A chemical survey of standing waters in south-east England, with reference to acidification and eutrophication

This study looks at the distribution and magnitude of acidification and eutrophication in south-east England where there are no natural lakes but a large number of shallow artificial ponds. The study area is defined as the region lying within a 100 km radius of central London but excluding the area within the M25 motorway. Water samples were taken from 120 sites between mid-January and the end of February 1990, with a subsequent monthly survey of a subset of 31 of these waters. Twelve chemical variables were measured in the laboratory using standard techniques. PH values for the full dataset ranged from 3.2 to 8.4, although the majority of sites had pH values in the range 7.0 to 8.5; only five sites had a pH of less than 6.0. The five low pH sites expectedly had low alkalinities and are the only sites with values below 0.1 meq per litre. Concentrations of calcium, sodium, potassium, magnesium, chloride, sulphate and nitrate had normal distributions. The majority of sites had total phosphorus concentrations in the range 25 to 200 mu g per litre, although 10 sites had concentrations above 400 mu g per litre. The low number of acid sites suggests that surface water acidity is not a widespread regional problem in south-east England. However the survey shows that a large number of standing waters in the region have high total phosphorus and nitrate concentrations, and 89% may be considered moderately to considerably eutrophic.

Chemical studies of viral entry mechanisms: I. Hydrophobic protein-lipid interactions during sendai virus membrane fusion. II. Kinetics of bacteriophage λ DNA injection.

Viruses possess very specific methods of targeting and entering cells. These methods would be extremely useful if they could also be applied to drug delivery, but little is known about the molecular mechanisms of the viral entry process. In order to gain further insight into mechanisms of viral entry, chemical and spectroscopic studies in two systems were conducted, examining hydrophobic protein-lipid interactions during Sendai virus membrane fusion, and the kinetics of bacteriophage λ DNA injection.

Sendai virus glycoprotein interactions with target membranes during the early stages of fusion were examined using time-resolved hydrophobic photoaffinity labeling with the lipid-soluble carbene generator3-(trifluoromethyl)-3-(m-^(125 )I] iodophenyl)diazirine (TID). The probe was incorporated in target membranes prior to virus addition and photolysis. During Sendai virus fusion with liposomes composed of cardiolipin (CL) or phosphatidylserine (PS), the viral fusion (F) protein is preferentially labeled at early time points, supporting the hypothesis that hydrophobic interaction of the fusion peptide at the N-terminus of the F_1 subunit with the target membrane is an initiating event in fusion. Correlation of the hydrophobic interactions with independently monitored fusion kinetics further supports this conclusion. Separation of proteins after labeling shows that the F_1 subunit, containing the putative hydrophobic fusion sequence, is exclusively labeled, and that the F_2 subunit does not participate in fusion. Labeling shows temperature and pH dependence consistent with a need for protein conformational mobility and fusion at neutral pH. Higher amounts of labeling during fusion with CL vesicles than during virus-PS vesicle fusion reflects membrane packing regulation of peptide insertion into target membranes. Labeling of the viral hemagglutinin/neuraminidase (HN) at low pH indicates that HN-mediated fusion is triggered by hydrophobic interactions, after titration of acidic amino acids. HN labeling under nonfusogenic conditions reveals that viral binding may involve hydrophobic as well as electrostatic interactions. Controls for diffusional labeling exclude a major contribution from this source. Labeling during reconstituted Sendai virus envelope-liposome fusion shows that functional reconstitution involves protein retention of the ability to undergo hydrophobic interactions.

Examination of Sendai virus fusion with erythrocyte membranes indicates that hydrophobic interactions also trigger fusion between biological membranes, and that HN binding may involve hydrophobic interactions as well. Labeling of the erythrocyte membranes revealed close membrane association of spectrin, which may play a role in regulating membrane fusion. The data show that hydrophobic fusion protein interaction with both artificial and biological membranes is a triggering event in fusion. Correlation of these results with earlier studies of membrane hydration and fusion kinetics provides a more detailed view of the mechanism of fusion.

The kinetics of DNA injection by bacteriophage λ. into liposomes bearing reconstituted receptors were measured using fluorescence spectroscopy. LamB, the bacteriophage receptor, was extracted from bacteria and reconstituted into liposomes by detergent removal dialysis. The DNA binding fluorophore ethidium bromide was encapsulated in the liposomes during dialysis. Enhanced fluorescence of ethidium bromide upon binding to injected DNA was monitored, and showed that injection is a rapid, one-step process. The bimolecular rate law, determined by the method of initial rates, revealed that injection occurs several times faster than indicated by earlier studies employing indirect assays.

It is hoped that these studies will increase the understanding of the mechanisms of virus entry into cells, and to facilitate the development of virus-mimetic drug delivery strategies.

Condições de trabalho de ambiente cirúrgico e a saúde dos trabalhadores de enfermagem

O Centro Cirúrgico é um serviço especializado com estrutura física e organizacional complexa, normas e rotinas rigorosas, intensa atividade técnica, aparato tecnológico que requer profissionais treinados. A pesquisa teve como objeto de estudo os fatores de riscos ocupacionais e os problemas de saúde decorrentes do trabalho, identificados pelos profissionais de enfermagem de um Centro Cirúrgico de um Hospital Universitário da cidade do Rio de Janeiro. Os objetivos foram: analisar os fatores de riscos ocupacionais que possibilitam o aparecimento de problemas de saúde nos profissionais de enfermagem do Centro Cirúrgico segundo esses trabalhadores; descrever as características sociodemográficas dos profissionais lotados no Centro Cirúrgico; levantar os fatores de risco do ambiente cirúrgico identificados pelos trabalhadores de enfermagem do Centro Cirúrgico de um Hospital Universitário; e, discutir a relação entre os riscos do ambiente de trabalho e os problemas de saúde autoreferidos por trabalhadores de enfermagem do Centro Cirúrgico. A metodologia usada foi uma pesquisa não-experimental, de natureza descritiva, com abordagem quantitativa, desenvolvida em um centro cirúrgico de um hospital universitário federal da cidade do Rio de Janeiro. A população escolhida foi composta de trabalhadores da equipe de enfermagem, lotados no mínimo há seis meses neste serviço e que aceitassem participar da pesquisa. O questionário de coleta de dados utilizado foi adaptado por Mauro dos Guias e Avaliação de riscos em indústrias de Boix e Vogel. O estudo foi submetido e aprovado pelo Comitê de Ética em Pesquisa (CEP) do Hospital Universitário em estudo, através Parecer Consubstanciado no. 287/10, protocolo no. 217/09. Os dados foram analisados através do Programa Statistical Package for the Social Sciences (SPSS), versão 13.0. Os riscos biológicos foram os mais apontados pelos trabalhadores de enfermagem, seguidos dos riscos químicos, ergonômicos e de acidentes ou mecânicos. As doenças provocadas pelo trabalho mais referidas foram o estresse, a lombalgia, as varizes, a fadiga muscular e os problemas de articulação. As doenças agravadas pelo trabalho mais citadas foram as varizes, a lombalgia, os problemas de articulação, o estresse, as lesões de coluna vertebral, os problemas digestivos e os transtornos do sono. Conclui-se que o Serviço estudado possui riscos inerentes às atividades desenvolvidas que caracterizam os problemas relacionados pelos trabalhadores, e que são passíveis de controle através da intensificação de um Programa de Prevenção de Riscos Ambientais voltado para o Centro Cirúrgico. A partir da NR 17 e a 32, pode-se consultar as diretrizes para prevenção dos riscos encontrados. Uma estratégia de reposição digna de pessoal de enfermagem é imprescindível, assim como estudo e implantação de um Programa de Prevenção de Riscos laborais aos trabalhadores do Centro Cirúrgico, e utilização do questionário aos demais membros da equipe multiprofissional.

A Percepção do usuário de drogas sobre o mundo do trabalho: uma contribuição para a prática do enfermeiro

Estudo qualitativo, com base na Análise de Conteúdo, a partir da interrogação sobre como o usuário de drogas em situação de tratamento para a dependência química percebe-se como trabalhador, e qual sua relação com o mundo do trabalho. O referencial teórico apoiou-se nas definições de drogas psicotrópicas, dependência química e trabalho, das seguintes fontes, respectivamente, Organização das Nações Unidas (ONU), Classificação Internacional das Doenças (CID-10) e Ministério do Trabalho (MT) e a teoria da Psicodinâmica do trabalho. A metodologia baseou-se na Análise de Conteúdo Temática. A coleta de dados desenvolveu-se por meio de entrevistas em profundidade, e pela obtenção de dados sociodemográficos e de trabalho a partir dos registros. Foram realizadas trinta e oitos entrevistas semi estruturadas com dez mulheres, quatorze homens usuários de múltiplas drogas e quatorze homens usuários somente de bebidas alcoólicas. Todos os sujeitos eram trabalhadores em tratamento no Centro de Atenção Psicossocial-álcool e drogas Centro Estadual de Tratamento e Reabilitação de Adictos (Caps-ad CENTRA-RIO). Foram organizadas e analisadas seis categorias: conciliação ente o trabalho e o consumo de drogas; trabalho e angústia; o mundo do trabalho favorecendo/estimulando o consumo; beneficio e UD; trabalho pleno; perspectivas de vida do UD. Discutiu-se a intensa relação de sofrimento que permeia o tempo todo o trabalhador usuário de drogas, as diversas alternativas experimentadas para conseguir conciliar o binômio trabalho e drogas, a submissão aos valores construídos no ambiente de trabalho, a função de integradora intragrupo dos trabalhadores e terapêutica das drogas para conseguir cumprir o trabalho real, sua função relaxante e domadora da angústia e do medo. Nas conclusões, discutem-se os limites do mundo do trabalho em acompanhar a evolução do campo da saúde mental e a Reforma Psiquiátrica, e a importância para a enfermagem do trabalho. O enfermeiro deve ser o articulador para que este trabalhador usuário de drogas atue como protagonista ativo da sua própria história, contribuindo com sua experiência, para que os profissionais de saúde, o trabalho e a sociedade em geral aperfeiçoem formas de cuidar integral.

Development and Application of Embedding Methods for the Simulation of Large Chemical Systems

The high computational cost of correlated wavefunction theory (WFT) calculations has motivated the development of numerous methods to partition the description of large chemical systems into smaller subsystem calculations. For example, WFT-in-DFT embedding methods facilitate the partitioning of a system into two subsystems: a subsystem A that is treated using an accurate WFT method, and a subsystem B that is treated using a more efficient Kohn-Sham density functional theory (KS-DFT) method. Representation of the interactions between subsystems is non-trivial, and often requires the use of approximate kinetic energy functionals or computationally challenging optimized effective potential calculations; however, it has recently been shown that these challenges can be eliminated through the use of a projection operator. This dissertation describes the development and application of embedding methods that enable accurate and efficient calculation of the properties of large chemical systems.

Chapter 1 introduces a method for efficiently performing projection-based WFT-in-DFT embedding calculations on large systems. This is accomplished by using a truncated basis set representation of the subsystem A wavefunction. We show that naive truncation of the basis set associated with subsystem A can lead to large numerical artifacts, and present an approach for systematically controlling these artifacts.

Chapter 2 describes the application of the projection-based embedding method to investigate the oxidative stability of lithium-ion batteries. We study the oxidation potentials of mixtures of ethylene carbonate (EC) and dimethyl carbonate (DMC) by using the projection-based embedding method to calculate the vertical ionization energy (IE) of individual molecules at the CCSD(T) level of theory, while explicitly accounting for the solvent using DFT. Interestingly, we reveal that large contributions to the solvation properties of DMC originate from quadrupolar interactions, resulting in a much larger solvent reorganization energy than that predicted using simple dielectric continuum models. Demonstration that the solvation properties of EC and DMC are governed by fundamentally different intermolecular interactions provides insight into key aspects of lithium-ion batteries, with relevance to electrolyte decomposition processes, solid-electrolyte interphase formation, and the local solvation environment of lithium cations.

Programming chemical kinetics: engineering dynamic reaction networks with DNA strand displacement

Over the last century, the silicon revolution has enabled us to build faster, smaller and more sophisticated computers. Today, these computers control phones, cars, satellites, assembly lines, and other electromechanical devices. Just as electrical wiring controls electromechanical devices, living organisms employ "chemical wiring" to make decisions about their environment and control physical processes. Currently, the big difference between these two substrates is that while we have the abstractions, design principles, verification and fabrication techniques in place for programming with silicon, we have no comparable understanding or expertise for programming chemistry.

In this thesis we take a small step towards the goal of learning how to systematically engineer prescribed non-equilibrium dynamical behaviors in chemical systems. We use the formalism of chemical reaction networks (CRNs), combined with mass-action kinetics, as our programming language for specifying dynamical behaviors. Leveraging the tools of nucleic acid nanotechnology (introduced in Chapter 1), we employ synthetic DNA molecules as our molecular architecture and toehold-mediated DNA strand displacement as our reaction primitive.

Abstraction, modular design and systematic fabrication can work only with well-understood and quantitatively characterized tools. Therefore, we embark on a detailed study of the "device physics" of DNA strand displacement (Chapter 2). We present a unified view of strand displacement biophysics and kinetics by studying the process at multiple levels of detail, using an intuitive model of a random walk on a 1-dimensional energy landscape, a secondary structure kinetics model with single base-pair steps, and a coarse-grained molecular model that incorporates three-dimensional geometric and steric effects. Further, we experimentally investigate the thermodynamics of three-way branch migration. Our findings are consistent with previously measured or inferred rates for hybridization, fraying, and branch migration, and provide a biophysical explanation of strand displacement kinetics. Our work paves the way for accurate modeling of strand displacement cascades, which would facilitate the simulation and construction of more complex molecular systems.

In Chapters 3 and 4, we identify and overcome the crucial experimental challenges involved in using our general DNA-based technology for engineering dynamical behaviors in the test tube. In this process, we identify important design rules that inform our choice of molecular motifs and our algorithms for designing and verifying DNA sequences for our molecular implementation. We also develop flexible molecular strategies for "tuning" our reaction rates and stoichiometries in order to compensate for unavoidable non-idealities in the molecular implementation, such as imperfectly synthesized molecules and spurious "leak" pathways that compete with desired pathways.

We successfully implement three distinct autocatalytic reactions, which we then combine into a de novo chemical oscillator. Unlike biological networks, which use sophisticated evolved molecules (like proteins) to realize such behavior, our test tube realization is the first to demonstrate that Watson-Crick base pairing interactions alone suffice for oscillatory dynamics. Since our design pipeline is general and applicable to any CRN, our experimental demonstration of a de novo chemical oscillator could enable the systematic construction of CRNs with other dynamic behaviors.

Cavity-enhanced spectroscopies for applications of remote sensing, chemical kinetics and detection of radical species

This thesis describes applications of cavity enhanced spectroscopy towards applications of remote sensing, chemical kinetics and detection of transient radical molecular species. Both direct absorption spectroscopy and cavity ring-down spectroscopy are used in this work. Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was utilized for measurements of spectral lineshapes of O₂ and CO₂ for obtaining laboratory reference data in support of NASA’s OCO-2 mission. FS-CRDS is highly sensitive (> 10 km absorption path length) and precise (> 10000:1 SNR), making it ideal to study subtle non-Voigt lineshape effects. In addition, these advantages of FS-CRDS were further extended for measuring kinetic isotope effects: A dual-wavelength variation of FS-CRDS was used for measuring precise D/H and ¹³C/¹²C methane isotope ratios (sigma>0.026%) for the purpose of measuring the temperature dependent kinetic isotope effects of methane oxidation with O(¹D) and OH radicals. Finally, direct absorption spectroscopic detection of the trans-DOCO radical via a frequency combs spectrometer was conducted in collaboration with professor Jun Ye at JILA/University of Colorado.

Riscos ocupacionais e problemas de saúde associados às condições de trabalho de enfermagem em unidades intensivas hospitalares

Trata-se de um estudo quantitativo, descritivo, visando uma análise das condições de trabalho em unidades intensivas de um hospital universitário no município do Rio de Janeiro. Foi definido como objeto de estudo a percepção dos trabalhadores de enfermagem sobre os riscos ocupacionais e os problemas de saúde inerentes às condições de trabalho em unidades intensivas e como problema de pesquisa: quais os riscos ocupacionais e problemas de saúde relacionados às condições de trabalho, percebidos pelos trabalhadores de enfermagem, em unidades intensivas de um hospital universitário? O objetivo geral foi estudar nas unidades intensivas os riscos ocupacionais e problemas de saúde da equipe de enfermagem e sua relação com condições de trabalho, a partir da percepção dos mesmos. Os objetivos específicos traçados foram: identificar as características pessoais e profissionais dos trabalhadores de enfermagem de unidades intensivas; descrever os fatores de risco do ambiente de trabalho percebidos pelos trabalhadores de enfermagem; levantar os problemas de saúde percebidos pelos trabalhadores e sua relação com o trabalho; analisar a associação entre os problemas de saúde percebidos pelos trabalhadores de enfermagem e as condições do trabalho em unidades intensivas. Participaram da pesquisa 125 profissionais de enfermagem de quatro unidades intensivas do Hospital Universitário (HU) entre Maio e Julho de 2009. A predominância foi de profissionais do sexo feminino, com idade acima dos 40 anos, com mais de um vínculo empregatício e trabalhando no HU há mais de 10 anos. Os riscos ocupacionais mais percebidos pelos trabalhadores foram os ergonômicos, seguido dos biológicos, de acidentes, físicos e químicos. Os problemas de saúde mais frequentes foram varizes, problemas oculares, lombalgias, estresse e depressão, transtornos do sono, lesões de coluna vertebral, dores de cabeça, mudanças no humor, dores musculares crônicas e hipertensão arterial. Pela associação entre riscos ocupacionais e problemas de saúde, conclui-se que os trabalhadores expostos a fatores de riscos ergonômicos e físicos têm maior probabilidade de adquirir problemas de saúde osteoarticulares e circulatórios (varizes). Diante dos dados desta pesquisa faz-se necessário aprofundamento da investigação sobre os fatores de riscos encontrados e possíveis medidas para minimizá-los, mediante novos estudos. Como recomendações destacam-se a criação de um espaço de discussão entre os gerentes e trabalhadores para a elaboração de um programa que vise a promoção e proteção da saúde do trabalhador de enfermagem de unidades intensivas; implementação de medidas de controle específicas para cada tipo de risco evidenciado e a criação de um Comitê de Ergonomia para operacionalizar a implementação das melhorias no HU, a fim de consolidar as transformações esperadas.

Chemical composition of Iraq water resources (abbreviated translation) [Translation from: Vodnye Resursy 1975(4,) 173-185]

This abbreviated translation summarises the chemical composition of Iraq water resources. Among the described water bodies are the River Euphrates, Shatt al Arab River and a number of standing waters.

The chemical budget of a lake

A progress report on research undertaken on the chemical budget of a lake, outlining the importance of nitrogen and phosphorus in governing the production of life in freshwater. The report uses the Rivers Brathay and Leven, which flow into Windermere, as examples. The report also refers to the Rivers Rothay, Troutbeck and Cunsey. A table is including which shows the monthly average nitrate content (mg per litre) of the River Brathey and River Leven for 1937 into 1938. The report also includes a figure showing Windermere lake levels, discharge and rainfall during 1937. It also briefly considers possible anthropogenic influences on water quality.

Changes in physical and chemical variables

An article reviewing the work undertaken looking at the seasonal variation of chemical conditions in water at various depths in lakes. The laboratory tests undertaken for the research is outlined, as well as details of the sampling locations and the staff involved with the work. One figure shows the seasonal variation in the amounts of dissolved substances in the surface water of Windermere during 1936. Another figure shows seasonal varation inthe dry weight of phyto- and zooplankton in Windermere. Seasonal changes are discussed further and a table is included showing chemical conditions in winter and summer for Windermere.

The changing chemical composition of chalk streams and rivers

The area studied was the River Frome system below Dorchester. The main river has its origins mainly in chalk springs, although some of its tributaries have surface run-off from farm lands and heath-lands. Thus the chemistry of the river is affected by changes in land practice and differences in the geology of the catchment area. Regular chemical analysis of chalk waters started at the River Laboratory in 1964, Regular weekly analyses have been carried out since 1965 at Bere Stream (a small chalk stream) and the River Frome (a large chalk stream); also single samples have been analysed to provide preliminary information. In 1970-71 an attempt was made to discover the contribution each main source made to the flow and chemical composition of the River Frome. Results of these investigations are presented in the paper.

Studies of chemical speciation in naturally anoxic basins

The chemical speciation of both metals and non-metals, the use of polarographic techniques, and application to the study of the chemistry of anoxic waters are considered. In the first part of the paper unfamiliar terminology is explained and then an example of simple lake chemistry is presented to illustrate why the concept of speciation is necessary.