Fred Wudl - US grants

This award, part of the Materials Chemistry and Chemical Processing Initiative, will support the collaborative research of Dr. F. Wudl and Dr. P. Pincus at the Univeristy of California at Santa Barbara. The research will focus on the preparation, characterization and theoretical studies of rigid carbon-heteroatom clusters (heterospherophanes). The grant is a joint action of the Divisions of Materials Research (Solid-State Chemistry) and Chemistry (Organic Synthesis). Heterospherophanes will be hollow molecular spheres consisting of alternating benzene rings and heteroatoms such as chalcogen or nitrogen. The heteroatoms within each cluster will be located, relative to each other, in a cubic closest packed lattice. The diameter of the sphere's cavity will depend on the nature of the heteroatom. Due to the high symmetry, electronic character and structural design of these clusters, they will exhibit unusual condensed matter properties depending on whether they are neutral or charged. The neutral heterospherophanes are likely to be hard, high-melting solids. The charged heterospherophanes will be capable of encapsulating a countercation, producing an atom of macromolecular dimensions. The encapsulated counterion should also allow the formation of three dimensional organic metals.

This award will support collaborative research between U.S. and Belgian scientists in the area of development and characterization of conjugated polymers. The U.S. investigators are Drs. A.J. Heeger and Fred Wudl, University of California, Santa Barbara. The Belgian collaborator is Professor Jean-Luc Bredas, University of Mons. The joint project will focus on the following three topics: 1) development and characterization of new polymer materials with small band gaps (2) evaluation of the electronic properties of soluble conducting polymers and (3) the role of charged nonlinear excitations (solitons, polarons and bipolarons) in the nonlinear optical properties of conjugated polymers. The investigators have a history of successful collaboration, based on their complementary expertise. Dr. Bredas has a background in quantum chemistry and has made outstanding contributions to the theory of quasi-one- dimensional solids and in particular to conducting polymers. The U.S. researchers have carried out leading experimental investigations in the area of highly conducting organic solids. The results of the proposed project will contribute to increased understanding of this important area of materials research, which has many potential industrial applications.

This work will complete the development of molecules which are designed to be molecular precursors to ferromagnetic organic metals (FOM). The neutral donors are expected to be trimethylene methanes and to retain this character once incorporated into stacks in the solid state. Synthetic precursors to HTTM and TDMT will also be diverted to prepare quinodimethanoid donors with a sulfur periphery; the latter, in analogy to bisethylenedithio tetrathiafulvalene, are expected to give rise to organic superocnductors. Studies on the physical properties of new electron acceptors based on multi- tricyanovinyl substituted benzenes will be continued and a trigonal, nonacyano-1,3,5-trivinylbenzene. Syntheses of oxygen analogs of TTF and ET as well as a quinodimethanoid donor are proposed in order to test if these lighter analogs will exhibit higher superconductor transition temperatures in their salts with various anions. Once prepared the solids will have their physical properties determined using the latest developments in experimental condensed matter physics.

Two families of new polymers will be prepared: a) methylenealkoxy-substituted poly(isocyanates) and the unknown poly(isocyanic acid) and b) methylenealkoxy-substituted poly(carbodiimides) and the unknown poly(carbodiimide) ?poly)cyanamide) or poly (guanidine)! as well as copolymers within each family. Because of the highly polar repeat unit, these polymers are expected, upon polarizing in high electric fields, to produce ferroelectric solids akin to poly (vinylidene fluoride). Ferroelectric solidss have applications as peizoelectrics (e.g., transducers such as sensitive microphones) and nonlinear optics (mode converters, modulators, Y-branch interferometers, and directional couplers). Other salient features of this research are: 1.) Poly(isocyanic acid), due to its high degree of hydrogen bonding and the strength of the amide linkage, is expected to be superior to any known synthetic fiber in strength, strength on compression, toughness and oxidative stability. 2.) The substituted poly(carbodiimides) will be prepared in chiral form and depolymerized. Thus, a novel carbodiimide optical resolution procedure based on thermal depolymerization of a chiral poly(carbodiimide will be prepared. The chiral carbodiimide is a fundamentally new functional group. 3.) The parent, unsubstituted poly(carbodiimide), will become conjugated at intermediate protonation levels and will be converted to a highly conducting form upon further protonation via a new concept of protonative positive soliton generation.

This award is for the renewal of research previously supported under a Materials Research Group grant (DMR 8703399) at the University of California - Santa Barbara. The research of the group focuses on the design and synthesis on the supermolecular length scale of multi-functional, high performance electronic and optical polymer blends using gel processing. The morphology of these gels is being determined using x-ray diffraction, optical, scanning, and electron microscopy, mechanical, and electrical measurements, optical spectroscopy, luminescence, and photo-induced absorption. Polymers being investigated include ultra-high molecular weight polyethylene, polyvinyl alcohol, polyacrylonitrile, unblended conjugated polymer systems, and phase-segregated highly oriented polymer blends such as polyaniline/poly(p-phenylene terephthalamide). Materials are being processed into fibers, thin films, and conducting foams taking care to control the morphology, phase stability, and spinodal decomposition. The research is multi-disciplinary, combining condensed matter physics, synthetic chemistry, theory, and polymer science. This grant provides the ideal mechanism to train students to synthesize, process and characterize polymers, with the interaction of all of the scientific approaches and methods used to study polymers.

The focus of this research is the synthesis and characterization of functionalized fulleroids that have the potential to bind to the active site of retroviral reverse transcriptases (RT) as well as the HIV protease (HIVP). %%% With this Small Grant for Exploratory Research (SGER), the Synthetic Organic Program is supporting the research of Dr. Fred Wudl of the Institute for Polymers and Organic Solids at the University of California, Santa Barbara. The focus of the research is the synthesis of novel functionalized hollow spheroidal molecules, fulleroids, that have the potential to be retrovirus-specific, biologically active molecules.

9315635 Wudl We will prepare and investigate a broad class of conjugated polymers which should exhibit improved environmental stability in the doped and undoped states and will be easily n-dopable. Some of these polymers, when processed, will have high strength while retaining the unusual electronic character of the conjugated polymers. Other members of the class will be polyelectrolytes based on stable carbanions. Still other polymers will be n-self- doped polymers. This group of polymers lends itself to the development of the concept of base-doping of conducting polymers concept which is complementary to acid doping of polyaniline emeraldine base. Two approaches will be pursued: (a) preparation of polymers where a number of cyanides are directly attached to the backbone and (b) preparation of polymers where a Huckel driving force is the principle for n-doping of the backbone. Once prepared, in collaboration with Professor Heeger's group in our Institute, the new polymeric materials will have their optical and electronic properties determined. These polymeric materials have potential applications as structural materials, as nonlinear optics substrates, as organic light emitting diode components, as all polymer p-n junction diodes, and as battery electrodes for all-polymer batteries and high-energy density batteries. ***

Abstract 9500888 Wudl The objective of this research is to continue the development of molecules which are designed to be molecular precursors to organic metals and high-temperature organic superconductors. Three approaches will be pursued: (a) synthesis of new methanofullerenes consisting of variously substituted C61 and C66, (b) preparation of new materials based on periconjugative effects of methanofullerenes C61-C66 with electron rich and super-electron rich olefins as well as alkali metals, and (c) preparation of new materials based on new electron donor methanofullerenes. Once prepared, the physical properties of solids will determined using the latest developments in experimental condensed matter physics, in collaboration with other groups. %%% It is a rare event in the history of science when a new starting material is uncovered for chemical transformations and the eventual development of exotic compounds and novel materials. That is the case with the discovery of buckminsterfullerene (C60 ) and the fullerenes. The family of spherical and oblong molecular allotropes of carbon, the fullerenes are formed at temperatures upward of 2000 C, yet the smaller, isolable and characterizable members of a large family are reactive molecules at room temperature. Because C60 (and C70) is a relatively strong electron acceptor, it is of interest to explore its reactions with a number of diazomethanes. This research has led to the discovery of methanofullerenes and fulleroids, functionalized fullerenes. The proposed work is the continuation of prior studies in the same area. Ultimately, these and other related new compounds may be utilized for the fabrication of novel molecular metals and superconductors.

9512503 Stucky A charge coupled device (CCD), high intensity X-ray diffractometer will be acquired and utilized for materials synthesis and biotechnology research. The CCD detector and associated software allow for nearly single photon detection efficiency and rapid readout time of 512x512 pixels. The ease of use and rapid screening time of this instrument will permit the quick characterization of crystals as small as a few micrometers and of molecular crystals that are unstable and tend to deteriorate in the X-ray beam. Biomolecular phases and liquid crystal/membrane based composites with large unit cell structures that produce a large range of scattered intensities will be structurally accessible with this instrument. Zeolites, porous mesostructured materials, and fullerine-type structures that cannot be otherwise characterized because of their low scattering cross section, will also be studied. The large improvement in sensitivity provided by this instrument, in combination with available nuclear magnetic resonance (NMR) resources, represents a unique capability for studying complicated partially ordered polymeric materials. %%% The high sensitivity, fast data collection, x-ray diffractometer will enable a new materials characterization capability that will impact an existing interdisciplinary program of over one hundred students and faculty. It will facilitate research programs concerned with the design, synthesis, and processing of advanced materials, studies of non- equilibrium transformations in complex fluids and biological systems, and protein structure-property relationships. ***

9704143 Wudl This project will develop a new approach to extended-network, very high strength organic polymeric materials. Some of these materials will be ultrahard, others will be "organic zeolites:. Three approaches will be pursued: (a) preparation of new polymers and copolymers where pleiadene (a hydrocarbon which becomes reactive at ca 220 degrees C) is a pendant group, (b) preparation of new polymers in which pleiadene undergoes cycloaddition polymerization to form the backbone, and c preparation of new extended network polymers based on reversible Diels Alder polymerizations and on the pleiadene cycloaddition dimerization reaction and multiple cycloaddition to C60. Once prepared, the new polymeric materials will have their mechanical, optical and electronic properties determined using the latest techniques in materials science and experimental condensed matter physics. %%% These novel polymeric materials should have potential applications as structural materials of strengths approaching diamond as catalyst supports, etc., and may open the door to new families of rationally designed, three-dimensional extended solids. ***

9812046
Wudl

This project focuses on the design and development of molecules for lightweight organic/inorganic lasers, semiconductors, and metals. The research will be carried out in three parts: (a) preparation of new materials based on stable dipolar molecules, (b) fabrication of thin film devices and (c) determination of device characteristics. The new molecules, and materials derived from them, belong to a novel special zwitterionic class of non-Kekule (NK) systems. These dipolar heteroacenes and poly(heteroacenes) will be functionalized to modify and improve various properties such as solubility, film-formation, luminescence for devices such as Light Emitting Diodes (LEDs) and lasers, and extended intermolecular interactions related to materials properties that include conductivity and ferroelectricity. The photophysics of the dyes will be evaluated, and the solids will be examined using the latest developments in experimental condensed matter physics.
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In addition to developing new materials for lasers and other devices such as LEDs, the goal is to produce materials scientists for the twenty-first century who not only have a much broader skills base than the usual student in terms of their technical scientific and engineering training, but also who develop ancillary talents rarely acquired in graduate school. These include: (a) working effectively in interdisciplinary teams to solve problems and (b) appreciating first-hand the research priorities, objectives, and modus operandi inside and outside of academia. The proposed research lends itself naturally to accomplishing these goals through the interdisciplinary interactions among physicists, chemists and engineers.
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The focus of this Focused Research Group proposal will develop the molecular science of fullerene nanotubes. These new materials have been hailed for their materials properties and the applications that these properties promise. The single greatest impediment to realizing this promise is the current poverty of chemical approaches for manipulating the tubes as individual molecules. Single-walled nanotubes (swnts) are truly molecular entities, owing to their high degree of structural perfection, but the molecular science of manipulating them in the sense that chemists manipulate other molecules is still quite embryonic. These manipulations include solubilization, covalent derivatization of tube ends and sides, sorting by length, electrical type, and diameter, assembly, cutting, and synthesis of tubes of specific helicity. These are the tasks that comprise the basis of nanotube manipulation, and are central technologies in the realization of the promise of swnt. One particular aim will be to develop a variety of strategies to solubilizing nanotubes in various solvents, including water, by supramolecular routes. Associations of swnts with other molecules will be designed - e.g., polymers or large macrocyclic compounds - both for solubilizing the tubes and for assembling them without making any covalent attachment to their sides, thus preserving fully their intrinsic materials properties. Sorting tubes by length, type, and diameter will be crucial to fulfilling hopes of using nanotubes as wires in molecular electronics. Crude separations by length and diameter have begun, but cleaner, scalable chromatographic and electrophoretic methods are needed. Sorting by electrical type will be approached by exploiting their different electrical and magnetic properties(e.g., using electrophoresis, electrochemistry, and electric or magnetic field gradients), as well as their structural differences to derivatize selectively by type.

A grand challenge is to synthesize tubes of a given electrical type. The plan is to utilize seed crystals of a particular type, (separated by methods developed as part of the proposed work), and use covalent chemistry at the end to assemble a catalyst for growth there. This challenge will make demands on several of the other goals, providing both a rich driving force, and, if successful, a remarkable new materials science with far-reaching technological impact.
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This Focused Research Group project will have a major impact in a fast-breaking area focused on the development of the molecular science of fullerene nanotubes. The research is highly synergistic, multidisciplinary, high-risk and high-impact, with a significant probability for technological payoff in areas that include molecular electronics and high performance composites. This team of intrnationally renown experts is being jointly supported by The Office of Mulitdisciplinary Affairs, The Division of Materials Research and The Chemistry Division of The Mathematical and Physical Sciences Directorate, and by the Division of Chemical and Transport Systems of The Engineering Directorate.

The Materials Creation Training Program (MCTP) at UCLA will train scientists to be leaders in the design, synthesis, and production of new materials for electronic, computer, communication, and nanoscale devices. The training and mentoring faculty come from departments in Physical Sciences (Physics and Astronomy, Chemistry and Biochemistry) and Engineering (Mechanical and Aerospace, Chemical, and Electrical Engineering, and Materials Science). All are associates of the UCLA Exotic Materials Institute (EMI), which will administer the MCTP. Many are also members of the California NanoSystems Institute (CNSI) - a state-supported venture that was created in 2001 to provide facilities and resources for materials and medical nanoscience. This resource will be available for training and research of MCTP Fellows. The MCTP unites a broad range of molecular and materials architects, synthetic chemists, and device fabricators, at UCLA and at partner industrial and national laboratories. MCTP Fellows are supported for two years of their graduate careers, during which they will work in teams with UCLA and off-campus scientist partners using state-of-the-art instrumentation and computational resources. Novel training aspects will include a new graduate course involving all aspects of materials and molecular design, synthesis, testing, and modification of materials, device fabrication and testing, and demonstration and marketing aspects of practical devices. This course will deal with science issues beyond the laboratory and will develop researchers versed in the importance of understanding materials properties across length scales, from molecular to macroscopic. Each MCTP Fellow will spend several months or more at an industrial or national laboratory partner site. Research projects will include the design and synthesis of new molecules, the transformation of these into molecular solids and polymers, the formation of new inorganic and organic/information composites, and the development of devices based on these new materials. Fellows will be selected for excellence and diversity. The new graduate program will be evaluated on a yearly basis by a board including university, industrial, and government representatives. Community outreach activities will emphasize the importance and potential of scientific research and attractiveness of graduate education in science. The Materials (MCTP), Bioinformatics, and Neuroengineering IGERTs at UCLA constitute a new graduate educational paradigm, emphasizing multidisciplinary research encompassing life and physical sciences, as well as computer science and engineering.

IGERT is an NSF-wide program intended to meet the challenges of educating Ph.D. scientists and engineers with the multidisciplinary backgrounds and the technical, professional, and personal skills needed for the career demands of the future. The program is intended to catalyze a cultural change in graduate education by establishing new, innovative models for graduate education and training in a fertile environment for collaborative research that transcends traditional disciplinary boundaries. In the fourth year of the program, awards are being made to twenty-two institutions for programs that collectively span all areas of science and engineering supported by NSF. The intellectual foci of this specific award reside in the Directorates for Mathematical and Physical Sciences; Engineering; and Education and Human Resources.

This Nanoscale Interdisciplinary Research Teams (NIRT) project will address the common problem of large pressure drops in microfluidics by nano-engineering novel channel surfaces and controlling their surface properties. The consequences are expected to be both dramatic and far-reaching. The research project is to develop a nano-engineered surface to drastically reduce viscous drag. Despite the explosive growth in microfluidics, as represented by such high-profile applications as biochips and lab-on-a-chip, this fundamental problem associated with miniaturization remains unsolved: the disproportional increase in the relative pressure drop and the power consumption as devices are reduced in size. Due to the severe retardation of velocity at the surface, transport of liquids through long, nano/microscale channels encounter to high losses to be practical. Fabrication of these surfaces will be developed by integrating the rich arsenal of MEMS and Nano-technologies with the extensive knowledge of surface and biomaterial sciences, based upon the specialized expertise of the four principal investigators. Following development and characterization of the novel surfaces, an electrically re-configurable bioreactor chip will be developed as a capstone device, which further promotes synergistic integration among the team members as well as public awareness.

Fusion of the traditionally disjoint areas in this research - mechanical engineering and chemistry - start from students, who will take a set of formal courses developed and cross-offered between two schools for nanoscale science and engineering. The students continue to develop their interdisciplinary mind from monthly team meetings and weekly task meetings for research.

This award from the Instrumentation for Materials Research program will support the University of California Los Angeles (UCLA) with the acquisition of a Fluorolog 3-22 Lifetime System from ISA/Jobin Yvon. The instrument consists of single excitation and double collection monochromators, with fully automated entrance and exit slit control. The instrument will have an immediate impact on the research projects of four research groups at UCLA. The first group will investigate interactions between chains of semiconducting polymers and the dynamics of energy flow in aligned conjugated polymer/mesoporous silica hybrid materials. The work should provide a new understanding of these important materials that will enhance the possibility of application in organic-based displays or photovoltaic devices. The second group will study the properties of newly synthesized molecular compasses and gyroscopes, as well as explore the effects of aromatic ring rotation in conjugated molecules. The information learned from these experiments will have direct application in the production of new organic materials that should have switching properties that are faster than the fastest known ferroelectric liquid crystals. The third group will explore the synthesis and properties of novel heteroacenes, which also will have unique applications in electroluminescent and photovoltaic devices. Finally, the fourth group will use time-resolved resonance energy transfer to study the spatial distributions of molecules deliberately placed in mesostructured silicas, and time-resolved fluorescence depolarization as an in situ probe of the formation dynamics of mesostructured silica films. The information gained in these experiments will improve our understanding of how the formation of mesostructured materials can be controlled and directed. The simplicity of the instrument will ensure routine usage and great productivity, especially in an undergraduate educational environment. Undergraduate students in the physical chemistry and analytical laboratory classes will be able to routinely measure the fluorescence lifetimes of dyes and other molecules, allowing them to explore the dynamics of intramolecular electron transfer and other important photochemical reactions.

This award from the Instrumentation for Materials Research program will support the University of California Los Angeles (UCLA) with the acquisition of a Fluorolog 3-22 Lifetime System from ISA/Jobin Yvon. The instrument consists of single excitation and double collection monochromators, with fully automated entrance and exit slit control. The instrument will have an immediate impact on the research projects of four research groups at UCLA. The information gained in these experiments will improve our understanding of how the formation of mesostructured materials can be controlled and directed. The simplicity of the instrument will ensure routine usage and great productivity, especially in an undergraduate educational environment. Undergraduate students in the physical chemistry and analytical laboratory classes will be able to routinely measure the fluorescence lifetimes of dyes and other molecules, allowing them to explore the dynamics of intramolecular electron transfer and other important photochemical reactions.

A radically new class of organic materials, the protected oligoacenes and polyacenes are proposed. Unlike the much-explored conjugated polymers, these unsaturated macromolecules will be electrical conductors without the need of a dopant; they will be they first of the oligocenes, the cyclacenes may exhibit even more exotic properties, such as superconductivity at higher temperatures. The proposed syntheses are relatively short, so that large amounts of materials will be available for the evaluation of physical properties and device (FET, LED, photodiode, etc.) fabrication.

Organic electronic materials have just entered the commercial engineering mainstream in the form of light-emitting diodes (LEDs), photodiodes (plastic solar cells) and thin film transistors (TFTs). The LEDs produce brighter and cooler light than standard incandescent lamps wand will have a large impact on society in terms of energy savings both in manufacturing and in use. The manufacture of organic TFTs will also be much more energy-efficient than the equivalent, current, silicon-based devices. Another important societal benefit of the research proposed here will be the considerably advance in the education of the graduate and undergraduate students supported by these funds. Development of these organic electronic devices will provide a truly interdisciplinary educational foundation for our future workforce.

This Integrative Graduate Education and Research Training (IGERT) award supports a program at the University of California, Santa Barbara, entitled Conversion of Energy Through Molecular Platforms. In this program, an interdisciplinary approach to graduate education is aimed at providing a new generation of chemical scientists and engineers with the technical skills, environmental awareness, business expertise, and teamwork approaches that will be required to address fundamental and applied issues in the generation and conversion of energy in efficient and environmentally-sustainable ways. The program is founded on the recognition that graduate students of Materials Chemistry and Engineering are conventionally trained to prepare and employ specific classes of functional materials to address particular technological needs. For a problem as broad and as urgent as global energy needs, these traditional modes of training do not suffice. In our new interdisciplinary model of education, the focus is on the better husbanding of fossil fuel resources, and on the inexpensive and large-scale conversion of solar energy to electricity. Graduate students with diverse backgrounds, drawn from a broad pool from across the country, are directed to address issues in energy conversion without being confined to any single material or technology, while learning to appreciate the economic and environmental issues that impact the implementation of technology. A mark of the program is a solid foundation in the entrepreneurial and communication skills needed to influence fundamental research directions, industrial advances, and national priorities in a significant and lasting manner. IGERT is an NSF-wide program intended to meet the challenges of educating U.S. Ph.D. scientists and engineers with the interdisciplinary background, deep knowledge in a chosen discipline, and the technical, professional, and personal skills needed for the career demands of the future. The program is intended to catalyze a cultural change in graduate education by establishing innovative new models for graduate education and training in a fertile environment for collaborative research that transcends traditional disciplinary boundaries.