Joint Density-Functional Theory of the Electrode-Electrolyte Interface: Application to Fixed Electrode Potentials, Interfacial Capacitances, and Potentials of Zero Charge

This work explores the use of joint density-functional theory, a new form of density-functional theory for the ab initio description of electronic systems in thermodynamic equilibrium with a liquid environment, to describe electrochemical systems. After reviewing the physics of the underlying fundamental electrochemical concepts, we identify the mapping between commonly measured electrochemical observables and microscopically computable quantities within an, in principle, exact theoretical framework. We then introduce a simple, computationally efficient approximate functional which we find to be quite successful in capturing a priori basic electrochemical phenomena, including the capacitive Stern and diffusive Gouy-Chapman regions in the electrochemical double layer, quantitative values for interfacial capacitance, and electrochemical potentials of zero charge for a series of metals. We explore surface charging with applied potential and are able to place our ab initio results directly on the scale associated with the Standard Hydrogen Electrode (SHE). Finally, we provide explicit details for implementation within standard density-functional theory software packages at negligible computational cost over standard calculations carried out within vacuum environments.Comment: 18 pages, 5 figures. Initially presented at APS March Meeting 2010. Accepted for publication in Physical Review B on Jul. 27, 201

Advancements in Sarcoma- and Nerve-Specific Fluorescence Imaging for Surgical Guidance

Fluorescence guided surgery (FGS) is an evolving field that aims to improve patient outcomes by using fluorophores to identify important tissues during surgery, such as tumors and nerves. In this thesis work, we explored different methods of identifying nerve and tumor tissues for FGS and a novel fluorescence-based method to determine the depths of these structures. Researchers have explored using fluorescence guided surgery for surgical resection of cancerous tissues, including recent work by our group focusing on identifying soft tissue sarcomas with ABY-029, an epidermal growth factor receptor targeting probe. However, our preclinical and clinical work shows no single reporter characterizes all areas of the tumor, which compromises our ability to reliably detect residual cancer in the tumor bed. We developed an innovative strategy to enhance tumor contrast by using multiple near-infrared fluorophore reporters with similar emission wavelengths that target different regions of the tumor milieu. In this work, fluorescence from single fluorophores (ABY-029, bevacizumab-IRDye800, indocyanine green (ICG), and 6QC-ICG) were compared in a murine STS model. Fluorescence guided surgery can not only be used to identify structures for removal, such as tumors, but also to distinguish structures that surgeons aim to avoid, such as nerves. Presently, intraoperative guidance for nerve and other normal structure identification is limited. In this work, we aimed to test the ability of a novel nerve targeting agent, LGW16-03, to label human nerve tissue in two ex vivo preclinical models using innovative methods that utilize freshly resected human specimens. We demonstrated that signal-to-background ratios could be achieved that are similar to preclinical studies of similar fluorophores. Therefore, ex vivo human tissue models appear to provide physiologically relevant preclinical evaluation of fluorophores with no known risks to patients and may aid in improved selection of lead agents prior to first-in-human trials. We then aimed to quantitatively evaluate depth of structures of interest using a newly developed multi-excitation wavelength emission ratio (MEWER) methodology tested in validated tissue simulating gelatin phantoms. Results suggest that MEWER has the potential to discern depths less than 6 mm. However, improved identification methods for optical properties of tissue are necessary to determine unknown depths

Dying with Dignity: Where is the Compassion in Compassionate Release Programs?

The prison population in the United States is on the rise. The fastest growing population in prisons are those who could be considered elderly. With the graying of our prison population comes many diseases of aging that will wreak havoc not just on the inmates, but on the costs of incarceration. Prison inmates cannot acquire their own medical care; it is the responsibility of society and hence the prison system itself. If the prisons cannot adequately care for terminally ill or elderly inmates then compassionate release should be considered. Compassionate Release Programs are designed to allow those inmates who are terminally ill or elderly to apply for early release. But it is very hard to get such petitions approved, much less understand who is truly eligible. Thus, very few inmates are being released to spend whatever time they have left with loved ones. Not only would Compassionate Release Programs save money but they would allow those inmates at the lowest risk of recidivism to die with dignity

The Role of Self-Brand Overlap in Consumer Evaluations of Brand Portfolio Management Decisions

Branding research has begun to explore how loved brands are included in consumers’ self-concepts. Such self-brand overlap can enable consumers to react to brand-relevant situations as though they were self-relevant. Synthesizing theories of self-other overlap and perspective taking, self-enhancement and self-protection, as well as brand portfolios, I articulate how self-serving biased cognitions can influence consumer attitudes and behaviours toward entire brand portfolios via the consumer’s self-brand overlap with a single portfolio member. Study 1 was designed to investigate how self-serving biases can positively affect consumer evaluations of multi-brand portfolios of which the consumer’s focal brand is a member. Potential reasons for the resulting inconclusive findings are discussed and prospects for future research are suggested. Study 2 was designed to investigate consumer interpretations of brand portfolio restructuring. Results indicate that consumers who have a high degree of self-brand overlap can interpret such brand portfolio management decisions as a personal rejection of themselves when the brand is eliminated, and personal acceptance or validation when their brand is retained after an elimination threat. Study 3 was designed to investigate the behavioural aftermath of such inferences. Partial results and prospects for future research are offered. Potential implications for brand managers and marketing theory are discussed

A computationally efficacious free-energy functional for studies of inhomogeneous liquid water

We present an accurate equation of state for water based on a simple microscopic Hamiltonian, with only four parameters that are well-constrained by bulk experimental data. With one additional parameter for the range of interaction, this model yields a computationally efficient free-energy functional for inhomogeneous water which captures short-ranged correlations, cavitation energies and, with suitable long-range corrections, the non-linear dielectric response of water, making it an excellent candidate for studies of mesoscale water and for use in ab initio solvation methods.Comment: 6 pages, 5 figure