SULFONATED POLYPHENYLENE POLYMERS

Improved sulfonated polyphenylene compositions, improved polymer electrolyte membranes and nanaocomposites formed there from for use in fuel cells are described herein. The improved compostitions, membranes and nanocomposites formed there from overcome limitations of Nafion membranes

Estuaries as Filters for Riverine Microplastics: Simulations in a Large, Coastal-Plain Estuary

Public awareness of microplastics and their widespread presence throughout most bodies of water are increasingly documented. The accumulation of microplastics in the ocean, however, appears to be far less than their riverine inputs, suggesting that there is a “missing sink” of plastics in the ocean. Estuaries have long been recognized as filters for riverine material in marine biogeochemical budgets. Here we use a model of estuarine microplastic transport to test the hypothesis that the Chesapeake Bay, a large coastal-plain estuary in eastern North America, is a potentially large filter, or “sink,” of riverine microplastics. The 1-year composite simulation, which tracks an equal number of buoyant and sinking 5-mm diameter particles, shows that 94% of riverine microplastics are beached, with only 5% exported from the Bay, and 1% remaining in the water column. We evaluate the robustness of this finding by conducting additional simulations in a tributary of the Bay for different years, particle densities, particle sizes, turbulent dissipation rates, and shoreline characteristics. The resulting microplastic transport and fate were sensitive to interannual variability over a decadal (2010–2019) analysis, with greater export out of the Bay during high streamflow years. Particle size was found to be unimportant while particle density – specifically if a particle was buoyant or not – was found to significantly influence overall fate and mean duration in the water column. Positively buoyant microplastics are more mobile due to being in the seaward branch of the residual estuarine circulation while negatively buoyant microplastics are transported a lesser distance due to being in the landward branch, and therefore tend to deposit on coastlines close to their river sources, which may help guide sampling campaigns. Half of all riverine microplastics that beach do so within 7–13 days, while those that leave the bay do so within 26 days. Despite microplastic distributions being sensitive to some modeling choices (e.g., particle density and shoreline hardening), in all scenarios most of riverine plastics do not make it to the ocean, suggesting that estuaries may serve as a filter for riverine microplastics

Advanced proton-exchange materials for energy efficient fuel cells.

The ''Advanced Proton-Exchange Materials for Energy Efficient Fuel Cells'' Laboratory Directed Research and Development (LDRD) project began in October 2002 and ended in September 2005. This LDRD was funded by the Energy Efficiency and Renewable Energy strategic business unit. The purpose of this LDRD was to initiate the fundamental research necessary for the development of a novel proton-exchange membranes (PEM) to overcome the material and performance limitations of the ''state of the art'' Nafion that is used in both hydrogen and methanol fuel cells. An atomistic modeling effort was added to this LDRD in order to establish a frame work between predicted morphology and observed PEM morphology in order to relate it to fuel cell performance. Significant progress was made in the area of PEM material design, development, and demonstration during this LDRD. A fundamental understanding involving the role of the structure of the PEM material as a function of sulfonic acid content, polymer topology, chemical composition, molecular weight, and electrode electrolyte ink development was demonstrated during this LDRD. PEM materials based upon random and block polyimides, polybenzimidazoles, and polyphenylenes were created and evaluated for improvements in proton conductivity, reduced swelling, reduced O{sub 2} and H{sub 2} permeability, and increased thermal stability. Results from this work reveal that the family of polyphenylenes potentially solves several technical challenges associated with obtaining a high temperature PEM membrane. Fuel cell relevant properties such as high proton conductivity (>120 mS/cm), good thermal stability, and mechanical robustness were demonstrated during this LDRD. This report summarizes the technical accomplishments and results of this LDRD

Ion Transport in Pendant and Backbone Polymerized Ionic Liquids

Polymerized ionic liquids (PILs) are single-ion conductors in which one of the ionic species is tethered to the polymer chain while the other is free to be transported. The ionic species can either be directly incorporated into the polymeric backbone (backbone PILs) or placed as pendant groups to the chain (pendant PILs). Here, we examined the morphology, conductivity, and rheology of imidazolium-based pendant and backbone PILs. We found that pendant PILs yielded higher ionic conductivity when scaled to Tg, but backbone PILs exhibited higher ionic conductivity on an absolute temperature scale, likely because of differences in the Tgs of the two systems. We also found that ion transport for backbone PILs was coupled to the segmental dynamics below Tg, where the decoupling of ionic conductivity from segmental relaxation was observed for pendant PILs. The results of this study will help the community to better understand the role of the PIL structure on conductivity to work toward the ultimate goal of designing high-performance solid polymer electrolytes

Review of microdialysis in brain tumors, from concept to application: First Annual Carolyn Frye-Halloran Symposium

In individuals with brain tumors, pharmacodynamic and pharmacokinetic studies of therapeutic agents have historically used analyses of drug concentrations in serum or cerebrospinal fluid, which unfortunately do not necessarily reflect concentrations within the tumor and adjacent brain. This review article introduces to neurological and medical oncologists, as well as pharmacologists, the application of microdialysis in monitoring drug metabolism and delivery within the fluid of the interstitial space of brain tumor and its surroundings. Microdialysis samples soluble molecules from the extracellular fluid via a semipermeable membrane at the tip of a probe. In the past decade, it has been used predominantly in neurointensive care in the setting of brain trauma, vasospasm, epilepsy, and intracerebral hemorrhage. At the first Carolyn Frye-Halloran Symposium held at Massachusetts General Hospital in March 2002, the concept of microdialysis was extended to specifically address its possible use in treating brain tumor patients. In doing so we provide a rationale for the use of this technology by a National Cancer Institute consortium, New Approaches to Brain Tumor Therapy, to measure levels of drugs in brain tissue as part of phase 1 trials. Originally published Neuro-oncology, Vol. 6, No. 1, Jan 200

Final report on LDRD project : elucidating performance of proton-exchange-membrane fuel cells via computational modeling with experimental discovery and validation.

In this report, we document the accomplishments in our Laboratory Directed Research and Development project in which we employed a technical approach of combining experiments with computational modeling and analyses to elucidate the performance of hydrogen-fed proton exchange membrane fuel cells (PEMFCs). In the first part of this report, we document our focused efforts on understanding water transport in and removal from a hydrogen-fed PEMFC. Using a transparent cell, we directly visualized the evolution and growth of liquid-water droplets at the gas diffusion layer (GDL)/gas flow channel (GFC) interface. We further carried out a detailed experimental study to observe, via direct visualization, the formation, growth, and instability of water droplets at the GDL/GFC interface using a specially-designed apparatus, which simulates the cathode operation of a PEMFC. We developed a simplified model, based on our experimental observation and data, for predicting the onset of water-droplet instability at the GDL/GFC interface. Using a state-of-the-art neutron imaging instrument available at NIST (National Institute of Standard and Technology), we probed liquid-water distribution inside an operating PEMFC under a variety of operating conditions and investigated effects of evaporation due to local heating by waste heat on water removal. Moreover, we developed computational models for analyzing the effects of micro-porous layer on net water transport across the membrane and GDL anisotropy on the temperature and water distributions in the cathode of a PEMFC. We further developed a two-phase model based on the multiphase mixture formulation for predicting the liquid saturation, pressure drop, and flow maldistribution across the PEMFC cathode channels. In the second part of this report, we document our efforts on modeling the electrochemical performance of PEMFCs. We developed a constitutive model for predicting proton conductivity in polymer electrolyte membranes and compared model prediction with experimental data obtained in our laboratory and from literature. Moreover, we developed a one-dimensional analytical model for predicting electrochemical performance of an idealized PEMFC with small surface over-potentials. Furthermore, we developed a multi-dimensional computer model, which is based on the finite-element method and a fully-coupled implicit solution scheme via Newton's technique, for simulating the performance of PEMFCs. We demonstrated utility of our finite-element model by comparing the computed current density distribution and overall polarization with those measured using a segmented cell. In the last part of this report, we document an exploratory experimental study on MEA (membrane electrode assembly) degradation

The Role of Practice Research Networks (PRN) in the Development and Implementation of Evidence: The Northern Improving Access to Psychological Therapies PRN Case Study

Practice research networks (PRNs) can support the implementation of evidence based practice in routine services and generate practice based evidence. This paper describes the structure, processes and learning from a new PRN in the Improving Access to Psychological Therapies programme in England, in relation to an implementation framework and using one study as a case example. Challenges related to: ethics and governance processes; communications with multiple stakeholders; competing time pressures and linking outcome data. Enablers included: early tangible outputs and impact; a collaborative approach; engaging with local research leads; clarity of processes; effective dissemination; and committed leadership

SULFONATED POLYPHENYLENE POLYMERS

Improved sulfonated polyphenylene compositions, improved polymer electrolyte membranes and nanaocomposites formed there from for use in fuel cells are described herein. The improved compostitions, membranes and nanocomposites formed there from overcome limitations of Nafion membranes

Quantitative ¹H NMR Analysis of Chemical Stabilities in Anion-Exchange Membranes

We compared the alkaline stability of three classes of anion exchange membranes that are leading candidates for applications in platinum-free fuel cells. A methodology is presented for the study of chemical stability of anion-exchange polymers in alkaline media that provides clear and quantitative ¹H NMR spectroscopic data of dissolved polymers containing benzyltrimethylammonium functionalities. Recent studies have investigated the stabilities of benzimidazolium- and alkylimidazolium-bearing polymers using periodic ¹H NMR sampling. These studies included varying alkaline concentrations, external heating sources, and excessive processing and contained no internal standard for absolute measurements. Key aspects of our time-resolved ¹H NMR method include in situ heating and sampling <i>within the spectrometer</i>, fixed stoichiometric relationships between the benzyltrimethylammonium functionalities of each polymer and potassium deuteroxide (KOD), and the incorporation of an internal standard for the absolute measurement of the polymer degradation. In addition, our method permits the identification of the degradation products to find the underlying cause of chemical lability. Our results demonstrate that a styrene-based polymer containing benzyltrimethylammonium functional groups is remarkably stable when exposed to 20 equivalents per cation of KOD at 80 °C with a half-life (<i>t</i>_1/2) of 231 h. Under these standard conditions, functionalized poly­(phenylene oxide) and poly­(arylene ether sulfone) copolymers, both bearing benzyltrimethylammonium functionalities were found to degrade with a half-lives of 57.8 and 2.7 h, respectively