Automatic assignment of absolute configuration from 1D NMR data

Opposite enantiomers exhibit different NMR properties in the presence of an external common chiral element, and a chiral molecule exhibits different NMR properties in the presence of external enantiomeric chiral elements. Automatic prediction of such differences, and comparison with experimental values, leads to the assignment of the absolute configuration. Here two cases are reported, one using a dataset of 80 chiral secondary alcohols esterified with (R)-MTPA and the corresponding 1H NMR chemical shifts and the other with 94 13C NMR chemical shifts of chiral secondary alcohols in two enantiomeric chiral solvents. For the first application, counterpropagation neural networks were trained to predict the sign of the difference between chemical shifts of opposite stereoisomers. The neural networks were trained to process the chirality code of the alcohol as the input, and to give the NMR property as the output. In the second application, similar neural networks were employed, but the property to predict was the difference of chemical shifts in the two enantiomeric solvents. For independent test sets of 20 objects, 100% correct predictions were obtained in both applications concerning the sign of the chemical shifts differences. Additionally, with the second dataset, the difference of chemical shifts in the two enantiomeric solvents was quantitatively predicted, yielding r2 0.936 for the test set between the predicted and experimental values.

Experimental Measurements and Correlation of the Solubility of Three Primary Amides in Supercritical CO2: Acetanilide, Propanamide, and Butanamide

Solubilities of three primary amides, namely, acetanilide, propanamide, and butanamide, in supercritical carbon dioxide were measured at T = (308.2, 313.2, and 323.2) K over the pressure range (9.0 to 40.0) MPa by a flow type apparatus. The solubility behavior of the three solids shows an analogous trend with a crossover region of the respective isotherms between (12 to 14) MPa. The solubility of each amide, at the same temperature and pressure, decreases from propanamide to acetanilide. Pure compound properties required for the modeling were estimated, and the solubilities of the amides were correlated by using the Soave-Redlich-Kwong cubic equation of state with an absolute average relative deviation (AARD) from (1.3 to 6.1) %.

Verificação dos desvios de setup e cálculo de margem de PTV em tumores de próstata com 3DCRT

Mestrado em Radioterapia

Controlo da qualidade dosimétrico no serviço de radioterapia do Hospital CUF Descobertas (HCD): importância do controlo da qualidade do sector da física e resultados da auditoria ESTRO-EQUAL

A calibração e o controlo da qualidade de um acelerador linear são passos muito importantes num serviço de Radioterapia, para garantir a qualidade dos tratamentos prestados. O sector da Física da Unidade de Radioterapia do Hospital Cuf Descobertas implementou um rigoroso Programa de controlo de qualidade ao equipamento produtor de radiação e aos equipamentos medidores de radiação, de acordo com o Dec-Lei 180/2002 e com os protocolos internacionais. Para tal, foram implementados procedimentos, criadas folhas de cálculo, instruções de trabalho e impressos. Foram ainda implementados testes aos equipamentos com periodicidade definida: controlo de qualidade diário e controlo de qualidade após intervenções (manutenções preventivas e correctivas). No decorrer do ano de 2005, o sector da Física colaborou activamente com toda a equipa da Radioterapia na implementação da Norma ISO 9001:2000 no serviço, contribuindo com o seu know how na implementação desta, numa área tão importante como a da garantia da qualidade dos feixes de radiação e das respectivas calibrações em dose. Numa procura de melhoria contínua da qualidade dos serviços prestados aos pacientes, decorre ainda uma auditoria externa da EQUAL-ESTRO*, intercomparação postal com dosímetros termoluminescentes. A qualidade dos feixes de energias utilizados diariamente é analisada, tanto ao nível das calibrações absolutas de cada um dos feixes de fotões e de electrões, como ao nível dos cálculos de dose obtidos com o sistema de planimetria XiO da CMS. Os resultados das duas primeiras fases da intercomparação, relativa aos dois feixes de fotões de 6 MV e 15 MV e feixes de electrões de 4 MeV, 8 MeV e 12 MeV, foram considerados pela EQUAL-ESTRO num nível óptimo (desvio máximo na dose medida em relação à dose de referência |d| ≤ 3%).

A fluorescente bicyclic Calix[4] Arene-Oxacyclophane with planar chirality: Resolution, chiroptical, properties, and absolute configuration.

A new inherently chiral calix[4]arene ICC 1 has been disclosed. The dissymmetry of 1 is generated from a chirality plane in the quinol moiety of a 1,3-bridged bicyclic calix[4]arene. ICC 1 has been resolved by enantioselective HPLC, and the chiroptical properties of both isolated antipodes (pS)-1 and (pR)-1 confirm their enantiomeric nature. The absolute configuration of the (pS)-1/(pR)-1 enantiomeric pair was established through time-dependent density functional theory (TDDFT) calculations of electronic circular dichroism (CD) spectra. (C) 2014 Elsevier Ltd. All rights reserved.

Layerwise mixed models for analysis of multilayered piezoelectric composite plates using least-squares formulation

This work provides an assessment of layerwise mixed models using least-squares formulation for the coupled electromechanical static analysis of multilayered plates. In agreement with three-dimensional (3D) exact solutions, due to compatibility and equilibrium conditions at the layers interfaces, certain mechanical and electrical variables must fulfill interlaminar C-0 continuity, namely: displacements, in-plane strains, transverse stresses, electric potential, in-plane electric field components and transverse electric displacement (if no potential is imposed between layers). Hence, two layerwise mixed least-squares models are here investigated, with two different sets of chosen independent variables: Model A, developed earlier, fulfills a priori the interiaminar C-0 continuity of all those aforementioned variables, taken as independent variables; Model B, here newly developed, rather reduces the number of independent variables, but also fulfills a priori the interlaminar C-0 continuity of displacements, transverse stresses, electric potential and transverse electric displacement, taken as independent variables. The predictive capabilities of both models are assessed by comparison with 3D exact solutions, considering multilayered piezoelectric composite plates of different aspect ratios, under an applied transverse load or surface potential. It is shown that both models are able to predict an accurate quasi-3D description of the static electromechanical analysis of multilayered plates for all aspect ratios.

Viscosity measurements of compressed liquid dipropyl and dibutyl adipates

The paper reports viscosity measurements of compressed liquid dipropyl (DPA) and dibutyl (DBA) adipates obtained with two vibrating wire sensors developed in our group. The vibrating wire instruments were operated in the forced oscillation, or steady-state mode. The viscosity measurements of DPA were carried out in a range of pressures up to 18. MPa and temperatures from (303 to 333). K, and DBA up to 65. MPa and temperature from (303 to 373). K, covering a total range of viscosities from (1.3 to 8.3). mPa. s. The required density data of the liquid samples were obtained in our laboratory using an Anton Paar vibrating tube densimeter and were reported in a previous paper. The viscosity results were correlated with density, using a modified hard-spheres scheme. The root mean square deviation of the data from the correlation is less than (0.21 and 0.32)% and the maximum absolute relative deviations are within (0.43 and 0.81)%, for DPA and DBA respectively. No data for the viscosity of both adipates could be found in the literature. Independent viscosity measurements were also performed, at atmospheric pressure, using an Ubbelohde capillary in order to compare with the vibrating wire results. The expanded uncertainty of these results is estimated as ±1.5% at a 95% confidence level. The two data sets agree within the uncertainty of both methods. © 2015 Published by Elsevier B.V.