Role of Hydrogen Bonds in the Fast Dynamics of Binary Glasses of Trehalose and Glycerol: a Molecular Dynamics Simulation Study

Trehalose-glycerol mixtures are known to be effective in the long time preservation of proteins. However, the microscopic mechanism of their effective preservation abilities remains unclear. In this article we present a molecular dynamics simulation study of the short time, less than 1 ns, dynamics of four trehalose-glycerol mixtures at temperatures below the glass transition temperature. We found that a mixture of 5% glycerol and 95% trehalose has the most suppressed short time dynamics (fast dynamics). This result agrees with the experimental analysis of the mean-square displacement of the hydrogen atoms, as measured via neutron scattering, and correlates with the experimentally observed enhancement of the stability of some enzymes at this particular concentration. Our microscopic analysis suggests. that the formation of a robust intermolecular hydrogen bonding network is most effective at this concentration and is the main mechanism for the suppression of the fast dynamics. (c) 2005 American Insititute of Physics

Coupling Between Lysozyme and Glycerol Dynamics: Microscopic Insights from Molecular-Dynamics Simulations

We explore possible molecular mechanisms behind the coupling of protein and solvent dynamics using atomistic molecular-dynamics simulations. For this purpose, we analyze the model protein lysozyme in glycerol, a well-known protein-preserving agent. We find that the dynamics of the hydrogen bond network between the solvent molecules in the first shell and the surface residues of the protein controls the structural relaxation (dynamics) of the whole protein. Specifically, we find a power-law relationship between the relaxation time of the aforementioned hydrogen bond network and the structural relaxation time of the protein obtained from the incoherent intermediate scattering function. We demonstrate that the relationship between the dynamics of the hydrogen bonds and the dynamics of the protein appears also in the dynamic transition temperature of the protein. A study of the dynamics of glycerol as a function of the distance from the surface of the protein indicates that the viscosity seen by the protein is not the one of the bulk solvent. The presence of the protein suppresses the dynamics of the surrounding solvent. This implies that the protein sees an effective viscosity higher than the one of the bulk solvent. We also found significant differences in the dynamics of surface and core residues of the protein. The former is found to follow the dynamics of the solvent more closely than the latter. These results allowed us to propose a molecular mechanism for the coupling of the solvent-protein dynamics. (c) 2005 American Institute of Physics

Coupling Between Lysozyme and Trehalose Dynamics: Microscopic Insights from Molecular-Dynamics Simulations

We have carried out molecular-dynamics simulations on fully flexible all-atom models of the protein lysozyme immersed in trehalose, an effective biopreservative, with the purpose of exploring the nature and extent of the dynamical coupling between them. Our study shows a strong coupling over a wide range of temperatures. We found that the onset of anharmonic behavior was dictated by changes in the dynamics and relaxation processes in the trehalose glass. The physical origin of protein-trehalose coupling was traced to the hydrogen bonds formed at the interface between the protein and the solvent. Moreover, protein-solvent hydrogen bonding was found to control the structural relaxation of the protein. The dynamics of the protein was found to be heterogeneous; the motions of surface and core atoms had different dependencies on temperature and, in addition, the surface atoms were more sensitive to the dynamics of the solvent than the core atoms. From the solvent perspective we found that the dynamics near the protein surface showed an unexpected enhanced mobility compared to the bulk. These results shed some light on the microscopic origins of the dynamical coupling in protein-solvent systems. (c) 2006 American Institute of Physics

Unusual Symmetries in the Kugel-Khomskii Hamiltonian

The Kugel-Khomskii Hamiltonian for cubic titanates describes spin and orbital superexchange interactions between $d^1$ ions having three-fold degenerate $t_{2g}$ orbitals. Since orbitals do not couple along "inactive" axes, perpendicular to the orbital planes, the total number of electrons in $|\alpha >$ orbitals in any such plane and the corresponding total spin are both conserved. A Mermin-Wagner construction shows that there is no long-range spin ordering at nonzero temperatures. Inclusion of spin-orbit coupling allows such ordering, but even then the excitation spectrum is gapless due to a continuous symmetry. Thus, the observed order and gap require more symmetry breaking terms.Comment: 4 pages (two column format with 2 figures), to appear in Phys. Rev. Lett. (submitted on Dec. 2002

Human factors in ship dismantling – a safety approach : reality vs best practice

Ship dismantling (SD) is often considered as reverse ship building. For many years, ship dismantling has been neglected by the shipping industry due to lack of rules and understanding, hence severe consequences affecting both nature and human life have occurred. There has been growing concern about the health and environmental impacts of ship dismantling [1]. Therefore the impact of ship dismantling has been severely criticized by governmental and international shipping authorities as well as non-governmental organizations (NGO). As a result the procedure of developing new rules and regulations has been triggered and the safety culture is being questioned in the ship dismantling business. Although most countries that are in the ship dismantling business have almost no regulations related to ship dismantling, the case investigated in this article is Turkey, and the situation in Turkey is very different than the other major ship dismantling countries. The main reason for this difference is of course Turkey’s governmental laws and regulations on environmental protection and safety at work, as well as Turkey’s negotiations with the EU parliament. Current rules and practice on safety in shipping have been discussed in this paper. This article is the combined work of the University of Strathclyde, the Ship Recycling Association of Turkey and Ege Celik Ship Dismantling Yard in Turkey, with the aim to compare a successful business with the available best practice in ship building in the UK

Monitoring pumping test response in a fractured aquifer using ground-penetrating radar

This is the published version. Copyright 2010 by the American Geophysical Union. All rights reserved.Fractured aquifers present a number of problems when attempting to characterize flow on the well scale (less than 100 m). Standard hydraulic testing methods are expensive because of the need for installation of monitoring wells. Geophysical methods may suffer from a lack of resolution and nonunique solutions to data interpretation. We used ground-penetrating radar (GPR) surveying during a pumping test in a well-characterized, fractured, carbonate aquifer to monitor the response of a permeable subhorizontal fracture plane. We observed radar signal amplitude and waveform variations along a fracture reflector and correlated the radar signal response to changes in the water saturation of the fracture. Combining hydraulic measurements with GPR data and electromagnetic modeling, we identified an asymmetric fracture drainage pattern, provided accurate spatial information about the saturation of the fracture, and detected the presence of hydraulic boundaries. This study demonstrates that GPR surveying can be used successfully for real-time monitoring of pumping tests in fractured carbonate aquifers

Magnetically Driven Ferroelectric Order in Ni\u3csub\u3e3\u3c/sub\u3eV\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e8\u3c/sub\u3e

We show that long-range ferroelectric and incommensurate magnetic order appear simultaneously in a single phase transition in Ni3V2O8. The temperature and magnetic-field dependence of the spontaneous polarization show a strong coupling between magnetic and ferroelectric orders. We determine the magnetic symmetry using Landau theory for continuous phase transitions, which shows that the spin structure alone can break spatial inversion symmetry leading to ferroelectric order. This phenomenological theory explains our experimental observation that the spontaneous polarization is restricted to lie along the crystal b axis and predicts that the magnitude should be proportional to a magnetic order parameter

Complex Magnetic Order in the Kagomé Staircase Compound Co\u3csub\u3e3\u3c/sub\u3eV\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e8\u3c/sub\u3e

Co3V2O8 (CVO) has a different type of geometrically frustrated magnetic lattice, a kagomé staircase, where the full frustration of a conventional kagomé lattice is partially relieved. The crystal structure consists of two inequivalent (magnetic) Co sites, one-dimensional chains of Co(2) spine sites, linked by Co(1) cross-tie sites. Neutron powder diffraction has been used to solve the basic magnetic and crystal structures of this system, while polarized and unpolarized single crystal diffraction measurements have been used to reveal a rich variety of incommensurate phases, interspersed with lock-in transitions to commensurate phases. CVO initially orders magnetically at 11.3K into an incommensurate, transversely polarized, spin density wave state, with wave vector k=(0,δ,0) with δ=0.55 and the spin direction along the a axis. δ is found to decrease monotonically with decreasing temperature and then locks into a commensurate antiferromagnetic structure with δ=1/2 for 6.9\u3cT\u3c8.6K. In this phase, there is a ferromagnetic layer where the spine site and cross-tie sites have ordered moments of 1.39μB and 1.17μB, respectively, and an antiferromagnetic layer where the spine-site has an ordered moment of 2.55μB, while the cross-tie sites are fully frustrated and have no observable ordered moment. Below 6.9K, the magnetic structure becomes incommensurate again, and the presence of higher-order satellite peaks indicates that the magnetic structure deviates from a simple sinusoid. δ continues to decrease with decreasing temperature and locks in again at δ=1/3 over a narrow temperature range (6.2\u3cT\u3c6.5K). The system then undergoes a strongly first-order transition to the ferromagnetic ground state (δ=0) at Tc=6.2K. The ferromagnetism partially relieves the cross-tie site frustration, with ordered moments on the spine-site and cross-tie sites of 2.73μB and 1.54μB, respectively. The spin direction for all spins is along the a axis (Ising-like behavior). A dielectric anomaly is observed around the ferromagnetic transition temperature of 6.2K, demonstrating that there is significant spin-charge coupling present in CVO. A theory based on group theory analysis and a minimal Ising model with competing exchange interactions can explain the basic features of the magnetic ordering