Freezing line of the Lennard-Jones fluid: a Phase Switch Monte Carlo study

We report a Phase Switch Monte Carlo (PSMC) method study of the freezing line of the Lennard-Jones (LJ) fluid. Our work generalizes to soft potentials the original application of the method to hard sphere freezing, and builds on a previous PSMC study of the LJ system by Errington (J. Chem. Phys. {\bf 120}, 3130 (2004)). The latter work is extended by tracing a large section of the Lennard-Jones freezing curve, the results for which we compare to a previous Gibbs-Duhem integration study. Additionally we provide new background regarding the statistical mechanical basis of the PSMC method and extensive implementation details.Comment: 18 pages, 6 figure

Modeling spontaneous formation of precursor nanoparticles in clear-solution zeolite synthesis

We present a lattice model describing the formation of silica nanoparticles in the early stages of the clear-solution templated synthesis of silicalite-1 zeolite. Silica condensation/hydrolysis is modeled by a nearest-neighbor attraction, while the electrostatics are represented by an orientation-dependent, short-range interaction. Using this simplified model, we show excellent qualitative agreement with published experimental observations. The nanoparticles are identified as a metastable state, stabilized by electrostatic interactions between the negatively charged silica surface and a layer of organic cations. Nanoparticle size is controlled mainly by the solution pH, through nanoparticle surface charge. The size and concentration of the charge-balancing cation are found to have a negligible effect on nanoparticle size. Increasing the temperature allows for further particle growth by Ostwald ripening. We suggest that this mechanism may play a role in the growth of zeolite crystals

Phase coexistence of cluster crystals: beyond the Gibbs phase rule

We report a study of the phase behavior of multiple-occupancy crystals through simulation. We argue that in order to reproduce the equilibrium behavior of such crystals it is essential to treat the number of lattice sites as a constraining thermodynamic variable. The resulting free-energy calculations thus differ considerably from schemes used for single-occupancy lattices. Using our approach, we obtain the phase diagram and the bulk modulus for a generalized exponential model that forms cluster crystals at high densities. We compare the simulation results with existing theoretical predictions. We also identify two types of density fluctuations that can lead to two sound modes and evaluate the corresponding elastic constants.Comment: 4 pages, 3 figure

Randomized controlled trial of patient-controlled sedation for colonoscopy: Entonox vs modified patient-maintained target-controlled propofol

Aim Propofol sedation is often associated with deep sedation and decreased manoeuvrability. Patient-maintained sedation has been used in such patients with minimal side-effects. We aimed to compare novel modified patient-maintained target-controlled infusion (TCI) of propofol with patient-controlled Entonox inhalation for colonoscopy in terms of analgesic efficacy (primary outcome), depth of sedation, manoeuvrability and patient and endoscopist satisfaction (secondary outcomes). Method One hundred patients undergoing elective colonoscopy were randomized to receive either TCI propofol or Entonox. Patients in the propofol group were administered propofol initially to achieve a target concentration of 1.2 μ g/ml and then allowed to self-administer a bolus of propofol (200 μ g/kg/ml) using a patient-controlled analgesia pump with a handset. Entonox group patients inhaled the gas through a mouthpiece until caecum was reached and then as required. Sedation was initially given by an anaesthetist to achieve a score of 4 (Modified Observer's Assessment of Alertness and Sedation Scale), and colonoscopy was then started. Patients completed an anxiety score (Hospital Anxiety and Depression questionnaire), a baseline letter cancellation test and a pain score on a 100-mm visual analogue scale before and after the procedure. All patients completed a satisfaction survey at discharge and 24 h postprocedure. Results The median dose of propofol was 174 mg, and the median number of propofol boluses was four. There was no difference between the two groups in terms of pain recorded (95% confidence interval of the difference -0.809, 5.02) and patient/endoscopist satisfaction. There was no difference between the two groups in either depth of sedation or manoeuvrability. Conclusion Both Entonox and the modified TCI propofol provide equally effective sedation and pain relief, simultaneously allowing patients to be easily manoeuvred during the procedures. © 2010 The Authors. Colorectal Disease © 2010 The Association of Coloproctology of Great Britain and Ireland

Hydration of a B-DNA Fragment in the Method of Atom-atom Correlation Functions with the Reference Interaction Site Model Approximation

We propose an efficient numerical algorithm for solving integral equations of the theory of liquids in the Reference Interaction Site Model (RISM) approximation for infinitely dilute solution of macromolecules with a large number of atoms. The algorithm is based on applying the nonstationary iterative methods for solving systems of linear algebraic equations. We calculate the solvent-solute atom-atom correlation functions for a fragment of the B-DNA duplex d(GGGGG).d(CCCCC) in infinitely dilute aqueous solution. The obtained results are compared with available experimental data and results from computer simulations.Comment: 9 pages, RevTeX, 9 pages of ps figures, accepted for publications in JC

Why are estimates of global isoprene emissions so similar (and why is this not so for monoterpenes)?

International audienceEmissions of biogenic volatile organic compounds (BVOC) are a chief uncertainty in calculating the burdens of important atmospheric compounds like tropospheric ozone or secondary organic aerosol, reflecting either imperfect chemical oxidation mechanisms or unreliable emission estimates, or both. To provide a starting point for a more systematic discussion we review here global isoprene and monoterpene emission estimates to-date. We note a surprisingly small variation in the predictions of global isoprene emission rate that is in stark contrast with our lack of process understanding and the small number of observations for model parameterisation and evaluation. Most of the models are based on similar emission algorithms, using fixed values for the emission capacity of various plant functional types. In some studies these values are very similar, but they differ substantially in others. The models differ also broadly with regard to their representation of net primary productivity, method of biome coverage determination and climate data. Their similarities with regard to the global isoprene emission rate would suggest that the dominant parameters driving the ultimate global estimate, and thus the dominant determinant of model sensitivity, are the specific emission algorithm and isoprene emission capacity. Contrary to isoprene, monoterpene estimates show significantly larger model-to-model variation although variation in terms of leaf algorithm, emission capacities, the way of model upscaling, vegetation cover or climatology used in terpene models are comparable to those used for isoprene. From our summary of published studies there appears to be no evidence that the terrestrial modelling community has been any more successful in "resolving unknowns" in the mechanisms that control global isoprene emissions, compared to global monoterpene emissions. Rather, the proliferation of common parameterization schemes within a large variety of model platforms lends the illusion of convergence towards a common estimate of global isoprene emissions. This convergence might be used to provide optimism that the community has reached the "relief phase", the phase when sufficient process understanding and data for evaluation allows for models to converge, when applying a recently proposed concept. We argue that there is no basis for this apparent "relief" phase. Rather, we urge modellers to be bolder in their analysis to draw attention to the fact that terrestrial emissions, particularly in the area of biome-specific emission capacities, are unknown rather than uncertain

Regular Incidence Complexes, Polytopes, and C-Groups

Regular incidence complexes are combinatorial incidence structures generalizing regular convex polytopes, regular complex polytopes, various types of incidence geometries, and many other highly symmetric objects. The special case of abstract regular polytopes has been well-studied. The paper describes the combinatorial structure of a regular incidence complex in terms of a system of distinguished generating subgroups of its automorphism group or a flag-transitive subgroup. Then the groups admitting a flag-transitive action on an incidence complex are characterized as generalized string C-groups. Further, extensions of regular incidence complexes are studied, and certain incidence complexes particularly close to abstract polytopes, called abstract polytope complexes, are investigated.Comment: 24 pages; to appear in "Discrete Geometry and Symmetry", M. Conder, A. Deza, and A. Ivic Weiss (eds), Springe

Clinical Use of Cinacalcet in MEN1 Hyperparathyroidism

Background. Management of multiple-endocrine neoplasia type 1- (MEN1-) associated hyperparathyroidism is associated with high recurrence rates and high surgical morbidity due to multiple neck explorations. Cinacalcet, a calcimimetic agent licensed for the treatment of secondary hyperparathyroidism and parathyroid carcinoma, may provide a medical alternative for the management of these complex patients. Methods. A prospective audit was performed of eight patients; three males and five females, aged 20–38 at diagnosis. Two patients commenced cinacalcet as primary treatment and six had previous surgery. Six patients had complications of hyperparathyroidism: renal calculi, renal dysfunction, and reduced bone mineral density. All were commenced on cinacalcet 30 mg bd for MEN1 associated hyperparathyroidism; doses were subsequently reduced to 30 mg od in four patients. Results. Significant reductions were observed in serum calcium and PTH measurements. Serum calcium reduced by a median of 0.35 mmol/L (P = .012 Wilcoxon Signed Rank). Serum PTH levels decreased by a median of 5.05 pmol/L (P = .012). There was no change in urine calcium. Duration ranged from 10–35 months with maintenance of control. Cinacalcet was well tolerated by six patients; one experienced nausea and one experienced diarrhoea. Conclusion. Cinacalcet is an effective and well-tolerated medical treatment for the management of complex primary hyperparathyroidism

The properties of fully flexible Lennard-Jones chains in the solid phase: Wertheim theory and simulation

NpT ensemble Monte Carlo simulations were performed for fully flexible Lennard-Jones chains in the solid phase. The bond length between monomers within the chains is fixed to $L=\sigma$ and the molecule is free to adopt any configuration. The solid structure of fully flexible chains is obtained by randomly locating the bonds of the chain within a face centered cubic close packed arrangement of atoms. For fully flexible chains it is believed that the stable solid phase is disordered. Such a solid is considered in this work. Computer simulations were performed for chains with $m=3, 4$ and 5 monomer units, and results were obtained for the equation of state and internal energy of the chains. An extension of Wertheim's TPT1 to the solid phase of Lennard-Jones chains (C.Vega, F.J.Blas and A.Galindo, J.Chem.Phys.,{\bf 116},7645,2002) has been proposed recently. The simulation results of this work provide a check on the performance of this theory. It is found that Wertheim's TPT1 successfully predicts the equation of state and internal energies of fully flexible LJ chains in the solid phase. Finally, a rigid LJ chain in a linear configuration has been considered. Computer simulations were also performed for the rigid chain in an ordered solid structure. It is found that fully flexible and linear rigid chains present quite different equations of state and different thermodynamic properties in the solid phase.Comment: PrEprint of the paper published in Molecular Physics volume 101, pp. 2241-2255 (2003