Rochester: documented

Over a two-year period certain unappreciated, visual and factual aspects of the City of Rochester were systematically documented. These aspects of the City of Rochester consisted of Mobil Gas Stations and their owners, closed gas stations, and new businesses in former gas stations; the City Limits and residents, animals, and other noisemakers existing proximal to the City Limits; places where I had to wait in line; the MEN and WOMEN of City Hall; the dotted lines that separate traffic lanes; and a short, dead-end street that was bull dozed over and left for field. The process of documenting these aspects of the City of Rochester emphasized ways of categorizing and cataloguing seemingly random events and unrelated people and objects with respect to both time and space. The final exhibition installation engaged the viewer in activities similar to those I had to perform in order to complete the work

Professor Marcos Eberlin, who is the chief executive of the Brazilian Society of Mass Spectrometry, recently spoke to BrJAC about his work

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Enol intermediates derived from carboxylic acids, esters and amides

A kinetic investigation into the enolisation mechanism and enol contents of simple carboxylic acids, esters and amides has been undertaken. Measurement of the enolisation rate constants for malonic acid, ethylhydrogenmalonate and 2- carboxyacetamide were obtained. The halogenation reactions were carried out under conditions where the rate determining step was the enolisation and the reactions were zero order in halogen. The measurements were carried out using u.v./visible spectrophotometry. Results obtained for malonic acid and ethylhydrogenmalonate support the idea of an intramolecular acid catalysed mechanism involving a hydrogen bonded six membered transition state. The enolisation mechanisms were investigated in a number of buffer solutions and were found to be catalysed by general bases. Catalytic coefficients for the following bases were calculated, HO(_2)CCH(_2)CO(_2)-, EtO(_2)CCH(_2)CO(_2)-,ClCH(_2)CO(_2)-, and H(_2)O. Deuterium exchange reactions were monitored using (^1)H N.M.R. and enolisation rate constants for cyano-containing esters and amides were calculated. The results show that the enolisation of amides occurs via an acid catalysed process whereas the enolisation of carboxylic acids and esters proceeds by an intramolecular acid catalysed or a general base catalysed mechanism. Enol contents for simple carboxylic acid derivatives were determined from their reactions with halogens under conditions where the reaction of the halogen with the enol is rate limiting and the reaction is found to be first order in the halogen. It was demonstrated that chlorine, bromine and iodine react with carboxylic ester enols at or very close to the diffusion controlled limit (ca 5x10(^9) 1 mol(^-1) sec(^-1)). The enol contents measured were found to be greater than expected, with the enol content of malonic acid very similar to that of acetone. An estimate of the acidity of carboxylic acid enols has shown them to be strong acids with pK(_a) values in the region 2-5

Novel Applications of Polyfunctionalised Organoboron and Nitroso Compounds

This thesis deals with the reactivity of dienylboronated compounds towards aryl- and carbonylnitroso derivatives. The first part of this focused on the reactivity of dienylboronate compounds with arylnitroso derivatives resulting in pyrrole or furan formation. The outcome and efficiency of the reaction is related to the boron substituents and the solvent used, thus giving pyrroles, boronated oxazines or nitrones. A one-pot strategy was then applied to synthesise oxazoline derivatives using nitrones as key intermediates. Theoretical, as well as experimental, works supported that the formation of the pyrrole via regioselective nitroso Diels-Alder reaction/rearrangement/borate elimination cascade process. Secondly, attention was focused on the reactivity of dienylboronate compounds with carbonylnitroso derivatives. The nature of the carbonylnitroso had a dramatic impact on reactivity and, for example, the product resulting from a nitroso-ene reaction was obtained with pinacol derivatives. This ene-species was further used as the key intermediate for the synthesis of different polycyclic compounds. Several one-pot multicomponent processes were developed, giving access to various heterocycles with a high functional and structural diversity

A Comprehensive Review of the Pharmacodynamics, Pharmacokinetics, and Clinical Effects of the Neutral Endopeptidase Inhibitor Racecadotril

Racecadotril, via its active metabolite thiorphan, is an inhibitor of the enzyme neutral endopeptidase (NEP, EC 3.4.24.11), thereby increasing exposure to NEP substrates including enkephalins and atrial natriuretic peptide (ANP). Upon oral administration racecadotril is rapidly and effectively converted into the active metabolite thiorphan, which does not cross the blood–brain-barrier. Racecadotril has mainly been tested in animal models and patients of three therapeutic areas. As an analgesic the effects of racecadotril across animal models were inconsistent. In cardiovascular diseases such as hypertension or congestive heart failure results from animal studies were promising, probably related to increased exposure to ANP, but clinical results have not shown substantial therapeutic benefit over existing treatment options in cardiovascular disease. In contrast, racecadotril was consistently effective in animal models and patients with various forms of acute diarrhea by inhibiting pathologic (but not basal) secretion from the gut without changing gastro-intestinal transit time or motility. This included studies in both adults and children. In direct comparative studies with loperamide in adults and children, racecadotril was at least as effective but exhibited fewer adverse events in most studies, particularly less rebound constipation. Several guidelines recommend the use of racecadotril as addition to oral rehydration treatment in children with acute diarrhea

Fast Analysis of Taurine in Energetic Drinks by Electrospray Ionization Mass Spectrometry

Santos, LS (Santos, Leonardo S.). Univ Talca, Inst Quim Recursos Nat, Lab Asymmetr Synth, Talca, ChileDirect infusion electrospray ionization tandem mass spectrometry in the negative ion mode with single reaction monitoring is show to allow high selectivity and sensitivity in the quantification of taurine in energetic drinks. The method is also simple and rapid (less than 2 min run time), with high recovery and repeatability. Commercially available energetic drinks were found to contain taurine in concentrations quite different (lower or higher) from the declared amounts

The principles and practice of open fracture care, 2018

The principles of open fracture management are to manage the overall injury and specifically prevent primary contamination becoming frank infection. The surgical management of these complex injuries includes debridement and lavage of the open wound with combined bony and soft tissue reconstruction. Good results depend on early high quality definitive surgery usually with early stable internal fixation and associated soft tissue repair. While all elements of the surgical principles are very important and depend on each other for overall success the most critical element appears to be achieving very early healthy soft tissue cover. As the injuries become more complex this involves progressively more complex soft tissue reconstruction and may even requiring urgent free tissue transfer requiring close co-operative care between orthopaedic and plastic surgeons. Data suggests that the best results are obtained when the whole surgical reconstruction is completed within 48-72 h

Assessment of intra-articular volume of the wrist: a comparative study between CT-arthrography and dissection

The aim of this study was to compare the intra-articular volumes of the wrist's joint measured by CT-arthrography and by dissection on ten cadavers. A good correlation was found between CT-arthrography and dissection in the assessment of the intra-articular volume of both wrist joints. A volume of 1.34 (±0.46) milliliter and 0.97 (±0.32) milliliter were found by Ct-arthrography for the radiocarpal and midcarpal joints, respectively. Dissection of the same wrists gives a volume of 1.24 (±0.33) and 0.90 (±0.21) for the radiocarpal and midcarpal joints, respectively. The knowledge of normal wrist-joint volume is a major prerequisite to evaluate carpal instability without ligaments' tears. We believe that CT-arthrography could be helpful in evaluating patients with suspected carpal instabilit

The free software as an alternative for digital cohesion of visually impaired people

Orientador: Luiz Cesar MartiniDissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de ComputaçãoResumo: A acelerada difusão do software "livre", tanto no Brasil como no exterior, vem se mostrando cada vez mais evidente nos mais diversos âmbitos (governo, empresas, escolas, etc.). A principal motivação para a transição do software "proprietário" para o "livre" é a redução de custos, mas para efetivar essa migração é necessário que ferramentas compatíveis estejam disponíveis para a manutenção da usabilidade do sistema. Essa é ainda uma barreira para a migração do usuário deficiente visual brasileiro, pois até este momento, nenhuma das tecnologias assistivas desenvolvidas para sistemas operacionais "livres" encontram-se disponíveis no idioma português. Como solução para esse problema, esta dissertação apresenta uma alternativa que efetivará essa migração, habilitando usuários cegos para realização de tarefas como edição de texto, acesso à internet, gerenciamento de arquivos, entre outras. O trabalho baseia-se na implementação de um sintetizador de voz para o português do Brasil e na tradução de uma tecnologia assistiva desenvolvida para sistemas operacionais "livres". Como parte integrante estão documentados também o desenvolvimento de um modelo compacto de computador pessoal e os resultados de testes realizados com usuários voluntáriosAbstract: The accelerated diffusion of the "free" software, as much in Brazil as in the foreign, has beem shown more and more evident in the most diverse scopes (government, companies, schools, etc) The main motivation to the transition from "proprietary" software to the "free" one is the costs reduction, but to accomplish this migration compatible tools need to be available for the maintenance of the system usability. This is still a barrier for the migration of the brazilian visually impaired user, because up to this moment, none of the assistive technologies developed to "free" operating systems are available in portuguese language. As solution for this problem, this dissertation presents an alternative that will accomplish this migration, enabling blind users to carrying out tasks like text edition, internet access, file management, among others. The work is based on the implementation of a voice synthesizer for the portuguese from Brazil and on the translation of an assistive technology developed to "free" operating systems. As integrated part are also documented the development of a compact model of personal computer and the results of tests carried out with voluntary usersMestradoTelecomunicações e TelemáticaMestre em Engenharia Elétric

Gas Phase Chemistry Of The 2-tert-butyl-3-phenylphosphirenylium Cation: Novel Onium Ions By Nucleophilic Attack At Phosphorus And De Novo P-spiro Bicyclic Phosphonium Ions Via [4 + 2+] Cycloaddition With Dienes

The 2-tert-butyl-3-phenylphosphirenylium ion 13 is formed in abundance in the gas phase from 1-chloro-1H-phosphirene 6 upon 70 eV electron ionization. Collision-induced dissociation (CID) and ion-molecule reactions followed by CID of the product ions were performed via pentaquadrupole mass spectrometry to probe the structure and reactivity of 13 towards representative nucleophiles and dienes. Under CID conditions, 13 produces a variety of fragment ions mainly via dissociation processes that are preceded by isomerizations. In ion-molecule reactions, 13 reacts readily with ethers, sulfides, pyridine and aniline to form hitherto unknown oxonium, sulfonium and azonium ions via nucleophilic attack at phosphorus. With butadiene, isoprene, 1-acetoxybutadiene, and with Danishefsky's diene (1-methoxy-3-silyloxybuta-1,3-diene), 13 undergoes [4 + 2+] cycloaddition at phosphorus to generate novel P-spiro bicyclic phosphonium ions. With butadiene and isoprene, a second [4 + 2] cycloaddition occurs which generates P-spiro tricyclic phosphonium ions. Whereas 13 also reacts readily with 1-acetoxybutadiene via [4 + 2+] cycloaddition, most of the nascent P-spiro cycloadducts are unstable and dissociate by the loss of either a neutral ketene or acetic acid molecule. B3LYP/6-31G(d,p) calculations were performed to gain insight into the structures of the product ions. The present study constitutes the first successful attempt to unravel the chemistry of 13, a unique 2π-Hückel phosphirenylium ion for which no direct solution chemical reactivity data are as yet available. The present findings also create a parallel with the solution reactivity of 1-halo-1H-phosphirenes and 1-triflato-1H-phosphirenes as precursors to phosphirenylium ions.12395400Laali, K.K., Geissler, B., Wagner, O., Hoffmann, J., Armbrust, R., Eisfeld, W., Regitz, M., (1994) J. Am. Chem. 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