28 research outputs found

    Optoelectronic Capillary Sensors in Microfluidic and Point-of-Care Instrumentation

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    This paper presents a review, based on the published literature and on the authors’ own research, of the current state of the art of fiber-optic capillary sensors and related instrumentation as well as their applications, with special emphasis on point-of-care chemical and biochemical sensors, systematizing the various types of sensors from the point of view of the principles of their construction and operation. Unlike classical fiber-optic sensors which rely on changes in light propagation inside the fiber as affected by outside conditions, optical capillary sensors rely on changes of light transmission in capillaries filled with the analyzed liquid, which opens the possibility of interesting new applications, while raising specific issues relating to the construction, materials and instrumentation of those sensors

    New synthetic methods using single-electron processes

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    This thesis presents investigations of alkoxy and aminyl radical cyclizations onto silyl enol ethers, as well as the development of a new photoinduced electron transfer-promoted redox fragmentation of N-alkoxyphthalimides. We investigated alkoxy radical cyclizations onto silyl enol ethers as a method for the synthesis of alpha-oxygenated oxacycles. Cyclizations to form tetrahydrofurans displayed a high degree of chemoselectivity relative to competing 1,5-hydrogen atom transfer, fragmentation and cyclization pathways. The rate acceleration imparted by the silyl enol ether allowed for a highly chemoselective 6-exo cyclization, a difficult mode of alkoxy radical reactivity to access due to competing 1,5-hydrogen atom transfers. We next examined the applications of silyl enol ether acceptors for aminyl radical cyclizations and the factors that lead to high diastereoselectivity in these cyclizations. This methodology allows for the synthesis of the 2-hydroxymethylpyrrolidine core found in many polyhydroxylated alkaloid natural products. In the course of our synthesis of the alkaloid CYB-3, we found that the cyclization diastereoselectivity was dependent on a complex combination of sterics and olefin geometry. Alkyl- and aryl-substituted substrates cyclized with high selectivity regardless of olefin geometry or substitution pattern. When electronegative substituents were introduced alpha to the silyl enol ether, only Z-silyl enol ethers provided high cyclization diastereoselectivities. Finally, we report a new fragmentation reaction of N-alkoxyphthalimides mediated by visible light and a Ru(bpy)₃²⁺ photocatalyst. Our mechanistic data support a unique concerted intramolecular fragmentation process, initiated by a single electron transfer to the phthalimide from either the metal catalyst or directly from a tertiary amine additive. The redox fragmentation reaction was applied to aryl, allyl and lactol derivatives. We found that the reaction could be carried out under catalyst-free conditions, but the yields of many substrates were improved in the presence of Ru(bpy)₃²⁺. The redox fragmentation of N-alkoxyphthalimides was applied to the mild and selective redox fragmentation of sensitive nitrogen-containing heterocycles.Science, Faculty ofChemistry, Department ofGraduat

    Timing of Income Assistance Payment and Overdose Patterns at a Canadian Supervised Injection Facility

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    Background: Little is known about the relationship between timing of income assistance provision and health behaviours among injection drug users (IDU). We therefore investigated associations between income assistance provision and overdose patterns among IDU utilizing Insite, a supervised injection facility in Vancouver, Canada. Methods: Using data collected at Insite between March 2004 and December 2010, we examined trends in overdoses and drugs injected. Data were stratified by proximity to the most recent day of issue of income assistance cheques, based on dates provided by the province. Results: After adjustment for frequency of use, the risk of overdose for those injecting at Insite on the three days starting with “cheque day” was higher than for those injecting on other days (Odds Ratio [OR]=2.06; 95% Confidence Interval [CI]: 1.80–2.36, p<0.001). These associations were also significant when drug-specific overdose rates were considered. The proportion of overdoses involving exclusive opioid use was lower for events occurring around cheque day than on other days (OR=0.63; 95% CI: 0.47–0.84, p=0.002), though we observed no significant association between the proportion of overdoses involving stimulants and cheque timing (p=0.129). Conclusions: The risk of overdose among IDU utilizing Insite was significantly higher on and immediately after cheque day than during other days, and may be associated with reduced tolerance and increases in binge drug use. Alternative models of income assistance administration should be evaluated to reduce overdoses around cheque day.Medicine, Faculty ofOther UBCNon UBCMedicine, Department ofPopulation and Public Health (SPPH), School ofSociology, Department ofArts, Faculty ofReviewedFacult

    Predicting salivary cortisol and sexual behavior stigma among MSM in the American Men’s Internet Survey 2019

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    Abstract Physiological stress levels in response to sexual behavior stigma among men who have sex with men (MSM) in the United States (US) are understudied. The current study aims to explore the relationship between sexual behavior stigma and salivary cortisol both overall and stratified by race/ethnicity. If such an association exists, it may suggest that sexual behavior stigma can be physiologically measured or indicated by the presence of heightened salivary cortisol. A subsample of 667 MSM participants from the 2019 American Men’s Internet Survey (AMIS; N = 10,129) submitted morning (AM) and evening (PM) saliva cortisol samples using at-home mail-in collection kits. Average daily cortisol and daily cortisol change were calculated; simple linear regressions estimated associations between cortisol measures and sexual behavior stigma characterized in four different ways (ever and recent experience of individual stigma items; average ever and recent experience of three stigma scales: stigma from family and friends, anticipated healthcare stigma, general social stigma). Participants reported a mean age of 36.0 years (SD = 14.9), with most being non-Hispanic white (n = 480, 72.0%), Hispanic (n = 164, 12.3%), or Black/African American (n = 146, 10.9%), and identified as homosexual/gay (n = 562, 84.3%). Reporting ever experiencing healthcare providers gossiping was significantly associated with higher PM cortisol (β = 0.12, p = 0.001) and higher average daily cortisol (β = 0.11, p = 0.004), while reporting ever experiencing police refusing to protect was associated with higher AM cortisol (β = 0.08, p = 0.03) and higher average daily cortisol (β = 0.09, p = 0.02). Recent experiences of stigma were not significant predictors of any measure of cortisol. Measures of salivary cortisol may be used to characterize sexual behavior stigma among MSM populations, however more insight is needed to determine its exact relationship and strength
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