Electronic, nonlinear optical, UV-vis and NBO analysis of methyl methacrylate for optoelectronic and optical applications: DFT study and impact of conformation.

Using Density Functional Theory (DFT) and time-dependent DFT (TD-DFT), we studied a compound widely used in daily life, namely: Methyl Methacrylate (MMA) monomer in its two stable isomers, cis-MMA and trans-MMA. The impact of conformation on the optical and electronic properties of MMA was highlighted. Structural parameters and thermodynamic properties were also assessed, and allowed to discuss the stability and reactivity of this compound. In addition, analysis of optoelectronic and electronic properties, global reactivity descriptors, natural bond orbital (NBO), and hole and electron reorganization energies was performed. The absorption and fluorescence properties, as well as the linear and nonlinear optical (NLO) properties of MMA were also investigated. The findings show that MMA is an insulator due to its wide band gap of 6.20 eV. It also exhibits good optoelectronic properties with high average electric field values of about 5.90 × 109 Vm-1 for cis-MMA and 5.42 × 109 Vm-1 for trans-MMA and high electric displacement values of at least 14.65 × 10-2 cm-2 for cis-MMA and 14.33 × 10-2 cm-2 for trans-MMA, suggesting a potential use for the design of piezoelectric and pyroelectric materials. In addition, trans-MMA has a dielectric constant close to that of good insulators; while cis-MMA exhibits a dielectric behaviour close to that of polymeric substances. Further, these materials are thermodynamically stable in its two conformations, with a good reactivity which can lead to good ability of polymerization. The analysis of the UV-vis spectra revealed that both forms of MMA absorb and emit mainly in the UV and that the Stokes shift of MMA is low, reducing its potential use in devices such as solar cells. At NLO level, MMA isomers exhibit weak optical properties such as second- and third-order optical susceptibility and cannot suitable for second and third harmonic generation; however, the conformation enhances second-order NLO response by at least 2 times when moving from cis- to trans-MMA, whereas the third-order response is almost unaffected. In addition, the conformation also affects the electronic and optoelectronic properties of MMA.

Determination of the structural, electronic, optoelectronic and thermodynamic properties of the methylxanthine molecules theophylline and theobromine.

RHF and DFT (wB97XD and B3LYP) methods with the 6-31++G** basis set have been used to study structural, optoelectronic and thermodynamic properties of Theophylline and Theobromine. Dipole moment, average polarizability, anisotropy, first-order molecular hyperpolarizability, second-order molecular polarizability, HOMO and LOMO energy gap, molar refractivity, chemical hardness, chemical softness, electronic chemical potential, electronegativity, electrophilicity index, dielectric constant, electric susceptibility, refractive index and their thermodynamic properties have equally been calculated. To understand the vibrational analysis of our system, IR and RAMAN frequencies were calculated and described. Results reveal that molecules can have applications in linear and nonlinear optical devices, photonic devices and in molecular electronics. Equally, from dipole moment, average polarizability, anisotropy, first-order molecular hyperpolarizability, second-order molecular polarizability, HOMO and LOMO energy gap, molar refractivity, chemical hardness, chemical softness, electronic chemical potential, electronegativity, electrophilicity index and literature we suggest that Theophylline and Theobromine be consider as candidates for the treatment of COVID-19 and other respiratory diseases.

Glass transition in hard-core fluids and beyond, using an effective static structure in the mode coupling theory.

The dynamical arrest in classical fluids is studied using a simple modification of the mode coupling theory (MCT) aimed at correcting its overestimation of the tendency to glass formation while preserving its overall structure. As in previous attempts, the modification is based on the idea of tempering the static pair correlations used as input. It is implemented in this work by computing the static structure at a different state point than the one used to solve the MCT equation for the intermediate scattering function, using the pure hard-sphere glass for calibration. The location of the glass transition predicted from this modification is found to agree with simulations data for a variety of systems --pure fluids and mixtures with either purely repulsive interaction potentials or ones with attractive contributions. Besides improving the predictions in the long-time limit, and so reducing the non-ergodicity domain, the same modification works as well for the time-dependent correlators.

Postoperative mediastinitis due to Candida tropicalis: first reported case in Morocco.

Mediastinitis is a rare and serious nosocomial complication of cardiac surgery. It is estimated at less than 2% of cases of median sternotomy. We report the case of a postoperative mediastinitis due to Candida tropicalis. A 9-month-old baby was operated for complete repair of tetralogy of Fallot in which we isolated C. tropicalis from sternal purulent fluid and blood culture. The child did not survive, despite the initiation of antifungal therapy. The management of this type of infection requires an early diagnosis and an appropriate prolonged treatment, associated with effective preventive measures.

[Surgery of aortic regurgitation with reduced left ventricular function]. / Chirurgie de l'insuffisance aortique avec dysfonction ventriculaire gauche.

BACKGROUND: Aortic valve replacement improves clinical symptoms and left ventricular systolic function in patients with chronic aortic regurgitation despite a higher surgical risk. The objective of this study is to determine if left ventricular function will be normalized after surgery. PATIENTS AND METHOD: This retrospective study included 40 patients (nine females and 31 males) with chronic aortic regurgitation and left ventricular systolic dysfunction who were evaluated by echocardiography Doppler. Were included patients with left ventricular ejection fraction less or equal to 45%. Ages ranged from 18 to 77 years (mean = 46.4 ± 12.6 years). Preoperatively, six patients (15%) were asymptomatic, ten (25%) were in NYHA II, half (50%) in NYHA III and four (10%) in NYHA IV. The mean preoperative ejection fraction (EF) was 36.2 ± 2%. The mean end systolic and diastolic dimensions were 61.7 ± 8.5 mm and 78.9 ± 9.7 mm respectively. Aortic regurgitation was quantified grade III in sixteen patients (40%) and grade IV in twenty-four (60%). RESULTS: Thirty-seven patients underwent aortic valve replacement and three Bentall operations. Hospital mortality was 7.5% (3/40). The mean follow-up period was 69.7 months. All survivor patients were investigated. Out of these, five were lost and 32 were controlled. Symptomatic improvement was noted in most of the survivors. Sixty percent (24/40) were severely symptomatic before and only 6.25% (2/32) during follow-up. The ejection fraction increased significantly after surgery (36.2 ± 2% in preoperative period vs. 55.2 ± 10% in postoperative period, P < 0.02). Left ventricular diameters decreased significantly also. Survival rates were 3-year 94%, 5-year 91% and 7-year 89%. CONCLUSION: Despite reduced left ventricular systolic function, aortic valve replacement in chronic aortic regurgitation was associated with acceptable operative risk. Surgery improves functional status, symptoms and ejection fraction in most patients.

Non-ergodicity transition and multiple glasses in binary mixtures: on the accuracy of the input static structure in the mode coupling theory.

We examine the question of the accuracy of the static correlation functions used as input in the mode coupling theory (MCT) of non-ergodic states in binary mixtures. We first consider hard-sphere mixtures and compute the static pair structure from the Ornstein-Zernike equations with the Percus-Yevick closure and more accurate ones that use bridge functions deduced from Rosenfeld's fundamental measures functional. The corresponding MCT predictions for the non-ergodicity lines and the transitions between multiple glassy states are determined from the long-time limit of the density autocorrelation functions. We find that while the non-ergodicity transition line is not very sensitive to the input static structure, up to diameter ratios D(2)/D(1) = 10, quantitative differences exist for the transitions between different glasses. The discrepancies with the more accurate closures become even qualitative for sufficiently asymmetric mixtures. They are correlated with the incorrect behavior of the PY structure at high size asymmetry. From the example of ultra-soft potential it is argued that this issue is of general relevance beyond the hard-sphere model.