Application of Transition Metal Catalysis to Small Molecule Synthesis

Over the past decade, transition metal catalysis has developed into a new field in organic synthesis, enabling numerous synthetic transformations that were previously not feasible. This thesis describes the application of both ruthenium and rhenium catalysis to the synthesis of several classes of small molecules. Ruthenium-catalyzed ring-opening cross-metathesis of five- through eight-membered ring cycloolefins was investigated for the synthesis of functionalized dienes (Chapter 1). Unsubstituted, trisubstituted, and allyl-substituted cycloolefins were studied. Regioselective reactions could be achieved with the use of unsymmetrical cycloolefins. Ruthenium-catalyzed cross-metathesis was explored for the synthesis of both di- and trisubstituted vinyl boronates (Chapter 2). These reactions proceeded efficiently for a wide variety of functionalized alkenes and generally exhibited high E-stereoselectivity. The resultant vinyl boronate products were stereoselectively converted into both Z-vinyl bromides and E-vinyl iodides. The rhenium-catalyzed 1,3-isomerization of allylic alcohols was employed in the synthesis of various allylic alcohols (Chapter 3). Two different strategies were developed to promote high product selectivity in these reactions: conjugated product synthesis and N,O-bis(trimethylsilyl)acetamide-promoted product trapping. These reactions enabled the synthesis of allylic alcohols with conjugated or non-conjugated, di- or trisubstituted, and electron-rich or electron-deficient alkene components. Partial chirality transfer was observed during the 1,3-isomerization of certain enantioenriched allylic alcohols. The fundamental reaction properties observed during these studies were all consistent with the operation of a mechanism involving a chair-like transition state, which contains a partially cationic allyl moiety, as the primary reaction pathway

Declaraciones de Deseo y Declaraciones de Realidad : State-Indigenous Relations and Intercultural-Bilingual Education in Peru and Guatemala

Ethnic diversity has historically created conflict in many nation-states throughout the globe. From the era of nation-state formation to the present, states have had various strategies for dealing with this diversity. These strategies can be divided into three distinct categories: assimilation, integration and pluralism. Because of the increasing strength and importance of the global indigenous peoples\u27 movement, relations between states and indigenous peoples are transforming away from assimilationist models toward integration and symbolic support. Why would governments nominally or symbolically support programs to preserve and revive indigenous culture? To answer this question, I compare government support for intercultural-bilingual education programs in Peru and Guatemala. I find that both states have reached a state of institutional paralysis in their implementation of intercultural-bilingual education. A comparative historical overview of both countries finds that internal conflicts were turning points in the states\u27 relationships with their indigenous peoples. Contention between the government and its populations resulted in transformation, either through co-optation or negotiation. Despite these distinct trajectories of change, both countries experience institutional paralysis when it comes to multicultural policy as a result of states\u27 efforts to maintain their authority through law, in accordance with the bureaucratic nature of nation-states

Acentric langmuir-blodgett: film assemblies

In recent years there has been considerable interest In the use of Langmuir-Blodgett (LB) films as the basis of active and passive thin film devices. One such application is in room temperature, pyroelectric thermal imaging systems. As the detectivity of these sensors is approximately inversely proportional to thickness, there may be significant advantage in exploiting the ability of the LB process to produce ultra-thin layers. Here we report the use of the LB technique to fabricate molecular assemblies with precisely defined symmetry properties. This has made possible the construction of ultra-thin organic films possessing the spontaneous polarisation necessary for the observation of the pyroelectric effect. Two distinct approaches are adopted to produce the required molecular packing arrangements. The first uses the ability of a novel alternate layer trough to assemble acentric ABAB structures. Various materials are studied for their suitability for alternate layer deposition. The co-deposition of fatty acids and amines produces alternate layer assemblies with a high degree of structural and electrical integrity. The second approach uses a novel polymeric LB film. Polybutadiene (PBD) is observed to deposit in highly asymmetric X-type layers if the transferred monolayer is exposed to u.v. radiation between each deposition step. The structural and electrical properties are characterised. The presence of the unique polar axis associated with pyroelectric materials is investigated using surface potential measurements. Dynamic and quasi-static detection techniques are employed to detect the pyroelectric activity within the assemblies. For the first time pyroelectric activity is observed in "thin" (11 layer) acid/amine assemblies. The pyroelectric coefficient is found to be thickness dependent, increasing for larger numbers of layers; the coefficient for a 99 layer sample is comparable to that of PVDF, a commercially available pyroelectric polymer. The incorporation of LB films into thin PVDF Metal Insulator Metal (MIM) structures is also investigated. The presence of a stable phthalocyanine LB film is shown to increase the electrical breakdown strength of the device. Finally the incorporation of highly polarisable sulphur substitutions into fatty acid LB films is reported. The permittivity is found to increase in proportion to the number of sulphur atoms introduced into the hydrocarbon chain

Recent Developments in Cultural Heritage Image Databases: Directions for User-Centered Design

published or submitted for publicatio

Evaluating Prescriber Adherence to Guideline-Based Treatment Pathways of a Newly Initiated Antimicrobial Stewardship Program at a Rehabilitation Hospital

Background: Inappropriate use of antimicrobials in the healthcare setting is associated with consequences including antimicrobial resistance, Clostridium difficile infection (CDI), adverse drug reactions, and increased healthcare costs. To combat this, hospitals are creating antimicrobial stewardship programs (ASPs) which seek to optimize antimicrobial utilization. To date, no studies have been done to assess adherence to an ASP in a rehabilitation hospital setting. The objective of this study is to evaluate prescriber compliance to treatment pathways for common infections before and after ASP implementation. Methods: This was a retrospective cohort study of patients admitted to the Rehabilitation Hospital of Indiana (RHI) who received an antibiotic between October 1, 2015-December 31, 2015 (pre-ASP group) and January 1, 2016-September 30, 2016 (post-ASP group) for one of the following indications: pneumonia, urinary tract infection, CDI, bone and joint infection, skin or skin structure infection, febrile neutropenia, or central/peripherally inserted central catheter line bloodstream infection. Data extracted from the hospital’s electronic medical record system included patient demographic and clinical information, laboratory data, culture and susceptibility results, and antibiotic information. The primary outcome of this study was prescriber compliance to treatment pathways defined as correct drug based on the documented indication before and after the implementation of the antimicrobial stewardship program on January 1, 2016. Descriptive statistics were performed to analyze baseline characteristics and culture data, as well as antimicrobial class, indication, and overall compliance to the guideline-based treatment pathways. Results: Data was extracted from the hospital’s electronic medical record system for 381 patients (n=381) who received an antibiotic at RHI. There were 121 and 260 patients included in the pre- and post-ASP study groups, respectively. Urinary tract infections were the most common infection for which antibiotics were prescribed (n=293; 76.9%). The three most common antibiotics prescribed were ciprofloxacin (n=101; 26.5%), sulfamethoxazole/trimethoprim (n=81; 21.3%), and nitrofurantoin (n=49; 12.9%). Compliance was found to be 81% in the pre-ASP group and 78.5% in the post-ASP group (p=0.571). Overall compliance was found to be the highest (100% in both pre- and postASP groups) for osteomyelitis infections and CDI. Urinary tract infections had the next highest rate of compliance in both the pre- and post-ASP groups (86.5% and 81.7% respectively). Conclusions: No difference in rates of prescriber compliance to guideline-based treatment pathways was found in the pre- and post-ASP groups. Urinary tract infections were found to be the most common indication requiring antimicrobial usage at RHI and had the third highest rate of compliance out of the infections included in this study. Our study highlights a need for further investigation regarding the impact of the ASP on appropriate antimicrobial dose, duration of therapy, administration, and de-escalation based on culture data. Additionally, our study identified a need for formal prescriber education focusing on how to utilize the treatment pathways, especially for those infections with the lowest compliance rates

A Comment on Restatement Third of Torts’ Proposed Treatment of the Liability of Possessors of Land

In §§ 51 and 52 of the forthcoming second volume of the Restatement (Third) of Torts: Liability for Physical and Emotional Harm, the reporters have sought to accommodate the trend to extend the liability of possessors of land to trespassers. The courts that have led the way in this legal transformation of the traditional common law have largely focused on the foreseeability of the trespasser and of the likelihood of injury from the disrepair of the premises. The Restatement (Third) takes a different approach by focusing on the flagrancy of the trespass, a concept with significant moral connotations. I argue that this approach has severe problems. The notion of flagrancy conjures up at least two overlapping visions. One is the purpose of the trespasser in committing the trespass, such as whether to commit a crime. The other is the frequency of the trespass; the more frequent the trespass the more foreseeable it is to the possessor of the premises. But since frequency, after a point, shows a total disregard of the rights of the possessor, it can lead to the conclusion that, what would have been an actionable injury, is now without a remedy because of the flagrant disregard of the rights of the possessor. Moreover, by focusing on the moral culpability of the injured trespasser, it requires juries and courts to make moral judgments with large subjective components. This possibility is recognized by the reporters in their explicit recognition and expectation that different jurisdictions might have different notions of what is \u27flagrant.\u27 Whether a restatement of the law that accepts that different states will look at things differently is actually a \u27restatement\u27 is a matter that deserves serious consideration