Molecular Mechanics Studies of Molybdenum Disulphide Catalysts Parameterisation of Molybdenum and Sulphur

Abstract

A method for the parameterisation of molybdenum disulphide is presented which reproduces the crystal structure accurately. The method involves calculating parameters such that there is no net force contribution from any individual term of the potential on any atom. Ideal bond lengths and bond angles are taken from the X-ray crystal structure; stretching and bending force constants are calculated from a combination of spectroscopic data and quantum mechanics calculations, whereby the energy function with bond length or bond angle is calculated and fitted with an harmonic potential. For the non-bonded Lennard-Jones parameters, the dispersion coefficient C was calculated by an interpolation of existing published parameters using a multiple regression and then the crystal energy was minimised with respect to the van der Waals radius r₀ using a fixed crystal fragment.

These parameters were tested for various models of the hexagonal and rhombohedral forms of MoS₂. RMS fits between structures minimised with molecular mechanics and experimental models ranged from 0.006 Å to 0.012 Å.     

Molecular simulation of polymers with a SAFT-γ Mie approach

ABSTRACT

We review the group contribution Statistical Associating Fluid Theory with Mie interaction potentials (SAFT-γ Mie) approach for building coarse-grained models for molecular simulation of polymeric systems. In this top-down method, force field parameters for coarse-grained polymer models can be derived from thermodynamic information on constituent monomer units using the SAFT-γ Mie equation of state (EoS). This strategy can facilitate high-throughput computational screening of polymeric materials, with a corresponding states correlation expediting the force field fitting. Accurate and transferable non-bonded parameters linked to macroscopic thermodynamic data allow for calculation of properties beyond those obtainable from the EoS alone. To overcome limitations of SAFT-γ Mie regarding polymer chain stiffness and branching, hybrid top-down/bottom-up approaches have combined non-bonded parameters from SAFT-γ Mie with bond-stretching and angle-bending potentials from higher-resolution force fields. Our review critically evaluates the performance of recent SAFT-γ Mie polymer models, highlighting the strengths and weaknesses in the context of other equation of state and coarse-graining methods.     

Note: NAMD–LP: Filtering and Translating NAMD-generated Files

Abstract

We have empirically tested limits of the magnitude of multiple time steps in molecular dynamics simulations of aqueous systems, and the extent to which these offer a means to shorten computation time. Three different steps were employed, δ₀t for calculation of “bonded” forces, δ₁t for calculations of short-range (< 6 Å) non-bonded forces, and δ₂t for long-range (< 10 Å) non-bonded forces. Each longer step was a multiple of the shortest one. The leap-frog integration algorithm was used with SHAKE for restraint of all bond lengths and water molecules. For a system of SPC water molecules, calculation of short-range non-bonded forces could be done with a time step δ₁t = 10 fs, without appreciable change of the average temperature and energy, radial distribution function or diffusion coefficient. These properties were found to be insensitive to the inclusion of long-range non-bonded forces. A multiple-step protocol with δ₀t = 2, δ₁t = 4 and δ₂t = 16 fs has been compared with a single-step procedure with δt 2 fs for small polypeptides in water. The exploration of conformation space, with crossing of low energy barriers, was tested with the glycine dipeptide and was found to proceed at similar rates. Mean, hysteresis and statistical error of the free energy for changing alanine to α-amino butyric acid in the dipeptide, calculated by the slow-growth method, proved independent of the cutoff distance or exact protocol, within 1 kJ/mol. In conclusion, we recommend, instead of use of a single time step of 2 fs at a 10 Å cutoff, use of a time step δ_t = 4 fs for short-range nonbonded forces and a time step δ₂t = 16 fs for long-range nonbonded forces for a 60% reduction of computation time.     

Inter-chain Proline: Proline Contacts Contribute to the Stability of the Triple Helical Conformation

Abstract

The triple helical conformation observed in the collagen group of proteins is related to the presence of large numbers of imino residues and is derived from the stereochemical properties of these residues. The triple helix is stabilized by increasing numbers of these residues. Hydrogen bonds are usually considered to be a major factor in the formation and stability of protein conformation, however, imino residues are not hydrogen bond donors. We have evaluated the role of these residues in stabilizing the triple helix by re-examining two X-ray based structures of the triple helical polypeptide (Pro-Pro- Gly)₁₀ using molecular mechanics calculations. The two minimized structures are comparable in energy and have helical parameters close to the starting values for each starting structure. Our studies suggest that clusters of close van der Waals contacts between proline residues in adjacent chains contribute significantly to the stability of the triple helix. Preliminary NMR studies support this concept. We propose that non-bonded interactions between proline residues may be a significant stabilizing force in the triple helix generated by (Pro-Pro-Gly)₁₀.     

Basic tests in mammography as a tool in quality improvement

BackgroundMammography is a radiological diagnostic method which relies on an X-ray examination of breasts and is a process involving the use of low-dose amplitude-X-rays (usually around 0.7 mSv). Combining the use of small doses and high quality images requires extensive quality protocols, part of them being included in regulations adopted by the Minister of Health.AimThe aim of this study was to check the usefulness and efficacy of selected quality tests associated with mammography.Material/methodsThe study was performed in the mammography service of the Greater Poland Cancer Centre in Poznan. Following equipment was used: densitometer, sensitometer, mammographic scales, electronic scales, thermometer, hygrometer, PMMA plates, Europhantom, screen film contact phantom, viewing boxes and magnifying glasses. The methods were based on basic mammography tests. Quality control in mammography demands: clean darkroom, marked and clean cassettes, clean viewing boxes with homogenous light.ResultsThe results of the “Development Process” test show that each sensitometer has to be used with an appropriate densitometer. Phantoms with abnormal structures cannot be used to “AEC System – Solidity exposure” test. “Compression – The force of compression” test may only be carried out with suitable scales and compressible material. Analysis of rejected films shows that the main reasons for rejection were wrong collimation and underexposure.ConclusionEvery quality control in mammography provides essential information about the functioning of a laboratory. Apart from recommended standard sterility, it should be remembered that equipment should always be adjusted and repaired.     

Effect of nestbox construction and colour on the occupancy and breeding success of nesting tits Parus spp.

Capsule Breeding performance was not affected, although variation in nestbox occupancy may result from perceived differences in protection from predators and insulation properties.

Aim To assess if nestboxes of different construction and colour were occupied differently by breeding tits and affected breeding success.

Methods A total of 292 nestboxes of different construction and colour were placed in a range of habitats and their occupancy, and the clutch size, brood size and number of young fledged of the birds that used them were measured.

Results Overall 272 tit nests were included in the analysis. Although there were species-related differences in the occupancy of the different types of nestboxes, more tits nested in the boxes constructed from woodcrete (64% of nests) compared to the wooden boxes (36%). More tits nested in green (72%) rather than brown boxes (28%) and in boxes with entrance holes (68%) rather than wedges (32%). The clutch size, brood size and number of young fledged did not vary in relation to nestbox type.

Conclusion Within the parameters of the experimental design of this study, tits are more likely to nest in woodcrete boxes than in wooden boxes, and in wooden boxes that are green and have holes rather than brown boxes with wedge entrances. It is likely that the smaller internal volume, internal darkness, insulating properties and perceived protection from predation were the reasons for these differences.     

Flexibility of 3′,5′ Deoxyribonucleooside Diphosphates

Abstract

In 3′,5′ deoxyribonucleoside diphosphates, in addition to the nature of the base and the sugar puckering, there are six single bond rotations. However, from the analysis of crystal structure data on the constituents of nucleic acids, only three rotational angles, that are about glycosyl bond, about C4′-C5′ and about C3′-O3′ bonds, are flexible. For a given sugar puckering and a base, potential energy calculations using non-bonded, electrostatic and torsional functions were carried out by varying the three torsion angles. The energies are represented as isopotential energy surfaces. Since the availability of the real-time color graphics, it is possible to analyse these isopotential energy surfaces. The calculations were carried out for C3′ exo and C3′ endo puckerings for deoxyribose and also for four bases. These calculations throw more light not only on the allowed regions for the three rotational angles but also on the relationships among them. The dependence of base and the puckering of the sugar on these rotational angles and thereby the flexibility of the 3′,5′ deoxyribonucleoside diphosphates is discussed. From our calculations, it is now possible to follow minimum energy path for interconversion among various conformers.     

Conformational-energy calculations for oligosaccharides: a comparison of methods and a strategy of calculation

A theoretical conformational analysis of dimethoxymethane, 2-methoxytetrahydropyran, cellobiose, and maltose has been performed. The validity of several commonly used classical approaches to conformational energy, assuming non-bonded interactions, torsional terms, and the exo-anomeric contribution, and the MM2CARB method (a modified version of the MM2 force-field program using the Jeffrey-Taylor parameters) was tested against available experimental data or previous quantum-chemical calculations. The MM2CARB method correctly reproduces the energies and the variations in bond lengths and bond angles for conformers of dimethoxymethane and 2-methoxytetrahydropyran. Prediction of the observed conformers with simple potential functions appears to be less satisfactory. In particular, calculations that take into account non-bonded interactions and the exo-anomeric contribution based on dimethoxymethane give predicted energy differences that are 2–3 times higher than the experimental values. The general shapes of the (Φ, Ψ) potential-energy surfaces for cellobiose and maltose provided by potential-function calculations suggest the presence of several minima whose energies depend, to a great extent, on the choice of molecular geometry. The MM2CARB-calculated structures of seven cellobiose and five maltose conformers demonstrate clearly the variation of disaccharide geometry with change of conformation around the glycosidic linkage. The relative energies calculated by simple methods differ from MM2CARB energies and indicate that the simple potential-functions methods give only a qualitative estimate of oligosaccharide conformers. Based on these results, we propose a general strategy and two different approaches for the investigation of conformational properties of oligosaccharides.     

Adaptive habitat preferences in the Tawny Owl Strix aluco

Capsule: Tawny Owls Strix aluco occupying nest boxes preferred habitats which were positively associated with the probability of nesting success.

Aims: We aimed to determine whether or not: (1) Tawny Owls showed habitat preferences when occupying nest boxes; (2) nesting performance was related to the habitats around occupied nest boxes and (3) habitat availability had changed around available and occupied nest boxes between 1995–2004 and 2005–14.

Methods: Tawny Owls were studied using nest boxes erected in a commercial forest. During nest boxes checks (724 cases), data on occupancy and nesting performance (88 cases) were recorded, and habitat within a 0.4?km radius around nest boxes was analysed.

Results: Tawny Owls had preferences for clearings within forests, mature forests and grasslands but avoided young forests. We found a positive relationship between nesting success and abundance of clearings within the forest, and a negative relationship between nesting success and abundance of young forests. A change in habitat preferences over the two decades was evident, but habitat availabilities remained similar.

Conclusions: Findings indicate adaptive habitat selection in Tawny Owls because preferred habitats were associated with higher fitness and this type of habitat became more frequently selected over time.     

An easy way to include weak alignment constraints into NMR structure calculations

We have recently shown that an energy penalty for the incorporation of residual tensorial constraints into molecular structure calculations can be formulated without the explicit knowledge of the Saupe orientation tensor (Moltke and Grzesiek, J. Biomol. NMR, 1999, 15, 77–82). Here we report the implementation of such an algorithm into the program X-PLOR. The new algorithm is easy to use and has good convergence properties. The algorithm is used for the structure refinement of the HIV-1 Nef protein using 252 dipolar coupling restraints. The approach is compared to the conventional penalty function with explicit knowledge of the orientation tensor's amplitude and rhombicity. No significant differences are found with respect to speed, Ramachandran core quality or coordinate precision.     

Molecular dynamics simulation of proteins under high pressure: Structure,function and thermodynamics

BackgroundMolecular dynamics (MD) simulation is well-recognized as a powerful tool to investigate protein structure, function, and thermodynamics. MD simulation is also used to investigate high pressure effects on proteins. For conducting better MD simulation under high pressure, the main issues to be addressed are: (i) protein force fields and water models were originally developed to reproduce experimental properties obtained at ambient pressure; and (ii) the timescale to observe the pressure effect is often much longer than that of conventional MD simulations.Scope of reviewFirst, we describe recent developments in MD simulation methodologies for studying the high-pressure structure and dynamics of protein molecules. These developments include force fields for proteins and water molecules, and enhanced simulation techniques. Then, we summarize recent studies of MD simulations of proteins in water under high pressure.Major conclusionsRecent MD simulations of proteins in solution under pressure have reproduced various phenomena identified by experiments using high pressure, such as hydration, water penetration, conformational change, helix stabilization, and molecular stiffening.General significanceMD simulations demonstrate differences in the properties of proteins and water molecules between ambient and high-pressure conditions. Comparing the results obtained by MD calculations with those obtained experimentally could reveal the mechanism by which biological molecular machines work well in collaboration with water molecules.     

A Systematic Search Method for the Identification of Tightly Packed Transmembrane Parallel α-Helices

Abstract

Membrane proteins play a major role in number of biological processes such as signaling pathways. The determination of the three-dimensional structure of these proteins is increasingly important for our understanding of their structure-function relationships. Due to the difficulty in isolating membrane proteins for X-ray diffraction studies, computational techniques are being developed to generate the 3D structures of TM domains. Here, we present a systematic search method for the identification of energetically favorable and tightly packed transmembrane parallel α-helices. The first step in our systematic search method is the generation of 3D models for pairs of parallel helix bundles with all possible orientations followed by an energy-based filter to eliminate structures with severe non-bonded contacts. Then, a RMS-based filter was used to cluster these structures into families. Furthermore, these dimers were energy minimized using molecular mechanics force field. Finally, we identified the tightly packed parallel α-helices by using an interface surface area. To validate our search method, we compared our predicted GlycophorinA dimer structures with the reported NMR structures. With our search method, we are able to reproduce NMR structures of GPA with 0.9Å RMSD. In addition, by considering the reported mutational data on GxxxG motif interactions, twenty percent of our predicted dimers are within in the 2.0Å RMSD. The dimers obtained from our method were used to generate parallel trimeric and tetramer TM structures of GPA and found that the structure of GPA might exist only in a dimer form as reported earlier.     

Gibbs-Ensemble Molecular Dynamics: Liquid-Gas Equilibria for Lennard-Jones Spheres and n-Hexane

Abstract

We present a novel method to simulate phase equilibria in atomic and molecular systems. The method is a Molecular Dynamics version of the Gibbs-Ensemble Monte Carlo technique, which has been developed some years ago for the direct simulation of phase equilibria in fluid systems. The idea is to have two separate simulation boxes, which can exchange particles (or molecules) in a thermodynamically consistent fashion. Here we pres the derivation of the generalized equations of motion and discuss the relation of the resulting trajectory averages to the relevant ensemble. We test this Gibbs-Ensemble Molecular Dynamics algorithm by applying it to an atomic and a molecular system, i.e. to the liquid-gas coexistence in a Lennard-Jones fluid and in n-hexane. In both cases our results are in good accord with previous mean field and Gibbs-Ensemble Monte Carlo results as well as with the experimental data in the case of hexane. We also show that our Gibbs-Ensemble Molecular Dynamics algorithm like other Molecular Dynamics techniques can be used to study the dynamics of the system. Self-diffusion coefficients calculated with this method are in agreement with the result of conventional constant temperature Molecular Dynamics.     

A Theoretical Study of the Aqueous Hydration of Canonical B d(CGCGAATTCGCG): Monte Carlo Simulation and Comparison with Crystallographic Ordered Water Sites

Abstract

Monte Carlo computer simulation is described for the dodecamer d(CGCGAATTCGCG) together with 1777 water molecules at an environmental density of 1 gm/cc in a cubic cell under periodic boundary conditions. Water-water interactions were treated using the TIP4P potential and the solute water interactions by TIP4P spliced with the non-bonded interactions from the AMBER 3.0 force field. The simulation was subjected to proximity analysis to obtain solute coordination numbers and pair interaction energies for each solute atom. Hydration density distributions partitioned into contributions from the major groove side, the minor groove side and the sugar-phosphate backbone were examined, and the probabilities of occurence for one- and two-water bridges in the simulation were enumerated. The results were compared with observations of crystallographic ordered water sites from x-ray diffraction studies on the native dodecamer by Dickerson and coworkers.     

An ab initio Linear-Scaling Schem

Abstract

In this paper we briefly survey the current state of ab initio calculations in terms of the accuracy and range of applicability of these methods for studying complex processes in real materials. We highlight some of the successes and limitations of these techniques and discuss the extent to which linear-scaling methods are able to extend the scope and scale of ab initio calculations. We argue that a combination of linear-scaling methods and hybrid modelling schemes is required to overcome many of the difficulties currently faced by conventional schemes, and present our own contributions towards the development of a robust and reliable linear-scaling method.     

Theoretical probes of conformational fluctuations in S-peptide and RNase A/3′–UMP enzyme product complex

The dynamic properties of the RNase A/3′–UMP enzyme/product complex and the S-peptide of RNase A have been investigated by molecular dynamics simulations using suitable generalization of ideas introduced to probe the energy landscape in structural glasses. We introduce two measures, namely, the kinetic energy fluctuation metric and the force metric, both of which are used to calculate the time needed for sampling the conformation space of the molecules. The calculation of the fluctuation metric requires a single trajectory whereas the force metric is computed using two independent trajectories. The vacuum MD simulations show that for both systems the time required for kinetic energy equipartitioning is surprisingly long even at high temperatures. We show that the force metric is a powerful means of probing the nature and relative importance of conformational substates which determine the dynamics at low temperatures. In particular the time dependence of the non-bonded force metric is used to demonstrate that at low temperatures the system is predominantly localized hi a single cluster of conformational substates. The force metric is used to show that relaxation of long range (in sequence space) interactions must be mediated by a sequence of local dihedral angle transitions. We also argue that the time needed for compact structure formation is intimately related to the time needed for the relaxation of the dihedral angle degrees of freedom. The tame for non-bonded interactions, which drive protein molecules to fold under appropriate conditions, to relax becomes extremely long as the temperature is lowered suggesting that the formation of maximally compact structure hi proteins must be a very slow process. © 1993 Wiley-Liss, Inc.     

Using matrix summation method for three dimensional dose calculation in brachytherapy

AimThe purpose of this study is to calculate radiation dose around a brachytherapy source in a water phantom for different seed locations or rotation the sources by the matrix summation method.BackgroundMonte Carlo based codes like MCNP are widely used for performing radiation transport calculations and dose evaluation in brachytherapy. But for complicated situations, like using more than one source, moving or rotating the source, the routine Monte Carlo method for dose calculation needs a long time running.Materials and methodsThe MCNPX code has been used to calculate radiation dose around a ¹⁹²Ir brachytherapy source and saved in a 3D matrix. Then, we used this matrix to evaluate the absorbed dose in any point due to some sources or a source which shifted or rotated in some places by the matrix summation method.ResultsThree dimensional (3D) dose results and isodose curves were presented for ¹⁹²Ir source in a water cube phantom shifted for 10 steps and rotated for 45 and 90° based on the matrix summation method. Also, we applied this method for some arrays of sources.ConclusionThe matrix summation method can be used for 3D dose calculations for any brachytherapy source which has moved or rotated. This simple method is very fast compared to routine Monte Carlo based methods. In addition, it can be applied for dose optimization study.     

Anisotropic Site-Site Potentials in Molecular Dynamics

Abstract

This paper describes techniques for calculating the forces and torques for molecular simulations that use anisotropic site-site potentials. The general techniques are illustrated for pairs of linear and tetrahedral molecules. A technique for combining anisotropic site-site potentials with constraint dynamics is described. These ideas are tested by simulating an anisotropic site-site potential model for the non-bonded interactions in liquid butane. This model is as accurate as the all-atom Williams potential from which it is derived but can be simulated using approximately half the computer time of the all-atom potential. Anisotropic site-site potentials offer a flexible and cost-effective method of simulating a range of hydrocarbon systems.     

Computer vision for LCA foreground modelling—an initial pipeline and proof of concept software,lcopt-cv

Purpose

The majority of LCA studies begin with the drawing of a process flow diagram, which then needs to be translated manually into an LCA model. This study presents an initial image processing pipeline, implemented in an open-source software package, called lcopt-cv, which can be used to identify the boxes and links in a photograph of a hand-drawn process flow diagram and automatically create an LCA foreground model.

Methods

The computer vision pipeline consists of a total of 15 steps, beginning with loading the image file and conversion to greyscale. The background is equalised, then the foreground of the image is extracted from the background using thresholding. The lines are then dilated and closed to account for drawing errors. Contours in the image are detected and simplified, and rectangles (contours with four corners) are identified from the simplified contours as ‘boxes’. Links between these boxes are identified using a flood-filling technique. Heuristic processing, based on knowledge of common practice in drawing of process flow diagrams, is then performed to more accurately identify the typology of the identified boxes and the direction of the links between them.

Results and discussion

The performance of the image processing pipeline was tested on four flow diagrams of increasing difficulty: one simple computer drawn diagram and three photographs of hand-drawn diagrams (a simple diagram, a complex diagram and a diagram with merged lines). A set of default values for the variables which define the pipeline was developed through trial and error. For the two simple flow charts, all boxes and links were identified using the default settings. The complex diagram required minor tweaks to the default values to detect all boxes and links. An ‘unstacking’ heuristic allowed the diagram with merged lines to be correctly processed. After some manual reclassification of link directions and process types, the diagrams were turned into LCA models and exported to open-source LCA software packages (lcopt and Brightway) to be verified and analysed.

Conclusions

This study demonstrates that it is possible to generate a fully functional LCA model from a picture of a flow chart. This has potentially important implications not only for LCA practitioners as a whole, but in particular for the teaching of LCA. Skipping the steep learning curve required by most LCA software packages allows teachers to focus on important LCA concepts, while participants maintain the benefits of experiential learning by doing a ‘real’ LCA.