Program and Abstracts Separations Program Heavy Element Chemistry Program Contractors’ Meeting Doubletree Hotel Rockville, Maryland April 27-30, 2005 Chemical Sciences, Geosciences, and Biosciences Division Office of Basic Energy Sciences Office of Science U.S. Department of Energy Cover graphics: Rigid and flexible calixarene-based ligands for selective metal ion separations (see abstract by BARTSCH et al.) Molecular structure of Pu(IV)-hyrdroxypyridonatye complex, a model for actinide decorporation agents (see abstract by GORDEN et al.) This document describes activities performed under contract number DE-AC05-00OR22750 between the U.S. Department of Energy and Oak Ridge Associated Universities. FOREWORD This abstract booklet provides a record of the sixth U.S. Department of Energy (DOE) contractors’ meeting in separations sciences and the third in heavy element chemistry. The Chemical Sciences, Geosciences and Biosciences Division of the Office of Basic Energy Sciences and its predecessors have sponsored research in heavy element chemistry and separations sciences for some sixty years. Although these are distinct disciplines, they have much in common for many reasons, in particular because novel separations research is needed to produce pure heavy-element samples and because heavy element chemistry provides the basis for many separations processes. In addition, separation processes are major industrial sources of energy consumption and waste generation. This is the second joint meeting of these programs. The objective of this meeting is to provide a fruitful environment in which researchers with common interests will present and exchange information about their activities, will build collaborations among research groups with mutually reinforcing strengths, will identify needs of the research community, and will focus on opportunities for future research directions. The agenda has keynote talks, oral presentations, and posters, organized so that papers in related disciplines – such as ligand design, theory and bonding, and interfacial science – are loosely clustered together. With ample time for discussion and interactions, we emphasize that this is an informal meeting for exchange of information and building of collaborations; it is not a review of researchers’ achievements or a forum to choose future directions. We are pleased to have the privilege of organizing this joint meeting and of serving as the managers of our respective research programs. In carrying out these tasks, we learn from the achievements and share the excitement of the research of the many sponsored scientists and students whose names appear on the papers in the following pages. We also hope that this meeting will enhance your research efforts and will nurture future collaborations and initiatives. We thank all of the researchers whose dedication and innovation have advanced our research and made this meeting possible and, we hope, productive. We hope that all of you will build on your successes and that we will assemble in a very few years for our next joint meeting. We thank Diane Marceau of the Chemical Sciences, Geosciences and Biosciences Division, and Sophia Kitts and Kellye Sliger of the Oak Ridge Institute for Science and Education for the technical and logistical features of this meeting. William S. Millman Gregory J. Fiechtner Lester R. Morss Norman Edelstein i Meeting Overview Time Wednesday, April 27 Thursday, April 28 Friday, April 29 Saturday, April 30 7 a.m. Continental Breakfast Continental Breakfast Continental Breakfast Regency Foyer Regency Foyer Regency Foyer 8 a.m. (8:30) Welcome and Intro’s: Keynote: Mike Ramsey Oral session 6 9 a.m. Walt Stevens, John Miller Oral Session 4: Theory and Polymers, Solutions, Thermodynamics (8:45) Keynote: Bruce Bursten Bonding Plaza Plaza 10 a.m. (9:45 – 10:10) Coffee Break (10:30 – 11:00) Coffee Break Discussion: Highlights and Opportunities for New Directions 11 a.m. Oral Session 1 Oral Session 4 cont’d. Ligand Design Plaza noon Lunch Plaza Lunch Plaza Lunch Atrium (Meeting adjourned) 1 p.m. Oral Session 2 Oral Session 5 2 p.m. Coordination Chemistry Plaza Surfaces and Interfaces Plaza 3 p.m. (3:00 – 3:30) Coffee Break 4 p.m. Poster Session 1 Poster Session 2 5 p.m. Regency/Randolph Regency/Randolph 6 p.m. Reg. PI’s Cash Cash Wrkg. PI’s Setup Dinner and evening on your own nd begins Setup Bar bar Dinner 2 set Regency st Posters 1 set Plaza Plaza Plaza Foyer Regency Posters 7 p.m. Regency No host Oral Session 3 Dinner Synthesis Plaza Plaza 8 p.m. 9 p.m. ii DOE Heavy Element Chemistry-Separations Contractors’ Meeting Rockville (MD) Doubletree Hotel, April 27-30, 2005 Agenda Wednesday April 27 Registration and cash bar 6:00 – 7:00 pm, followed by no-host dinner at Rockville Doubletree for those interested Thursday April 28 8:30 Welcome and Introductions (Walt Stevens, John Miller) 8:45 Keynote lecture 1: Bruce Bursten – From Large Molecules to Small Molecules to Grand Challenges: A Personal Perspective on Molecular Electronic Structure Theory Applied to Heavy Element Chemistry 9:45 Coffee break Oral session 1: Ligand design 10:10 O1-1 Bosnich – Weak Force Generated Allosteric Effects 10:30 O1-2 Alexandratos – Ion-Selective Polymer-Supported Reagents: Tuning Ionic Affinities of Primary Ligands with Auxiliary Groups 10:50 O1-3 Paine – Preorganized and Immobilized Ligands for Metal Ion Separations 11:10 O1-4 Raymond – Actinide Coordination Chemistry: from just Super to Supramolecular 11:30 O1-5 Sessler – Actinide Coordination to Expanded Porphyrins 11:50 Discussion 12:00 Working lunch Oral session 2: Coordination chemistry 1:00 O2-1 Hupp – Supramolecular-Coordination-Chemistry-Derived Membranes Featuring Nanoscale Porosity and Selective Chemical Separation Capabilities 1:20 O2-2 Bartsch – New Proton-Ionizable Calixarene-Based Ligands for Selective Metal Ion Separations 1:40 O2-3 Davis – Self-Assembled Ionophores 2:00 O2-4 Assefa – Syntheses, X-ray crystallography, Raman and luminescence studies of coordination polymers of actinides and group 11 dicyanides 2:20 O2-5 Meyer – CO/CO2 Activation and Nitrogen-Atom Transfer Chemistry Utilizing Low- and High- Valent Uranium Coordination Complexes 2:40 O2-6 Kiplinger – Tuning Metal-Ligand Bonding Interactions and Novel Reactivity Patterns in Organometallic Actinide Complexes 3:00 Discussion 3:10 Coffee break 3:30-5:30 Poster session 1 P1-1 Belfort – Chemical Interactions Between Protein Molecules and Polymer Materials P1-2 Burns/Soderholm – Actinide Aggregation Studies P1-3 Choppin – Actinide Research: Cyclohexyl Separation Agents and Room Temperature Ionic Liquids P1-4 Dorhout/Selby – Syntheses, Structures, and Physical Properties of K/Cu/An(Th,U)/S Phases: KCuAnS3, K2Cu2AnS4, K3Cu3Th2S7, and K3Cu2 US6 P1-5 Freeman – Nanostructured Hybrid Materials for Advanced Membrane Separations P1-6 Gorden – Plutonium Encaged: The First Structurally Characterized Pu-Hydroxypyridonate Complex P1-7 Haire – Probing the Bonding and Electronic Nature of Actinides P1-8 Heaven – Spectroscopic Studies of Prototype Actinide Compounds P1-9 Miller – Flotation Chemistry of Soluble Salt Minerals P1-10 Moody/Stoyer – Production and Chemical Properties of the Heaviest Elements P1-11 Nitsche – Heavy Element Nuclear and Radiochemistry P1-12 Pemberton – Vibrational Spectroscopy of Chromatographic Interfaces P1-13 Scuseria – Non-stoichiometry and magnetic ordering in plutonium oxides: A hybrid density functional theory study P1-14 Wirth – Spectroscopic probing of the function of membrane proteins iii 6:00-7:00 Working dinner Oral session 3: Synthesis 7:00 O3-1 Yaghi/Sudik – Metal-Organic Frameworks and Polyhedra for Separation of Gases and Organic Molecules 7:20 O3-2 Clearfield – The Synthesis, Structures and Chemical Properties of Macrocyclic Ligands Covalently Bonded into Layered Arrays 7:40 O3-3 Bruening – Investigation of Size-Selective Separations and Mitigation of Fouling by Multilayer Polyelectrolyte Membranes 8:00 O3-4 Custelcean – Principles of Chemical Recognition and Transport in Extractive Separations: Metal- Organic Frameworks as Solid-Phase Anion Exchangers 8:20 O3-5 Albrecht-Schmitt – Synthesis, Structure, and Ion-Exchange Properties of Open-Framework Actinyl Materials 8:40 O3-6 Ibers – Actinide Transition-Metal Chalcogenides and Pnictides 9:00 Discussion Friday April 29 8:00 Keynote lecture 2: Mike Ramsey – Molecular Transport Through Fabricated Nanoscale Channels Oral session 4: Theory and Bonding 9:00 O4-1 B. Hay – Principles of Chemical Recognition and Transport in Extractive Separations: Molecular Modeling and Host Design 9:20 O4-2 Batista – Theoretical Studies of Thermochemistry and Excited States of Actinide Complexes 9:40 O4-3 Scuseria – All-electron relativistic methods for molecules and extended systems 10:00 O4-4 Ray – A Fully-Relativistic Density Functional Study of the Role of 5f Electrons in Chemical Bonding in Transuranium Elements 10:20 Discussion 10:30 Coffee break 11:00 O4-5 Conradson – Intrinsic Nanoscience: Nanoscale Heterogeneity and Collective Properties of Complex Materials 11:20 O4-6 Jensen – Understanding Bonding in Actinide-Soft Donor Complexes 11:40 O4-7 Gibson – Gas-Phase Actinide Ion Chemistry—Reaction Kinetics and Molecular Thermodynamics 12:00-1:00 Working lunch Oral session 5: Surfaces and interfaces 1:00 O5-1 Koros – Thickness & History Dependent Effects on Crosslinked Polyimide Membrane Materials for Natural Gas Separation 1:20 O5-2 Yeung – Motion of Single DNA Molecules at a Liquid-Solid Interface as Revealed by Variable- Angle Evanescent-Field