PubMed Health⌕ Search

Biomedical subjects

David M Ford

Publications and source records attributed to David M Ford.

8 recordsLinked to original sources

Synthesis and characterization of uniform alumina-mesoporous silica hybrid membranes.

The synthesis and characterization of alumina-mesoporous silica (alumina-MS) hybrid membranes are reported. The hybrids are formed using a variation of the evaporative-induced self-assembly (EISA) process reported by Hayward et al. (Langmuir 2004, 20, 5998) based on dip coating of an Anopore 200 nm membrane with a Brij-56/TEOS/HCl/H2O solution. Numerous analytical methods are used to probe both the hybrid material and the silica phase after dissolution of the Anopore substrate. Most importantly, He/N2 permeation measurements show that the effective pore size of the membrane can be tuned from 20 to 5 nm based on the number of dip-coating cycles used. The observed He/N2 permselectivity of 2.7 +/- 0.11 is nearly identical to the theoretical value obtained (2.65) assuming Knudsen diffusion dominates. The selectivity of these membranes is higher than that of most commercial "5 nm" membranes (2.29), which is ascribed to the lack of pinhole defects in the materials reported here. The hybrid membranes as well as the silica obtained after dissolution of the Anopore substrate have been characterized using scanning and transmission electron microscopy and X-ray diffraction. Those results indicate that the silica deposited in the Anopore membrane possesses uniform pores approximately 5 nm in size, consistent with the permeation studies. The current work presents an alternative approach to materials that possess many of the properties of mesoporous silica thin films (i.e., pores of controlled size and topology) without the difficulty of growing mesoporous silica thin films on porous supports.

Journal Article↗

Enthalpy-entropy compensation is not a general feature of weak association.

Relationships between the enthalpy and entropy changes resulting from perturbations of a system have been discussed in the literature for some time. Both positive correlations (compensation) and negative correlations (anti-compensation) between deltaH and DeltaS have been observed in various experimental contexts, including chemical reaction, physical association, solvation, and protein folding. Many examples have been demonstrated to be statistical artifacts, but some are genuine signatures of the perturbations in molecular characteristics. In particular, recent literature claims that compensation is a general feature of bimolecular associations arising from weak intermolecular interactions. We employ a statistical mechanical framework to predict the magnitude and direction of enthalpy-entropy correlation in bimolecular association. The theory links the macroscale thermodynamic correlation to the relationship between the intermolecular potential parameters. Using a harmonic approximation to the Lennard-Jones model and potential parameters taken from the literature, we show examples of both compensation and anti-compensation for gas-phase self-association among five homologous series. Furthermore, an aggregate presentation of data for 48 different chemical species shows no correlation in either direction, for the case of self-association in a dilute gas phase.

Journal Article↗

Inverse density-functional theory as an interpretive tool for measuring colloid-surface interactions in dense systems.

Recent advances in optical microscopy, such as total internal reflection and confocal scanning laser techniques, now permit the direct three-dimensional tracking of large numbers of colloidal particles both near and far from interfaces. A novel application of this technology, currently being developed by one of the authors under the name of diffusing colloidal probe microscopy (DCPM), is to use colloidal particles as probes of the energetic characteristics of a surface. A major theoretical challenge in implementing DCPM is to obtain the potential energy of a single particle in the external field created by the surface, from the measured particle trajectories in a dense colloidal system. In this paper we develop an approach based on an inversion of density-functional theory (DFT), where we calculate the single-particle-surface potential from the experimentally measured equilibrium density profile in a nondilute colloidal fluid. The underlying DFT formulation is based on the recent work of Zhou and Ruckenstein [Zhou and Ruckenstein, J. Chem. Phys. 112, 8079 (2000)]. For model hard-sphere and Lennard-Jones systems, using Monte Carlo simulation to provide the "experimental" density profiles, we found that the inversion procedure reproduces the true particle-surface-potential energy to an accuracy within typical DCPM experimental limitations (approximately 0.1 kT) at low to moderate colloidal densities. The choice of DFT closures also significantly affects the accuracy.

Journal Article↗

Making the business case for process safety using value-at-risk concepts.

An increasing emphasis on chemical process safety over the last two decades has led to the development and application of powerful risk assessment tools. Hazard analysis and risk evaluation techniques have developed to the point where quantitatively meaningful risks can be calculated for processes and plants. However, the results are typically presented in semi-quantitative "ranked list" or "categorical matrix" formats, which are certainly useful but not optimal for making business decisions. A relatively new technique for performing valuation under uncertainty, value at risk (VaR), has been developed in the financial world. VaR is a method of evaluating the probability of a gain or loss by a complex venture, by examining the stochastic behavior of its components. We believe that combining quantitative risk assessment techniques with VaR concepts will bridge the gap between engineers and scientists who determine process risk and business leaders and policy makers who evaluate, manage, or regulate risk. We present a few basic examples of the application of VaR to hazard analysis in the chemical process industry.

Chemical Industry↗

Poly-L-lysine templated silicas: using polypeptide secondary structure to control oxide pore architectures.

Utilizing polypeptide secondary structure as a means for controlling oxide pore architectures is explored. Poly-L-lysine is used as a model polypeptide as its folding behavior is well understood and compatible with the sol-gel chemistry of silica. Here, we show that silicas synthesized with poly-L-lysine in a alpha-helix conformation possess cylindrical pores that are approximately 1.5 nm in size, whereas silicas synthesized with poly-L-lysine in a beta-sheet conformation possess larger pores, the size of which are a function of the poly-L-lysine concentration, or in other words the size of the aggregate. In both cases, highly porous materials are obtained. In-situ circular dichroism measurements of the synthesis mixtures show that the poly-L-lysine secondary structure is not perturbed during synthesis. Infrared spectroscopy of the as-synthesized materials is consistent with the poly-L-lysine retaining its secondary structure. Grand canonical Monte Carlo simulations were also performed to validate the interpretation of the experimental adsorption results. The experimental isotherms are consistent with simulated isotherms of cylindrical pores 1.3-1.7 nm in size, in good agreement with expected values. Our results suggest a new avenue for synthesizing porous oxides with highly tuneable pore sizes and shapes under mild conditions.

Adsorption↗

Coarse-grained nonequilibrium approach to the molecular modeling of permeation through microporous membranes.

We present a modeling technique that combines a statistical-mechanical coarse-graining scheme with a nonequilibrium molecular simulation algorithm to provide an efficient simulation of steady-state permeation across a microporous material. The coarse-graining scheme is based on the mapping of an atomistic model to a lattice using multidimensional free-energy and transition-state calculations. The nonequilibrium simulation algorithm is a stochastic, lattice version of the recently developed atomistic dual-control-volume grand canonical molecular dynamics. We demonstrate the approach on a model of methane permeating through a bulk portion of siliceous zeolite ZK4 at 300 K under imposed fugacity differences. We predict the coarse-grained (cage-level) density profiles and observe the development of nonlinearities as the magnitude of the fugacity difference is increased. From the net flux of methane we also predict a mean permeability coefficient under the various conditions. The simulation results are obtained over time scales on the order of microseconds and length scales on the order of dozens of nanometers.

Journal Article↗

Responding to a crisis: a stakeholder analysis of community health organizations.

On May 11, 2001, the Bureau of Primary Health Care notified West Alabama Health Services, doing business as Family HealthCare of Alabama, that it was terminating $6 million in grants due to non-compliance and amid allegations of financial mismanagement and fraud. West Alabama Health Services, a not-for-profit organization, operated 19 community health centers that provided preventive and primary care services for 17 counties in Alabama. This disruption of health services engendered considerable stakeholder debate. Within this context, the authors examine how a small, newly established rural health center and a well-established, federally qualified community health center responded to this crisis. The authors use a stakeholder analysis framework to highlight how key relationships with stakeholders may change with the perceived credibility of the organizational leaders and the legitimacy of their actions.

Accounting↗

Behavioral and thalamic nociceptive responses in rats following noxious ischaemia of the tail.

In rats anaesthetized with urethane, we have investigated the response of neurones in the ventrobasal complex of the thalamus to noxious ischaemia of the tail, and to graded noxious thermal stimulation of the tail before and after ischaemia. In behavioural experiments conscious rats were exposed to the same experimental procedure. After ischaemia the threshold tail temperature required to elicit both a neuronal response and aversive behaviour in conscious rats, to thermal stimulation, was decreased significantly (P less than 0.01 paired t tests). Threshold temperatures for the neuronal response and the behavioural response were not significantly different, either before or after ischaemia. The time course of recovery to pre-ischaemic threshold temperatures was the same for both the behavioural and neuronal responses. Most thalamic neurones responding to noxious thermal stimulation of the tail also increased firing rate during ischaemia. The latency of response of the thalamic neurones to ischaemia was 12.1 +/- 1.8 min and the latency of the behavioural response to the same stimulus was 11.9 +/- 2.1 min. Ventrobasal thalamic neurones, therefore, which responded to noxious thermal stimulation of the tail also responded to noxious ischaemia, and exhibited a neuronal correlate of post-ischaemic hyperalgesia which paralleled behavioural responses closely.

Action Potentials↗