Applications of Infrared Synchrotron Radiation Workshop

Abstracts

The Canadian Consortium for Synchrotron Infrared Spectroscopy: Who, What, When, Where and Why?

Thomas Ellis

Members of the Canadian scientific community are in the process of building an important new research facility, the Canadian Light Source. This is Canada's first synchrotron.

From the beginning of this project, a high priority has been given to the infrared applications of synchrotron light. This is partly because Canada has a long tradition-and an enormous pool of expertise-in the area of infrared spectroscopy. Further, synchrotron infrared spectroscopy offers significant advantages for measuring complex systems.

In this presentation, the basic concepts of synchrotron light and its particular advantages in the infrared region will be presented. Subsequent speakers will expand on this subject. In addition, I will describe the capabilities of the infrared beamlines that are currently being built in Saskatoon, and I will discuss the opportunities that are available for new users.

High-Resolution Far Infrared Spectroscopy at the CLS

Wolfgang Jaeger

Synchrotron radiation finds most of its uses in short wavelength regimes, where laser sources are either extremely complex, or not available at all. However, there is also a lack of convenient coherent and tunable sources in the far infrared region of the electromagnetic spectrum. Synchrotron radiation promises to be a viable alternative in this range, which has been termed the "dark spot" of the electromagnetic spectrum.

In this presentation, the properties of far infrared synchrotron radiation will be described and compared with the properties of radiation from incandescent sources.

This will be followed by a report about the design and the current status of the High Resolution Far Infrared Beamline at the CLS, and a description of the proposed endstation.

Using this beamline, new experiments on a variety of molecular systems will be possible. The final part of this presentation will give an overview of the proposed experiments.

Photoacoustic Infrared Spectroscopy

Kirk Michaelian

Photoacoustic (PA) infrared spectroscopy allows the characterization of a wide variety of samples, but avoids the traditional infrared sample preparation techniques. For solids, this means that grinding is not required: samples are analyzed as received, and do not need dispersion in infrared-transparent diluents. Moreover, samples can be opaque solids or liquids, because there is no requirement that the sample transmit a fraction of the incident radiation. Dispersions, pastes and films can also be examined.

Another major advantage of PA infrared spectroscopy exists in its inherent capability for restricting sampling depth. This enables depth profiling-at distances on the order of micrometres-of layered or inhomogeneous solids. PA infrared profiling may be of interest in studies of surface oxidation, catalysis, and interfacial phenomena.

The elimination of sample preparation in infrared spectroscopy creates many new opportunities for the analysis of difficult or unusual samples. PA infrared spectra have been obtained at the CANMET Western Research Centre for a number of solids and liquids, including the following: hydrocarbons (coals, cokes, bitumens, middle distillate fuels); metal powders; wood products (wood chips, paper, sawdust); clays and clay complexes; and carbon-filled rubber. Representative PA infrared spectra of some of these substances are presented in this seminar.

PA infrared spectroscopy has recently been implemented using synchrotron radiation instead of a thermal infrared source. Synchrotron PA infrared spectra are more intense than the analogous spectra obtained with a thermal source in some circumstances. This presentation will show that a synchrotron source tends to be preferable for longer wavelengths and for smaller beam (or sample) sizes.

Synchrotron IR in Medical Research

Kathy Gough

The purpose of this seminar is to provide an overview, with examples, of ways in which synchrotron infrared (IR) spectroscopy may be used to study biomolecules, both in vitro and in situ. This well-established technique is based on the concept that the atoms and bonds of a molecule behave like small masses connected by springs. When illuminated with light of the right energy, these "springs" can absorb photon energy and begin to vibrate (stretching, bending and rocking). In general, the energy range required to excite molecular vibrations for most molecules is the mid-infrared portion of the spectrum. The specific energy required for any given vibration is dependent on the masses of the atoms and the strength of the bond connecting them, as well as the type of vibration. Specific functional groups (for example, carbonyl, amide, glucose ring) are known to exhibit common absorption patterns. Every unique molecule exhibits a unique overall pattern, or fingerprint.

Because of their complexity, (the size, structure and variety of molecules), it might be anticipated that biological samples would be poor candidates for IR analysis. In practice, this is most definitely not the case. Moreover, when the source of the IR illumination is the extremely bright light provided by a synchrotron, it is possible to obtain an excellent IR spectrum on the order of 10 x 10 microns. Untreated tissue may be mapped for the presence of specific functional groups or conformations. The tissue is not damaged by this low energy light; thus, secondary analyses of the same tissue may be performed.

Recent data on IR mapping of molecular changes in diseased tissue (Alzheimer-diseased brain tissue and cardiomyopathic heart tissue), as well as examples of other types of studies (lipid plus protein in aqueous solution, and bacteria) will be presented, with a survey of techniques, possibilities and limitations.

Biological, Medical, and Environmental Applications of Synchrotron Infrared Micro-Spectroscopy

Lisa Miller

Infrared (IR) micro-spectroscopy is an excellent technique for examining the inherent chemical makeup of biological cells and tissues. Synchrotron infrared light is an ideal source for infrared micro-spectroscopy due to its high brightness and broadband nature. These characteristics permit the collection of high signal-to-noise spectra through small apertures (3-5 microns in the mid-infrared region) and optically dense samples (0.1 % transmission). Thus, by using infrared light from a synchrotron, we are able to chemically image samples that are too small or too thick to examine with a conventional globar IR source.

In this talk, biological, medical, and environmental applications of synchrotron infrared micro-spectroscopy will be presented. Topics will include: (1) the role of bone chemical composition in osteoarthritis and osteoporosis; (2) tissue composition and tumor growth in skin cancer; (3) enzyme structure and biopolymerization; (4) differences in single cell chemistry during mitosis, necrosis, and apoptosis; (5) plant root composition for bioremediation; and (6) soil content and poly-cyclic aromatic hydrocarbon (PAH) uptake.

This work was performed at Beamline U10B at the National Synchrotron Light Source, Brookhaven National Laboratory. Scientific personnel on these projects include: Cathy Carlson (U. of Minnesota); David Hamerman, Mark Chance, and Raymond Huang (Albert Einstein College of Medicine); David Burr (Indiana U.); Silvina Federman and Irit Sagi (Weizmann Institute); Ying Mei and Richard Gross (Polytechnic U.); Paul Dumas, Nadege Jamin, and Jean-Luc Teillaud (LURE and Institute Curie- Paris); Mark Furhmann (BNL); Upal Ghosh (Stanford U.).

More information on the infrared programs at the NSLS can be found at http://www.nsls.bnl.gov/beamlines/infrared.

Vibrational Circular Dichroism

Helmut (Hal) Wieser

Vibrational circular dichroism (VCD) is a spectroscopic technique which uses circularly polarized infrared light to extract information about the three-dimensional structure of chiral molecules. This technique is unique in that the chiral molecules are studied according to their characteristic vibrations.

Specifically, vibrational circular dichroism (VCD) is a spectroscopic technique that measures the differential absorption of left versus right circularly polarized infrared light.

Similar to electronic circular dichroism (CD), VCD provides information on the stereochemical structure of a chiral sample in solution. Although the signal is generally a few orders of magnitude smaller than that obtained from CD, VCD has the advantage that it is applicable to a wider range of molecules.

VCD spectra complement the parent absorption spectra from which they originate, yet also provide additional information that is not available through traditional FT-IR spectroscopy. VCD spectroscopy can differentiate between enantiomers.

The aims of this research are twofold: one is to provide insight into chiral systems and chiral environments, and the other is to advance the development of the necessary instrumentation. The research that has recently been undertaken in this laboratory includes the following:

The study of small to medium sized chiral molecules
The study of biological systems such as DNA
The study of optically active polymers

However, any system that possesses asymmetry may be a candidate for future research projects. Potential areas of research may include applications of VCD to pheromones, pharmaceuticals, molecular recognition, and asymmetric syntheses. Additional areas include research on VCD instrumentation and computation techniques.

The Canadian Light Source - Opportunities for Alberta

Ken Schmidt

The first synchrotron in Canada is now under construction: this is the Canadian Light Source (CLS) at the University of Saskatchewan in Saskatoon. A wide variety of Alberta researchers will be well situated to utilize this national facility when it is commissioned in 2003. This synchrotron will be a $173.5M advanced technology facility producing extremely bright light to investigate the nature and structure of molecules.

An initial Alberta capital investment of $9.2M in the project will facilitate timely Alberta access to the initial suite of synchrotron beamlines. Beamlines are individual laboratory facilities attached to the synchrotron ring, each specialized for synchrotron light applications in a particular research discipline.

The Alberta funding will assist in the construction of two essential components of the Canadian Light Source, a protein crystallography beamline and an X-ray microprobe beamline.

Protein crystallography is the state-of-the-art technique for determining the 3D structures of large biological molecules. It has direct applications to biomedical and pharmaceutical research.

The X-ray microprobe will allow detailed and specific chemical analysis of microscopic areas of many kinds of samples. This is relevant to a variety of industries, including oil and gas, oil sands, mining, petrochemicals, pipelines, mineral exploration, microchip manufacturing, micromachining, and advanced materials.

The remainder of the initial suite of CLS beamlines will also be discussed.

The Alberta Synchrotron Institute (ASI) will invest more than $5.1M in operating money over the next five years to coordinate Alberta interests in developing synchrotron science applications. The ASI's mandate is to expand Alberta's awareness and expertise in synchrotron science, to assist Alberta scientists in accessing synchrotron technology, and to encourage local industries to make use of the CLS. The ASI will also provide a liaison between university researchers, government laboratories, and industry.

Speakers

Thomas Ellis

Département de chimie, Université de Montréal

Thomas Ellis obtained his Ph.D. at the University of Waterloo in 1984, and now is a professor of chemistry at the Université de Montréal.

His area of expertise is the application of vibrational spectroscopies (infrared, Raman, electron energy loss) to the study of materials and surfaces. His current research interests include self-assembled systems, the surfaces of biological materials, dental materials and dental adhesives.

Wolfgang Jaeger

Department of Chemistry, University of Alberta

Wolfgang Jaeger grew up in the northernmost part of Germany. He graduated with a Diploma in Chemistry from the Christian Albrechts University, Kiel, Germany, in 1985. He continued with Ph.D. research in the area of high-resolution molecular spectroscopy under the supervision of Professor H. Mäder at the same school. Following his thesis defense in 1989, he spent one year as a postdoctoral fellow at the University of British Columbia with Professor M. C. L. Gerry. After a short stay at the University of Cologne, he returned to Vancouver as a Research Associate. Dr. Jaeger has been a faculty member of the Chemistry Department at the University of Alberta since 1995.

Wolfgang Jaeger's research interests center around the theoretical characterization of weak intermolecular interactions. His research group uses a combination of molecular beam and high-resolution spectroscopic techniques for experimental and computational approaches. A further interest of his research group lies in the application of spectroscopic techniques to environmental trace gas monitoring.

Kirk Michaelian

CANMET Western Research Centre, Devon, AB

Kirk Michaelian obtained his Ph.D. at Simon Fraser University in 1976. After post-doctoral research at the Universities of Toronto and Alberta, he joined CANMET in 1981. He is now a senior research scientist at the CANMET Western Research Centre, a regional laboratory of Natural Resources Canada.

Dr. Michaelian's research is primarily concerned with photoacoustic infrared and Raman spectroscopies, and the application of these methods to the characterization of hydrocarbon fuels. He has utilized photoacoustic spectroscopy in the study of clays and a variety of other materials. Numerical methods-including signal averaging, phase correction, deconvolution, and curve fitting-have also been investigated.

Kathleen M. Gough

Department of Chemistry, University of Manitoba

Dr. Gough graduated with her Ph.D. from the University of Manitoba in 1984. Her thesis work, supervised by Dr. Bryan Henry, studied near IR CH stretching overtone spectroscopy of small gas-phase hydrocarbons, including substituted aromatics.

From 1984-86, she was at the NRC in Ottawa as a Research Associate, Molecular Spectroscopy, under Dr. William Murphy. Research work included measurement of Raman trace scattering intensities of alkanes, force field analyses, and intensity parameterization.

From 1987-89, she furthered her studies as an NSERC post-doctoral fellow under Professor Richard Bader, Department of Chemistry, McMaster University. Her research projects included a theoretical analysis of Raman trace scattering intensities with the theory of atoms in molecules.

Her first university appointment was as an assistant professor in the Chemistry Department at Brock University (1990-95). This was followed by her current appointment in the Chemistry Department of the University of Manitoba.

Dr. Gough's research interests include experimental and theoretical studies of vibrational intensities in IR, and near IR and Raman spectroscopy (hydrocarbons and organometallics). Directly relevant to the present workshop are her interests in synchrotron IR spectromicroscopy of biological tissues. Research projects include studies of brain tissue (Alzheimer's disease), cardiac tissue (cardiomyopathy, aging), and the formation of scar tissue (bone).

Timothy May

Canadian Light Source Inc., Saskatoon, Saskatchewan

Tim May is the beamline scientist for the Infrared Facility at the CLS. He obtained his B.S. in Physics at the University of Wisconsin, Platteville, in 1977, and his M.S. in Physics at Case Western Reserve University, Cleveland, in 1979.

Dr. May was employed at Nicolet Instruments (Madison, WI) for twelve years in various engineering positions, from field service to manufacturing and system design of Fourier Transform Infrared (FTIR) spectrometers; he developed fiber optic interfaces and sampling probes for FTIR, as well as an acousto-optic tunable filter spectrometer. Subsequently, he worked with Millipore Extrel FTMS (Madison, WI) as a manufacturing engineer on laser desorption and external ion sources for mass spectrometry. He also worked at Pike Technologies (Madison, WI) as a system designer of VIS-NIR spectrometers and IR reflectance interfaces for FTIR.

In 1994, Dr. May was hired to design and build the first infrared beamline at the Synchrotron Radiation Center (SRC) at the University of Wisconsin, Madison; this beamline was commissioned in 1996 for diffraction-limited micro-spectroscopy in the mid-infrared range. He became a consulting engineer in optical spectroscopic instrumentation, and worked on the design and construction of the SRC far-IR branch line that was added in 1999.

Since 2000, Dr. May has been employed at the Canadian Light Source to develop, design and help construct their infrared beamlines and facilities. He assists the Canadian infrared community in performing synchrotron-based academic and industrial research, communicates with beamline users to determine research needs in synchrotron instrumentation, collaborates in research where possible, and performs independent research. His research areas include optical design, opto-mechanical development, and spectroscopic instrumentation.

Lisa M. Miller

National Synchrotron Light Source, Brookhaven National Laboratory, Upton, NY, USA

Dr. Lisa Miller is a biophysical chemist at the National Synchrotron Light Source at the Brookhaven National Laboratory (BNL) and a Visiting Assistant Professor in the Department of Medicine at Albert Einstein College of Medicine. She obtained her B.S. in Chemistry from John Carroll University (Cleveland, OH) in 1989, her M.S. degree in Chemistry from Georgetown University (Washington, DC) in 1992, and her Ph.D. in Biophysics from the Albert Einstein College of Medicine (Bronx, NY) in 1995. Her Ph.D. research involved using X-ray and infrared spectroscopies to study the binding of oxygen and carbon monoxide to hemoglobin and myoglobin.

After graduating, Dr. Miller worked at the Lawrence Berkeley National Laboratory (Berkeley, CA), where she used soft X-ray absorption spectroscopy at the Advanced Light Source to probe the manganese ions in photosynthesis. Dr. Miller returned to the east coast in 1997 when she took a faculty position at the Albert Einstein College of Medicine. She worked in collaboration with scientists at Brookhaven National Laboratory using synchrotron light to develop new micro-spectroscopic tools to study biological and medical problems.

In 1999, Dr. Miller became a staff scientist at BNL, where she is currently focusing on the applications of synchrotron X-ray and infrared micro spectroscopies to diseases such as osteoarthritis, osteoporosis, and cancer.

Helmut (Hal) Wieser

Department of Chemistry, University of Calgary

Dr. Wieser received his B.Sc. from the University of British Columbia in 1962, and graduated with a Ph.D. from the University of Alberta, Calgary, in 1966. Currently he has positions at the University of Calgary both as a Professor in the Department of Chemistry and as an Associate Dean in the Faculty of Graduate Studies.

Vibrational circular dichroism (VCD) spectroscopy is at the centre of various research activities of Dr. Wieser's group. VCD in this context entails the use of existing theories, the development of modifications to these theories, and the measurement of experimental spectra. It further requires as an essential component the evaluation of molecular force fields, generally by ab initio computations and based on observed vibrational spectra.

Among VCD investigations that are currently in progress are the following:

Conformational changes in DNA molecules arising from interactions with various agents, such as drugs or hormones
Characterization and dynamic changes of polymeric materials as evidenced in VCD spectra of certain chiral subunits
Series of selected chiral monocyclic and polycyclic molecules, in particular those that are known insect pheromones

The aspects mentioned in the third point are being pursued as part of a major ongoing and long-term research program attempting to illuminate the molecular basis for the mechanism of olfaction, with specific reference to insect pheromone action. In particular, this involves the examination of biological activity of certain groups of pheromones by means of field and laboratory bioassays, and specifically includes the investigation of pheromone-mediated operational strategies for monitoring and manipulating forest insect pests.

Ken Schmidt

Alberta Synchrotron Institute; DK Cubed Scientific

Ken Schmidt is currently General Manager and Head of Outreach for the Alberta Synchrotron Institute, and Senior Consultant with DK Cubed Scientific. He is also the Supervisor for the Infrared Synchrotron projects at the Alberta Synchrotron Institute, and has extensive experience in the vibrational analysis of academic and industrial samples. Current research interests include the application of synchrotron-based IR microspectroscopy to the analysis of sulphur-mediated corrosion, and the use of X-Ray and vibrational spectroscopies to provide speciation information on the formation of polysulphide anions in industrial solutions.

Dr. Schmidt holds a Ph.D. in Inorganic Chemistry from the University of Calgary, and a Combined Honours B.Sc. in Chemistry/Biochemistry from McMaster University. Prior to helping to form and operate the Alberta Synchrotron Institute, he previously spent eight years in industry working on high-tech ceramics production, CVD coatings, sulphur chemistry, and industrial analytical development and implementation.

The Alberta Synchrotron Institute is a partnership of the three major Alberta Universities, dedicated to readying Alberta for the opening of the Canadian Light Source in early 2004. DK Cubed Scientific is a privately owned Alberta-based chemical consulting company, specializing in analytical and process development, and scientific communication and project management.