A pilgrimage to the shrines of patriotism, being the report of the commission to dedicate the monument erected by the state of New York, in Andersonville, Georgia, to commemorate the heroism, sacrifices and patriotism of more than nine thousand of her sons who were confined in that prison ... with an account of services of the New York resident surviving Andersonville veterans held thereat and also enroute at Richmond and Danville, Va., Salisbury N.C., and Lookout mountain, Tenn., April 26-30, 1914.

"List of New York state soldiers buried in Andersonville national cemetary": p. 171-241.

A numerical approach to modeling the catalytic voltammetry of surface-confined redox enzymes

A finite difference method for simulating voltammograms of electrochemically driven enzyme catalysis is presented. The method enables any enzyme mechanism to be simulated. The finite difference equations can be represented as a matrix equation containing a nonlinear sparse matrix. This equation has been solved using the software package Mathematica. Our focus is on the use of cyclic voltammetry since this is the most commonly employed electrochemical method used to elucidate mechanisms. The use of cyclic voltammetry to obtain data from systems obeying Michaelis-Menten kinetics is discussed, and we then verify our observations on the Michaelis-Menten system using the finite difference simulation. Finally, we demonstrate how the method can be used to obtain mechanistic information on a real redox enzyme system, the complex bacterial molybdoenzyme xanthine dehydrogenase.

Evaluation of 1-site and 5-site models of methane on its adsorption on graphite and in graphitic slit pores

In this paper, we evaluate the performance of the 1- and 5-site models of methane on the description of adsorption on graphite surfaces and in graphitic slit pores. These models have been known to perform well in the description of the fluid-phase behavior and vapor-liquid equilibria. Their performance in adsorption is evaluated in this work for nonporous graphitized thermal carbon black, and simulation results are compared with the experimental data of Avgul and Kiselev (Chemistry and Physics of Carbon; Dekker: New York, 1970; Vol. 6, p 1). On this nonporous surface, it is found that these models perform as well on isotherms at various temperatures as they do on the experimental isosteric heat for adsorption on a graphite surface. They are then tested for their performance in predicting the adsorption isotherms in graphitic slit pores, in which we would like to explore the effect of confinement on the molecule packing. Pore widths of 10 and 20 angstrom are chosen in this investigation, and we also study the effects of temperature by choosing 90.7, 113, and 273 K. The first two are for subcritical conditions, with 90.7 K being the triple point of methane and 113 K being its boiling point. The last temperature is chosen to represent the supercritical condition so that we can investigate the performance of these models at extremely high pressures. We have found that for the case of slit pores investigated in this paper, although the two models yield comparable pore densities (provided the accessible pore width is used in the calculation of pore density), the number of particles predicted by the I-site model is always greater than that predicted by the 5-site model, regardless of whether temperature is subcritical or supercritical. This is due to the packing effect in the confined space such that a methane molecule modeled as a spherical particle in the I-site model would pack better than the fused five-sphere model in the case of the 5-site model. Because the 5-site model better describes the liquid- and solid-phase behavior, we would argue that the packing density in small pores is better described with a more detailed 5-site model, and care should be exercised when using the 1-site model to study adsorption in small pores.

Organic-inorganic poly(methyl methacrylate) hybrids with confined polyhedral oligosilsesquioxane macromonomers

We herein report the synthesis of organic-inorganic hybrid poly(methyl methacrylate) containing 1 polyhedral oligosilsesquioxanes. Octakis(3-hydroxypropyldimethylsiloxy)octasilsesquioxane (OHPS) was synthesized from octakis(hydridodimethylsiloxy)octasilsesquioxane [Si8O12(OSiMe2H)(8), Q(8)M(8)(H)] following literature procedures. Octakis(tnethacryloxypropyldimethylsiloxy) octasilsesquioxane (OMPS) was synthesized via the reaction of methacryloyl chloride or methacrylic acid anhydride with OHPS, with the latter giving improved purity. Polymerization of OMPS with methyl inethacrylate using a dibenzoylperoxide initiator gave a highly cross-linked polymer. Characterization of the polymer was performed using Fourier transform IR spectroscopy, Si-29 NMR, differential scanning calorimetry, thermogravimetric analysis, atomic force microscopy, and transmission electron microscopy with energy-dispersive X-ray analysis. The polymer was found to be largely homogeneous. Increasing the OMPS concentration in the polymer gave increased decomposition and glass transition temperatures.

Projected Gross-Pitaevskii equation for harmonically confined Bose gases at finite temperature

We extend the projected Gross-Pitaevskii equation formalism of Davis [Phys. Rev. Lett. 87, 160402 (2001)] to the experimentally relevant case of thermal Bose gases in harmonic potentials and outline a robust and accurate numerical scheme that can efficiently simulate this system. We apply this method to investigate the equilibrium properties of the harmonically trapped three-dimensional projected Gross-Pitaevskii equation at finite temperature and consider the dependence of condensate fraction, position, and momentum distributions and density fluctuations on temperature. We apply the scheme to simulate an evaporative cooling process in which the preferential removal of high-energy particles leads to the growth of a Bose-Einstein condensate. We show that a condensate fraction can be inferred during the dynamics even in this nonequilibrium situation.

Health and developmental outcome of children following prenatal diagnosis of confined placental mosaicism

Objective To determine the long-term health and development of a cohort of children in whom confined placental mosaicism (CPM) was diagnosed at prenatal diagnosis. Methods A retrospective cohort study was performed comparing 36 children in whom CPM had been diagnosed prenatally with 195 controls subjects in whom a normal karyotype had been detected prenatally. Data comprising birth information, health, health service utilisation, growth, development, behaviour, and the family were collected by a maternal questionnaire administered when the subjects were aged between 4 and 11 years. Results CPM cases did not differ from controls across a broad range of health measures and there were no major health problems or birth defects among the CPM group. No increase was detected in the incidence of intrauterine growth retardation (IUGR) among CPM cases; however, postnatal growth was reduced compared with controls (p = 0.047). Development and behaviour in CPM cases was similar to that of controls. Conclusions The prenatal diagnosis of CPM is not associated with an increased risk of birth defects or developmental problems, but may be associated with decreased growth. Copyright (C) 2006 John Wiley & Sons, Ltd.

Influence of adsorbate interaction on transport in confined spaces

This article provides a review of the recent theory of transport in nanopores developed in the author's laboratory. In particular the influence of fluid-solid interactions on the transport coefficient is examined, showing that such interactions reduce the value of the coefficient by almost an order of magnitude in comparison to the Knudsen theory for non-interacting systems. The activation energy and potential energy barriers for diffusion in smooth pores with a one-dimensional potential energy profile are also discussed, indicating the inadequacy of the commonly used assumption of proportionality between the activation energy and heat of adsorption or the minimum pore potential energy. A further feature affected by fluid-solid interactions is the nature of the reflection of fluid molecules colliding with a pore wall surface, varying from being nearly specular - such as in carbon nanotubes - to nearly diffuse for amorphous solids. Diffuse reflection leads to momentum loss and reduced transport coefficients. However, fluid-solid interactions do not affect the transport coefficient in the single-file diffusion regime when the surface reflection is diffuse, and the transport coefficient in this case is largely independent of the adsorbed density.

Structure of saccharose-based carbon and transport of confined fluids: hybrid reverse Monte Carlo reconstruction and simulation studies

We present results of the reconstruction of a saccharose-based activated carbon (CS1000a) using hybrid reverse Monte Carlo (HRMC) simulation, recently proposed by Opletal et al. [1]. Interaction between carbon atoms in the simulation is modeled by an environment dependent interaction potential (EDIP) [2,3]. The reconstructed structure shows predominance of sp(2) over sp bonding, while a significant proportion of sp(3) hybrid bonding is also observed. We also calculated a ring distribution and geometrical pore size distribution of the model developed. The latter is compared with that obtained from argon adsorption at 87 K using our recently proposed characterization procedure [4], the finite wall thickness (FWT) model. Further, we determine self-diffusivities of argon and nitrogen in the constructed carbon as functions of loading. It is found that while there is a maximum in the diffusivity with respect to loading, as previously observed by Pikunic et al. [5], diffusivities in the present work are 10 times larger than those obtained in the prior work, consistent with the larger pore size as well as higher porosity of the activated saccharose carbon studied here.

Highly efficient luminescence from a hybrid state found in strongly quantum confined PbS nanocrystals

We report that high quality PbS nanocrystals, synthesized in the strong quantum confinement regime, have quantum yields as high as 70% at room temperature. We use a combination of modelling and photoluminescence up-conversion to show that we obtain a nearly monodisperse size distribution. Nevertheless, the emission displays a large nonresonant Stokes shift. The magnitude of the Stokes shift is found to be directly proportional to the degree of quantum confinement, from which we establish that the emission results from the recombination of one quantum confined charge carrier with one localized or surface-trapped charge carrier. Furthermore, the surface state energy is found to lie outside the bulk bandgap so that surface-related emission only commences for strongly quantum confined nanocrystals, thus highlighting a regime where improved surface passivation becomes necessary.

The tectonically-confined Firenzuola turbidite system (Miocene, Marnoso-arenacea Formation, northern Apennines, Italy): an example of facies variations related to the basin morphology

The Firenzuola turbidite system formed during a paroxysmal phase of thrust propagation, involving the upper Serravallian deposits of the Marnoso-arenacea Formation (MAF). During this phase the coeval growth of two major tectonic structures, the M. Castellaccio thrust and the Verghereto high, played a key role, causing a closure of the inner basin and a coeval shift of the depocentre to the outer basin. This work focuses on this phase of fragmentation of the MAF basin; it is based on a new detailed high-resolution stratigraphic framework, which was used to determine the timing of growth of the involved structures and their direct influence on sediment dispersal and on the lateral and vertical turbidite facies distribution. The Firenzuola turbidite system stratigraphy is characterized by the occurrence of mass-transport complexes (MTCs) and thick sandstone accumulation in the depocentral area, which passes to finer drape over the structural highs; the differentiation between these two zones increases over time and ends with the deposition of marly units over the structural highs and the emplacement of the Visignano MTC. According to the stratigraphic pattern and turbidite facies characteristics, the Firenzuola System has been split into two phases, namely Firenzuola I and Firenzuola II: the former is quite similar to the underlying deposits, while the latter shows the main fragmentation phase, testifying the progressive isolation of the inner basin and a coeval shift of the depocentre to the outer basin. The final stratigraphic and sedimentological dataset has been used to create a quantitative high-resolution 3D facies distribution using the Petrel software platform. This model allows a detailed analysis of lateral and vertical facies variations that can be exported to several reservoirs settings in hydrocarbon exploration and exploitation areas, since facies distributions and geometries of the reservoir bodies of many sub-surface turbidite basins show a significant relationship to the syndepositional structural activity, but are beyond seismic resolution.

Three-dimensional simulations of gravitationally confined detonations compared to observations of SN 1991T

The gravitationally confined detonation (GCD) model has been proposed as a possible explosion mechanism for Type Ia supernovae in the single-degenerate evolution channel. It starts with ignition of a deflagration in a single off-centre bubble in a near-Chandrasekhar-mass white dwarf. Driven by buoyancy, the deflagration flame rises in a narrow cone towards the surface. For the most part, the main component of the flow of the expanding ashes remains radial, but upon reaching the outer, low-pressure layers of the white dwarf, an additional lateral component develops. This causes the deflagration ashes to converge again at the opposite side, where the compression heats fuel and a detonation may be launched. We first performed five three-dimensional hydrodynamic simulations of the deflagration phase in 1.4 M⊙ carbon/oxygen white dwarfs at intermediate-resolution (2563computational zones). We confirm that the closer the initial deflagration is ignited to the centre, the slower the buoyant rise and the longer the deflagration ashes takes to break out and close in on the opposite pole to collide. To test the GCD explosion model, we then performed a high-resolution (5123 computational zones) simulation for a model with an ignition spot offset near the upper limit of what is still justifiable, 200 km. This high-resolution simulation met our deliberately optimistic detonation criteria, and we initiated a detonation. The detonation burned through the white dwarf and led to its complete disruption. For this model, we determined detailed nucleosynthetic yields by post-processing 106 tracer particles with a 384 nuclide reaction network, and we present multi-band light curves and time-dependent optical spectra. We find that our synthetic observables show a prominent viewing-angle sensitivity in ultraviolet and blue wavelength bands, which contradicts observed SNe Ia. The strong dependence on the viewing angle is caused by the asymmetric distribution of the deflagration ashes in the outer ejecta layers. Finally, we compared our model to SN 1991T. The overall flux level of the model is slightly too low, and the model predicts pre-maximum light spectral features due to Ca, S, and Si that are too strong. Furthermore, the model chemical abundance stratification qualitatively disagrees with recent abundance tomography results in two key areas: our model lacks low-velocity stable Fe and instead has copious amounts of high-velocity 56Ni and stable Fe. We therefore do not find good agreement of the model with SN 1991T.