38 research outputs found
Administrator Experiences With Placement of Transgender Women in Coed Residential Homeless Facilities
Researchers have found that transgender women have difficulty accessing appropriate and inclusive services due to inadequate housing placements. The purpose of this generic qualitative study was to explore the experiences of administrators of coed homeless facilities when making housing placement decisions for transgender women. Queer theory provided the theoretical lens for the study. As part of the qualitative generic study design, 10 interviews were conducted via telephone with participants selected through snowball sampling. The interviews were transcribed, and several iterations of thematic analysis were conducted to construct codes, categories, and themes. The findings revealed that there is (a) a lack of policies and training related to service provision for homeless transgender women in residential, coed homeless settings and (b) increased administrator discretion in decision-making when working with transgender women. The results indicate that there is an increased need for inclusive services for homeless, transgender individuals. This research may influence organizational leaders to develop specific policies and resources for the homeless transgender community. The study has the potential to foster positive societal change by encouraging the creation of an inclusive system of care to minimize hardship for transgender individuals experiencing homelessness and build confidence in the performance of administrators serving this population, which may pave the way toward community collaboration
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Synthetic Approaches to the A-74528 and Enterocin Polyketides and Catalytic Asymmetric Radical–Polar Crossover Reactions
This dissertation communicates new methods in cyclopropane activation and hydrogen-atom-transfer-initiated alkene hydrofunctionalizations to access novel catalytic asymmetric reaction manifolds and challenging polyketide scaffolds. Chapter One delineates the discovery of the enterocin polyketide antibiotics and subsequent efforts to identify the biosynthetic origin of their intriguing architecture. A review of the synthetic efforts towards the enterocin polyketides demonstrates significant challenges associated with construction of their highly oxidized caged core. Chapter Two describes our efforts to synthesize deoxyenterocin utilizing a biomimetic aldol cascade strategy. Our attempts to build the core are thwarted, however, due to inherent instability observed in synthetic analogues of the putative biosynthetic octaketide precursor. In Chapter Three, a lack of synthetic technology to install bridgehead oxidation contained in the enterocin core is identified, and a propellane activation strategy to directly forge bis-bridgehead functionalization is devised. Successful implementation of an unexploited propellane activation mode enables difunctionalization of the bridged propellane bond. Chapter Four describes the isolation, structure elucidation, and bioactivity studies of A-74528, an aromatic polyketide bearing a densely functionalized perhydrophenanthrene core. Identification of the biosynthetic gene cluster reveals an unusual polycyclization operative in the biosynthesis. The single reported synthetic effort towards A-74528 demonstrates that the biomimetic cascade proposed likely remains unfeasible. Our development of a route utilizing a hydrogen-atom-transfer (HAT) mediated semi-pinacol ring expansion provides access to a key tetracyclic intermediate for further elaboration to a key cyclopropanol substrate for investigation of an oxidative cleavage-induced radical cyclization cascade. Chapter Five focuses on our laboratory’s development of the first catalytic asymmetric HAT-initiated alkene hydrofunctionalization. Identification of a cation-π interaction in the Co(salen) catalyst employed enables optimization to achieve a highly enantioselective hydroalkoxylation of alkenes
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Synthetic Approaches to the A-74528 and Enterocin Polyketides and Catalytic Asymmetric Radical–Polar Crossover Reactions
This dissertation communicates new methods in cyclopropane activation and hydrogen-atom-transfer-initiated alkene hydrofunctionalizations to access novel catalytic asymmetric reaction manifolds and challenging polyketide scaffolds. Chapter One delineates the discovery of the enterocin polyketide antibiotics and subsequent efforts to identify the biosynthetic origin of their intriguing architecture. A review of the synthetic efforts towards the enterocin polyketides demonstrates significant challenges associated with construction of their highly oxidized caged core. Chapter Two describes our efforts to synthesize deoxyenterocin utilizing a biomimetic aldol cascade strategy. Our attempts to build the core are thwarted, however, due to inherent instability observed in synthetic analogues of the putative biosynthetic octaketide precursor. In Chapter Three, a lack of synthetic technology to install bridgehead oxidation contained in the enterocin core is identified, and a propellane activation strategy to directly forge bis-bridgehead functionalization is devised. Successful implementation of an unexploited propellane activation mode enables difunctionalization of the bridged propellane bond. Chapter Four describes the isolation, structure elucidation, and bioactivity studies of A-74528, an aromatic polyketide bearing a densely functionalized perhydrophenanthrene core. Identification of the biosynthetic gene cluster reveals an unusual polycyclization operative in the biosynthesis. The single reported synthetic effort towards A-74528 demonstrates that the biomimetic cascade proposed likely remains unfeasible. Our development of a route utilizing a hydrogen-atom-transfer (HAT) mediated semi-pinacol ring expansion provides access to a key tetracyclic intermediate for further elaboration to a key cyclopropanol substrate for investigation of an oxidative cleavage-induced radical cyclization cascade. Chapter Five focuses on our laboratory’s development of the first catalytic asymmetric HAT-initiated alkene hydrofunctionalization. Identification of a cation-π interaction in the Co(salen) catalyst employed enables optimization to achieve a highly enantioselective hydroalkoxylation of alkenes
Catalytic Asymmetric Radical-Polar Crossover Hydroalkoxylation
Asymmetric intramolecular hydrofunctionalization of tertiary allylic alcohols is described. This metal hydride-mediated catalytic radical-polar crossover reaction delivers corresponding epoxides in good to high enantioselectivity and constitutes the first example of asymmetric hydrogen atom transfer-initiated process. A series of modified cobalt salen complexes has proven optimal for achieving good efficiency and asymmetric induction. Experimental data suggest that cationic cobalt complexes are involved in enantio-determining step, where cation–π interactions in the catalyst contribute to the asymmetric induction
Lock Free Data Structures using STM in Haskell
Abstract. This paper explores the feasibility of re-expressing concurrent algorithms with explicit locks in terms of lock free code written using Haskell’s implementation of software transactional memory. Experimental results are presented which show that for multi-processor systems the simpler lock free implementations offer superior performance when compared to their corresponding lock based implementations.
Endoscopic transpapillary stenting for the management of acute cholecystitis.
INTRODUCTION: Cholecystectomy is the gold standard treatment of acute cholecystitis. Patients who are considered not to be candidates for cholecystectomy are commonly recommended to undergo percutaneous transhepatic gallbladder drainage (PTGBD) tube placement; however, external drainage is undesirable for many patients. Endoscopic transpapillary stent placement (ETSP) has been described as an alternative method for decompression of the gallbladder. Data in support of this technique is limited to a handful of observational studies with variable indications. Our study sought to expand on the available data for the use of ETSP exclusively in the context of acute cholecystitis.
METHODS: We performed a retrospective chart review of patients with cholecystitis who underwent ETSP at our institution between January 2012 and July 2018. We collected data on indication, comorbidities, length of stay, laboratory values, outcomes, additional procedures, and whether cholecystectomy was eventually performed.
RESULTS: During the study period, 12 patients underwent ETSP. The mean age was 68.2 years (± SD 12.4) with an average Anesthesia Society Assessment (ASA) class of 3.2. The Charlson Comorbidity Index was greater than seven in 75% of patients, indicating a 0% estimated 10-year survival. The National Surgical Quality Improvement Program (NSQIP) surgical risk calculator was used to estimate an average mortality risk for laparoscopic cholecystectomy of 4.8% (± 3.3, 95% CI) in our study population; the estimated risk in the general population is 0.1%. Immediate resolution of symptoms with endoscopic drainage was achieved in 11 of 12 patients (91.7%); one patient experienced no symptom resolution with endoscopic drainage nor subsequent PTGBD tube placement. Six of 12 (50%) patients experienced recurrence of symptoms requiring hospitalization, and two of 12 patients (16.7%) died secondary to biliary sepsis.
CONCLUSION: Endoscopic transpapillary stent placement is an alternative method for the management of acute cholecystitis patients who are not candidates for surgery. ETSP has a high technical success rate; however, it may result in a high rate of symptom recurrence and should only be utilized in select patients. Randomized studies would be beneficial to further investigate the utility and safety of ETSP in the management of acute cholecystitis
Regio- and Stereospecific <i>C</i>- and <i>O</i>‑Allylation of Phenols via π‑Allyl Pd Complexes Derived from Allylic Ester Carbonates
Two complementary strategies have
been developed for the <i>C</i>- and <i>O</i>-allylation
of phenols via a common
Ï€-allyl Pd complex. While <i>O</i>-allylation of phenols
by this method is a well-recognized reaction of general utility, the
associated <i>para</i>-selective <i>C</i>-allylation
reaction is still in its infancy. Cationic π-allyl Pd intermediates,
derived from allylic ester carbonates and palladium(0) catalyst, were
found to undergo the Friedel–Crafts-type <i>para</i>-selective <i>C</i>-allylations with nine different phenols.
Both <i>C-</i> and <i>O-</i>allylated products
were obtained in good to excellent yields following a metal-catalyzed
regio- and stereospecific substitutive 1,3-transposition. Conditions
were also identified that control access to either allylated product.
Finally, a study of the equilibrium established between the two allylation
products revealed that the <i>O-</i>allylated compound was
the kinetic product and the <i>C-</i>allylated compound
the thermodynamic product
Feeding Performance and Outcomes in Infants With Robin Sequence Undergoing Mandibular Distraction Osteogenesis
Objective:
To describe perioperative feeding performance in infants with Robin sequence (RS) who underwent mandibular distraction osteogenesis (MDO).
Design:
A retrospective study of infants that underwent MDO from May 2010 to December 2019.
Setting:
Tertiary pediatric hospital.
Patients:
A total of 40 patients underwent MDO and 20 met inclusion criteria. Of the included infants, 6 had an associated syndrome and 80% were male.
Main Outcome Measures:
Time to full oral feeds, rate of G-tube placement, and change in weight percentile following MDO.
Results:
Average oral intake prior to MDO was 22.1% of individual goal feeds. Among the 15 (75%) children that did not require G-tube placement, mean time to full oral feeds after MDO was 11 days ± 5.7 days, with 80% of infants reaching full oral feeds within 2 weeks after extubation. The proportion of G-tube placement in patients with a syndrome was higher than in isolated RS (−0.6; 95% CI: −1.0, −0.2). Mean percentages of weight-for-age percentile decreased during the first 3 months after the procedure. This was followed by a mean upturn in weight starting after the third month after MDO with a recovery to preoperative mean weight-for-age percentiles by 6 months after surgery.
Conclusions:
This study suggests that infants with RS may achieve full oral feeds despite poor feeding performance before MDO. Infants with syndromic RS are more likely to require G-tube. These findings may be used to inform G-tube discussion and offer a timeline to work toward goal oral feeds for infants with RS after MDO