Electronic and steric substituent effects on the fluorescence emission of 2-pyrazoline derivatives.

A series of substituted 2-pyrazolines were synthesized, and the steric and electronic effects of substituents on the C3 - and C5 -positions of the heterocyclic ring on their fluorescent ability were investigated. Two different conjugative intramolecular charge transfer (ICT) and intramolecular charge transfer through space (spiro-conjugation) affect the fluorescence intensity of these compounds. The extent of the ICT process and spiro-conjugation depends on the electronic nature of the additional substitution and its position on the attached aryl rings. In addition, the effects of the concentration and the solvent polarity on the fluorescence emission were studied. Density functional theory (DFT) calculations were carried out to gain insight into the geometric, electronic, and spectroscopic properties of the pyrazoline derivatives. The results of both experimental and computational studies explain the effects of the geometrical orientation of the C3 - and C5 -aryl rings toward the heterocyclic ring and also the electronic nature of their additional substitutions on the fluorescence intensity.

Machine learning-based demand forecasting in cancer palliative care home hospitalization.

OBJECTIVE: To develop an effective Management Information System (MIS) that is empowered by predictive models that can forecast the demand of end-stage cancer home hospitalized patients in individual and population levels, and help palliative care service systems operate smoothly where the demand is highly fluctuating, resources are limited, expensive, and hardly adjustable in a short time, and the backlog and shortage costs are high. METHOD: Inspired by real problems faced by a palliative care center providing various medical, nursing, psychological, and social services in a home-based setting, two Long Short-Term Memory (LSTM) based deep learning models are proposed for demand forecasting at both individual and population levels. The individual-level model can predict the type and time of the next service required for a specific patient with a given demographic and health profile, and the population-level model helps with the prediction of next week's demand for various services in a center supporting a specific patient population. Predicted demand informs on optimal resource and operations plan through a well designed MIS. RESULTS: Experiments were conducted on a dataset consisting of more than 4000 cancer patients with a Palliative Performance Scale (PPS) of 40 and below discharged from hospital to home under a national palliative care center's home hospitalization service in Iran from September 2012 to July 2019. The models outperformed conventional time-series forecasting methods where applicable. Results indicate that the proposed models were capable of forecasting patients' demand with astonishing performances both individually and on larger scales. CONCLUSION: Intelligent demand forecasting can help palliative care home hospitalization systems to overcome the challenge of progressive demand growth when a considerable portion of patients are approaching death, followed by a sudden drop in demand when those patients pass away. It helps to improve resource utilization and quality of care concurrently.

Cyclic Voltammetric Study of 3,5-Diaryl-1-phenyl-2-pyrazolines.

Cyclic voltammetry is used to derive HOMO energies of the 1-phenyl-2-pyrazolines containing electron-donating or electron-withdrawing substituted phenyl rings and or naphthalenyl substitution on the C3- or C5-positions of the heterocyclic ring to investigate the steric and electronic effects of the aryl substitutions and the type of aryl system on their electrochemical behaviors. The optical HOMO-LUMO gaps needed for the calculation of LUMO (excited state) energies of these compounds are obtained from their UV-vis spectra. Results show that the substitution on the C3-aryl ring has significant effect via its π-donor/acceptor ability, compared to the σ-donor/acceptor ability of the C5-aryl ring, on the CV oxidation peak and onset potentials. Comparative analysis showed very good agreement between the experimentally obtained HOMO and (apparent) LUMO energies and the (TD)DFT/6-311++G(d,p) calculated ground and excited states energies. These computational results indicate also that for all chloro- and methoxy-substituted 2-pyrazolines, the HOMO → LUMO is the most intense transition. While the strong acceptor NO2 substitution on all positions of either C3- or C5-aryl rings, except for one compound, increases the intensity of the HOMO → LUMO+1 (LUMO+2) transition significantly, the first (the first two) transition(s) HOMO → LUMO (and HOMO → LUMO+1) has (have) much smaller or negligible intensity (intensities).

The impact of emotionally focused therapy on emotional distress in infertile couples.

BACKGROUND: The present study investigated the effect of emotionally focused therapy (EFT) on factors contributing to emotional distress among infertile couples. MATERIALS AND METHODS: In this semi-experimental study, the subjects consisted of 12 Iranian couples: six infertile men and six infertile women. They were assessed as depressed, anxious and stressful individuals using depression, anxiety and stress scale (DASS). The subjects were randomly divided into control and experimental groups. The experimental group with six couples (i.e. three infertile men and three infertile women) received EFT, while the control group with similar number of couples (i.e. three infertile men and three infertile women) was deprived of the treatment. RESULTS: There were no significant differences between the two groups regarding job, educational level, income, age, marriage and infertility duration. The pre- and post-test comparisons of DASS subscales showed that level of depression, anxiety and stress among couples with EFT instruction was significantly less than those without such in- structions (p<0.0001). CONCLUSION: Emotionally focused therapy could reduce the rate of depression, anxiety and stress in infertile couples, regardless of the man or woman as the cause of infertility.