A comparison of the fcc(111) and (100) crystal-melt interfaces by molecular dynamics simulation

The molecular dynamics simulation technique is employed to study the fcc (100) and (111) crystal—melt interfaces of a system of Lennard-Jones atoms near the triple-point. A comparison of the structure and thermodynamics of the two interfaces results in a simple picture concerning the role of crystal orientation on the structure of the liquid neighboring the crystal face.     

Reductive alkylation of lipase

Candida rugosa lipase was modified via reductive alkylation to increase its hydrophobicity to work better in organic solvents. The free amino group of lysines was alkylated using propionaldehyde with different degrees of modification obtained (49 and 86%). Far-ultraviolet circular dichroism (CD) spectroscopy of the lipase in aqueous solvent showed that such chemical modifications at the enzyme surface caused a loss in secondary and tertiary structure that is attributed to the enzyme unfolding. Using molecular modeling, we propose that in an aqueous environment the loss in protein structure of the modified lipase is owing to disruption of stabilizing salt bridges, particularly of surface lysines. Indeed, molecular modeling and simulation of a salt bridge formed by Lys-75 to Asp-79, in a nonpolar environment, suggests the adoption of a more flexible alkylated lysine that may explain higher lipase activity in organic solvents on alkylation.     

Thermal validation of a simple moving boundary model to determine the frying time of a thin potato crisp

A simple moving boundary model was redesigned to describe the immersion frying of a thin cut potato crisp of thickness 2 mm. The model took into account the effects of a variable oil convection heat transfer coefficient. In the model, the centre temperature was defined as a value of a region rather than a point. The model also predicted the effect of some shift in the location of the thermocouple on the measurements. Experiments at oil temperatures of 170, 180 and 190 °C were conducted to verify whether or not the model predictions were accurate. Good agreement was found between the experimental and predicted values, which were generally within the t ₉₉(0.01) confidence interval of the experimental data. Received on 3 November 1998     

The non-Fermi-liquid nature of the metallic states of the Hubbard Hamiltonian

It has long since been argued that the metallic states of the single-band Hubbard Hamiltonian ? in two spatial dimensions (i.e. for d = 2) should be non-Fermi liquid, a possibility that would lead to the understanding of the observed anomalous behaviour of the doped copper-oxide-based superconducting compounds in their normal metallic states. Here we present a formalism which enables us to express, for arbitrary d, the behaviour of the momentum-distribution function nσ(k) pertaining to uniform metallic ground states of ? close to S _F; σ (the Fermi surface of the fermions with spin index σ, σ = ↑, ↓) in terms of a small number of constant parameters which are bound to satisfy certain inequalities implied by the requirement of the stability of the ground state of the system. These inequalities restrict the range of variation in nσ(k) for k infinitesimally inside and outside the Fermi sea pertaining to fermions with spin index σ and consequently the range of variation in the zero-temperature limit of nσ(k) for k on S _F; σ On the basis of some available accurate numerical results for nσ(k) pertaining to the Hubbard and the t-J Hamiltonian, we conclude that, at least in the strong-coupling regime, the metallic ground states of ? for d = 2 cannot be Fermi-liquid nor can they in general be purely Luttinger or marginal Fermi liquids. We further rigorously identify the pseudogap phenomenon, or 'truncation' of the Fermi surface, clearly observed in the normal states of underdoped copper-oxide-based superconductors, as corresponding to a line of resonance energies (i.e. these energies strictly do not relate to quasiparticles) located below the Fermi energy, with a concomitant suppression to zero of the jump in nσ(k) over the 'truncated' parts of the Fermi surface. Our analyses make explicit the singular significance of the non-interacting energy dispersion ε _k underlying ? in determining the low-energy spectral and transport properties of the metallic ground states of ?.     

Modeling of stress transfer behavior in fiber-matrix composite under axial and transverse loadings

Interface between fiber and matrix as a stress transfer medium determines composite performances in load-bearing structures. For instance, failures in composite are most likely initiated by an accumulation of interfacial cracks allowing little or no stress transfer from the matrix to the fiber and vice versa. This paper studies stress transfer behaviors at the interface subject to axial and transverse loadings using the finite element method. Single fiber surrounded by matrix was modeled by introducing a cohesive zone model (CZM) at the interface taking into account the bonding mechanism. By the proposed technique, plastic deformation in the matrix and exerted friction at the interface was verified to govern the role of stress transfer at the interface. Further, the influence of other fibers in matrix surrounding the model was also discussed.     

Dissociation and kinetic of hydrochloric acid in mixed isomeric alcoholic-aqueous solvents — A conductance study

The effect of water and the effect of time on the conductance behavior of dilute solutions of hydrochloric acid in n-butanol–water and iso-butanol–water mixtures with the alcohol percentages; 97.00%, 97.50%, 98.00%, 98.50%, 99.00%, 99.50%, 99.70% and 99.98% at 298 K are reported. The data were analysed with a computer program for the Lee–Wheaton conductivity equation. The molar conductance (Λ), limiting molar conductance (Λ₀), dissociation constants (K_d), and the standard free energy of dissociation (?G^°_d) were calculated and discussed. The kinetic of hydrochloric acid conductance was also discussed and the results showed a first order interaction between HCl and the alcoholic solvents. In agreement with previous experiments in alcohol–water mixtures the limiting molar conductance decreases when water is added to the alcohol and then increases again. The results show that, the dissociation constant decreased as the relative permittivity of the solvent decreased.     

Matrix‐grafted multiwalled carbon nanotubes/poly(methyl methacrylate) nanocomposites synthesized by in situ RAFT polymerization: A kinetic study

A new approach was developed to functionalize multiwalled carbon nanotubes (MWCNTs) with a polymerizable methyl methacrylate (MMA) groups, and the structure of functionalized MWCNTs were characterized by FTIR, Raman, XPS, and TEM. Using the strategy of “grafting through,” poly(methyl methacrylate) (PMMA) chains were grafted onto the surface of MWCNTs during the in situ synthesis of MWCNT/PMMA nanocomposites over reversible addition‐fragmentation chain transfer (RAFT) polymerization. Kinetics of RAFT‐mediated polymerization of MMA in the presence of MMA‐grafted MWCNTs was studied by using gas chromatography and gel permeation chromatography. To further study, attached polymers were detached and their molecular characteristics were compared to freely formed chains. Results of kinetic studies showed that the utilized commercial chain transfer agent strictly reduced the rate of polymerization as well as relatively controlled molecular weights and narrow molecular weight distributions of free chains. MWCNTs showed a radical activity, retarding the polymerization and reducing the rate of reaction. The effect of MWCNTs concentrations on molecular weights and polydispersity indexes (PDI) was different at the surface and in the bulk. The molecular weights of free chains increased, and the PDI was decreased with increasing MWCNTs. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 555–569, 2012