Magnetohydrodynamic natural convection of hybrid nanofluid in a porous enclosure: numerical analysis of the entropy generation

Journal of Thermal Analysis and Calorimetry - The effect on the entropy production and MHD convection of the hybrid nanofluid Al2O3–Cu/water (water with Cu and Al2O3 nanoparticles) in a...     

Density functional theoretical study on enantiomerization of 2,2'-biphenol

The S-R enantiomerization processes of 2,2'-biphenol (biphenol) have been investigated using density functional theory (DFT). Five isomers for biphenol were identified: I0, which is the most stable isomer; I1a and I1b, which are formed by a restricted rotation of one OH group; and I2a and I2b, which are formed by a restricted rotation of the two OH groups where a and b denote cis and trans configurations, respectively. Each isomer has R- and S-enantiomers. The energies relative to the most stable isomer I0 are 1.6, 3.3, 5.3, and 5.5 kcal mol(-1) for I1a, I1b, I2a, and I2b, respectively. The direct enantiomerization of I0, in which the phenol-ring rotation is considered to be the reaction coordinate while the OH rotations are frozen, is forbidden because of the repulsion between the two OH groups. The transition states for isomerizations of I0 to other isomers (I1a, I1b, I2a, or I2b) were calculated as well as those for the other direct enantiomerizations except for that of I0. From the viewpoint of the least number of the transition states and their low energy levels, the probable S-R enantiomerization of I0 is expressed as a sequential process of isomerization: I0,S --> I1a,S, a direct enantiomerization induced by one of the two OH rotations, I1a,S --> I1a,R, and another isomerization, I1a,R --> I0,R, that is, I0,S --> I1a,S --> I1a,R --> I0,R as the whole process. This process is effective in quantum control of the enantiomerization of biphenol and can be carried out by a sequence of a pump-dump IR laser-pulse scheme.     

Theoretical investigation of the stability of highly charged C60 molecules produced with intense near-infrared laser pulses

We theoretically investigated the stability of highly charged C(60) (z+) cations produced from C(60) with an ultrashort intense laser pulse of lambda approximately 1800 nm. We first calculated the equilibrium structures and vibrational frequencies of C(60) (z+) as well as C(60). We then calculated key energies relevant to dissociation of C(60) (z+), such as the excess vibrational energy acquired upon sudden tunnel ionization from C(60). By comparing the magnitudes of the calculated energies, we found that C(60) (z+) cations up to z approximately 12 can be produced as a stable or quasistable (microsecond-order lifetime) intact parent cation, in agreement with the recent experimental report by V. R. Bhardwaj et al. [Phys. Rev. Lett. 93, 043001 (2004)] that almost only intact parent C(60) (z+) cations up to z=12 are detected by a mass spectrometer. The results of Rice-Ramsperger-Kassel-Marcus calculation suggest that the lifetime of C(60) (z+) drastically decreases by ten orders of magnitude as z increases from z=11 to z=13. Using the time-dependent adiabatic state approach, we also investigated the vibrational excitation of C(60) and C(60) (z+) by an intense near-infrared pulse. The results indicate that large-amplitude vibration with energy of >10 eV is induced in the delocalized h(g)(1)-like mode of C(60) (z+).     

Development of the overpotential simulator for polymer electrolyte fuel cells and application for optimization of cathode structure

We developed a novel computational method to investigate the influences of the microstructure of the polymer electrolyte fuel cell cathode catalyst layer on the overpotential characteristic toward its optimization. Three-dimensional cathode catalyst layer models were constructed by applying three-dimensional porous structure simulator and developed simulator was used to study the overpotential characteristics. Our results showed that the overpotential decreased as decrease of the standard deviation of the ionomer thickness distribution due to the increase of number of active sites.     

First-principle calculations of structural, electronic and optical properties of BaTiO3 and BaZrO3 under hydrostatic pressure

A theoretical study of structural, electronic and optical properties of cubic BaTiO₃ and BaZrO₃ perovskites is presented, using the full-potential linear augmented plane wave (FP-LAPW) method as implemented in the WIEN2K code. In this approach the local density approximation (LDA) is used for the exchange-correlation (XC) potential. Results are given for lattice constant, bulk modulus, its pressure derivative, band structure, density of states, pressure coefficients of energy gaps and refractive indices. The results are compared with previous calculations and experimental data.     

Synthetic and characterization aspects of dimethylaminoethyl methacrylate reversible addition fragmentation chain transfer (RAFT) polymerization

2‐cyanoprop‐2‐yl dithiobenzoate (CPDB) mediated RAFT polymerization of dimethylaminoethyl methacrylate (DMAEMA) was carried out in dioxane at 90 °C. The influence of several parameters, such as the monomer to CPDB molar ratio (100 to 500), the monomer concentration (2 mol·L^?1 to 5.9 mol·L^?1), and CPDB to initiator molar ratio (1 to 10), was evaluated with regards to conversion and polymerization duration, as well as control of molar mass and molar mass distributions. Number average molar masses from 10,000 to 70,000 g·mol^?1 can be targeted. The determination of the molar masses has been carried out by size exclusion chromatography (SEC) with a refractometer detector with poly(methyl methacrylate) (PMMA) standards. The experimental values were lower than the expected ones. Then, SEC in aqueous medium with an online laser light scattering detector was used both to get absolute molar masses and to recalibrate the SEC column in THF. Characterization of well‐controlled PDMAEMA samples has been performed by proton NMR spectroscopy and matrix assisted laser desorption ionization time of flight mass spectrometry. Finally, a chain extension experiment was evaluated with regard to living features. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3551–3565, 2005     

Effects of delocalised π-electrons around the linear acenes ring (n = 1 to 7): an electronic properties through DFT and quantum chemical descriptors

Π-electrons in chemical structure are the unique part of the fundamental particles that modify many interesting properties among the organic semiconductor molecules. By comparing the ground state energy, electronic properties and chemical indices within RHF/6-311G, B3LYP/6-311(G), B3LYP/6-311G(d,p), MP2/6-311G* and Cam-B3LYP/aug-cc-pvdz basis set at level of the theory, we identify that the resonance and the inductive effect of the delocalisation of electrons around the acene molecules could be responsible for acenes electronic and chemical properties. The total energies, energy gaps, HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energy gaps, electron affinity and ionisation potential are close to the experimental and theoretical results. Among the chemical indices, electrophilicity (ω), electronegativity (χ) and chemical hardness (η) observed to decrease as the acenes ring increasing, whereas the softness (S) and chemical potential (μ) increase with increasing the number of carbons around the acene molecules. The study is extended to electronics and chemical properties of the acene.     

A graph theoretical approach to the effect of mutation on the flexibility of the DNA binding domain of p53 protein

Tumor suppressor protein p53 becomes inactive due to mutation on its DNA binding core domain leading to misbehavior of this protein and preventing its interaction with DNA. In the present study, changes of the protein conformation by five hot spot mutations of T-p53C were assessed preventing the mutants wild-type (WT) behavior. While studies of this nature were undertaken both experimentally and theoretically, the focus is fundamentally on the effects of the mutation on the dynamics of the protein. Hence, the basic concept underlying this study is the change in flexibility or rigidity of the protein. It was found that stable variant T-p53C (PDB-ID: 1uol) that is structurally and functionally very close to wild-type p53 is the most rigid structure and each single carcinogenic mutation on it makes the structure more flexible. We hypothesize that these changes of the molecule’s flexibility disrupt the network of hydrogen bonds associated with the interaction of WT not only at interaction but in the internal structures of the mutants as well, which prevents them from interacting in the WT fashion loosing the anti-cancer properties of WT.     

Results of the search for strange quark matter and Q-balls with the SLIM experiment

The SLIM experiment at the Chacaltaya high altitude laboratory was sensitive to nuclearites and Q-balls which could be present in the cosmic radiation as possible Dark Matter components. It was sensitive also to strangelets, i.e. small lumps of Strange Quark Matter predicted at such altitudes by various phenomenological models. The analysis of 427 m² of Nuclear Track Detectors exposed for 4.22 years showed no candidate event. New upper limits on the flux of downgoing nuclearites and Q-balls at the 90% C.L. were established. The null result also restricts models for strangelets propagation through the Earth atmosphere.     

Cs2CO3 in pyrrolidinone promoted hydration of functionalized (hetero)aryl nitriles under metal-free conditions

An efficient hydration reaction of various (hetero)aryl nitriles using Cs₂CO₃ in pyrrolidinone is described. This new metal-free protocol proved to be highly effective and general to synthesize a variety of (hetero)aryl amides.