Investigation of nanostructured conducting polymers and graphene/polyaniline nanocomposite based thin films for hydrogen gas sensing

Novel conductometric and layered Surface Acoustic Wave (SAW) hydrogen gas sensors based on nanostructured conducting polymers and graphene/polyaniline nanocomposite are reported in this PhD dissertation. Template-free electropolymerization and/or chemical polymerization methods were employed during the synthesis of the nanostructured polythiophene, polypyrrole, polyaniline, polyanisidine, polyethylaniline and graphene/polyaniline nanocomposite which were investigated for their hydrogen gas sensing characteristics. The nanostructured gas sensitive films' physical and chemical properties were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, Ultraviolet-visible spectroscopy (UV-Vis), and X-ray photoemission spectroscopy (XPS). A programmable gas calibration and data acquisition system was utilized to measure the sensors' responses towards several concentrations of hydrogen gas at room temperature. A comparative study on the performance of conductometric hydrogen gas sensors based on electropolymerized polythiophene nanostructured films was conducted for the first time in this thesis according to the best of the author's knowledge. Polythiophene gas sensitive films featuring nanofibers with diameters of 10-40 nm were successfully electrodeposited on conductometric transducers. Electropolymerization parameters such as counterion's type, the concentration of the electrolyte, the electropolymerization potential and the deposition time were shown to affect the morphology of the gas sensitive film and ultimately its response towards hydrogen gas. Electropolymerized polypyrrole nanowires with diameters of 40-90 nm and chemically polymerized polypyrrole nanofibers of 18 nm in diameter were employed for hydrogen gas sensing for the first time herein. The effect of polypyrrole's counterion type on the resultant gas sensor electrical characteristics was investigated herein. Via a comprehensive investigation, it was found that chemically synthesized chloride-doped polypyrrole nanofibers to be more sensitive to hydrogen gas than the perchlorate-doped electropolymerized polypyrrole nanowires due to the smaller molecular size of the incorporated counterion into the polymer matrix. Novel layered SAW gas sensors based on polythiophene nanofibers, polypyrrole nanofibers, nanoporous polyaniline, polyanisidine nanofibers and polyethylaniline nanofibers were developed and tested at room temperature. The highest response was observed for the polyanisidine nanofibers/ZnO/36° YX LiTaO 3 SAW gas sensor with a 294 kHz frequency shift from the centre frequency upon exposure to hydrogen gas with the concentration of 1% in ambient air. Morphological analysis of the deposited polyanisidine nanofibers based thin film revealed that the nanofibers, ~55 nm in diameter, were not densely packed that allows deep and efficient penetration of target gas molecules into the sensitive film and makes gas sensing possible over the entire length of a nanofiber into a mesh. To the best knowledge of the author of this dissertation, the first ever reported hydrogen gas sensor based on graphene/polyaniline nanocomposite was developed and characterized for the first time in this PhD program. This sensor outperformed hydrogen gas sensors based on polyaniline nanofibers at room temperature. After analysing the nanocomposite's characterization results, the author of this thesis suggested that the observed high response is attributed to the graphene/polyaniline nanocomposite's high surface area compared to that of the pure polyaniline nanofibers due to the growth of polyaniline nanofibers in the order of 25-50 nm in diameter on the graphene nanosheets' surfaces

Conductometric hydrogen gas sensor based on polypyrrole nanofibers

Polypyrrole nanofibers are synthesized through a template-free chemical route and used as the active component for hydrogen gas sensing at room temperature. The synthesis of polypyrrole nanofibers was achieved by using bipyrrole as an initiator to speed up the polymerization of pyrrole with FeCl as the oxidizing agent. Scanning and transmission electron microscopy studies indicate that the resulting polypyrrole forms a nanofibrous mat with average nanofiber diameter of 18 nm. Fourier transform infrared spectroscopy and elemental analysis confirms that the structure of the nanofibers is comparable to bulk polypyrrole. Gas sensing properties of polypyrrole nanofibers were investigated by depositing nanofiber dispersions on an interdigited conductometric transducer. The sensor performance was tested through programmable exposure towards different concentrations of hydrogen gas diluted in synthetic air in an environmental cell at different temperatures. A short response time of 43 s was observed upon exposure to a concentration of 1% hydrogen with a decrease in film resistance of 312 at room temperature. The sensor sensitivity was analyzed with gradual elevation of the operating temperature

Sister Mary Joseph's Nodule at a University Teaching Hospital in Northwestern Tanzania: A Retrospective Review of 34 cases.

Sister Mary Joseph's nodule is a metastatic tumor deposit in the umbilicus and often represents advanced intra-abdominal malignancy with dismal prognosis. There is a paucity of published data on this subject in our setting. This study was conducted to describe the clinicopathological presentation and treatment outcome of this condition in our environment and highlight challenges associated with the care of these patients, and to proffer solutions for improved outcome. This was a retrospective study of histologically confirmed cases of Sister Mary Joseph's nodule seen at Bugando Medical Centre between March 2003 and February 2013. Data collected were analyzed using descriptive statistics. A total of 34 patients were enrolled in the study. Males outnumbered females by a ratio of 1.4:1. The vast majority of patients (70.6%) presented with large umbilical nodule > 2 cm in size. The stomach (41.1%) was the most common location of the primary tumor. Adenocarcinoma (88.2%) was the most frequent histopathological type. Most of the primary tumors (52.9%) were poorly differentiated. As the disease was advanced and metastatic in all patients, only palliative therapy was offered. Out of 34 patients, 11 patients died in the hospital giving a mortality rate of 32.4%. Patients were followed up for 24 months. At the end of the follow-up period, 14(60.9%) patients were lost to follow-up and the remaining 9 (39.1%) patients died. Patients survived for a median period of 28 weeks (range, 2 to 64 weeks). The nodule recurred in 6 (26.1%) patients after complete excision. Sister Mary Joseph's nodule of the umbilicus is not rare in our environment and often represents manifestation of a variety of advanced intra-abdominal malignancies. The majority of the patients present at a late stage and many with distant metastases. The patient's survival is very short leading to a poor outcome. Early detection of primary cancer at an early stage may improve the prognosis

Revisiting Egyptian Foreign Policy towards Israel under Mubarak: From Cold Peace to Strategic Peace

This article is the first academic study of Egyptian foreign policy towards Israel under Hosni Mubarak (1981–2011). It challenges a deeply entrenched conventional wisdom that Egypt pursued a cold-peace foreign policy towards Israel throughout this period. We demonstrate that Egyptian foreign policy towards Israel was dynamic – comprising cold peace (1981–91), a hybrid foreign policy of cold peace and strategic peace (1991–2003), and a pure strategic peace posture (2003–11). We also use the case of Egyptian foreign policy towards Israel as a heuristic to develop a conception of a new type of peace, strategic peace, as an intermediary analytical category between cold and stable peace

Magnetodielectric effect of Graphene-PVA Nanocomposites

Graphene-Polyvinyl alcohol (PVA) nanocomposite films with thickness $120 \mu m$ were synthesized by solidification of PVA in a solution with dispersed graphene nanosheets. Electrical conductivity data were explained as arising due to hopping of carriers between localized states formed at the graphene-PVA interface. Dielectric permittivity data as a function of frequency indicated the occurrence of Debye-type relaxation mechanism. The nanocomposites showed a magnetodielectric effect with the dielectric constant changing by 1.8% as the magnetic field was increased to 1 Tesla. The effect was explained as arising due to Maxwell-Wagner polarization as applied to an inhomogeneous two-dimensional,two-component composite model. This type of nanocomposite may be suitable for applications involving nanogenerators.Comment: 13 pages, 11 figure

Elective Cancer Surgery in COVID-19-Free Surgical Pathways During the SARS-CoV-2 Pandemic: An International, Multicenter, Comparative Cohort Study.

PURPOSE: As cancer surgery restarts after the first COVID-19 wave, health care providers urgently require data to determine where elective surgery is best performed. This study aimed to determine whether COVID-19-free surgical pathways were associated with lower postoperative pulmonary complication rates compared with hospitals with no defined pathway. PATIENTS AND METHODS: This international, multicenter cohort study included patients who underwent elective surgery for 10 solid cancer types without preoperative suspicion of SARS-CoV-2. Participating hospitals included patients from local emergence of SARS-CoV-2 until April 19, 2020. At the time of surgery, hospitals were defined as having a COVID-19-free surgical pathway (complete segregation of the operating theater, critical care, and inpatient ward areas) or no defined pathway (incomplete or no segregation, areas shared with patients with COVID-19). The primary outcome was 30-day postoperative pulmonary complications (pneumonia, acute respiratory distress syndrome, unexpected ventilation). RESULTS: Of 9,171 patients from 447 hospitals in 55 countries, 2,481 were operated on in COVID-19-free surgical pathways. Patients who underwent surgery within COVID-19-free surgical pathways were younger with fewer comorbidities than those in hospitals with no defined pathway but with similar proportions of major surgery. After adjustment, pulmonary complication rates were lower with COVID-19-free surgical pathways (2.2% v 4.9%; adjusted odds ratio [aOR], 0.62; 95% CI, 0.44 to 0.86). This was consistent in sensitivity analyses for low-risk patients (American Society of Anesthesiologists grade 1/2), propensity score-matched models, and patients with negative SARS-CoV-2 preoperative tests. The postoperative SARS-CoV-2 infection rate was also lower in COVID-19-free surgical pathways (2.1% v 3.6%; aOR, 0.53; 95% CI, 0.36 to 0.76). CONCLUSION: Within available resources, dedicated COVID-19-free surgical pathways should be established to provide safe elective cancer surgery during current and before future SARS-CoV-2 outbreaks

Elective cancer surgery in COVID-19-free surgical pathways during the SARS-CoV-2 pandemic: An international, multicenter, comparative cohort study

PURPOSE As cancer surgery restarts after the first COVID-19 wave, health care providers urgently require data to determine where elective surgery is best performed. This study aimed to determine whether COVID-19–free surgical pathways were associated with lower postoperative pulmonary complication rates compared with hospitals with no defined pathway. PATIENTS AND METHODS This international, multicenter cohort study included patients who underwent elective surgery for 10 solid cancer types without preoperative suspicion of SARS-CoV-2. Participating hospitals included patients from local emergence of SARS-CoV-2 until April 19, 2020. At the time of surgery, hospitals were defined as having a COVID-19–free surgical pathway (complete segregation of the operating theater, critical care, and inpatient ward areas) or no defined pathway (incomplete or no segregation, areas shared with patients with COVID-19). The primary outcome was 30-day postoperative pulmonary complications (pneumonia, acute respiratory distress syndrome, unexpected ventilation). RESULTS Of 9,171 patients from 447 hospitals in 55 countries, 2,481 were operated on in COVID-19–free surgical pathways. Patients who underwent surgery within COVID-19–free surgical pathways were younger with fewer comorbidities than those in hospitals with no defined pathway but with similar proportions of major surgery. After adjustment, pulmonary complication rates were lower with COVID-19–free surgical pathways (2.2% v 4.9%; adjusted odds ratio [aOR], 0.62; 95% CI, 0.44 to 0.86). This was consistent in sensitivity analyses for low-risk patients (American Society of Anesthesiologists grade 1/2), propensity score–matched models, and patients with negative SARS-CoV-2 preoperative tests. The postoperative SARS-CoV-2 infection rate was also lower in COVID-19–free surgical pathways (2.1% v 3.6%; aOR, 0.53; 95% CI, 0.36 to 0.76). CONCLUSION Within available resources, dedicated COVID-19–free surgical pathways should be established to provide safe elective cancer surgery during current and before future SARS-CoV-2 outbreaks

Polypyrrole nanofiber surface acoustic wave gas sensors

We present for the first time, to the best of authors' knowledge, surface acoustic wave (SAW) gas sensors featuring polypyrrole nanofibers as the active component for hydrogen (H2) and nitrogen dioxide (NO2) detection at room temperature. Polypyrrole nanofibers were synthesized through a template-free chemical route by introducing bipyrrole as an initiator to speed up the polymerization of pyrrole in the presence of iron (III) chloride (FeCl3) as the oxidizing agent. Polypyrrole nanofibers were characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopic (FT-IR) techniques which indicated that the average diameter of the nanofibers was 18 nm with lengths in the order of several microns. The polypyrrole nanofibers were dispersed onto the surface of a ZnO/36°YX LiTaO3 SAW transducer. Gas testing towards H2 and NO2 was conducted in an enclosed environmental cell at room temperature. Measured frequency shifts due to sensor responses were 20 kHz towards 1% of H2 and 4.5 kHz towards 2.1 ppm NO2, respectively. The sensor performance was assessed during a five-day period and repeatable results were obtained

Hydrogen gas sensor fabricated from polyanisidine nanofibers deposited on 36° YX LiTaO3 layered surface acoustic wave transducer

Polyanisidine nanofibers gas sensor based on a ZnO/36° YX LiTaO3 surface acoustic wave (SAW) transducer was developed and tested at different concentrations of hydrogen gas in synthetic air. Nanofibrous mats of polyanisidine were synthesized without the need for templates or functional dopants by simply introducing an initiator into the reaction mixture of a rapidly mixed reaction between the monomer (anisidine) and the oxidant. The polyanisidine nanofibers are characterized using scanning electron microscopy (SEM) and Ultraviolet-Visible Spectroscopy (UV-vis). Polyanisidine nanofibers were deposited onto the SAW transducer and exposed to different concentrations of hydrogen gas. The frequency shift due to the sensor response was 294 kHz towards 1% of H2. All tests were conducted at room temperature and the sensor performance was assessed for a two day period with a high degree of reproducibility obtained