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A new approach was taken in the elucidation of the stereochemistry of the symmetrically 1,4-disubstituted 1,4-dihydronaphthalene systems which show deceptively simple NMR spectra. Thus, the stereochemistry of 1,4-di-tert-butyl-1,4-dihydronaphthalene was established unequivocally. The epoxide derivative, the subject compound, 1,4-di-tertbutyl-2, 3-epoxy-1, 4-dihydronaphthalene, was formed and its trans stereochemistry was established by ¹H NMR and ¹³C NMR. A lanthanide shift study was also conducted on the epoxide derivative, further proving the trans stereochemistry. One of the lanthanide shifted spectra was analyzed using the LAACOON III computer program and the true coupling constants obtained this way were in excellent agreement with the experimental spectrum. Establishing the trans stereochemistry of the epoxide derivative proved the trans stereochemistry of 1,4-di-tert-butyl-1,4-dihydronaphthalene.

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No description available.

We developed an approach to the β-thioenamide linkage contained in the S-(2-aminovinyl)cysteine (avCys) residue of thioviridamide.1,2 Kinetic and thermodynamic control of radical additions of thiols to ynamides were studied for the formation of β-thioenamide linkage. Thiyl radicals are electrophilic and ynamides are electron-rich alkynes. This complementary polarity of the radical and acceptor increases the likelihood of a successful radical addition reaction. Because little is known about these types of compounds (β-thioenamides), we were unsure what kinds of yields and stereoselectivities (cis vs. trans) to expect. The adduct stability is another issue to consider. Fortunately, under typical radical addition conditions, the two separable isomers (cis and trans) are formed in good yield. Selective formation of kinetic (cis) and thermodynamic (trans) isomers are controlled by reaction time and equivalents of thiol. We converted the kinetic isomer to the thermodynamic isomer to confirm that isomerization can occur under the reaction conditions. Alkyl and aryl thiols including cysteine-derived thiols with different ynamides were used in this process.

This study investigated (1) how and where queer young adults remembered playing and exploring gender and sexuality in their child and youthhoods, and (2) how those memories influenced their identities as queer young adults. Eight young adults from Southern Vancouver Island were recruited to the study using non-probability and purposive sampling. Each participant took part in a narrative interview and was asked to recreate in a sand tray one or more places where they remembered exploring gender and/or sexuality in their childhood or youthhood. Data were analyzed using thematic analysis through a queer phenomenological lens inspired by Sara Ahmed. It was determined that “queer failure,” as described by Jack Halberstam, was a critical, formative process that contributed to the reorienting of queer children and youth towards queer futures. The way that queer failure was responded to by significant adults appeared to have enduring impacts on participants’ self-esteem and self-regard, with having a supportive caregiver being associated with positive self-regard as a queer adult, and a lack of support associated with long-term poor mental health and lower likelihood of experiencing pride in being queer. Additionally, participants demonstrated how access to the outdoors provided a meaningful locus of self-discovery wherein the limitations and structures of gender were less omnipresent and they felt more external and internal acceptance of their queer identities. / Graduate / 2023-08-10

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This thesis examines the changes that occurred in the French identity of Huguenot immigrants to colonial Carolina. In their pursuit of prosperity and religious toleration, the Huguenots' identity evolved from one of French religious refugees to that of white South Carolinians. How and why this evolution occurred is the focus of this study. Upon arriving in the colony in the 1680s and 1690s, the Huguenots' identity was based on several common factors: their French language, their Calvinist religion, and their French heritage. As the immigrant group began to build their new lives in Carolina, these identifying factors began to disappear. The first generation's identity evolved from French immigrants to British subjects when they were challenged on the issues of their political and religious rights and, in response to these challenges, requested to become naturalized subjects. The second generation faced economic challenges that pitted planters against the wealthier merchants in a colony-wide debate over the printing of paper currency. This conflict created divisions within the Huguenot group as well and furthered their identity from British subjects to planters or merchants. Another shift in the Huguenots' identity took place within the third generation when they were faced with a slave uprising in 1739. The Huguenots' involvement in finding a legislative solution to the revolt completes this evolutionary process as the grandchildren of the immigrant generation become white South Carolinians. This thesis expands the historical data available on immigrant groups and their behaviors within colonial settlements.

Anopheles stephensi is a potent vector of malaria throughout the Indian subcontinent and Middle East. An. stephensi is emerging as a model for molecular and genetic studies of mosquito-parasite interactions. Here we conducted a series of genomic and transcriptomic studies to improve the understanding of the biology of Anopheles stephensi and mosquito in general. First we reported the genome sequence and annotation of the Indian strain of the type form of An. stephensi. The 221 Mb genome assembly was produced using a combination of 454, Illumina, and PacBio sequencing. This hybrid assembly method was significantly better than assemblies generated from a single data source. A total of 11,789 protein-encoding genes were annotated using a combination of homology and de novo prediction. Secondly, we demonstrated the presence of complete dosage compensation in An. stephensi by determining that autosomal and X-linked genes have very similar levels of expression in both males and females. The uniformity of average expression levels of autosomal and X-linked genes remained when An. stephensi gene expression was normalized by that of their Ae. aegypti orthologs, strengthening the conclusion of complete dosage compensation in Anopheles. Lastly, we investigated trans-splicing events in Anopheles stephensi. We identified six trans-splicing events and all the trans-splicing sites are conserved and present in Ae. aegypti. The proteins encoded by the trans-spliced mRNAs are also highly conserved and their orthologs are co-linearly transcribed in out-groups of family Culicidae. This finding indicates the need to preserve the intact mRNA and protein function of the broken-up genes by trans-splicing during evolution. In summary, we presented the first genome assembly of Anopheles stephensi and studied two interesting evolution events" dosage compensation and trans-splicing - via transcriptomic analysis. / Ph. D.

yes / Background: Minimum toe clearance is a critical gait event because it coincides with peak forward velocity of the swing foot, and thus, there is an increased risk of tripping and falling. Trans-tibial amputees have increased risk of tripping compared to able-bodied individuals. Assessment of toe clearance during gait is thus clinically relevant. In able-bodied gait, minimum toe clearance increases with faster walking speeds, and it is widely reported that there is synchronicity between when peak swing-foot velocity and minimum toe clearance occur. There are no such studies involving lower-limb amputees. Objectives: To determine the effects of walking speed on minimum toe clearance and on the temporal relationship between clearance and peak swing-foot velocity in unilateral trans-tibial amputees. Study design: Cross-sectional. Methods: A total of 10 trans-tibial participants walked at slow, customary and fast speeds. Minimum toe clearance and the timings of minimum toe clearance and peak swing-foot velocity were determined and compared between intact and prosthetic sides. Results: Minimum toe clearance was reduced on the prosthetic side and, unlike on the intact side, did not increase with walking speed increase. Peak swing-foot velocity consistently occurred (~0.014 s) after point of minimum toe clearance on both limbs across all walking speeds, but there was no significant difference in the toe–ground clearance between the two events. Conclusion: The absence of speed related increases in minimum toe clearance on the prosthetic side suggests that speed related modulation of toe clearance for an intact limb typically occurs at the swing-limb ankle. The temporal consistency between peak foot velocity and minimum toe clearance on each limb suggests that swing-phase inter-segmental coordination is unaffected by trans-tibial amputation. Clinical relevance The lack of increase in minimum toe clearance on the prosthetic side at higher walking speeds may potentially increase risk of tripping. Findings indicate that determining the instant of peak swing-foot velocity will also consistently identify when/where minimum toe clearance occurs.