Quantum entanglement between electronic and vibrational degrees of freedom in molecules

We consider the quantum entanglement of the electronic and vibrational degrees of freedom in molecules with tendencies towards double welled potentials. In these bipartite systems, the von Neumann entropy of the reduced density matrix is used to quantify the electron-vibration entanglement for the lowest two vibronic wavefunctions obtained from a model Hamiltonian based on coupled harmonic diabatic potential-energy surfaces. Significant entanglement is found only in the region in which the ground vibronic state contains a density profile that is bimodal (i.e., contains two separate local maxima). However, in this region two distinct types of density and entanglement profiles are found: one type arises purely from the degeneracy of energy levels in the two potential wells and is destroyed by slight asymmetry, while the other arises through strong interactions between the diabatic levels of each well and is relatively insensitive to asymmetry. These two distinct types are termed fragile degeneracy-induced entanglement and persistent entanglement, respectively. Six classic molecular systems describable by two diabatic states are considered: ammonia, benzene, BNB, pyridine excited triplet states, the Creutz-Taube ion, and the radical cation of the "special pair" of chlorophylls involved in photosynthesis. These chemically diverse systems are all treated using the same general formalism and the nature of the entanglement that they embody is elucidated.     

Synthesis, characterization and antifungal evaluation of 5-substituted-4-amino-1,2,4-triazole-3-thioesters

A series of 5-substituted-4-amino-1,2,4-triazole-3-thioesters was synthesized by converting variously substituted organic acids successively into the corresponding esters, hydrazides, 5-substituted-1,3,4-oxadiazole-2-thiols, 5-substituted-1,2,4-triazole-2-thiols and 5-substituted-1,3,4-oxadiazole-2-thioesters. Finally the target compounds were obtained by refluxing 5-substituted-1,3,4-oxadiazole-2-thioesters in the presence of hydrazine hydrate and absolute alcohol. The structures of the synthesized compounds were established by physicochemical and spectroscopic methods. The synthesized compounds were evaluated for their in vitro antifungal activity. Some of the evaluated compounds possessed significant antifungal activity as compared to a terbinafine standard.     

Synthesis of simple heparanase substrates

Heparanase degrades heparan sulfate (HS) chains on proteoglycans; elevated levels of heparanase expression correlate with tumour cell metastatic potential and vascularity, and reduced post-operative survival of cancer patients. Consequently, heparanase expression is considered a biomarker for cancer detection. Although several heparanase assays have been developed, most require the preparation of heterogeneous, (radio)labelled HS substrates and rely on the separation of enzymatically-degraded products on the basis of molecular size. In studies directed towards the development of a more direct heparanase assay, a series of glucuronides and glycosyl glucuronides were synthesised as putative heparanase substrates. These compounds were designed with various aryl aglycones that could be measured spectrophotometrically upon hydrolysis of the glycosidic linkage by heparanase. It was found that the N-sulfated 4-nitrophenyl glycosyl glucuronide 24 and the N-sulfated methylumbelliferyl glycosyl glucuronide 26 were hydrolysed by recombinant human heparanase. These compounds represent the simplest substrates of heparanase reported to date.     

Inf–sup conditions for twofold saddle point problems

Necessary and sufficient conditions for existence and uniqueness of solutions are developed for twofold saddle point problems which arise in mixed formulations of problems in continuum mechanics. This work extends the classical saddle point theory to accommodate nonlinear constitutive relations and the twofold saddle structure. Application to problems in incompressible fluid mechanics employing symmetric tensor finite elements for the stress approximation is presented.     

Products formed at intermediate stages of electrochemical perfluorination of propionyl and n-butyryl chlorides. Further evidence in support of NiF3 mediated free radical pathway

The partially fluorinated HF soluble intermediates formed during the electrochemical perfluorination of propionyl chloride (PC) and n-butyryl chloride (n-BC) were analyzed after passing 0%, 25%, 50%, 75% and 100% of theoretical charge required for the fluorination of PC and n-BC. The acid fluorides formed were converted to their corresponding sodium salt by alkali treatment and were separated by methanol extraction. The methanol was subsequently removed from the extract by vacuum distillation and the residue containing partially fluorinated sodium carboxylates was analyzed using ¹⁹F and ¹H NMR spectra. Initial perfluorination on activated electrode surface indicates the operation of ‘zipper-mechanism’. Formation of partially fluorinated product mixture, initial selectivity towards primary and secondary carbon, carbon chain isomerization and formation of cleaved and coupled products support the general operation of free radical pathway in the overall electrochemical process.     

A semi-analytical description of protein folding that incorporates detailed geometrical information

Much has been done to study the interplay between geometric and energetic effects on the protein folding energy landscape. Numerical techniques such as molecular dynamics simulations are able to maintain a precise geometrical representation of the protein. Analytical approaches, however, often focus on the energetic aspects of folding, including geometrical information only in an average way. Here, we investigate a semi-analytical expression of folding that explicitly includes geometrical effects. We consider a Hamiltonian corresponding to a Gaussian filament with structure-based interactions. The model captures local features of protein folding often averaged over by mean-field theories, for example, loop contact formation and excluded volume. We explore the thermodynamics and folding mechanisms of beta-hairpin and alpha-helical structures as functions of temperature and Q, the fraction of native contacts formed. Excluded volume is shown to be an important component of a protein Hamiltonian, since it both dominates the cooperativity of the folding transition and alters folding mechanisms. Understanding geometrical effects in analytical formulae will help illuminate the consequences of the approximations required for the study of larger proteins.     

Interference-induced electron- and hole-conduction asymmetry

Principles established by Shephard and Paddon-Row for optimizing and controlling intramolecular electron transport through the modulation of interfering pathways are employed to design new molecules for steady-state conduction experiments aimed at manifesting electron?Chole conduction asymmetry in a unique way. First, a review of the basic principles is presented through application to a pertinent model system in which a molecule containing donor and acceptor terminal linking groups with an internal multiple-pathway bridge is used to span two metal electrodes. Different interference patterns are produced depending on whether the through-molecule coupling pathways are symmetric or antisymmetric with respect to a topological bisecting plane, giving rise to asymmetric electron and hole conductances at the tight-binding (Hückel) level; this process is also described from a complementary molecular-orbital viewpoint. Subsequently, a new molecular system based on organic polyradicals is designed to allow such asymmetry to be realized in single-molecule conduction experiments. These polyradicals are analyzed using analogous simple models, density-functional theory (DFT) calculations of steady-state transmission, and intermediate neglect of differential overlap (INDO) calculations of intramolecular connectivity, verifying that polyradicals at low temperatures should show experimentally measureable electron?Chole conduction asymmetry. A key feature of this system is that the polyradicals form a narrow partially occupied band of orbitals that lie within and well separated from the HOMO and LUMO orbitals of the surrounding molecular scaffold, allowing for holes and electrons to be transported through the same molecular band.     

Microscale prediction of deformation in an austenitic stainless steel under uniaxial loading

In this study, the deformation behaviour of polycrystalline austenitic 316H stainless steel under uniaxial loading is investigated by means of in-situ neutron diffraction (ND) measurement and crystal plasticity-based finite element (FE) modelling. Data have been obtained for the macroscopic stress–strain response and the lattice strain evolution in the longitudinal and transverse direction relative to the uniaxial loading axis. Comparison between the model predictions and the ND measurements suggests that in most cases the FE model can predict the lattice strain evolution at the microscale and capture the general trends observed in the experiments. Both ND measurements and FE modelling simulations identify little effect of micromorphology effect on the longitudinal lattice strain evolution, while the transverse lattice strain response appears to be sensitive to the microstructure, in particular the initial crystallographic orientation of the material.     

Modulation theory solution for nonlinearly resonant,fifth‐order Korteweg–de Vries,nonclassical, traveling dispersive shock waves

A new class of resonant dispersive shock waves was recently identified as solutions of the Kawahara equation— a Korteweg–de Vries (KdV) type nonlinear wave equation with third‐ and fifth‐order spatial derivatives— in the regime of nonconvex, linear dispersion. Linear resonance resulting from the third‐ and fifth‐order terms in the Kawahara equation was identified as the key ingredient for nonclassical dispersive shock wave solutions. Here, nonlinear wave (Whitham) modulation theory is used to construct approximate nonclassical traveling dispersive shock wave (TDSW) solutions of the fifth‐ order KdV equation without the third derivative term, hence without any linear resonance. A self‐similar, simple wave modulation solution of the fifth order, weakly nonlinear KdV–Whitham equations is obtained that matches a constant to a heteroclinic traveling wave via a partial dispersive shock wave so that the TDSW is interpreted as a nonlinear resonance. The modulation solution is compared with full numerical solutions, exhibiting excellent agreement. The TDSW is shown to be modulationally stable in the presence of sufficiently small third‐order dispersion. The Kawahara–Whitham modulation equations transition from hyperbolic to elliptic type for sufficiently large third‐order dispersion, which provides a possible route for the TDSW to exhibit modulational instability.     

5 μm thick 3C-SiC layers grown on Ge-modified Si(100) substrates

The effect of the germanium coverage prior to the epitaxial growth of 5 μm thick 3C-SiC on Si(100) substrates were evaluated with Atomic Force Microscopy and μ-Raman spectroscopy. The 3C-SiC layers were grown by atmospheric pressure chemical vapor deposition via a special procedure leading to layers with compressive instead of tensile stress. The Ge amount was varied from 0 up to 2 ML. The obtained results showed that the residual stress inside the layers is shifted in the compressive direction; the crystalline quality is improved with the Ge introduction but on the account of the surface roughness. These results open the route for the use of Ge-modified Si(100) as a potential substrate in order to improve the heteroepitaxial growth of 3C-SiC on silicon substrates.