Vicki L. Colvin, Ph.D. - US grants

This CAREER award to Vicki L. Colvin at Rice University is supported by the Advanced Materials Program in the Chemistry Division. The main focus of the research will be the behavior and properties of nanomaterials from two different aspects. The first project will address the nature of the interface between nanoparticles such as zinc selenide, titania and zirconia and polymers such as polyacrylates and polymethacrylates. By exploiting the recent advances in the size and and surface control of inorganic nanoparticles, model interfaces will be chemically created. The effect of the interfaces on the bulk polymer structure will be explored by NMR and thermomechanical analysis. Atomic force microscopy will be used as a nanomechanical probe of the interfacial region. The second project will exploit the ability to create clusters of different sizes to probe the origins of disorder in glass. The stability of disordered silica clusters will be measured by monitoring the temperature and/or pressure at which the systems undergo structural changes. The size dependence of cluster stability over the 1 to 100 nm range will provide an important test for models of glass formation. Size transformations will be probed by vibrational spectroscopy. These projects will help bridge the gap between the laboratory synthesis of nanoscale solids and their ultimate use in real world technologies. The teaching aspect of this CAREER award will focus on the synergy between basic and applied science in the area of materials. A graduate level course will be developed that provides students with an appreciation of technological issues. The curriculum will focus on the technical assessment of three to four emerging technologies which rely on complex materials such as read-writeable CD disks or electroluminescent flat panel displays. Students will combine technical data from the literature and analysis of potential markets to evaluate the potential for these new applications. This approach will also benefit undergraduate level courses, especially physical chemistry. Examples suggested by the graduate course, such as the photophysics of a laser printer will be used in lectures to illustrate the wide-ranging applications of physical chemical principles.

This award from the Chemistry Research Instrumentation and Facilities (CRIF) Program and the Office of Multidisciplinary Activities (OMA) will assist the Department of Chemistry at William Marsh Rice University to acquire a 500 MHz nuclear magnetic resonance (NMR) spectrometer. This equipment will enhance research in a number of areas such as the following: (1) new synthetic methods towards natural products, (2) biosynthesis of nucleoside and polyketide antibiotics, (3) heteronuclear compounds of the aluminum, gallium, and indium metal complexes, (4) chemical synthesis and intermediary metabolism of sterols, and (5) titania nanoparticles for solar cells. Nuclear Magnetic Resonance (NMR) spectroscopy is the most powerful tool available to chemists for the elucidation of the structure of molecules. It is used to identify unknown substances, characterize specific arrangements of atoms within molecules, and to study the dynamics of interactions between molecules in solution. Access to state-of-the-art NMR spectrometry is essential to chemists who are carrying out frontier research. The results from these NMR studies are useful in the areas such as polymers, catalysis, and in biology.

9802892
Smalley
This award provides partial support for the acquisition of equipment to provide Rice University researchers with a state-of-the-art ultrahigh vacuum, variable-temperature scanning tunneling/atomic force microscope instrument. This instrument will address the needs for nanoscale imaging, localized spectroscopy, and single molecule device fabrication and transport measurement capabilities for a cluster of faculty members in the Physics, Chemistry, and Electrical and Computer Engineering Departments. A primary focus for this instrument is the study of fullerene nanotubes in a range of scientific and technological contexts.

The system will allow the following research activities:

1) imaging and spectroscopy of fullerene nanotubes and other nanoparticles of interest,
2) assembly of single-molecule and nanoparticle-based device structures,
3) characterization of hybrid e-beam lithography/molecular self-assembly device fabrication methods,
4) fabrication, characterization, and imaging applications of fullerene STM tips: C60- adsorbed STM tips, and fullerene nanotube AFM/STM tips,
5) structural imaging and spectroscopic investigations of functionalized fullerene nanotubes and nanotube defects using C60-adsorbed STM tips,
6) temperature-dependent nanoscale imaging and analysis of the phase transitions and structural transformations in nanosized polymers.

This instrument will be the only ultrahigh vacuum or variable temperature STM/AFM instrument at Rice University. It will therefore provide significant new experimental capabilities, enhancing the ongoing programs of several research groups as well as providing a state-of-the-art nanoscale facility for junior faculty with growing research programs.
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Stiil Valid

A workshop entitled NSF-EC: From Nanomaterials to Nanotechnology will provide an opportunity for U.S. scientists and engineers to address together with their European colleagues nanomaterials research activities in four thematic areas: Nano-Chemistry to include nanoparticle, nanotube and nanowire formation and properties; Nano-materials research activities to include atomic and molecular assembly into functional materials; Nano-biosystems research to include nanomaterials in bioengineering activities; and nano-devices to include nanomagnetics, nanoelectronics, nanophotonics and sensors. In addition to presentations by both National Science Foundation (NSF) and European Community (EC) participants in each of these four theme areas, two roundtable discussions will cover issues such as the differences between U.S. and European nanotechnology development, and the role of the academic lab in addressing priority areas such as nanomaterials scale-up challenges. The outcome for the workshop will be a report co-authored by participants highlighting opportunities in basic nanomaterials research for US-EC collaborations.

Nanotechnology research enables discoveries and innovations over a broad range of academic and industrial areas of high priority to the United States. This is the last in a series of five nanotechnology workshops jointly organized by the U.S. National Science Foundation and the European Commission to define the broader context for possible NSF-EC materials research collaborations. A significant emphasis on the societal impact of nanoscience and nanotechnology has been a focus of these workshops.

This grant supports the acquisition of a scanning electron spectroscopy for chemical analysis (ESCA) instrument for interface characterization of bio- , geo- and nanomaterials at Rice University. ESCA, also known as x-ray photoemission spectroscopy (XPS), is a powerful and versatile method for evaluating the surfaces of complex materials. The characterization of material interfaces is an important activity in much of materials research; for bio-, geo- and nanomaterials it is essential for developing new materials and understanding their properties. It is intrinsically a surface technique sensitive only to the top several angstroms of a sample, but with the appropriate conditions can be used to probe depths up to 20 nanometers. Several projects require depth profiling of atomic concentrations at surfaces while others need information about the nature of chemical bonding at interfaces. Still others are interested in chemical mapping of interfaces at the tens of micron level. Nearly all participants must be able to measure the atomic composition of surfaces, and the ability to analyze multiple samples quickly and consistently is of particular value. ESCA can measure the relative amounts of carbon and nitrogen at a surface and can determine whether the carbon is graphitic or bound to nitrogen. ESCA works by bombarding surfaces with a controlled X-ray source and resolving the kinetic energy of the photoemitted electrons; these energies are then used to identify surface atoms and their chemical state. Both the relative amounts of atomic species at surfaces, as well as their chemical environment can be deduced from XPS data. Though samples are evaluated under vacuum conditions, the technique is flexible- conductive and non-conductive powders and thin films have been analyzed with this method. The specific system has a focused, intense x-ray source, leading to small spot sizes (10 microns and high x-ray flux. This feature speeds data collection and its large sample platforms allow for rapid analysis of multiple samples. The scanning capability also enables a wider range of surface chemical experiments, such as depth profiles of atomic composition near surfaces and chemical mapping at the tens of micron length scale.

The acquisition of a scanning ESCA will be especially significant to student training and development, specialized courses for undergraduates and graduates, and workshops. Over thirty graduate students, and tens of post-docs and undergraduates will be able to use this system to understand how surface chemistry plays a role in their research. The existence of a scanning ESCA will allow us to implement a set of programs that not only teaches students how to use the instrument, but also highlights the importance of interface chemistry in areas such as bio- and nanoengineering.

CBET- 0829158
Alvarez

Rapid industrial scale production, coupled with unique material properties, underpin rising concerns of engineered nano-scale materials inadvertently impacting the health and function of natural systems. Carbon based nano-scale materials such as fullerenes and nanotubes in particular have been proposed for a variety of applications and are on track to be produced at industrial scales. Building a fundamental, quantitative understanding of material behavior in natural and engineered systems allows for accurate predictive behavior models which are critical for material life cycle assessment(s) necessary for risk mitigation and sustainability. Of particular interest is the biological interface at which these materials may interact as biologically mediated transformations of fullerenes could significantly influence their mobility, bioavailability, reactivity, toxicity and overall environmental impact. Yet, to date, no systematic evaluations of fullerene biotransformation has been conducted. They will seek to evaluate the susceptibility of aqueous available fullerene species to biochemical transformations and their biological significance. Specifically, they will: (1) characterize the rates and byproducts of biotransformation through, in part, the use of radio labeled P14PCB60B, (2) determine how biotransformation affects the toxicity of CB60B, and (3) quantify the bioavailability and bioaccumulation potential of P14PCB60B and its byproducts through model earthworm systems. They will test the hypotheses that: 1) CB60B can be oxidized by non-specific enzyme systems such as manganese peroxidase, which is involved in complex carbon macromolecules degradation via radical (OH) attack, and/or by other enzymes produced by cellulytic fungi or bacteria that degrade recalcitrant compounds; and (2) such biotransformations will decrease the toxicity and bioaccumulation potential of CB60B, but may increase its solubility and bioavailability. Using chemically unique CB60B with differential isotopic signatures, biotransformation investigations will be conducted with cell free (e.g. purified manganese peroxidase which catalyzes non-specific radical (OH) oxidation), and with whole cell, in vivo cultures of cellulytic fungi, PAH-degrading mixed cultures, and PAH-degrading pure cultures. Reaction kinetics and products will be characterized by a battery of analyses (Radiochromatography (HPLC), P13PC-NMR, MALDI-MS, UV/Vis, Scintillation Counting, among others). Corresponding toxicity studies will measure microbial heterotrophic activity before and after exposure to water available CB60B and bio-transformed derivatives. Bioaccumulation and availability of both C60 and corresponding derivatives will be evaluated through whole organism (model earthworm systems) and biomimetic sorbent experiments similar to previous studies done with polyaromatic hydrocarbons.

This work responds to calls for reliable data on nanoparticle behavior in the environment that have come from environmental advocacy groups, the emerging nanotechnology industry and the regulatory community. Understanding how biotransformation affects the behavior of engineered nanomaterials in the environment is important to ensure that nanotechnology improves material and social conditions without exceeding the ecological capabilities that support them. Furthermore, students on this project will gain valuable interdisciplinary and collaborative experience with applications of nanochemistry and environmental engineering. This project will strengthen the nation?s research and human resource base in an emerging need area where qualified researchers are in short supply, and will contribute to the development of nanotechnology as a tool for sustainability rather than as an environmental liability.

0903936
Kulinowski

Rice University will host an international workshop on environmental nanotechnology, to contribute towards a sound, science-based document that identifies the tools and practices needed to assess and mitigate the potential impacts of engineered nanoparticles (NPs) in the environment and inform eco-responsible design and disposal. This workshop, tentatively scheduled for March 9-10, 2009, will be partially sponsored by the British Consulate General-Houston, the TX-UK Collaborative, and the International Council on Nanotechnology. The workshop will address issues of research & education in a meaningful and focused dialogue through an integrated experience that will provide valuable mentorship and international networking opportunities to emerging leaders in this rapidly growing field. The goal of this workshop is to distill information on environmental impacts of NPs into a format that can
direct research efforts toward the most critical issues in the next five to ten years and lead to methodologies to predict their environmental impacts.

As governments overcome barriers to international collaboration, new funding streams are becoming available to researchers interested in engaging with their counterparts abroad. Therefore the workshop will have an explicit emphasis on stimulating trans-Atlantic and trans-Pacific research collaboration and will recruit talented junior faculty to the workshop, both to benefit from their fresh perspectives and to connect them with potential collaborators here in the US and abroad.

The extrinsic merit of this workshop emanates from its design and participation. This workshop will engage members of the environmental, toxicological, nanotechnology and legal communities in a meaningful and focused dialogue through a unique, integrated, and holistic experience. This experience will foster dialogue among diverse participants around the most pressing questions related to understanding the impacts of engineered NPs. The broader impacts will result from the active engagement of the workshop's participants. This engagement will enhance and strengthen the opportunities for and interest in international, interdisciplinary collaboration on NPs and the environment. In addition, the workshop will provide a solid foundation for the academic communitys future collaboration in research and education programs, projects, and activities at greater and closer levels than was previously possible. The proposed work will have substantial benefit to society by providing current, high quality information on environmental health and safety of nanomaterials which will enable the development and implementation of sound risk management practices.

The sustainable and responsible development of nanotechnology requires an integrated and proactive strategy to recognize and assess possible material risks to workers, consumers and the environment. Such data can be used to both minimize unintended consequence of engineered nanomaterial (ENP) exposures as well as to accelerate innovation by enabling safe nanomaterial design, use and disposal practices. This strategy requires that research into nanotechnology risk(s) be as broad and far-reaching as the possible applications of nanotechnology itself. Rapid developments in research and industrial production of advanced materials at the nanoscale have increased the potential for such technologies to impact the environment. To appropriately address this broad issue, it is critical to understand the impact and role of plant and nanomaterial interactions. Plants are critical species in the ecosystem, and the history of environmental science makes apparent the diverse ways in which they can influence environmental impact. When plants are affected by foreign substances, corresponding consequences to ecosystem health are wide ranging. Furthermore, plants can concentrate, passivate and even degrade contaminants through specific and nonspecific biochemical processes.

Researchers will study the interactions between engineered nanoscale materials (ENM) and plants. Such data is critical for accurate life cycle(s) and ecosystem risk(s) assessments, both of which are the foundation for sustainable nanotechnology. A hypothesis to be tested in this work is that under certain circumstances plants are capable of nanomaterial uptake. Defining the combination of nanoparticle characteristics (composition, size and surface chemistries) including potential plant protein/polysaccharide coatings (from root exudates and turnover or within plant tissue) that facilitate uptake and assimilation is a major goal of this award. Of particular interest is quantitative characterization of the accumulation process and, furthermore, if edible portions of the plant are involved which could lead to transfer of potentially harmful materials up the throughout the food web. Interwoven into plant uptake and assimilation studies, additional experiments are designed to probe known plant biochemical(biotransformation) processes/pathways that may affect engineered (often organic) ENM coatings and ENM directly including nanomaterial phytotoxicity and evaluate material impacts on plant gross development and health.

The work will result in important information for both nanotechnology policymakers and industry alike. The relevance derives from three specific features: first, the research will fill the glaring data gap in plant-ENP interactions and will evaluate species differences; second, the breadth of the materials to be considered is broad enough to encompass a wide variety of existing and future engineered nanomaterials; and finally, the central role that plants play in any description of environmental impact of contaminants. Results will enable nanotechnology risk management strategies that ensure eco-responsible use and disposal.

This award provides funding for a three year continuing award to support a Research Experiences for Teachers (RET) in Engineering Site program at Rice University, entitled, "RET Site: Nanotechnology Research Experience for Teachers", under the direction of Dr. Vicki Colvin.

The objectives of this RET in Engineering Program include enhancing the science and engineering content knowledge and teaching skills of 35 Houston, Texas high school teachers each year for three years. The site will combine a full semester spring content course (CHEM 570) and summer internship, followed by a set of school year activities to keep participants engaged with each other and with Rice University. The participants will improve the quality of secondary school science education through the development of inquiry-based learning activities based on laboratory research and create a community of high school and higher education teachers that can motivate secondary students towards careers in science and engineering. The program is designed not only to facilitate teacher professional development but to scale-up the research experience by forming a network of master teachers that can train new teachers. Since the innovative developments at the nanoscale are integrated across biology, physics and chemistry, this program will provide teachers with new insights on basic science that is also well-aligned with Texas State standards and targets underserved teachers and schools.

Rice University will work closely with the Houston Independent School District (HISD), a large, urban, majority historically underrepresented minority school district in South Texas. This year long RET is designed to be scalable to have a large impact on science teaching via community workshops for students and teachers.

Prof. Vicki Colvin of Rice University is funded by the NSF Chemistry Division to chair an NSF Workshop on Macromolecular, Supramolecular and Nanochemistry along with co-chairs, Prof. Heather Maynard of UCLA and Prof. Colin Nuckolls of Columbia University. The workshop will be held on June 14th through June 16th, 2010 in Arlington, VA. This workshop will engage a diverse group of scientists to discuss the challenges and opportunities for chemists facing the common challenge of understanding and exploiting chemistry at length scales beyond that relevant for conventional molecules. The workshop will seek to articulate the grand challenges in this area, draw attention towards its promise for game changing technologies, provide valuable educational benchmarks, and identify characterization and instrumentation needs for understanding such complex systems. The workshop discussions will be widely disseminated to the scientific community through a website and workshop report.

Recent instances of human exposure to environmental contaminants include the situation with lead in Flint, Michigan tap water and per- and polyfluoroalkyl substances (PFAS) in the Cape Fear River Basin, which serves as a drinking water supply for Wilmington, North Carolina. These cases have contributed to a public awakening and recognition about a range of environmental contaminants. This project supports the purchase of a high-resolution mass spectrometer, called the QExactive Orbitrap. The unique capabilities of the QExactive Orbitrap mass spectrometer allow for the separation of thousands of chemicals contained in a single sample and the identification of these chemicals at trace concentrations. This instrument will enable research and training on the measurement of organic contaminants in environmental samples (for example, in soil and water) and biological samples (for example, in blood and urine). The mass spectrometer also will help researchers assess changes in human metabolism in response to contaminant exposure.

This project brings together a diverse and active research team to determine the prevalence of contaminants in the environment and to advance our understanding of the effects of chemical exposures on human health. The specific research activities supported by the acquisition of a QExactive Orbitrap mass spectrometer include: (a) identifying metabolic alterations associated with exposure to environmental contaminants, (b) detecting contaminants in soil, water and air samples, (c) measuring the contaminant levels in humans, and (d) identifying biomarkers associated with adverse health outcomes. These activities will support research conducted by undergraduate and graduate students, who will receive personalized training related to instrument operation, data extraction, and analysis. The mass spectrometer will be available to both internal and external researchers and will be used to support environmental monitoring efforts affiliated with local schools, research centers and community organizations.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

This award is funded in whole or in part under the American Rescue Plan Act of 2021 (Public Law 117-2).

Remarkable materials can be engineered from carbon. Fullerenes, carbon nanotubes, and most recently graphene have garnered huge interest due to their special chemical, optical, magnetic, and mechanical properties. Whether it is protecting metals from corrosion or enabling the next generation of lightweight and strong plastics, these new carbon materials are poised to enable a greener and more sustainable society. To fully exploit these systems requires transformative approaches to their manufacturing. The highly inefficient and energy consuming techniques used by researchers to make these special carbons, while adequate for the laboratory, are poorly suited to the large scale and sustainable production needed to translate them to widespread commercial use. This Boosting Research Ideas for Transformative and Equitable Advances in Engineering (BRITE) Relaunch award capitalizes on a recent discovery that will support the manufacturing of graphene at relatively low temperatures, and it will apply this advanced manufacturing technique in order to form intricately shaped magnetic polymers as well as porous carbon sponges. Such sponges are excellent bulk materials for removing waste materials from contaminated water. This effort will offer an alternative manufacturing route to the rapidly expanding graphene industry and provide intensive research training for graduate students and undergraduates alike, with efforts aimed at increasing the retention of STEM undergraduates in engineering. It also supports the development of sustainable materials education for engineers, providing a quantitative framework for assessing the overall impact of a manufacturing process.

The research goals in this work center on the development and optimization of a liquid phase process for forming carbon materials. This project tackles this challenge by forming carbon materials directly in a liquid phase process, much like processes used to make specialty polymers. The method exploits the recent discovery that a fine powder of iron oxide can catalyze formation of carbon nanomaterials. By instrumenting the reaction process, real-time information will result in the efficient formation of materials with tailored formats and properties. Control algorithms will be developed for optimized manufacturing using this real-time information. This will also create new knowledge about how graphene forms within a solution environment. Graphene formation will first occur on nanoparticles, followed by porous structures and 2D graphene sheets. The magnetic carbons formed will also be blended with polymers in an additive manufacturing approach using three-dimensional printing to form shaped permanent magnets. Other formats of these carbons, such as porous sponges and thin films, will be applied to problems in water treatment and transparent electronics.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.