ANYL Sem Abstracts

This page contains the abstracts for upcoming and past Analytical & Environmental Chemistry Seminars at CU. Please post newer seminars at the top, but do not erase the abstracts from old seminars.

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TUESDAY, March 2, 2010

Dry powder formulation development for nasal vaccination

Regina Westmeier, Department of Pharmaceutics and Biopharmaceutics, Christian Albrecht University, Kiel, Germany

Abstract

I will briefly talk about some aspects of the mucosal immune system, which are important for the nasal vaccination strategy. I will then focus on the nose as delivery location, introduce a nasal cast model for the determination of formulation deposition in the different parts of the nose and show some delivery devices I have been characterising. Further on I will shortly review the vaccine delivery systems described in literature and will then talk about our formulation strategies. Besides I will introduce a rapid in vitro test to assess the respiratory toxicity of both excipients and complete formulations.

TUESDAY, March 9, 2010

Nathalie Carrasco, Laboratoire Atmosphères, Milieux, Observations Spatiales, IPSL, Verrières le Buisson, France

Title: Experimental simulation of Titan’s atmosphere by a radio-frequency plasma

• Recent papers: JPCA-2009, JPCA-2010

Titan is the biggest satellite of Saturne (about half the Earth). Its dense atmosphere of 1.5 bar at the surface is mainly composed of nitrogen and methane. So Titan is considered as an interesting analog of a frozen primitive Earth. Despite the very low temperature, between 100 and 200 K, atmospheric layers undergo efficient reaction chains, initiated by the solar flux and the Saturn magnetospheric electrons. Complex organic matter made of nitrogenated hydrocarbons is produced into the gaseous phase leading to a brownish photochemical fog surrounding the whole satellite.

Several techniques have been developed to simulate lab analogs, called tholins, of Titan’s haze. Most efficient methods presently known involve plasma techniques. Such a plasma device, named PAMPRE, has been developed in LATMOS, using a RF plasma discharge (13.6 MHz) in a stationary flux of nitrogen and methane gaz mixture, at various temperature and pressure conditions. Recent results will be presented concerning in situ mass spectrometry analysis of the gaseous phase and ex-situ chemical and morphological analysis of the tholins.

TUESDAY, February 16, 2010

Observations of iodine oxide and reactive gaseous mercury at a coastal site in Pensacola, FL

Sean Coburn

Abstract

An increasing body of evidence suggests that atmospheric halogens, marked largely by the presence of BrO and IO, are ubiquitous components of the lower troposphere in coastal and oceanic areas. The role of halogen chemistry in mercury oxidation in coastal regions remains unknown. Simulations of atmospheric mercury oxidation suggest that chemistry initiated by atomic Br may have been underestimated. Synergistic effects of the iodine compounds can be expected and little is known about the possible direct role I atoms may play to oxidize mercury. Finally, other reactive trace gases, such as CH2O and C2H2O2, can suppress the oxidation of Hg by converting bromine-radicals into chemically inert reservoir species. Here we present data from several months of MAX-DOAS measurements of halogen oxides, O4, CH2O and C2H2O2 in parallel with measurements of speciated mercury (Hg0, Hg2+) that are currently being conducted along the U.S. Gulf Coast.

TUESDAY, February 9, 2010

Light Emitting Diode Cavity Enhanced Differential Optical Absorption Spectroscopy (LED-CE-DOAS): a novel technique for monitoring atmospheric trace gases

Ryan Thalman and Rainer Volkamer

Abstract

The combination of Cavity Enhanced Absorption Spectroscopy (CEAS) with broad-band light sources (e.g. Light-Emitting Diodes, LEDs) lends itself to the application of cavity enhanced DOAS (CE-DOAS) to perform sensitive and selective point measurements of multiple trace gases with a single instrument. In contrast to other broad-band CEAS techniques, CE-DOAS relies only on the measurement of relative intensity changes, i.e., does not require knowledge of the light intensity in the absence of trace gases and aerosols (I0) and is therefore insensitive to lamp drifts and/or the presence of aerosols. We have built a prototype LED-CE-DOAS instrument in the blue spectral range (420-490nm) to measure nitrogen dioxide (NO2), glyoxal (CHOCHO), methylglyoxal (CH3COCHO), iodine monoxide (IO), water (H2O) and oxygen dimers (O4). Aerosol extinction is retrieved at two wavelengths by means of observing water and O4 and measuring pressure, temperature and relative humidity independently. The instrument components are presented, and the approach to measure aerosol extinction is demonstrated by means of a set of experiments where laboratory generated monodisperse aerosols are added to the cavity. The aerosol extinction cross section agrees well with Mie calculations, demonstrating that our setup enables measurements of the above gases in open cavity mode.

TUESDAY, February 2, 2010

Environmental Analysis of Water and Food Samples by Advanced Mass Spectrometry Techniques

Imma Ferrer and E. Michael Thurman
Environmental, Civil, and Architectural Engineering
CU, Boulder

Abstract

The analysis of pharmaceuticals and pesticides in water and food is one of the hot topics in environmental analysis. Recently the Associated Press published an article that much of the drinking water of the US is affected by pharmaceuticals coming from our wastewater. This article was backed up by numerous scientific studies since the late 1990s showing pharmaceuticals occurring in surface waters of the US. We have established a Laboratory for Environmental Mass Spectrometry soon to be a Center for Environmental Mass Spectrometry that uses an array of state of the art MS, including LC/time-of-flight MS, triple quadrupole MS with Jetspray, LC/MS ion trap, and other instrumentation to examine questions such as pharmaceuticals in drinking water and pesticides in food. Our seminar will discuss our new Center of Environmental MS, instrumentation, and applications to pharmaceuticals in drinking water and pesticides in food.

FRIDAY, January 22, 2010 (note special day)

Pedro Campuzano-Jost
University of British Columbia, Canada

CIRES Auditorium @ 4:00 p.m University of Colorado, Boulder

Abstract

Trapping organic aerosol ions for molecular identification: Some lessons learned

The incapability of off-line techniques to resolve a significant part of the organic fraction of atmospheric aerosols has resulted in a stronger focus in recent years on developing real time aerosol mass spectrometers that are able to identify not just compound classes, but specific molecules. The approach chosen in most cases has been reducing fragmentation by use of soft-ionization techniques. While use of soft ionization can greatly simplify the mass spectra of complex mixtures, it also tends to erase the chemical information provided by the fragmentation pattern. Therefore, the ability to isolate and obtain tandem MS spectra of individual molecular ions is key to be able to id individual compounds.

Ion traps are compact, versatile devices that are similarly well suited for use in single particle mass spectrometers (SP-MS) than the more ubiquitous reflectron time-of-flight-MS; however, unlike reTOFs, they can also be used for tandem MS experiments. We have recently build a single particle ion trap mass spectrometer (SPIT-MS) that combines in-trap IR laser desorption of particles with a state-of-the-art laser based tabletop tunable VUV source. This allows separate optimization of both the desorption and ionization step for minimal fragmentation and -at high enough IR fluencies- a quantitative response. At the same time, measurements of the first ionization energy of the molecular ion together with their tandem MS spectrum can be used for molecular identification.While the SPIT-MS works as intended with certain types of test aerosol, it mostly fails with mixtures of aliphatic compounds, its intended target. The reasons for this failure will be examined in detail and some of its implications for alternative designs discussed.

In the second part of the talk, two other simpler SPIT-MS designs recently developed at UBC will be discussed:

- A laboratory prototype that uses pulsed IR laser desorption and conventional pulsed 70 eV electron impact for ionization. While its overall performance is comparable to the Aerodyne TOF in single particle mode, in addition it allows for analysis of refractory material as well as tandem MS analysis of larger ions.

- A new field capable ITMS that combines a novel aerosol beam alignment design with a mass spectrometer with dual polarity detection. Ionization occurs by laser ablation at 266 nm. This instrument is currently being deployed to the top of Whistler Mountain, BC to study long range transport of Asian dust.

MONDAY, November 30, 2009

4:00 p.m. CIRES Auditorium University of Colorado, Boulder

Synthesis of Catalyst Arrays from Nanoparticle Precursors

Bryan Tienes

Abstract

The desire to develop novel, more efficient heterogeneous catalysts is a vital area of research in renewable energy applications. Due to the huge compositional and structural parameter space under which solid state materials can exist, it is nearly impossible to develop new heterogeneous catalysts a-priori. Therefore, many research groups have turned to combinatorial methods to identify new materials. While methods of synthesizing combinatorial arrays of bulk materials are well established, combinatorial arrays of nano-materials have been more elusive. Here we present a novel synthesis methodology for arrays of nanoparticles on solid supports using nanoparticles as synthetic precursors. The combinatorial arrays are generated by utilizing multidirectional nanoparticle gradients created by exploiting the kinetics of electrostatic adhesion of nanoparticles to a solid support. Subsequent reaction of the solid supports at elevated temperatures causes adjacent particles to alloy yielding nanoparticles with a gradient of compositions. These reactions have been demonstrated to take place on solid supports in both gaseous and liquid environments. Nanoparticle arrays adsorbed onto indium tin oxide (ITO) coated glass have been shown to alloy in a similar fashion. The arrays on ITO glass were subsequently fabricated into working electrodes for an electrochemical cell. The electrodes were then demonstrated as a catalyst screening tool for methanol fuel cell catalysts.

MONDAY, November 2, 2009

4:00 p.m. CIRES Auditorium University of Colorado, Boulder

A Novel Method for Analysis of Respirable Particle Size Distributions using an Andersen Cascade Impactor

Lia Rebits

Andersen cascade impactors (ACIs) are widely used throughout the pharmaceutical industry to obtain aerodynamic particle size distributions for inhalable products. An ACI separates aerosolized particles by passing them through a series of orifice‐containing stages and plates; the plate on which a certain particle will deposit depends on its velocity and aerodynamic diameter. A limitation encountered with the use of this instrument is that the analytical method chosen to quantify the deposition of particles on each plate must be precise, accurate, and have a low detection limit. A method that measures the total organic carbon (TOC) content on each plate has been found to fulfill many of the requirements needed to obtain accurate particle size distributions.

Amperometric S-Nitrosothiol Sensors: Applications and Methods

Candice Smith

It has been discovered that the right amount of S-nitrosothiol (RSNO) species in blood prevents the activation of clotting agents. A new RSNO detection technique, based on an electrochemical sensor, rapidly measures the level of RSNOs in whole blood. Use of this S-nitrosothiol sensor during surgical procedures, like Extra Corporeal Life Support (ECLS), could provide physicians with a novel method of monitoring a patient’s health. This seminar is an opportunity to describe the methods of the S-nitrosothiol biosensor’s assembly and in vivo testing.

MONDAY, October 26, 2009

4:00 p.m. CIRES Auditorium University of Colorado, Boulder

Practical Analytical Chemistry - Colorimetric Wet Chemistry Methods for Wastewater, Drinking Water, and Natural Water

Kristin Boles

Abstract

Analytical chemistry is an essential tool in drinking water and wastewater regulation. Wet Chemistry specifically refers to analytical chemistry performed in aqueous solution. It is therefore easily performed in the same matrix as wastewater and drinking water. This presentation will cover three wastewater testing methods: EPA 420.1, which tests for all phenols/phenolic compounds; EPA 365.3 dissolved, which tests for the orthophosphate ion in a filtered solution; and SM 3500-Cr B, which tests for hexavalent chromium in natural or treated water. Each of these tests is colorimetric, and the chemistry of their respective color-producing reaction will be discussed, as well as typical matrix interferences.

MONDAY, October 19, 2009

4:00 p.m. CIRES Auditorium University of Colorado, Boulder

Sources of organic aerosols: atmospheric transformations of emissions from combustion systems

Allen Robinson

Carnegie Mellon University

Abstract

Atmospheric particles play an important role in climate forcing; they are also strongly associated with adverse human health effects. Organic aerosols account for a large fraction of ambient fine particle mass, but their sources and transformation processes are still poorly understood. Motor vehicles, wood stoves, and other combustion systems are major sources of organic aerosols. This talk discusses recent field, laboratory, and modeling results on organic particle emissions from combustion systems. The results reveal a dynamic picture in which low-volatility organics evaporate, oxidize, and recondense as they are transported away from the source. This new picture alters our understanding of the contribution of combustion sources to urban and regional pollution and brings chemical transport model predictions into better agreement with field observations. The talk concludes with a discussion of the implications of these recent findings on human exposures and the design of regulations to control organic aerosols.

MONDAY, October 12, 2009

4:00 p.m. CIRES Auditorium University of Colorado, Boulder

New Insights Into the Mechanism of 3-Hydroxy-3-Methylglutaryl Coenzyme A Reductase

Gregory Schill

Abstract

Class II 3-hydroxy-3-methylglutaryl coenzyme A (HMG-CoA) reductase, the rate limiting enzyme of the mevalonate pathway, represents an attractive potential target for the development of antibiotics the against multiple drug-resistant strains of Gram-positive cocci. However, recent steady-state spectrofluorimetric studies suggest that the mechanism of catalysis does not go through a mevaldehyde intermediate as accepted in the literature. The objective of this study was to investigate HMG-CoA reductase catalysis prior to steady-state conditions to determine if this incongruence was the result of a fast equilibrium. Stopped-flow kinetic assays, with dead times of 8 ms, were conducted to probe for the elusive mevaldehyde intermediate. Results found that a fast equilibrium can not account for the absence of mevaldehyde, suggesting a revision of the current literature-accepted mechanism of catalysis to one where coenzyme A plays a more integral role.

A NEGATIVE ION PHOTOELECTRON SPECTROSCOPIC STUDY OF Mo2-.

Sunil Baidar

Abstract

The homonuclear diatomic metal ion Mo2- was studied using negative ion photoelectron spectroscopy. This bare, homonuclear group 6 transition metal dimer allows the study of multiple metal-metal bonding free of ligand effects. The photoelectron spectra, obtained at 488 nm with an instrumental resolution of about 6 meV (50 cm-1), provide measurements of the electron affinities, vibrational frequencies for both the anion and the neutral states, and bond length changes upon electron detachment. The Mo2- spectra displays a transition to the multiply-bonded 1Σg+(dπ)4(dδ)4(dσ)2(sσ)2 ground state of the neutral molecule. In the anion, the extra electron occupies the vacant antibonding sσ* orbital, giving a 2Σu+ ground state.

MONDAY, October 5, 2009

4:00 p.m. CIRES Auditorium University of Colorado, Boulder

Aerosols of the Past: Lessons from Saturn’s Moon Titan

Margaret Tolbert

Dept. Chem & Biochem., and CIRES, CU-Boulder

Abstract

An organic haze layer in the upper atmosphere of Titan plays a crucial role in the atmospheric composition and climate of that moon. Photochemistry in the atmosphere of the early Earth shortly after the time of planetary formation may have led to a similar haze. However, due to differences in atmospheric chemistry, the aerosols formed on the early Earth may have had distinct chemical and optical properties from those suspected to make up the hazes on Titan. We have conducted laboratory experiments simulating photochemical haze production on Titan and early Earth. The resulting aerosols are analyzed using an Aerosol Mass Spectrometer (AMS) to obtain compositional information and extinction cavity ring down (CRD) spectroscopy to determine the optical properties of the particles. The hazes on the two worlds will be compared and the implications of haze on the climate and habitability of ancient Earth will be discussed.

What have we learned about organic aerosol sources and processing? What’s next?

Jose-Luis Jimenez

Dept. Chem & Biochem., and CIRES, CU-Boulder

Abstract

Aerosols play major roles in climate forcing and the hydrological cycle, and also on human health effects, visibility degradation, and deposition of acids, toxics, and nutrients to ecosystems. Organic aerosols (OA) account for a large fraction (~50%) of ambient submicron aerosol mass, but their sources and transformation processes are still poorly understood. I will summarize recent findings about the sources, processing and budget of OA arising from multiple field and lab studies, as well as comparisons to 1D and 3D models. OA from all sources evolves in the atmosphere by becoming more oxygenated and hygroscopic and less volatile, and partially losing the chemical signature of the original source and gaining a common signature of atmospheric oxidation. Secondary OA (SOA) formation in urban areas is greatly underestimated by traditional models, in contrast with biogenic SOA formed under pristine conditions which is reasonably predicted. New models close the gap and even exceed the observed SOA in urban areas, but it is not clear whether this is for the right reasons. Further progress necessitates more complete high-quality measurements at one location as well as new measurement & analysis techniques, and we are preparing for two such campaigns in Los Angeles, CA in 2010 and Manitou Springs, CO in 2011.

MONDAY, September 28, 2009

4:00 p.m. CIRES Auditorium University of Colorado, Boulder

Water and photon mediated chemistry relevant to atmospheric aerosol formation

Veronica Vaida

Dept. Chem & Biochem., and CIRES, CU-Boulder

Abstract

Research in the Vaida group explores the interface between physical chemistry and atmospheric science using tools of spectroscopy, photochemistry and photoreaction dynamics. This presentation will exemplify discuss water catalyzed photochemical reactions of oxidized organic species (acids, alcohols, aldehydes and ketones) relevant to atmospheric chemistry. Our approach utilizes electronic and vibrational spectroscopy to explore chemical reactions. Theoretical modeling in collaboration with the skodje group elucidates the roles of cluster conformation and dynamical effects in the photochemical processes. The specific example of methyl glyoxal, and pyruvic and glyoxilic acids and of their hydrates will be presented. The discussion will point to the role of water and photon mediated chemistry of organic molecules to the generation and processing of secondary organic aerosols and, more generally, to climate.

Instrument development for use in field and laboratory experiments in the ATMOSpeclab

Rainer Volkamer

Dept. Chem & Biochem., and CIRES, CU-Boulder

Abstract

The Atmospheric Trace Molecule Spectroscopy Laboratory (ATMOSpeclab) was established in 2007 at CU Boulder to develop and apply optical spectroscopic instruments to measure atmospheric composition of reactive trace gases in polluted urban, and pristine natural atmospheric environments. Specific atmospheric chemistry projects in the ATMOSpeclab will be discussed, and include: - Impact of halogen chemistry on Mercury deposition in the coastal environment - Airborne MAX-DOAS from research aircraft - Ship based MAX-DOAS in the Southern Hemisphere Pacific Ocean - Laboratory studies of SOA formation from glyoxal in simulation chambers - Development of a detailed model to represent SOA formation via the aerosol aqueous phase

MONDAY, September 21, 2009

4:00 p.m. CIRES Auditorium University of Colorado, Boulder

CU Inhalable Dry Powder Vaccines have Provided Protection Against Infection

R. Sievers, S. Cape, J. Burger, D. McAdams, J. Manion, L. Rebits, S. Winston, B. Quinn, J. Searles, D. Krank, P. Bhagwat, P. Pathak, A. Genosar, R. Dhere, V. Vaidya, R. Muley, D. Griffin, W-H Lin, and P. Rota

Abstract

Protection against infection with measles virus has been demonstrated in animal models immunized 14 months earlier by inhalation of CU-invented dry powder vaccine microparticles. Needle-free aerosol delivery of dry powder vaccines may provide an effective and low-cost means of immunization. Powder manufacturing with gentle, rapid drying by Carbon Dioxide Assisted Nebulization with a Bubble Dryer (CAN-BD) appears to be an attractive alternative to freeze drying of sensitive biologicals like live attenuated Edmonston-Zagreb measles virus vaccine. Stability of measles virus in glassy, dry, respirable microparticles made by CAN-BD with less than 1% water sealed in unidose aluminum foil has been demonstrated. The dry powder aggregate, upon dispersion from an active dry powder inhaler, deposits in the moist respiratory tract where the microparticles rapidly dissolve within minutes. Antibiotics are also being studied and delivered as microparticles against infectious diseases.

Funded by FNIH Grant 1077.

Improving the Performance of Li Ion Batteries Using Atomic Layer Deposition

Steven M. George

Depts. of Chemistry and Chemical Engineering University of Colorado, Boulder, CO 80309 Steven.George@Colorado.Edu

Abstract

Lithium ion batteries (LIBs) are emerging as the dominant power source for portable electronics. Improvement in their capacity lifetime during charge-discharge cycles must be achieved before LIBs can be used for plug-in-hybrid and electric vehicles. LiCoO2 and graphite are common cathode and anode materials, respectively, for LIBs. The capacity loss of LIBs is linked to electrode deterioration caused by interfacial reactions with the electrolyte, dissolution of the metal oxide cathodes and structural instabilities caused by volume expansion during lithium intercalation. Atomic layer deposition (ALD) is based on the strategy of sequential, self-limiting surface reactions to deposit inorganic materials. ALD can deposit thin, conformal films on cathode and anode materials in LIBs to provide chemical protection, restrict dissolution and stabilize structural changes. Our recent work has demonstrated that ultrathin Al2O3 ALD films can improve the capacity stability of LiCoO2 cathodes and graphite anodes. Additional work is developing new protective coatings that will serve as an artificial solid-electrolyte interphase (SEI) for further stability improvement.

MONDAY, September 14, 2009

4:00 p.m. CIRES Auditorium University of Colorado, Boulder

Renewable and Sustainable Energy Institute (RASEI): What does this mean for the Dept. of Chemistry and Biochemistry (and other departments and institutes)?

Carl A. Koval, Co-Director

Abstract

In June 2009, the University of Colorado’s Board of Regents approved the formation of a new campus institute: RASEI (pronounced ‘racy”). This formation of this institute grew out of the former CU-Boulder Energy Initiative (EI), which was created in early 2006. In addition, administrators at CU-Boulder and the National Renewable Energy Laboratory (NREL) in Golden signed a MOU to operate RASEI as a joint institute. In this presentation, I will focus on:

• the transition of the EI to RASEI, from initiative to institute;

• opportunities for faculty to be involved in RASEI governance and programs;

• opportunities for students to be involved RASEI’s research, teaching, commercialization and outreach activities.

For more information about RASEI, go to http://rasei.colorado.edu.

Research at the Interface of Nanoscale Materials and Biology

Daniel L. Feldheim

Dept. Chem & Biochem., CU-Boulder

Abstract

Between the size scale of individual biomacromolecules and cellular organelles lies a size regime―the few nm to 100 nm range―that is not readily probed using existing technologies. Thus, while a vast inventory of RNA and protein sequences and structures are being catalogued, a quantitative cellular context for these structures is lagging. Yet to understand this context would be to know how collections of individual macromolecules assemble into the dynamic machines that form a living cell. Once these interactions are revealed, a new picture of the cell and its disease states is sure to emerge.

With achievable 2 nm resolution and perfect preservation of cellular structure, electron tomography (ET) now represents the highest resolution technique for examining biomolecules in their native cellular context. Indeed, cell biologists now dream of generating 3D images containing the entire proteome of a living cell. This dream remains out of reach, not because ET cannot visualize individual proteins, but because it is simply not possible currently to know which protein is which in a tomographic cellular reconstruction.

This presentation will describe methods being developed in our lab for creating electron dense nanoparticle tags for identifying cellular biomolecules by ET. These methods rely on the discovery of materials ribozymes and enzymes―RNA and protein/peptide sequences that can catalyze the formation of inorganic nanoparticles and control nanoparticle growth. The isolation and structure-function relationships of a number of materials ribozymes and enzymes will be shown.

In addition to visualizing biomolecule interactions in cells, we are working on ways to mimic and disrupt such interactions for disease treatment. We view this largely as a materials problem as well, and have been learning how to design metal nanoclusters to effectively interact with cellular biomolecules. A few lessons learned in our studies of cell and nuclear targeting and the prevention of viral infection will be described.

THURSDAY, September 10, 2009

4:00 p.m. CIRES Auditorium (note change of location) University of Colorado, Boulder

What controls the diurnal variability of carbon dioxide and reactive species? (a.k.a. "Boundary Layers for Chemists")

Jordi Vilà-Guerau de Arellano Meteorology and Air Quality Section Wageningen University (The Netherlands) e-mail: jordi.vila@wur.nl http://www.met.wau.nl/medewerkers/vila/index.html

Abstract

We examine the main physical and chemical processes that determine the diurnal variability of atmospheric compounds in the boundary layer. In addition to surface processes, turbulent mixing and reactivity, we put special emphasis on investigating the role of the exchange of heat, water and chemical species between the free troposphere and the atmospheric boundary layer, namely the entrainment process. This process enhances the dilution of compounds and introduces free tropospheric air masses with different characteristics into the atmospheric boundary layer.

In the seminar, I will discuss several cases where entrainment plays a major role in the evolution of atmospheric compounds. By analyzing observational evidence or performing numerical experiments by the large eddy simulation technique and a conceptual (mixed-layer theory) model, we are able to find the contribution of entrainment to the diurnal variability of carbon dioxide or isoprene. Particular emphasis is placed on the need to maintain a balance in dynamic processes and the specific characteristic of each atmospheric compound.