The Raman spectra of serine and 3,3-dideutero-serine in aqueous solution

The Raman spectra of serine [[alpha]-amino-[beta]-hydroxypropionic acid; HOCH2CH(NH3)+COO-] and 3,3-dideutero-serine [HOCD2CH(NH3)+COO-] in aqueous solution were studied in the range 4000-300 cm-1. The data obtained for the deuterated compound are novel and provide compelling evidence that previously reported assignments for the undeuterated amino acid should be revised.http://www.sciencedirect.com/science/article/B6THW-4KNMB16-1/1/19da7b30f32b5efeacb053228a66c4a

IR-Induced Photoisomerization of Glycolic Acid Isolated in Low-Temperature Inert Matrices

Glycolic acid (HO−CH2−COOH) monomers isolated in low-temperature argon and krypton matrices were studied using FTIR spectroscopy. The most stable SSC conformer of the compound dominated in the matrices immediately after their deposition. Upon broadband infrared irradiation, two minor conformers (GAC and AAT) were photogenerated. No other forms of glycolic acid were populated, either thermally or photochemically. Systematic monitoring of the progress of the IR-induced phototransformations (over a time scale of 20−140 min) allowed one to distinguish between the primary (GAC) and secondary (AAT) photoproducts. The assignment of experimental spectra to the different conformers was based on the results of IR irradiation of the samples and was assisted by the theoretical calculations carried out at the MP2/aug-cc-pVDZ level. Theoretical pathways for intramolecular rotation in the glycolic acid monomer were investigated at the MP2/6-31++G(d,p) level. Lack of conformers other than SSC, GAC, and AAT in the IR-irradiated matrices was explained in terms of energy barriers separating different forms of the compound

Infrared and Raman spectroscopic characterization of the hydrogen-bonding network in l-serine crystal

The IR spectra (4000-400 cm-1) of neat and isotopically substituted (ND/OD <= 10% D and [congruent with]30% D) polycrystalline l-serine ([alpha]-amino-[beta]-hydroxypropionic acid; HO-CH2-CH(NH3)+-COO-) were recorded in the temperature range 300-10 K and assigned. The isotopic-doping/low-temperature methodology, which allows for decoupling of individual proton vibrational modes from the crystal bulk vibrations, was used for estimating the lengths and energies of the different H-bonds present in l-serine crystal. To this end, the frequency shifts observed in both the NH/OH stretching and out-of-plane bending spectral regions (relatively to reference values for these vibrations in non-hydrogen-bonded l-serine molecules) were used, together with previously developed empirical correlations between these spectral parameters and the H-bond properties. In addition, the room-temperature Raman spectrum (4000-150 cm-1) of a single crystal of neat l-serine was also recorded and interpreted. A systematic comparison was made between the spectroscopic data obtained currently for l-serine and previously for dl-serine, revealing that the vibrational spectra of the two crystals reflect well the different characteristics of their hydrogen-bond networks, and also correlate accurately with the different susceptibility of the two crystals to pressure-induced strain.http://www.sciencedirect.com/science/article/B6THW-4K4WMR3-2/1/211ac428c09ebc9eb45cf3b81d93fcb

Low-temperature infrared spectra and hydrogen bonding in polycrystalline dl-serine and deuterated derivatives

The FT-IR spectra of polycrystalline dl-serine [[alpha]-amino-[beta]-hydroxypropionic acid; HO-CH2-CH(NH3)+-COO-] and isotopically substituted [ND/ODAlcohol (90% D); CD2 (>98% D)] dl-serine were recorded in the range 4000-500 cm-1 in the temperature range 300-10 K, and fully assigned. The isotopic-doping/low-temperature methodology, which allows for decoupling of individual proton vibrational modes from the crystal bulk vibrations, was used to estimate the energies of the different H-bonds present in dl-serine crystal. To this end, the frequency shifts observed in both the NH/OH stretching and out-of-plane bending spectral regions (relatively to reference values for these vibrations in non-hydrogen-bonded dl-serine molecules) were used, together with previously developed empirical correlations. The results are compared with available structural data on this amino acid.http://www.sciencedirect.com/science/article/B6THW-4J91R39-2/1/f8f35f435466c8a5204879d330cbade

A Autodeterminação e as Emoções Positivas

A Autodeterminação e a Positividade, nomeadamente, as Emoções Positivas abordam questões importantes referentes ao bem-estar e à saúde dos indivíduos e, por essa mesma razão, têm vindo a ser exaustivamente explorados ao longo de vários anos, também devido à sua enorme complexidade e multidimensionalidade de construtos. Atendendo ao facto de que a fase desenvolvimental da adolescência se trata de um período fulcral, quer para o estabelecimento de relações com os outros, quer para a formação pessoal dos indivíduos, o presente estudo tem como principal objetivo verificar e descrever a relação entre a Autodeterminação e a vivência de emoções positivas em adolescentes. Para tal, foram inquiridos um total de 81 adolescentes – 36 do sexo feminino e 44 do sexo masculino - com idades compreendidas entre os 14 e os 18 anos. A recolha de dados foi realizada em diferentes estabelecimentos de Ensino da zona centro do país. A esta amostra foram aplicados três instrumentos de avaliação: (1) Questionário Sociodemográfico, (2) a Escala da Autodeterminação (Sheldon & Deci, 1996; versão portuguesa de Silva et al., 2010), atualmente designada Perceived Choice and Awareness of Self Scale (PCASS) e (3) a Escala de Positividade (versão original Positivity Scale ou P-Scale, Fredrickson, 2009; versão portuguesa de Batista, 2012; Luís, 2015). Em termos gerais, os resultados obtidos suportam a existência de uma relação positiva entre a Autodeterminação e as Emoções Positivas, o que nos sugere que quando os adolescentes se sentem mais autodeterminados num determinado comportamento ou tomada de decisão, tendem a experienciar emoções e/ou sentimentos positivos.Self-Determination and Positivity, namely, Positive Emotions address important issues related to the well-being and health of individuals and, for this same reason, have been extensively explored over several years, also due to their enormous complexity and multidimensionality of constructs. Given the fact that the developmental phase of adolescence is a pivotal period, both for establishing relationships with others and for the personal training of individuals, the present study has as main objective to verify and describe the relationship between Self-determination and the experience of positive emotions in adolescents. To this end, a total of 81 adolescents - 36 female and 44 male - aged between 14 and 18 years were surveyed. Data collection was carried out in different educational establishments in the central part of the country. Three assessment instruments were applied to this sample: (1) Sociodemographic Questionnaire, (2) the Self-Determination Scale (Sheldon & Deci, 1996; Portuguese version by Silva et al., 2010), currently called Perceived Choice and Awareness of Self Scale (PCASS) and (3) the Positivity Scale (original version Positivity Scale or P-Scale, Fredrickson, 2009; Portuguese version of Batista, 2012; Luís, 2015). In general terms, the results obtained support the existence of a positive relationship between Self-Determination and Positive Emotions, which suggests that when adolescents feel more self-determined in a certain behavior or decision making, they tend to experience emotions and / or feelings positive

Preferred Conformers and Photochemical (λ > 200 nm) Reactivity of Serine and 3,3-Dideutero-Serine In the Neutral Form

A systematic investigation of the conformational potential energy surface of neutral serine [HOCH2CHNH2COOH] and 3,3-dideutero-serine [HOCD2CHNH2COOH] was undertaken, revealing the existence of 61 different minima. The structures and vibrational spectra of the most stable conformers, which were estimated to have relative energies within 7 kJ mol-1 and account for ca. 93% of the total conformational population at room temperature, were calculated at both the MP2 and DFT/BLYP levels of theory with the 6-311++G(d,p) basis-set and used to interpret the spectroscopic data obtained for the compounds isolated in low-temperature inert matrixes. The assignment of the main spectral infrared features observed in the range 4000−400 cm-1 to the most stable conformers of serine was undertaken. In addition, UV irradiation (λ > 200 nm) of the matrix-isolated compounds was also performed, leading to decarboxylation, which was found to be strongly dependent on the conformation assumed by the reactant molecule

Construção da parentalidade: o papel do enfermeiro de família

Mestrado em Enfermagem de Saúde FamiliarEnquadramento: O presente relatório reporta-se ao estágio de natureza profissional desenvolvido na Unidade de Saúde Familiar Rainha D. Tereza de Albergaria-a-Velha, no período de 19 de setembro de 2016 a 23 de fevereiro de 2017. Objetivos: Pretendemos descrever e refletir sobre o percurso desenvolvido no contexto da prática clínica dos cuidados de saúde primários na aquisição de competências específicas em enfermagem de saúde familiar. Assim como, apresentar o estudo empírico desenvolvido em contexto de estágio, intitulado: “Construção da Parentalidade – O Papel do Enfermeiro de Família”. Com o objetivo de conhecer a forma como os pais da USF Rainha D. Tereza constroem o seu modelo de parentalidade durante o primeiro semestre de vida do primeiro filho. Métodos: Desenvolvemos um estudo fenomenológico de natureza qualitativa, com uma amostragem não probabilística de conveniência que inclui 11 sujeitos participantes, pais com o primeiro filho a completar seis meses de vida entre outubro e dezembro de 2016, inscritos na USF Rainha D. Tereza. Realizámos entrevistas semiestruturadas, obtendo as narrativas das vivências e a sua compreensão mais profunda. Cumprimos os procedimentos éticos e submetemos as informações colhidas a análise de conteúdo com auxílio do Software WEBQDA. Resultados: Destacamos a vivência da parentalidade no desejo de ser pai/mãe e nas expetativas criadas na gravidez contribuindo para o modelo parental. Esta é influenciada por fatores como as características da criança, as características e experiências prévias dos pais e as dinâmicas familiares. Os pais apresentam dificuldades relativas à prestação de cuidados à criança e à conciliação dos papéis parental, conjugal, familiar e social. Perante estas dificuldades os pais utilizam recursos humanos, comunitários e monetários. Realçamos o recurso comunitário no apoio dos cuidados de saúde, o qual é valorizado pelos pais. O enfermeiro de família, quando é identificado e o seu papel é reconhecido, é descrito como recurso efetivo e acessível na adaptação á parentalidade. Conclusão: Este trabalho expôs o percurso em contexto de estágio na aquisição das competências exigidas e demonstrou que os objetivos propostos foram alcançados. Os resultados obtidos pela investigação desenvolvida permitiram conhecer a vivência da transição para a parentalidade dos pais entrevistados e afirmar o papel do enfermeiro de família na capacitação destes para a construção do seu próprio modelo de parentalidade, assim como contribuir com conhecimento a valorizar nas intervenções de enfermagem.Background: The present report refers to the professional internship that took place at Unidade de Saúde Familiar Rainha D. Tereza in Albergaria-a-Velha, between the September 19th 2016 and February 23rd 2017. Aim: We intend to describe and reflect on the course developed in the context of the clinical practice of primary health care in the acquisition of specific competences in family health nursing. As well as, present the empirical study developed in an internship context, titled: "Construction of Parenthood – The Role of the Family Nurse". With the purpose of knowing how the parents of the USF Rainha D. Tereza build their model of parenting during the first semester of life of the first child. Methods: We developed a phenomenological study of qualitative nature, with a non-probabilistic sampling of convenience that includes 11 subjects, parents with the first child to completing six months of life between october and december 2016, enrolled in USF Rainha D. Tereza. We conducted semi-structured interviews, obtaining the narratives of the experiences and their deepest understanding. We comply with ethical procedures and submit the information collected to complied analysis with the help of WEBQDA Software. Results: We highlight the experience of parenting in the desire to be a parent, and in the expectations created in pregnancy, contributing to the parental model. This is determined by factors such as the characteristics of the child, the characteristics and previous experiences of the parents and the family dynamics. Parents face difficulties in providing care for the child and reconciling parental, marital and family and social roles. Faced with these difficulties parents use human, community and monetary resources. We highlight the community resource in support of health care, which is valued by parents. The family nurse, when identified and recognized, is described as an effective and accessible resource in adapting to parenting. Conclusion: This work exposed the trajectory in the acquisition of the required competences and demonstrated that the proposed objectives were achieved. The results obtained by the research carried out allowed us to acknowledge the experience of the transition to parenthood of the parents interviewed and to affirm the role of the family nurse in their capacity to build their own model of parenting, as well as contributed with knowledge to be valued in nursing interventions

Identification of stillbirths in NSW linked population health datasets

This manuscript has not been submitted for publication. It compares stillbirth reporting from four different population data sources, and develops an algorithm for maximum identification of definite and probable stillbirths in linked population data while avoiding false positive and duplicate reports. By placing the results on this repository we are hoping to inform future use of population data for research on stillbirths in NSW.This work was supported by the Stillbirth Foundation Australia. Christine Roberts is supported by a NHMRC Senior Research Fellowship (APP1021025). We thank the NSW Ministry of Health for access to the population health data and the Centre for Health Record Linkage (CHeReL) for linking the data sets

Foldamers of β-peptides : conformational preference of peptides formed by rigid building blocks : The first MI-IR spectra of a triamide nanosystem

To determine local chirality driven conformational preferences of small aminocyclobutane-1-carboxylic acid derivatives, X-(ACBA) n -Y, their matrix-isolation IR spectra were recorded and analyzed. For the very first time model systems of this kind were deposited in a frozen (~10 K) noble gas matrix to reduce line width and thus, the recorded sharp vibrational lines were analyzed in details. For cis-(S,R)-1 monomer two “zigzag” conformers composed of either a six or an eight-membered H-bonded pseudo ring was identified. For trans-(S,S)-2 stereoisomer a zigzag of an eight-membered pseudo ring and a helical building unit were determined. Both findings are fully consistent with our computational results, even though the relative conformational ratios were found to vary with respect to measurements. For the dimers (S,R,S,S)-3 and (S,S,S,R)-4 as many as four different cis,trans and three different trans,cis conformers were localized in their matrix-isolation IR (MI-IR) spectra. These foldamers not only agree with the previous computational and NMR results, but also unambiguously show for the first time the presence of a structure made of a cis,trans conformer which links a “zigzag” and a helical foldamer via a bifurcated H-bond. The present work underlines the importance of MI-IR spectroscopy, applied for the first time for triamides to analyze the conformational pool of small biomolecules. We have shown that the local chirality of a β-amino acid can fully control its backbone folding preferences. Unlike proteogenic α-peptides, β- and especially (ACBA) n type oligopeptides could thus be used to rationally design and influence foldamer’s structural preferences

An experimental and computational IR and hybrid DFT-D3 study of the conformations of L-lactic and acrylic acid: new insight to the dehydration mechanism of lactic acid to acrylic acid

We have studied with hybrid Density Functional Theory (DFT) with an aug-cc-pVTZ basis set and D3 dispersion corrections the intra-molecular hydrogen bond of L-lactic acid and L-lactic-acid analogs with the hydroxyl group on the alpha carbon atom substituted by α -XH (where X = S, Se, Te) as well as the conformations of acrylic acid. The results show there are three types of intramolecular hydrogen bonds that can form only when α-OH is present, whereas other less electronegative functional groups such as -SH, -SeH and -TeH do not exhibit the formation of an intramolecular H-bond. We show that the intra-molecular H-bond formed between the alpha-OH hydrogen and the COOH carbonyl oxygen would enhance the rate of the nucleophilic subsitution of alpha-OH to the K+ sites for the previously suggested dehydration mechanism of L-lactic to acrylic acids. We find that a temperature range between 190-210 °C would be optimum to maximise the rate of the nuleophilic substitution of the alpha-OH group onto the potassium sites during the dehydration mechanism of L-lactic acid to acrylic acid. Additionally, our hybrid-DFT simulation of the infrared spectrum of the various conformers shows that the lowest energy conformer can be identified by a single vibrational band at 3734 cm-1 whereas the other conformers this vibrational band is split with Δν that ranges between 6 cm-1 - 176 cm-1. We also find that the various conformers of acrylic acid can be identified by a double peak for the C=O and O-H vibrations which have Δν' of Δν'' 24 and 42 cm-1, respectively. This computational study is useful for spectroscopic experimental efforts that try to identify the various conformers of L-lactic acid and acrylic acid and to gain mechanistic insight into the dehydration mechanism over K substituted NaY Zeolites