Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase

1-Phenyl-1,2-propanedione has been isolated in low-temperature xenon matrixes and studied by FTIR spectroscopy, supported by DFT(B3LYP)/6-311++G(d,p) calculations. In good agreement with previous electron diffraction data [Shen, Q.; Hagen, K. J. Phys. Chem. 1993, 97, 985], the calculations predicted the existence of only one stable conformation for the compound, in which the O=C-C=O dihedral angle is 135.6 degrees. On the other hand, the experimental data clearly reveals that, in the as-deposited xenon matrixes (T = 20 K), there is a distribution of molecules with different O=C-C=O dihedral angles around the equilibrium value. This distribution results from the efficient trapping of the conformational distribution existing in the gas phase, prior to deposition, which is determined by the low frequency, large amplitude torsional vibration around the C-C central bond. Upon annealing to higher temperatures (T approximately 45 K), the initially trapped conformational distribution can be modified in a certain degree, favoring more polar structures (corresponding to smaller O=C-C=O dihedral angles), as a result of the interactions with the matrix media. Irradiation of the matrix with UV light (lambda > 235 nm) led to decarbonylation of the compound, with generation of acetophenone and carbon monoxide, with an almost complete consumption of the reagent after 1100 min of irradiation (k = 2.8 x 10(-2) min.(-1)). Aggregation of the compound resulting from the matrix warming was also investigated, providing useful information for interpretation of the spectroscopic data obtained for the low-temperature amorphous state of the neat compound.Fil: Lopes, Susy. Universidad de Coimbra; PortugalFil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina. Universidad de Buenos Aires; ArgentinaFil: Lapinsky, Leszek. Polish Academy of Sciences; ArgentinaFil: Fausto, Rui. Universidad de Coimbra; Portuga

Structure and IR Spectra of 3(5)-Aminopyrazoles and UV-induced tautomerization in argon matrix

The prototropic tautomerism in 3(5)-aminopyrazoles was investigated by matrix isolation infrared (IR) spectroscopy, supported by DFT(B3LYP)/6-311++G(d,p) calculations. In consonance with the experimental data, the calculations predict tautomer 3-aminopyrazole (3AP) to be more stable than the 5-aminopyrazole (5AP) tautomer (calculated energy difference: 10.7 kJ mol−1 ; Gibbs free energy difference: 9.8 kJ mol−1 ). The obtained matrix isolation IR spectra (in both argon and xenon matrices) were interpreted, and the observed bands were assigned to the tautomeric forms with help of vibrational calculations carried out at both harmonic and anharmonic levels. The matrix-isolated compound (in argon matrix) was then subjected to in situ broadband UV irradiation (λ > 235 nm), and the UV-induced transformations were followed by IR spectroscopy. Phototautomerization of the 3AP tautomer into the 5AP form was observed as the strongly prevalent reaction.UI0313B/QUI/2020, UI0313P/QUI/2020info:eu-repo/semantics/publishedVersio

Formic and acetic acids in a nitrogen matrix: Enhanced stability of the higher energy conformer.

Non Peer reviewe

A assistência de enfermagem diante à uma reanimação cardiopulmonar no âmbito pré-hospitalar

The aim was to identify in the literature the performance of the nurse and the actions performed to direct a cardiorespiratory arrest in the extra-hospital environment. Integrative review, carried out through the survey of scientific data from the last 10 years, through PubMed databases and the Virtual Health Library portal. Original articles in English, Portuguese and Spanish referring to the period from 2012 to 2021 were selected. First, the titles and abstracts were read, and then recruitment of journals that responded to the research intention so that they were analyzed in full. The research complied with the ethical aspects of Resolution CNS n.º 466/12. In view of the evaluation of those selected, the fragmentation into three categories was clarified, namely: performing care in different locations, using the criteria for completing cardiopulmonary resuscitation and identifying the needs for adequate patient care. Presenting scientific knowledge and having autonomy in the face of cardiopulmonary resuscitation favors adequate assistance, regardless of the location where the procedure is performed, and reduces impasses in the handling of human and material resources.Objetivou-se identificar na literatura a atuação do enfermeiro e as ações desempenhadas para o direcionamento de uma parada cardiorrespiratória no ambiente extra-hospitalar. Revisão integrativa, realizada através do levantamento de dados científicos dos últimos 10 anos, por meio das bases PubMed e o portal da Biblioteca Virtual em Saúde. Foram selecionados artigos originais na língua inglesa, portuguesa e espanhola referente ao período de 2012 a 2021. Primeiramente, foram lidos os títulos e resumos, e em seguida, recrutamento dos periódicos que respondiam a intenção da pesquisa para que fossem analisados na íntegra. A pesquisa respeitou os aspectos éticos da Resolução CNS n.º 466/12. Frente à avaliação dos selecionados, elucidou-se a fragmentação em três categorias, sendo: realizando o atendimento em diferentes localidades, utilizando os critérios para o término de reanimação cardiopulmonar e identificando as necessidades para o atendimento adequado ao paciente. Apresentar conhecimentos científicos e ter autonomia diante à reanimação cardiopulmonar favorece a assistência adequada, independentemente da localização em que o procedimento é realizado, e diminui impasses no manuseio de recursos humanos e materiais

A assistência de enfermagem diante à uma reanimação cardiopulmonar no âmbito pré-hospitalar

The aim was to identify in the literature the performance of the nurse and the actions performed to direct a cardiorespiratory arrest in the extra-hospital environment. Integrative review, carried out through the survey of scientific data from the last 10 years, through PubMed databases and the Virtual Health Library portal. Original articles in English, Portuguese and Spanish referring to the period from 2012 to 2021 were selected. First, the titles and abstracts were read, and then recruitment of journals that responded to the research intention so that they were analyzed in full. The research complied with the ethical aspects of Resolution CNS n.º 466/12. In view of the evaluation of those selected, the fragmentation into three categories was clarified, namely: performing care in different locations, using the criteria for completing cardiopulmonary resuscitation and identifying the needs for adequate patient care. Presenting scientific knowledge and having autonomy in the face of cardiopulmonary resuscitation favors adequate assistance, regardless of the location where the procedure is performed, and reduces impasses in the handling of human and material resources.Objetivou-se identificar na literatura a atuação do enfermeiro e as ações desempenhadas para o direcionamento de uma parada cardiorrespiratória no ambiente extra-hospitalar. Revisão integrativa, realizada através do levantamento de dados científicos dos últimos 10 anos, por meio das bases PubMed e o portal da Biblioteca Virtual em Saúde. Foram selecionados artigos originais na língua inglesa, portuguesa e espanhola referente ao período de 2012 a 2021. Primeiramente, foram lidos os títulos e resumos, e em seguida, recrutamento dos periódicos que respondiam a intenção da pesquisa para que fossem analisados na íntegra. A pesquisa respeitou os aspectos éticos da Resolução CNS n.º 466/12. Frente à avaliação dos selecionados, elucidou-se a fragmentação em três categorias, sendo: realizando o atendimento em diferentes localidades, utilizando os critérios para o término de reanimação cardiopulmonar e identificando as necessidades para o atendimento adequado ao paciente. Apresentar conhecimentos científicos e ter autonomia diante à reanimação cardiopulmonar favorece a assistência adequada, independentemente da localização em que o procedimento é realizado, e diminui impasses no manuseio de recursos humanos e materiais

Molecular and crystal structure, spectroscopy, and photochemistry of a dispiro compound bearing the tetraoxane pharmacophore

The molecular structure and photochemistry of dispiro[cyclohexane-1,3′-[1,2,4,5]tetraoxane-6′,2′′-tricyclo[3.3.1.13,7]decan]-4-one (TX), an antiparasitic 1,2,4,5-tetraoxane was investigated using matrix isolation IR and EPR spectroscopies, together with quantum chemical calculations undertaken at the DFT(B3LYP)/6-311++G(3df,3pd) level of theory, with and without Grimme's dispersion correction. Photolysis of the matrix-isolated TX, induced by in situ broadband (λ>235 nm) or narrowband (λ in the range 220–263 nm) irradiation, led to new bands in the infrared spectrum that could be ascribed to two distinct photoproducts, oxepane-2,5-dione, and 4-oxohomoadamantan-5-one. Our studies show that these photoproducts result from initial photoinduced cleavage of an O−O bond, with the formation of an oxygen-centered diradical that regioselectivity rearranges to a more stable (secondary carbon-centered)/(oxygen-centered) diradical, yielding the final products. Formation of the diradical species was confirmed by EPR measurements, upon photolysis of the compound at λ=266 nm, in acetonitrile ice (T=10–80 K). Single-crystal X-ray diffraction (XRD) studies demonstrated that the TX molecule adopts nearly the same conformation in the crystal and matrix-isolation conditions, revealing that the intermolecular interactions in the TX crystal are weak. This result is in keeping with observed similarities between the infrared spectrum of the crystalline material and that of matrix-isolated TX. The detailed structural, vibrational, and photochemical data reported here appear relevant to the practical uses of TX in medicinal chemistry, considering its efficient and broad parasiticidal properties.JP17H03022; 20K21197; 21H01921; 22K19033; JPMJCR18R4; JPMJCR18R4info:eu-repo/semantics/publishedVersio

Desempenho profissional ou doméstico das pacientes em quimioterapia para câncer de mama

OBJETIVOS: Analisar os aspectos epidemiológicos, clínicos, desempenho profissional e doméstico nas pacientes com câncer de mama em tratamento quimioterápico. MÉTODOS: O estudo foi transversal, com 52 mulheres entrevistadas, divididas em dois grupos: afastadas e não afastadas das atividades profissionais e domésticas, durante o tratamento com quimioterapia para câncer de mama. As pacientes foram provenientes de dois hospitais, um situado no município de Santo André e o outro no município de São Bernardo do Campo. Ambos são hospitais públicos de referência, que atendem a população de Santo André, São Bernardo do Campo, São Caetano do Sul, Diadema e Mauá, que são municípios vizinhos, pertencentes ao Estado de São Paulo, próximos da capital. Utilizou-se o questionário WPAI-GH (Work Productitity and Actitity Impairment) para avaliar a atividade profissional e/ou doméstica das pacientes. RESULTADOS: As pacientes tinham idade média de 55,7 anos (dp=13,8), a maior parte de etnia branca (88,5%), casada (55,8%), assalariada (65,3%) e a maioria se afastou das atividades (51,0%), com estadiamento da doença mais avançado (pOBJECTIVES: Evaluate patients with breast cancer undergoing chemotherapy with respect to their epidemiologic and clinical variables as well as performance at work or at home. METHODS: this was a cross-sectional study including 52 women interviewed during breast cancer chemotherapy, stratified in two groups: those who continued to work and do household tasks, and did not continue to work or do household tasks. Patients were from two public hospitals in the State of São Paulo, one in Santo Andre and the other in São Bernardo do Campo. The WPAI - GH (Work Productivity and Activity Impairment) questionnaire was used to evaluate work and household performance of professionals or housewives, respectively. RESULTS: Mean age of the patients was 55.7 (SD=13.8), most were Caucasian (88.5%), married (55.8%), employed (65.3%) and the majority had to stop working because of treatment (51.0%), at more advanced stage (p<0.05), fatigue and nausea (p<0.05). Mean WPAI - GH was 67.04 (|SD = 5.62) for patients who stopped working and 49.17 (SD = 6.89) for those who continued to work (Mann-Whitney U test: p = 0.04). CONCLUSION: Chemotherapy leads to a decrease in performance of a sizable fraction of women with breast cancer undergoing chemotherapy. A more advanced stage of neoplasia was positively associated with withdrawal from these activities probably due to side effects such as fatigue and nausea

Mortality from gastrointestinal congenital anomalies at 264 hospitals in 74 low-income, middle-income, and high-income countries: a multicentre, international, prospective cohort study

Summary Background Congenital anomalies are the fifth leading cause of mortality in children younger than 5 years globally. Many gastrointestinal congenital anomalies are fatal without timely access to neonatal surgical care, but few studies have been done on these conditions in low-income and middle-income countries (LMICs). We compared outcomes of the seven most common gastrointestinal congenital anomalies in low-income, middle-income, and high-income countries globally, and identified factors associated with mortality. Methods We did a multicentre, international prospective cohort study of patients younger than 16 years, presenting to hospital for the first time with oesophageal atresia, congenital diaphragmatic hernia, intestinal atresia, gastroschisis, exomphalos, anorectal malformation, and Hirschsprung’s disease. Recruitment was of consecutive patients for a minimum of 1 month between October, 2018, and April, 2019. We collected data on patient demographics, clinical status, interventions, and outcomes using the REDCap platform. Patients were followed up for 30 days after primary intervention, or 30 days after admission if they did not receive an intervention. The primary outcome was all-cause, in-hospital mortality for all conditions combined and each condition individually, stratified by country income status. We did a complete case analysis. Findings We included 3849 patients with 3975 study conditions (560 with oesophageal atresia, 448 with congenital diaphragmatic hernia, 681 with intestinal atresia, 453 with gastroschisis, 325 with exomphalos, 991 with anorectal malformation, and 517 with Hirschsprung’s disease) from 264 hospitals (89 in high-income countries, 166 in middleincome countries, and nine in low-income countries) in 74 countries. Of the 3849 patients, 2231 (58·0%) were male. Median gestational age at birth was 38 weeks (IQR 36–39) and median bodyweight at presentation was 2·8 kg (2·3–3·3). Mortality among all patients was 37 (39·8%) of 93 in low-income countries, 583 (20·4%) of 2860 in middle-income countries, and 50 (5·6%) of 896 in high-income countries (p<0·0001 between all country income groups). Gastroschisis had the greatest difference in mortality between country income strata (nine [90·0%] of ten in lowincome countries, 97 [31·9%] of 304 in middle-income countries, and two [1·4%] of 139 in high-income countries; p≤0·0001 between all country income groups). Factors significantly associated with higher mortality for all patients combined included country income status (low-income vs high-income countries, risk ratio 2·78 [95% CI 1·88–4·11], p<0·0001; middle-income vs high-income countries, 2·11 [1·59–2·79], p<0·0001), sepsis at presentation (1·20 [1·04–1·40], p=0·016), higher American Society of Anesthesiologists (ASA) score at primary intervention (ASA 4–5 vs ASA 1–2, 1·82 [1·40–2·35], p<0·0001; ASA 3 vs ASA 1–2, 1·58, [1·30–1·92], p<0·0001]), surgical safety checklist not used (1·39 [1·02–1·90], p=0·035), and ventilation or parenteral nutrition unavailable when needed (ventilation 1·96, [1·41–2·71], p=0·0001; parenteral nutrition 1·35, [1·05–1·74], p=0·018). Administration of parenteral nutrition (0·61, [0·47–0·79], p=0·0002) and use of a peripherally inserted central catheter (0·65 [0·50–0·86], p=0·0024) or percutaneous central line (0·69 [0·48–1·00], p=0·049) were associated with lower mortality. Interpretation Unacceptable differences in mortality exist for gastrointestinal congenital anomalies between lowincome, middle-income, and high-income countries. Improving access to quality neonatal surgical care in LMICs will be vital to achieve Sustainable Development Goal 3.2 of ending preventable deaths in neonates and children younger than 5 years by 2030

Molecular structure and infrared spectra of dimethyl oxalate

Infrared spectra of dimethyl oxalate isolated in low-temperature argon matrix and of the compound in the solid amorphous and crystalline state are reported. The experimental observations are interpreted in terms of a large amplitude, low frequency vibration along the torsional coordinate OC–CO. Assumption of the large amplitude vibration allows consistent explanation of the spectra observed in matrixes and in the gas phase, and the differences between these and the spectrum of the compound in the crystalline state, in which the planar trans structure is fixed. IR spectra of crystalline dimethyl oxalate clearly show that in the relaxed crystal lattice only the trans form is populated. Davydov splitting, due to the presence of two molecules per unit cell, was observed for several bands in the IR spectrum of the crystalline compound

Conformational study of arbutin by quantum chemical calculations and multivariate analysis

A conformational study of the molecule of arbutin (4-hydroxyphenyl-β-d-glucopyranoside) has been undertaken. The molecule is composed by a glucopyranoside moiety bound to a phenol ring. It has eight conformationally relevant dihedral angles, five of them related with the orientation of the hydroxyl groups and the remaining three taking part in the skeleton of the molecule. A systematic search on the conformational space of arbutin was performed using molecular orbital methods, followed by the identification of structural similarities between the different conformers, using multivariate analyses. This approach allowed the grouping of conformers according to their structural affinity and the establishment of correlations between their structures and several properties. Intramolecular interactions involving OH groups were also investigated and correlations between spectroscopic, structural and thermodynamic properties established. The developed strategy might be useful to investigate the structure and structure/properties correlations in other conformationally flexible molecule