. Therefore, ASCVD risk calculation was performed on all patients aged 40-79 presenting for a fasting lab visit (FLV) at a primary care practice comprised of 3 clinics in East Tennessee between January 17, 2022 and February 28, 2022. Excluded patients included: patients outside of the age range, who did not have a lipid level done at their FLV, or who had a total cholesterol (TC) level greater than 320mg/dL. Once calculation was performed, results were given to the patient’s PCP for medical decision making on primary prevention treatment. After providers were given the results, chart reviews were completed to assess for primary prevention treatment initiations or increases within three months of receiving the results. Preliminary results show that a total of 443 patients presented for a FLV during the timeframe. A total of 132 patients were ineligible due to age (n=70), not having a lipid level completed (n=61) or having a TC level greater than 320 mg/dL (n=1). A total of 133 patients did not show or rescheduled their FLV. Chart reviews are just beginning, and insufficient data is currently available regarding intervention results. Limitations to this project include: all participants were Caucasian therefore, result may not be applicable to a more diverse population, the project was completed during a pandemic where patients were hesitant to come into the office, even for FLV, and a considerable number of patients who risk calculation could not be completed on. Having ASCVD calculation integrated within the EHR could promote use by providers. Future long-term research is needed to identify the accuracy of this calculator. This calculator has been modified based on research. However, research to identify the accuracy could lead to modification of the calculation to provide the most accurate result possible. One way this can be done is through use of the calculator by providers across the US.

Electricity-driven water splitting reaction achieved by electrochemical method to produce hydrogen and oxygen is utilized as an energy carrier in the form of highly pure hydrogen gas. However, the development of earth-abundant, durable, and highly effective electrocatlyst to overcome the high overpotentials of hydrogen, and oxygen evolution reaction (HER, OER) is extremely challenging. This dissertation presents firstly the catalytic properties of tungsten disulfide (WS2) as highly effective HER catalyst through direct growth of 2H-WS2 layered materials on a conductive substrate. Effect of various gaseous atmosphere and temperatures was studied and it was found that the amorphous structure of WS2 can be strongly affected under H2S environment which leads to the formation of bridging disulfide ligands S2 2- and apical S2- from WS3 phase, which is consequently contribute to the catalytic enhancement toward HER with extremely low overpotential (η10 = 184 mV). On the other hand, OER is the major bottleneck in water splitting reaction due to its poor kinetics originated from the complex four electrons transfer process. Chemical vapor deposition strategy is used here to enable stoichiometric tuning and phase engineering of CoP2 OER electrocatalyst followed by deposition of carbonaceous protection layer to overcome surface oxidation. Electrochemical studies indicate that C@CoP2/CC can achieve a remarkable activity (η10 = 234 mV), with minor decay from its initial current density after continuous operation of 80 hours. Lastly, electrolysis of alkaline water is the most common industrial method to produce H2; however, it is a formidable challenging to compete with Pt catalyst in base at industrial scale. For that, temperature-dependent phase evolution was studied in details and it is found that (Co(OH)2) precursor undergoes phase transition under a unique phosphidation system starting with partially phosphatized phase CoP-CoxOy, followed by phosphorus rich phase CoP2, and ultimately to pure CoP phase under elevated temperatures. Comprehensive analysis revealed that concerted composite CoP-CoxOy is the most active phase to produce H2 electrochemically from alkaline water which is contributed to the unique role of integrated phase and its ability to overcome the sluggish hydrogen kinetics in base.