John W. Birks - US grants

Small aggregates of molecules often have properties unique and different from their respective isolated molecules or bulk phase. The simplest aggregate is the two molecule complex or dimer. Low concentrations of dimers are expected in the atmosphere, but their numbers may be sufficient to influence certain atmospheric chemical processes. Little is known about the properties of dimers containing species of atmospheric relevance. The project will explore the hypothesis that the photolysis of weakly bound molecular dimers may be an important source for some atmospheric species. The study will use both conventional methods in which quantum yields are measured for photolysis of gas mixtures at a variety of partial pressures and temperatures and the method of supersonic jet expansion with Fourier Transform spectroscopy and multiphoton ionization coupled with mass spectrometric detection. This approach will obtain fundamental physical parameters such as shifts in absorption spectra, absorption cross-sections, dimer binding energies, and entropies of formation. The data obtained will be directly applicable to computer models of atmospheric chemistry.

9411761 Balsley In this project the researchers plan to extend the capabilities of state-of-the-art kite technology for atmospheric sampling and related research. The workplan will accomplish this feasibility experiment by (1) increasing the current maximum attainable height from around 3 km to over 13-14 km, and by (2) using the tethered kite as a "sky hook" to enable a small device (a "WindTRAM") to travel up and down the kite tether to obtain high- resolution profiles of ozone, temperature, pressure, and humidity. If successful, the project results will be a unique and inexpensive technique to study vertical profiles of critical atmospheric species throughout the entire troposphere and possibly the lower stratosphere.

This award from the Chemistry Research Instrumentation and Facilities program is to aid the Department of Chemistry at University of Colorado at Boulder in the purchase of a scanning probe microscope (SPM). This instrument will be used in the following research programs: 1) Heteroepitaxial 2-D crystals on highly oriented pyrolytic graphite which grow under liquid crystal films; and Self-assembled monolayers on glass. 2) Synthesis and topographic characterization by SPM of chemically deposited films. The scanning probe microscope (SPM) enables researchers to image atoms directly. The technique uses the piezoelectric effect which involves bringing an extremely sharp metal needle within a few angstroms of the samples surface. The distance is small enough for electrons to leak or tunnel across the gap and generate a minute current. As the gap between the tip and the sample increases, the current decreases. As the probe crosses the sample, moving back and forth across its surface, the probe traces out a contour map of the sample's surface atoms. The SPM is used in the control of material used to fabricate semiconductor circuits.

9302748 Caruthers The Department of Chemistry and Biochemistry and the Cooperative Institute for Research in the Environmental Sciences (CIRES) at the University of Colorado are requesting funds from the National Science Foundation to purchase a sequential stopped-flow spectrophotometer with both fluorescence and UV/vis detection. This instrument will play an important role in the education of graduate and post-doctoral students and in the research of faculty members in areas as diverse as organic chemistry, analytical chemistry and biochemistry.

This award from the Chemistry Research Instrumentation and Facilities Program will assist the Department of Chemistry at the University of Colorado--Boulder in the purchase of a modern single-crystal diffraction system. This new instrumentation will enhance greatly research in a number of areas, including the following: (1) transition metal complexes containing quinone and radical semiquinone ligands; (2) role of metal sulfides in carbon-heteroatom and metal sulfur bond cleavage; (3) intramolecular Lewis acids as stereochemical control elements; (4) 2,5-Dicarboxy-Stabilized 1,4-Dihydropyrazines as electron donors in the synthesis of organic conductors and magnets; (5) extended skeletally stabilized cyclic and linear phosphazanes; and (6) single crystal x-ray structures of molecular rods and connectors. The x-ray diffractometer is used to make accurate and precise measurements of the full three- dimensional structure of a molecule. The information obtained gives the precise values of all the bond distances and bond angles of a given molecule and it gives accurate information about the spatial arrangement of that molecule relative to the neighboring molecules.

This award from the Chemistry Research Instrumentation and Facilities Program will assist the Department of Chemistry at the University of Colorado--Boulder in the purchase of a Raman spectrometer with a laser excitation source tunable in the visible region. This equipment will enhance research in a number of areas including the following: (a) Investigation of the Interaction between 3-Chlorocatechol and the Active Site of Catechol 1,2-Dioxygenase II; (b) Application of Resonance Raman Spectroscopy for the Determination of the Vibrational Reorganization Energies in Charge Transfer Complexes; and (c) Matrix Isolation (MI) Raman Spectroscopy. Raman spectroscopy is concerned with vibrational and rotational transition in molecules, similar to infrared spectroscopy. The information obtained from a Raman spectrometer sometimes complements that obtained from an infrared study and provides valuable structural information.

This award from the Chemistry Research Instrumentation and Facilities Program will assist the Department of Chemistry at University of Colorado in the purchase of a tunable Femtosecond laser system. This equipment will be used in the following areas of research: (1) Mechanism of pericyclic photochemical reactions, (2) structure of gaseous cluster ions, (3) dynamics of photoinduced bond homolysis and heterolysis. A tunable femtosecond laser can provide important information about chemical reactivity. Its use may enable breakthroughs in our understanding of the properties of reactive and of nonreactive molecules. f8 Û-ª þ ; + + Ûª? ÑOh ª' +'ª?0 Ý + ] $ H l + ¢ ? D h + ++++++++++++++++++++++++++++++++ R:\WWUSER\TEMPLATE\NORMAL.DOT

This award from the Chemistry Research Instrumentation and Facilities Program will help the Department of Chemistry at the University of Colorado--Boulder acquire a 500 MHz NMR Spectrometer. The research activities to be supported include: (1) development of stereoselective synthetic methods and sequential reactions schemes; (2) investigations of adriamycin-mediated DNA cross-links; (3) the development of stereoselective and catalytic asymmetric methods for organic synthesis; (4) synthetic and bioorganic studies of DNA and RNA; (5) structure determination of proteins; (6) the total synthesis and bioorganic studies of natural products and complex carbohydrates. 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 and catalysis, and in biology.

This award from the Chemistry Research Instrumentation and Facilities Program will assist the Department of Chemistry at the University of Colorado at Boulder to acquire an automated solid- phase peptide synthesizer and a high performance liquid chromatograph (HPLC). This equipment will enhance research in a number of areas including the following: (1) studies utilizing peptides to probe intermolecular tuning of protein signaling, (2) studies of the structural ramifications of glycosylation on peptide conformation, (3) synthesis and characterization of phosphopeptide analogues, (4) structural characterization of the protein folding intermediates and protein design, and (5) studies of the MAP kinase signal transduction pathway. The peptide synthesizer and the high performance liquid chromatograph (HPLC) are used by biological scientists to make and purify analogs of the natural substrates/effectors of a variety of proteins.

This award from the Chemistry Research Instrumentation and Facilities (CRIF) Program and the Office of Multidisciplinary Activities (OMA) will help the Department of Chemistry at the University of Colorado purchase a parallel processing computer. This equipment will enhance research in a variety of areas including reactions studies relevant to atmospheric chemistry, fundamental studies of molecular reactivity, and aspects of materials. A network of fast, modern computer workstations is a new way to satisfy the computing needs of chemistry departments. Such a `computer network` also serves as a development environment for new theoretical codes and algorithms, provides graphics and visualization facilities, and supports research in state-of-the-art applications of parallel processing.

This proposal seeks funds to investigate the vertical distribution of ozone, carbon monoxide, temperature, humidity, wind speed, wind direction, pressure throughout the atmospheric boundary layer at Summit Greenland in the summer of 2000. Cooperating programs are assessing the photochemical processes occurring in the snow pack which deplete ozone and increase the concentrations of other atmospheric contaminants. This SGER proposal would help in evaluating the relative importance of the snow pack processes by determining the concurrent distributions in the atmospheric boundary layer above the snow pack. At least 10 vertical profiles to altitudes of 2000 m above the snow surface will be conducted over a 2 week period in mid-summer.

Sesquiterpenoid compounds have been identified in plant emissions in numerous studies and are suspected to participate in aerosol-forming processes and heterogeneous reactions in the atmosphere. Understanding the role of these compounds in atmospheric processes is challenged by the lack of analytical capabilities and ambient measurements. In this project, a capillary diffusion-based calibration system will be built to generate well-defined gas-phase concentrations of sesquiterpenoid compounds. A gas chromatography/flame ionization detection instrument will provide automated and continuous on-line monitoring of the system output. The calibration system will be designed to allow addition of potential analytical interferences to the analytes, such as water and ozone, in order to study the effects of these atmospheric components on the SQT recovery rate and the analytical precision and accuracy. Sampling, storage and analysis methods using either whole air sampling techniques into bags and canisters and collection onto solid adsorption cartridges will be investigated for their analytical suitability. These studies will develop methodology for the reliable measurement of sesquiterpenoid compounds in air for ambient measurements and flux studies.

[unreadable] DESCRIPTION (provided by applicant): In this proposal we respond to the PHS 2005-2 Omnibus Solicitation's call for the development of diagnostic tools for "non-invasive methodologies for measuring airways inflammation in asthma." We propose to develop, test and evaluate a low cost, portable analyzer for the measurement of nitric oxide (NO) in human breath as an indicator of airway inflammation, especially for the diagnosis and treatment of asthma. A method for NO measurement in exhaled breath recently was approved by the U.S. Food and Drug Administration and its equivalent in the European Union for the purpose of diagnosing, monitoring and treating patients with asthma and other airway diseases. The instrumental approach (NIOX(r) of Aerocrine AB) makes use of the highly sensitive technique of NO + O3 chemiluminescence, but that method is too complicated and expensive for use in the home. In preliminary results, we have demonstrated the use of a much simpler technique that uses the NO + O3 reaction in a different way. Instead of measuring chemiluminescence, the loss of O3 is measured by UV absorption at 254 nm using a low pressure mercury lamp. This approach, which recently has been successfully marketed in for atmospheric measurements, gives adequate precision ([unreadable]2 ppbv) and accuracy ([unreadable]2%) for breath analysis. In addition to being small, light weight and having low power requirements, this new approach eliminates the need for gas standards contained in high pressure gas cylinders. The simplified "stopped flow" design proposed here eliminates the possibility of interference from major components in breath such as water vapor and carbon dioxide. Because of their slow reaction, VOCs such as isoprene also are not expected to interfere. In Phase I we will develop and test a prototype instrument that will be used in a clinical intercomparison with the FDA-approved NIOX apparatus for establishment of equivalency during Phase II. RELEVANCE TO PUBLIC HEALTH The objective of this work is to develop a low cost, accurate and reliable instrument for use in the home that can be used for optimizing the use of therapeutic drugs in the management of asthma. [unreadable] [unreadable]

[unreadable] DESCRIPTION (provided by applicant): Project Summary/Abstract: Iodide deficiency disorders (IDDs) have been identified by the World Health Organization as a serious global health problem affecting 740 million people in 130 countries. Iodine deficiency is the most common cause of preventable brain damage, with nearly 50 million people suffering some degree of IDD-related brain damage. IDD is preventable and treatable by iodization of table salt. Identification of individuals suffering from IDD and populations at risk requires the development of an instrument capable of measuring iodine in urine and table salt. We propose to develop a small, lightweight, inexpensive instrument to achieve quantification of iodine. The Rapid Iodine Analyzer (RIA) will allow measurement of iodine present as either iodide or iodate. The instrument will be based on a novel and proprietary detection method described in the text of the proposal. It will be highly automated and will require very little sample preparation. The portable instrument is expected to have a limit of detection of ~1 ppb and to be free of interferences. Thus, the sensitivity will be adequate to diagnose patients as having moderate (20-49 ppb) or severe iodine deficiency (<20 ppb), as well as those having normal (100-199 ppb) or excess iodine (>300 ppb) in their urine. Because of its low cost (~$2,000 retail), portability (<5 lb), and low power requirements (~2 watt), the iodine instrument will be highly useful for assessing iodine deficiency in populations in remote locations around the globe and for testing for the presence of iodine additives to salts dispensed in those regions. Project Narrative(Relevance): A high sensitive (.~ 1ppb) portable instrument will be developed for the measurement of iodide and iodate in urine and table salt. The Rapid Iodine Analyzer will be highly useful in addressing the problem of iodine deficiency disorder currently affecting 740 million people in 130 countries. [unreadable] [unreadable] [unreadable]

DESCRIPTION (provided by applicant): In this proposal we respond to the call by the National Institute of Environmental Health Sciences (NIEHS) in the PHS 2009-2 Omnibus Solicitation, Exposure Biology Program, Section 1, Technologies for Generating Precise Measures of Environmental Exposures for "new products/devices, tools, assays to improve our ability to precisely measure environmental exposures to individuals with high temporal and spatial resolution." According to the solicitation, the device should be of appropriate scale to be field deployable and/or wearable. Ozone, formed in photochemical air pollution, has well documented adverse effects on human health, including reduction of lung function and aggravation of preexisting respiratory disease such as asthma. Emergency department visits, daily hospital admissions and mortality increase during episodes of high ozone concentration. A Personal Ozone Monitor (POM) is required for environmental health studies of the physiological effects of ozone and for validating computer models of human exposure. In the Phase I project we successfully developed a small (4 x 3 x 1.5 inch), light weight (0.7 lb), low power (2.9 watts), low cost ($795 in parts), battery-operated POM based on the well established method of UV absorbance (an EPA Federal Reference Method). The pocket-sized POM has a precision and accuracy of # 2 ppb, makes new measurements every 10 s and has an internal data logger for downloading data to a personal computer. During the Phase II project proposed here, we will further improve and finalize the development of the POM to include the following: 1) dedicated ground plane on the printed circuit board to further reduce noise, 2) ruggedized, easily manufactured enclosure, 3) human interface consisting of liquid crystal display and keypad, 4) docking station with battery charger, 5) GPS for co-locating measurements with geographical coordinates, and 6) wireless communication between the POM and docking station. Firmware will be developed to support the new functions, and software will be developed for data acquisition and graphing by a computer and for uploading ozone data to the web. The efficacy and accuracy of the POM will be evaluated in personal exposure monitoring studies conducted at the Environmental and Occupational Health Sciences Institute (EOHSI) of the University of Medicine and Dentistry of New Jersey. Several large markets for a pocket-sized ozone monitor have been identified in addition to personal ozone monitoring;these include rapidly growing industrial applications of ozone and the Global Ozone (GO3) Project, an international educational project in which high school students build and operate an ozone monitoring station and share their data as an overlay on the Google Earth" map. PUBLIC HEALTH RELEVANCE: Development of a pocket-sized, battery powered Personal Ozone Monitor (POM) will be completed and evaluated as a means of measuring the time-resolved exposure of individuals during normal daily activities. The POM will facilitate physiological studies of the adverse effects of ozone, formed in air pollution, on human health.

DESCRIPTION (provided by applicant): We propose to make air pollution personal by enabling K-12 students to act as citizen scientists using sophisticated, mobile air pollution monitors to measure their individual exposures to black carbon, a primary pollutant, and ozone, a secondary pollutant. Through their experiments and specially designed curricula, students will learn when and where they and others are exposed to these damaging air pollutants and how that exposure can affect their health. Ozone and black carbon are two of the most damaging air pollutants to human health, and it has been shown that both are asthma triggers and can lead to other health problems, including heart disease and even premature death. Heightened awareness of the way air quality impacts health is vital, and nothing is more impactful than understanding exposure at a personal level. Through our nonprofit partner the GO3 Project, ~50 schools will be loaned a 2B Tech Personal Ozone Monitor (POM) and microAeth personal black carbon monitor (AethLabs), both accurate, pocket-sized monitors, for a period of two weeks each, allowing up to ~1,000 day-long personal monitoring experiments. The instruments are equipped with GPS capabilities so students can track their daily activities or planned excursions and upload their data to share with other students and citizens online. Furthermore, these excursions will highlight air quality disparities in different regions or neighborhoods, raising awareness of environmental justice issues. We will develop specific software for online analysis and display on Google Earth and Google Maps. Students will be able to compare and discuss data with students at ~85 schools around the world via the already established GO3 Social Network. The project includes full curricula and activities on the science and health effects of ozone, black carbon and other air pollutants, allowing students to further their understanding in conjunction with hands-on experimentation with sophisticated, mobile instrumentation. Near the end of the Phase I project, we will assess its success in terms of logistical problems encountered, equipment and software, data quantity and quality, learning, experiences, and what can be done to improve the GO3 Project for implementation in 500 schools during Phase II. The Phase II commercialization plan will show how the GO3 Project with personal monitoring can be expanded to thousands of schools through self-funding in an already established educational Green Fundraiser and through additional personal and corporate donations.

? DESCRIPTION (provided by applicant): Personal Exposure Monitoring of Air Pollutants as an Educational Tool in the GO3 Treks project launched by the Phase I grant, ~2,500 students at 50 schools throughout the U.S. used personal monitors to measure the air pollutants black carbon and ozone along treks of their own design. The ~275 treks were uploaded to blogs in the GO3 website where they were displayed on Google Earth and where students, teachers, GO3 staff and air quality scientists discussed the results. The students learned about the sources, transformations and sinks of air pollutants by acting as citizen scientists, forming and testing their own hypotheses using real scientific instruments. Highlights include comparisons of rural vs. urban exposures, discovery of increased pollution levels during pick-up/drop-off traffic at schools, comparisons of pollutant levels along busy and residential streets, analysis of exposures during commutes to school, a trek at a hydraulic fracturing site, treks from urban areas into the mountains, and investigation of emissions from different types of sources such as lawnmowers and buses. One school explored an area that is known to have an underground coal mine fire and even launched the ozone monitor on a balloon to 30 km (100,000 ft.) where ozone in the stratosphere was measured. We propose to improve upon and expand GO3 Treks in the Phase II project by: 1) implementing a quality assurance (QA) program for GO3 Treks data; 2) developing a universal Personal Air Monitoring Module (PAMM) that will allow any air quality sensor to upload data in real time to GO3 Treks via a smart phone app; 3) expanding the suite of miniaturized instruments available to GO3 Treks to include CO2 and Equivalent PM2.5 in addition to O3 and black carbon; and 4) revising the GO3 online curriculum to be smaller bite-sized modules, each of which can be completing in an hour or less, and awarding digital badges for completion of each module. Individuals, who earn all GO3 Air Quality digital badges, including those awarded for participation in a trek and for achieving a prescribed level of activit on the GO3 network, will be awarded a Mozilla Open Badge that can be included in their digital resume. The commercialization plan expands GO3 Treks to include citizen monitoring by environmental advocates and local government agencies in addition to schools and proposes rental of instruments at a fee of only $50/week. A business model is proposed that provides exponential growth of the project by continuous reinvestment of all but 5% of profit in new inventory. Model results using reasonable assumptions show that in four years GO3 Treks could be grown to annual rentals of ~$3M with servicing of ~10,000 organizations from an inventory of ~2,000 instruments.