Methyl hydrogen peroxide dimer: A structural study

Methyl hydrogen peroxide (MHP) exhibits a tendency to form a stable dimer by hydrogen-bonding. Ab initio theoretical investigations on methyl hydrogen peroxide dimer (MHPD) carried out herein lead to several energetically stable structures that have a direct bearing on the reactivity of the monomer in terms of its molecular electrostatic potential (MESP). To gauge the role played by the electron-correlation in lending stability to MHP and its dimer, we employ the density functional theory (DFT) (as implemented by B3LYP-functional), and subsequently second order Møller-Plesset (MP2) perturbation theory, using the basis sets 6-31G(d, p) and 6-311++G(2d, 2p). Simulated infra-red vibrational spectra lead to spectral intensity redistribution upon dimerization. Energetically the lowest MHPD is endowed with inversion symmetry and has two hydrogen bonds, while three other structures emerge: one energetically very close with two H-bonds, and the two others, with three H-bonds each, yet higher by about 2 kcal mol⁻¹.     

Hydroxyapatite coating on stainless steel pre-coated with bovine serum albumin at ambient conditions

A biomimetic process for coating of nanosized hydroxyapatite on stainless steel, which capitalises the dual nature of the protein bovine serum albumin in both metal binding and a strong affinity for calcium ions, has been developed. The novelty of the process lies in pre-conditioning the metallic surface using the above protein prior to its mineralization with hydroxyapatite at ambient conditions. The microporous morphology of these coatings may provide favourable solubility and resorbability as desired by many orthopaedic and orthodontic applications.     

Theoretical study of unimolecular rearrangements of vinylidenes to acetylenes

The rearrangement of vinylidene to acetylene has been studied in detail by the density functional method, using Becke's three‐parameter exchange functional and the gradient‐corrected functional of Lee, Yang, and Parr. The rearrangement of the anion, as well as that of fluoro‐substituted systems, has also been investigated, in order to determine the effect of fluorine substitution on the activation barrier to the 1,2‐hydrogen shift, as well as the relative migratory aptitudes of hydrogen and fluorine. Natural bond orbital analysis is invoked to gain insight into the mechanisms of the rearrangements. Basis size effects are also discussed, particularly in relation to anionic systems. The need to include diffuse functions in geometry optimizations of anionic systems is reinforced by the present calculations. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Fixed point results for set-valued contractions by altering distances in complete metric spaces

Nadler’s contraction principle has led to fixed point theory of set-valued contraction in non-linear analysis. Inspired by the results of Nadler, the fixed point theory of set-valued contraction has been further developed in different directions by many authors, in particular, by Reich, Mizoguchi–Takahashi, Feng–Liu and many others. In the present paper, the concept of generalized contractions for set-valued maps in metric spaces is introduced and the existence of fixed point for such a contraction are guaranteed by certain conditions. Our first result extends and generalizes the Nadler, Feng–Liu and Klim–Wardowski theorems and the second result is different from the Reich and Mizoguchi–Takahashi results. As a consequence, we derive some results related to fixed point of set-valued maps satisfying certain conditions of integral type.     

First enantiospecific synthesis of (+)-β-herbertenol

The first enantiospecific synthesis of (+)-β-herbertenol, from naturally occurring R-(+)-citronellal, employing Taber's diazo decomposition protocol as the key step, is described.     

Recovery of plutonium from aqueous waste solutions using porous zirconia spherical particles

Based on the Linssi database and UniSampo/Shaman software, an automated analysis platform has been setup for the analysis of large amounts of gamma-spectra from the primary coolant monitoring systems of a CANDU reactor. Thus, a database inventory of gaseous and volatile fission products in the primary coolant of a CANDU reactor has been established. This database is comprised of 15,000 spectra of radioisotope analysis records. Records from the database inventory were retrieved by a specifically designed data-mining module and subjected to further analysis. Results from the analysis were subsequently used to identify the reactor coolant half-life of ¹³⁵Xe and ¹³³Xe, as well as the correlations of ¹³⁵Xe and ⁸⁸Kr activities.     

233Pa(2nth, f ) cross-section determination using a fission track technique

The νp process is a primary nucleosynthesis process which occurs in core-collapse supernovae. An essential role in this process is being played by electron antineutrinos. They generate, by absorption on protons, a supply of neutrons which, by (n, p) reactions, allow to overcome waiting point nuclei with rather long beta-decay and proton-capture lifetimes. The synthesis of heavy elements by the νp process depends sensitively on the $\bar \nu _e$ luminosity and spectrum. As has been shown recently, the latter are affected by collective neutrino flavor oscillations which can swap the $\bar \nu _e$ and $\bar \nu _{\mu ,\tau }$ spectra above a certain split energy. Assuming such a swap scenario, we have studied the impact of collective neutrino flavor oscillations on the νp-process nucleosynthesis. Our results show that the production of light p-nuclei up to mass number A = 108 is very sensitive to collective neutrino oscillations.     

Esterification of butyric acid with n-butanol: Kinetic study using experimental data and modeling

Present study involves the investigation of the esterification kinetics between butyric acid and n-butanol. This reaction was conducted in a batch reactor, utilizing homogeneous methanesulfonic acid (MSA) catalyst. Response surface methodology (RSM) was conducted prior to the kinetic study using “Design Expert; version-11.0” for finding the causal factors influencing the conversion of butyric acid. Most important factors identified with their limits against conversions (during optimization of the process using RSM) were taken up to critically analyze the effect of them on butyric acid conversion. Concentration and activity-based model of the process were proposed assuming second order reversible reaction scheme using homogeneous MSA catalyst. During the study of non-ideal behavior of the system, UNIFAC model was adapted for assessing the activity coefficients of species present in equilibrated liquid phase. Experimental data were used to evaluate kinetic and thermodynamic parameters such as rate constants, activation energy, enthalpy, and entropy of the system. The endothermic nature of esterification was confirmed by positive value of enthalpy obtained. The effect of various levels of causal variables like temperature (60–90°C), catalyst concentration (0.5–1.5 wt.%), and molar ratio of n-butanol to butyric acid (1–3) on conversion kinetics of butyric acid was investigated during transient and equilibrium phase of the reaction. It has been observed that molar ratio of butanol to butyric acid has the highest influence on the conversion. The rate equation derived offered a kinetic and thermodynamic framework to the generated data. It also exhibits a notable degree of conformity of predicted data to the experimental ones and effectively characterizes the system across different reaction temperatures, reactant molar ratio, and catalyst concentration.     

Magnetic, magnetocaloric, and magnetotransport properties of RCo1.8Mn0.2 (R=Er, Ho, Dy, and Tb) compounds

The magnetic, magnetocaloric, and magnetotransport properties of RCo_1.8Mn_0.2 (R=Er, Ho, Dy, and Tb) were studied by room temperature X-ray diffraction, magnetization, and resistivity measurements at a temperature interval of 5-400 K and magnetic fields up to 5 T. The Curie temperature of RCo₂ was found to increase significantly when 10% Mn was substituted for Co. The effective paramagnetic moments were found to be in reasonable agreement with their theoretical values. A large magnetoresistance (MR) of Δρ/ρ_o≈−13.5% for R=Ho at T≈153 K for ΔH=5 T has been observed. The maximum relative cooling capacities vary from 467 J/kg at low temperature for R=Er to 202 J/kg at the near room temperature for R=Tb.