FOREWORDWelcome to the Midwestern Symposium on Undergraduate Research in Chemistry! This symposium is an opportunity for undergraduate scientists, who have been working diligently in their labs, to get together, present their results for the first time, discuss science with other excited researchers, and get a glimpse of the broader scientific community. We have a busy weekend planned, with two poster sessions, a series of talks covering a range of cutting edge research, and tours of various research facilities on the MSU campus. We hope that you will leave this weekend with renewed enthusiasm for your work, fresh ideas, and a new network of friends in science.

ORGANIZING COMMITTEEViktor V. Poltavets Assistant Professor Department of Chemistry Michigan State University E-mail: poltavets@chemistry.msu.edu

Benjamin G. Levine Assistant Professor Department of Chemistry Michigan State University E-mail: levine@chemistry.msu.edu

Joni Tucker Graduate Office Secretary Office: 382 Chemistry Phone: 517-355-9715 ext. 343  E-mail: tucker@chemistry.msu.edu

Joshua Davis Graduate Student Department of Chemistry Michigan State University

Scott Fales Graduate Student Department of Chemistry Michigan State University

MSU-R:CHEM has been made possible by the generous support of our sponsors:

• National Science Foundation (NSF DMR-1206718) • Department of Chemistry at MSU• College of Natural Science at MSU• Office of the Vice President for Research and Graduate Studies • Center of Research Excellence in Complex Materials• MSU Local Section of the ACS

EVENT LOCATIONS:FRIDAY

Presentations: Room 1410 BPS BuildingPoster sessions: Atrium, BPS BuildingDinner: Room 1400 BPS Building 

SATURDAYPresentations: Room 136 Chemistry BuildingPoster sessions: Chemistry Building 1st floor hallwayLunch:  The Gallery at Snyder/Phillips (~0.5 mi) or

Brody Square (~1.3 mi) dining halls

SCHEDULEFRIDAY, OCTOBER 5, 20123:30 – 5:00 pm Registration / Tour of Instruments

5:00 - 5:10 pm Welcome and Opening Remarks

5:10 - 5:40 pm Prof. Kevin Metz (Albion College) “Composites in a coffee pot”

5:40 - 6:00 pm Michael Kuszpit (Graduate Student, MSU)“One-Pot Synthesis of 2-Imidazolines via the Ring Expansion of Imidoyl Chlorides with Aziridines”

6:00 - 6:10 pm Group photo

6:10 – 8:00 pm Poster Session I (Undergraduate attendees)

8:00 – 9:30 pm Dinner

SATURDAY, OCTOBER 6, 2012 If you are staying at Gatehouse Suites or TownePlace Suites:

• a complimentary hot breakfast buffet is served beginning at 8:00 a.m. •you need to check out in the morning due to the busy Symposium schedule

9:30 - 9:50 am Behnaz Ghaffari (Graduate Student, MSU)“Regiospecific Ester Directed C-H Borylation: A Mechanistic Study”

9:50 - 10:20 am Graduate Student Panel / Ice Cream Get Together

9:50 - 10:50 am Faculty gathering (room 481)

10:20 - 11:30 am Poster Session II (presented by grad students)

11:30 am - 12:00 pm Prof. Benjamin Levine (MSU)“Applying Computation to Understand Non-Radiative Decay in Oxygen-Containing Silicon Clusters”

12:00 - 12:15 pm Presentation of Awards and Closing Words

12:15 pm Lunch

REGISTRATION AND PARKINGThe Registration Desk will be located in the Atrium of the BPS Building. The BPS Building and the Chemistry Building are connected. Enter the Chemistry Building and follow the signs to BPS.

Free parking permits will be provided at the Registration Desk. Parking is available in Lot 41 and the Shaw Lane Parking Ramp, right across S. Shaw Lane from the Chemistry Building. Parking permits are not needed after 6 pm, nor on weekends.

LIST OF PARTICIPANTS

Undergraduate Attendees

Name Affiliation Area Poster Board

Abbasi, Ramina DePaul University Analytical A1

Alkaabi, Mohammed University of Michigan-Dearborn Physical N/A

Banisafar, Arash Michigan State University Organic O1

Barres, Alexa The University of Michigan - Flint Organic N/A

Birdsall, David Ferris State University Organic O2

Bokhart, Mark Michigan State University Analytical A2

Buurma, Bradley Grand Rapids Community College Organic N/A

Clausen, Katherine DePaul University Analytical A3

Cogan, Dillon Michigan State University Organic O3

DePorre, Yvonne Michigan State University Organic O4

Dix, Michael Albion College Inorganic I1

Dymm, Braydon University of Detroit Mercy Analytical A4

Fini, Melika University of Illinois at Urbana-Champaign Physical P1

Groenenboom, Mitchell Calvin College Organic O5

Hutson, William The University of Chicago Physical P2

Jackman, Brianna Grand Valley State University Physical P3

Karp, Lindsey University of Michigan Organic O6

Kieser, Jerod Indiana University – Purdue University Fort Wayne Inorganic I2

Konja, Alexis University of Detroit Mercy Physical P4

Kruppe, Chris Albion College Analytical A5

Ludwig, Jake Michigan State University Organic O7

Mazer, Trent Grand Valley State University Physical P5

Moore, David University of Detroit Mercy Analytical A5

Orow, Branden University of Detroit Mercy — N/A

Parker, Kalia DePaul University Analytical A6

Phillips, Andrew University of Michigan Organic O8

Plath, Logan Adrian College, The University of Toledo Analytical A7

Polaskey, Brandon DePaul University Analytical A8

Name Affiliation Area Poster Board

Rozemberg, Jessica DePaul University Analytical A9

Sanders, Stephanie Albion College Analytical A10

Shephard, Logan University of Michigan - Flint Inorganic I3

Stroeters, Nicholas University of Detroit Mercy Analytical A11

Suchyta, Dakota University of Michigan Analytical A12

Talicska, Courtney University of Michigan – Ann Arbor Physical P6

Tenbusch, Chad Michigan State University Inorganic I4

Viola, Ciara University of Detroit Mercy Organic N/A

Voce, Allison DePaul University Analytical A13

Wirth, Katherine Hope College, Grand Rapids Community College Analytical A14

Zavesky, Blane University of Michigan Organic O9

Undergraduate Attendees (cont.)

Faculty Attendees

Name Affiliation

Benvenuto, Mark University of Detroit Mercy

Kingsley, Nicholas University of Michigan – Flint

Linn, Donald Indiana University – Purdue University Fort Wayne

Martic, Sanela Oakland University

Metz, Kevin Albion College

Roberts-Kirchhoff, Liz University of Detroit Mercy

Stevens, Jonathan University of Detroit Mercy

Plus many MSU faculty will be attending, as well.

Abstracts

A1Analysis of the Structural Changes of the Wild Type Peptide

(AB22-35) Using Attenuated Total Reflectance Infrared Spectroscopy and Ultraviolet Visible Spectroscopy

Ramina Abbasi, Sarah Zawadski , Sean Reinsalu, Elizabeth Rohn, and Dr. Sandra Chimon Peszek

DePaul University

Neurodegenerative disorders such as Alzheimer’s disease (AD) are perpetuated by the neurotoxicity created by amyloid formation and the misfolding of proteins. The accumulation of amyloid plaque demonstrated in AD-afflicted brains is caused by the neurotoxicity of beta-amyloid (Aß) fibril aggregation. The intermediates that have formed during these aggregations have resulted in the impaired synaptic function of neurons, particularly in the hippocampus region, and increased loss of neurons, resulting in cognitive dysfunction. Of particular interest to our research has been the accumulation of beta-sheets and of the beta amyloid peptide Aß(1-40) and Aß(1-42), specifically the Wild Type (WT) fragment Aß(22-35) that contains the ionic salt bridge. Our studies of this “hair pin” region have proven that the section is the site of notable structural changes that can be seen in the varying beta-sheet aggregation times of the WT, as compared to mutants on the residues of the “hair pin” region. Though the “KLVFFA” region has been widely studied as the shortest sequence which is able to form fibrils, we have found that the WT and single-point mutations such as the Iowa mutant (Aß(22-35) D23N) have produced similar results with regards to neurotoxicity and fibril formation. Using Attenuated Total Reflectance Infrared Spectroscopy (ATR-IR) and Ultraviolet Visible Spectroscopy (UV-Vis), we have monitored the structural changes in the peptide samples from random coil to beta-sheet. Because the nature of the Congo Red dye used in the UV-Vis trials relies upon pentimirical binding to the aggregated fibrils, we confirmed that the secondary structures that are present in the peptide are beta-sheets and have been able to monitor their accumulation to determine their peak hours of fibrillization. Our methods of identifying and observing the structural changes and behaviors of fibril formation in the WT Aß(22-35) and related mutants have enabled our work to focus on the amyloid plaque at a magnified level using a technical approach that few others have attempted.

A2Validation of QuEChERS Based Extraction for the Determination of

Organochlorine Pesticides in Liver and Serum using GC-MS/MSMark Bokhart ¹, Andreas Lehner ², Margaret Johnson ², John Buchweitz ²

¹ MSU Chemistry Department; ² MSU, College of Veterinary Medicine, DCPAH

Organochlorine pesticides are chemically stable, have low volatility, and low rates of degradation which leads to their persistence in the environment and classification as a persistent organic pollutant (POP). Organochlorines bioaccumulate and biomagnify in animals at higher trophic levels due to their high lipid solubility. These compounds affect the nervous system of the target organism. The mechanism of action involves the disruption of chemical ion movement in neurons but the major pathologic changes are observed in the liver and reproductive systems. Michigan State University Diagnostic Center for Population & Animal Health has developed and validated a quantitative fast extraction QuEChERS method for 24 organochlorine analytes in liver tissue and blood serum. Identification and quantitation of the 24 compounds is by gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS). Depending on compound and matrix, the limits of detection vary from 0.1-7.4 ppb. Compared to other multiresidue methods for trace pesticides, the QuEChERS extraction method has many advantages including use of smaller sample size, higher throughput of samples, and less solvent used per sample leading to less cost and greater safety.

A3Can Melatonin Help Prevent Alzheimer's Disease?

Katherine Clausen, Lianna Di Maso, Kalah Bermudez, Shannon Naughton, and Dr. Sandra Chimon-Peszek

DePaul University

In previous studies, the orthomolecular species melatonin has been found to have a tremendous impact on the β-amyloid peptide that causes Alzheimer's disease. Melatonin has been shown to inhibit oxidative stress and the death of neurons and neuroblastoma cells exposed to the peptide. The purpose of research on an orthomolecular species such as melatonin is to determine how the chemical substance reacts with a disease or abnormality by restoring proper levels of the chemical substance in the brain. The first step in the process of researching the effects of melatonin on the Alzheimer’s β-amyloid peptide is to make melatonin water soluble. Studies suggest that melatonin powder can become water soluble when mixed with water at 20 °C or 50 °C. Studies have also shown that melatonin is soluble in ethanol. This study utilized all three techniques to create melatonin solutions. Melatonin in a fine powder was added to water at 20 °C, water at 50 °C , and ethanol at 20 °C. All three of the solutions were centrifuged in order to gather only the water soluble aspects of the melatonin solutions. The melatonin concentration of each solution was determined by using a calibration curve. The calibration curve was created by using a UV/vis machine to measure the absorbances of serially diluted solutions with known concentrations made from pure melatonin. The presence of melatonin in each solution was confirmed using ATR-IR spectroscopy by comparing the spectra of each solution to a melatonin reference spectra. Each solution was then combined with the β-amyloid peptide and Congo red and measured in the UV/vis machine for a week. Each solution was combined with the β-amyloid peptide and measured with ATR-IR for a week. The data was then analyzed and compared to solutions with β-amyloid peptide and no melatonin.

A4Automated Liquid Chromatography-Mass Spectrometry System for

Continuous Monitoring of Neurotransmitters and ProteinsDavid C. Moore, Braydon L. Dymm, Lina A. Basal, Alyssa V. Colbert, Joshua J. Eby, Braden D. Iveson, Enas Karim, and Kendra R. Evans

University of Detroit Mercy

Biological molecules throughout the body respond to both external and internal stimuli in a dynamic manner. For example, recent evidence suggests rhythms or cycles exist in the secretion and uptake of endocrine hormones such as insulin and leptin. These rhythms are of particular interest because biological cycles are believed to have an important role in regulating the drive to eat, and changes in the rhythms may be associated with metabolic conditions such as diabetes and obesity. Alterations in levels of neurotransmitters such as dopamine, serotonin, and adenosine have been implicated in addiction and in numerous diseases, such as depression, schizophrenia, Parkinson's, and Alzheimer's. The conventional methods for monitoring hormones and neurotransmitters often involve fraction collection and are time- and labor-intensive. To enable closer study of biomolecule dynamics, it is important to use reliable, rapid methods of monitoring multiple compounds simultaneously. We have developed a liquid chromatography-mass spectrometry-based method for automated sampling, injection, and detection of multiple analytes. The system employs a 10-port switching valve for computer-controlled injections and can be coupled to in vitro or in vivo sampling systems for continuous online injection and detection of biomolecules.

A5Analyzing the Effects of Varied Shapes on Catalytic Activity of

Palladium Nanoparticles Attached to Carbon SupportsChris Kruppe & Dr. Kevin Metz

Albion CollegeThe use of nanoparticles in catalytic applications is well established. There has been a growing interest in the use of shaped nanoparticles, including nanocubes, for catalysis because they often display selectivity and can be used for asymmetric catalysis. One drawback in the use of nanoparticles for catalysis is removing the particles from the reaction mixture. Often, this is alleviated by first synthesizing the nanoparticles and then incorporating them into or onto a micro or macro sized support. This approach, however, is a two step process which can be difficult and time consuming. Our lab is interested in synthesizing shaped nanoparticles anchored directly onto supports, specifically, palladium nanocubes on graphite. Currently SEM characterization has established that we have developed a reproducible method for synthesizing these nanoparticles (Figure 1). Here, we report a comparative study on the catalytic effects of shaped nanoparticles as a catalyst in the Suzuki coupling reaction. The Suzuki coupling reaction produces a carbon-carbon bond by combining an aryl- or vinyl- halide with an aryl- or vinyl- boronic acid over a palladium catalyst. This reaction is advantageous since it can be done at room temperature in polar solvents. The results of a model Suzuki reaction bromotoluene and phenylboronic acid, in various solvents (DI H2O, MeOH, EtOH, and (1 : 1) EtOH : DI H2O), as determined by GC-MS will be presented.

Figure 1

A6Curcumin Solubility and its Effect on Alzheimer's Disease

Kaila Parker, Julia Justusson, Luke Mochaitis, Raymond Wenk, Katherine Clausen, and Dr. Sandra Chimon Peszek

DePaul UniversityAlzheimer's disease is a degenerative disorder where plaque forms in the brain and a protein unbinds from microtubules, causing neurons to stop sending signals to the brain and body and die. This fatal disease can hit as early as age 40 and is irreversible.

Several studies have tested the efficacy of the natural ingredient curcumin to delay the occurrence of this Alzheimer's. Curcumin is the yellow pigment of the root turmeric, a member of the ginger family. Curcumin has been named “Indian gold” for all of its healing abilities. It has been used to treat arthritis, cancer, and as an anti-inflammatory agent and antioxidant. Curcumin’s status as an anti-inflammatory is important to Alzheimer's prevention because studies have shown that inflammation may increase the degenerative outcomes of the disease. However, Curcumin’s full pharmacological potential is hindered by its solubility in water. Our goal is to successfully find a method to make curcumin dissolve in aqueous solution. After extensive investigation, we hypothesized that heating a solution of curcumin and water would be the best technique to increase the solubility of our orthomolecular species. To aid in determining the concentration of curcumin in water we will initially create a standard curve of the absorbance of serial dilutions of curcumin in ethanol.To test curcumin’s effectiveness on preventing fibril formation, curcumin will be mixed in solution with Congo Red, the beta-amyloid peptide, and a phosphate buffer. This will be analyzed using the UV-visible spectrophotometer. The curcumin solution with peptide will be analyzed using the ATR-IR spectrophotometer.

A7The Combined Use of Mass Spectrometry and

X-ray Crystallography for the Complete Determination of the Primary Sequence of Lion Hemoglobin

Logan D. Plath1,2, Jingshu Guo2, Wendell P. Griffith2

1Adrian College and 2The University of Toledo

Here we present the complete amino acid sequence of Lion (Panthera leo) hemoglobin (Hb) determined using a combination of electrospray ionization mass spectrometry (ESI-MS) and X-ray cryatallography. Mass spectrometry alone was able to provide 82% and 72% sequence coverage for the a- and the β-globin chains of lion Hb, respectively. The incomplete mass spectrometry-determined sequences were used in the processing of X-ray diffraction data of lion Hb crystals solved to 2.0 Å. By using tandem mass spectrometry and the electron density maps from the X-ray structure, we were able to achieve 100% sequence coverage for both globin chains. One advantage of this combined approach is that we were also able to distinguish between isomeric (leucine and isoleucine) and isobaric (glutamine and lysine) residues. These results demonstrate and highlight the synergy between mass spectrometry and X-ray crystallography for full amino acid sequence determination of abundant proteins and protein complexes. Mass spectra were collected at the University of Toledo on a Synapt HDMS, a nano-electrospray ionization quadrupole time-of-flight mass spectrometer from Waters Corp.; or the UltrafleXtreme, a matrix-assisted laser desorption/ionization tandem time-of-flight mass spectrometer from Bruker Daltonics. X-ray diffraction data for lion cyanomethemoglobin crystals was collected at the Advanced Photon Source at Argonne National Laboratory in Lemont, IL. The National Science Foundation-funded Research Experience for Undergraduates Program at the University of Toledo supported the work completed in this project.

A8The Effects of Alcohol on the Alzheimer’s Peptide, Aβ (22-35).

Can we Drink and Prevent Alzheimer’s Disease?Brandon Polaskey, Luke Mockaitis, Cassandra Shah, and Dr. Sandra Chimon Peszek

DePaul University

Alzheimer’s disease (AD) is characterized by the toxic accumulations of misfolding amyloid proteins in the extracellular region of the brain. Toxic amyloid plaque build up is also found in other neurodegenerative diseases, such as Parkinson’s and Huntington’s. AD is characterized by the excessive production and deposition in senile plaques. The intermediate species involved, are seen in the amyloid beta peptides (Aβ) (1-40) and Aβ (1-42). This intermediate species has shown high neurotoxicity which is presumed to cause the neurodegeneration of the brain in people with AD. The Aβ fragment 22-35 is the fragment utilized for this research from the wild-type mutant because it contains a hairpin turn and a salt bridge. Alcohol was utilized in this experiment to determine if it is able to slow the rate of accumulation of amyloid fibrils. Recent studies have shown that moderate drinking decrease the chance of Aβ neurodegeneration due to preconditioning. These studies give us hope that this, combined with other treatments, will be an effective treatment for AD.

A9Can Milk Thistle Prevent Alzheimer’s Disease?

Jessica Rozemberg, Devyn Kahl, Belinda Dagaas, and Dr. Sandra Chimon Peszek1

DePaul University

Large deposits of amyloid beta plaques have been found in brains affected with Alzheimer's disease. Studies have shown the amyloid beta peptide intermediate has higher neurotoxicity than the plaques, and if misfolding of the fibrils can be prevented then Alzheimer's can be prevented or slowed (2).  In this study, we will increase the solubility of silymarin by defatting it via extraction of milk thistle capsules and seeds with a Soxhlet.  The experimental groups with the most pure silymarin sample will be tested for water If successful,, the effect of silymarin binding to the peptide will be studied in PC12 rat brain cells to see if slows or stops fibril formation thus helping prevent Alzheimer’s.

A10Shaped Palladium Nanoparticle Synthesis on Carbon Substrates

Stephanie Sandersa, Paul Duffyb, Paula Colavitab, Kevin M. Metza

aAlbion College, MI and bTrinity College, Dublin, Ireland

Shaped palladium nanoparticles (PdNPs) have the potential to be selective catalysts. Unfortunately, there are some obstacles that hinder their use in heterogeneous catalysis, e.g., nanoparticles are difficult to remove from solution after a reaction. Additionally, shaped nanoparticle synthesis usually occurs at high temperatures, which is counterproductive to the energy saving goals of catalysis. We have developed a method to create shaped nanoparticles directly onto carbon supports using a mild reductant at room temperature. Thus our new method circumvents some of the obstacles to using shaped PdNPs as catalysts. Specifically we have developed a method to created shaped PdNPs directly on graphite disks and porous carbon microspheres using coffee as a room temperature reductant. By adding stabilizing agents, including Br- and ethylene glycol, the surface energy of the {100} face is lowered, thus promoting its growth and yielding cubic nanoparticles. Analysis by SEM indicates that our synthesized NPs are roughly 50 nm in dimension The size, shape, and distribution of nanoparticles varied based on the ratios of the reactants in the synthetic process. Under the best current conditions, SEM imaging suggests that cubic PdNP have successfully been synthesized. XRD analysis will be run to confirm the increase of the {100} face. Different ratios of reactants and adjustments in the synthetic process are being tested in hopes of maximizing the percentage of cubic particles. If successful, our PdNP show promise in being effective, environmentally friendly selective catalysts.

A11Analysis of Various Edible Clay Supplements via

Energy Dispersive X-Ray Fluorescence SpectrometryNicholas H. Stroeters, Jessica L. LaBond, Elizabeth S. Roberts-Kirchhoff*, Mark A. Benvenuto*

Department of Chemistry and Biochemistry, University of Detroit Mercy

The elemental compositions of nine edible clay powder supplements were analyzed using energy dispersive x-ray fluorescence (ED-XRF). The samples were all from different manufacturers that harvest clay from a variety of locations around the world. Each product was measured out to five equal samples and all samples were analyzed once. A NIST San Joaquin soil standard (2709) as well as two NIST soil containing lead from paint standards (2586 and 2587) were also analyzed to check for instrumental method accuracy. The purpose of the analyses was to look for trace amounts of heavy metals such as As, Cd, Pb, Hg, Th. Some samples contained detectable amounts of these heavy metals, and their significance is further discussed.

A12Electrochemical Modulation of Nitric Oxide Release using

Diazeniumdiolated SpeciesDakota Suchyta, Bo Peng, Mark Meyerhoff

University of Michigan

Nitric oxide (NO) has many different potential applications in healthcare. It functions as a primary vasodilator, which helps to widen arteries and allow unrestricted blood flow. Nitric oxide has also been confirmed to kill microbes in the body (bacteria and fungi). Further, NO is known to enhance wound healing and is a potent antiplatelet agent (i.e., prevents blood from clotting). This research project focuses on developing a method to control/modulate the release of NO effectively to a given site in the body in small, concentrated amounts for whatever purpose (e.g., killing of microbes, preventing thrombosis, or killing cancer cells). The method is based on electrochemical modulation of NO release from diazeniumdiolates, well known NO donors. Nitric oxide release from these molecules is proton dependent. Hence, by oxidizing water at an electrode surface, the local pH of a layer adjacent to the electrode will decrease, greatly increasing the rate of NO release from a diazeniumdiolate solution reservoir in contact with the electrode. Our initial goal is to devise a small silicone rubber catheter with electrodes and a diazeniumdiolate reservoir within the lumen, and allow NO to flow through the tubing wall to the surrounding area. Such an approach can yield a combined thromboresistant and bacteriocidal intravascular catheter design. Preliminary data on this concept will be presented.

A13Alzheimer’s Disease at the Early Age of 30? Can this Happen?

Allison Voce, Nadrine Omar, Anjeanette Mendez , Tzvetosara Kyoseva, Amanda Abuaf, Jennifer Sepe , and Dr. Sandra Chimon Peszek

DePaul University

Amyloid diseases, such as Alzheimer’s disease, are neurodegenerative disorders that have been introduced by protein misfoldings into amyloid fibrils. The Amyloid Precursor Protein irregularly cleaves the β-amyloid (Aβ) peptide, causing protein misfoldings to aggregate to form the hallmark plaques. For both Aβ(1-40) and Aβ(1-42), a tendency of fibril formation has demonstrated to self-assemble from a non-toxic monomer state to a lethal fibrillar state. Prior research focused only on the 16-21 region of the peptide, however, it is equally important to examine the hair-pin region without the presence of residues 16-21. In order to study the effect on fibril formation without this “KLVFFA” region, the 22-35 sequence was chosen. The Italian (E22K) and Arctic (E22G) point mutations lead to changes in time of fibril formation as well as solubility and toxicity of fibrils. The single-point mutations are believed to promote early onset of AD compared to the wild type (WT), prematurely producing clinical and neuropathological features which are unchanged from those of late onset AD. The use of Attenuated Total Reflection Infrared Spectroscopy, ATR-IR, and Ultraviolet Visible Spectroscopy, UV-Vis, on the 22-35 sequence confirmed the formation of structures synonymous with toxic beta sheets. Using Congo Red dye, which binds pentamerically to beta sheet fibrils, secondary structures have been confirmed.

A14The Quantitative Analysis of Genistein Concentration and

Total Protein in Apios PlantKatherine Wirth a, Emily Wilkinsb, and Kenneth Brownc

aGrand Rapids Community College, bUniversity of New Orleans, and cChemistry Department, Hope College

Genistein, an isoflavone found in soy and other sources, has been linked with anti-cancer activity in animal and human models. Studies done on countries with soy isoflavanone rich diets have correlated their intake with lowering the occurrence of breast cancer and prostate cancers. With the dietary benefit of genistein established, the apios groundnut has been focused on as a promising new root crop because of high protein content and genistein concentration. Concentrations ranged from 1.9 to 2.8 milligrams of genistein per gram of tuber. Also, the total protein concentration in the Apios extraction solutions will be determined by a Lowry Protein Assay.

I1Palladium Nanoparticles on Carbon Microspheres as a

Catalyst for Hydrogenation ReactionsMichael Dix,a Paul Duffy,b Paula Colavita,b Kevin M. Metza

aAlbion College, bTrinity College, Dublin, Ireland

The conversion of double and triple bonded carbons to single bonds via the hydrogenation reaction is an industrially important process. One of the major uses for this reaction is the refining of crude oil for use in cars. In many modern applications of the hydrogenation reaction, metal nanoparticles are used as the catalyst due to their high surface area to volume ratio. The major issue with using these particles is that their small size makes them very difficult to remove from a reaction mixture. In this study, we synthesized porous carbon microspheres that are approximately 1-2 mm in diameter. Palladium nanoparticles were then synthesized directly on the surface of the carbon microspheres. The advantage of using the carbon microspheres is two-fold. First, it provides a way to remove the metal nanoparticles from solution using simple methods such as centrifuging and vacuum filtering. Second, similar to the nanoparticles, the microspheres have a very high surface area relative to their weight. BET analysis of the carbon microspheres showed that they had a surface area of 631 m2/g. Initial testing has shown that the palladium nanoparticles on carbon microspheres (Pd/CMS) have similar catalytic activity to that of commercial 10% Pd/C catalyst that is often used to catalyse hydrogenation reactions. SEM imaging of the surface of the microspheres has shown that the nanoparticles being made are in the 5-25 nm range and have a very sparse distribution. Given the small size and thin distribution, we believe that the weight-% of Pd will be lower than commercial catalyst. We are currently waiting on TGA results to either confirm or deny this hypothesis. Since the price of Pd is very high, the Pd/CMS catalyst shows promise as a lower cost way of catalyzing hydrogenation reactions.

I2A Novel Binuclear Hydrogen-Rich Cobalt Hydride:

Synthesis, Spectroscopy, and DFT CalculationsJerod M. Kieser1, Donald E. Linn1, and Jason M. Shearer2

1Indiana University-Purdue University Fort Wayne, 2University of Nevada, Reno

Soluble, hydrogen-rich cobalt hydrides have been produced following a modified procedure that was designed to produce the earlier reported hexahydridoferrate(4–) complex. (Linn 2002) One yellow complex was collected from the precipitate of a tetrahydrofuran solution of phenylmagnesium bromide and cobalt (II) bromide after stirring in an atmosphere of hydrogen. A second darker complex was collected by drying the filtrate of the reaction mixture and then stirring it with dioxane for an extended time. This precipitated MgBr2·dioxane, leaving the second hydride in solution. Elemental analyses for Co, Br, Mg, and hydride are in agreement that two, different hydrides have been produced. 1H NMR analysis of each hydride shows the characteristic high-frequency shift of the strongly shielded hydrogen. IR spectroscopy shows a similar asymmetric Co-H stretching mode for both compounds, though DFT calculations suggest that this mode is easily affected by dielectric fields in the sample. Preliminary structure data from XAFS reveals that the yellow complex is most likely a dimer, though a complete structure is still being analyzed. Previously supposed monomers, [CoH5][MgBr(THF)2]4 and [CoH5][Mg(DIOX)2]2, have been studied by DFT calculations. Though the initial XAFS data has removed the validity of these structures, calculated IR frequencies, 1H NMR shifts, and Co-H bond lengths remain in agreement with experimentally observed data. Current DFT calculations are focused on finding a suitable structure for a cobalt hydride dimer.

I3Synthesis and Characterization of Orthometallated Arylimines

Logan E. Shephard, Nicholas B. Kingsley*

University of Michigan-Flint

In recent years there has been a plethora of research in the area of main group organometallic catalysts incorporating calcium, magnesium, and aluminum. Our research group has particular interest in the use of organoaluminum complexes in organic transformations. Recently we have started investigating the use of arylimine ligands as a support framework for aluminum alkyls. This ligand framework offers a unique electronic structure compared to commonly used N,N-, N,O,N-, and N,N,N- ligands that are drawing increasing attention. The synthetic route to these arylimine ligands also allows for great flexibility and control in electronic and structural properties.

We have prepared a series of group 13 orthometallated arylimine complexes that will serve as precatalysts for hydroamination of aminoalkenes. Details of the syntheses and characterization of ligands and complexes will be presented.

I4Synthesis and Characterization of Novel Energy Materials

Chad M. Tenbusch, Jonathon B. Clapham, Shaun R. Bruno, Colin K. Blakely, Joshua D. Davis, and Viktor V. Poltavets

Department of Chemistry, Michigan State University

Solid state chemistry has a become a competitive field in the synthesis of novel compounds for energy materials. Most synthesis techniques rely on one pot reactions that form the most stable compound, resulting in very few compounds and multiple ways to synthesize them. By using multistep reaction or novel techniques the synthesis of metastable and thermodynamically stable compounds can be synthesized.

Multi-step synthesis is employed in the preparation of novel compounds such as LiFeTiO4, LiFeO2, and the series LixCa1-xMO2 (0 < x < 0.75)(M = Co, Fe, Mn and Ni). These compounds were studied for the purpose of secondary cathode materials in lithium ion batteries, thermoelectrics, and superconductors.

The novel synthesis technique of using metal-hydrides and different solvents under solvothermo-conditions allows us to produce reduced compounds at lower temperatures while using high pressures. This technique has been shown to be useful in the formation of metastable compounds that would normally decompose under hydrogen conditions. It also provides the high pressures that may be required for the formation of the reduced phases.

Many compounds are synthesized using sealed metal ampoules, at high temperatures, in different atmospheres, to produce single crystals that may have only formed due to a reaction with the metal ampoule. Using a two zone furnace, metal/metal-oxide buffers and a sealed quartz tube, these reactions that may otherwise have taken place can be eliminated. This approach also provides the ability to regulate the oxygen pressure, allowing for the synthesis of the compounds in bulk. Compounds containing divalent metals or compounds that can easily be oxidized or reduced can be synthesized using this method.

O1The Direct Demethoxylation of

Weinreb Amides using SiGNa Materials.Arash Banisafar, Brittany O’Brien, Michael Caldwell, Dr. James Jackson, and Dr. James Dye

Michigan State University

Weinreb amides (N-methoxy-N-methylamides) are often used as intermediates in the synthesis of a variety of organic moieties. A useful transformation for these compounds is their direct demethoxylation to their respected secondary amide. While other groups have explored this transformation with complex aromatic compounds serving as electron donors or alkali metals aided with additional reagents, those methodologies are experimentally complex and require harsh reagents. To perform the demethoxylation of Weinreb amides, our group has been using silica gel loaded with sodium metal. This strategy not only yields the same desired transformation, but it utilizes a relatively stable reagent and a simple experimental method.

R N

O

O

R NH

O

NaSG

O2Cocrystal Behavior of Saccharin

David Birdsall

Ferris State University

A cocrystal is a crystalline structure made up of two or more components in a definite ratio, where each component is either an atom, ion, or molecule. Cocrystallization applications and theory are important to many fields including pharmacy and pharmaceuticals. Properties like solubility and bioavailability can be manipulated with the presence of a cocrystal, and thus is important for active pharmaceutical ingredients. Many factors are attributed to cocrystal formation: type of solvent and solubility, different pKa values (strength of acidity), shape of the molecule, and stacking properties.

My research was identifying the effects of cocrystalization specific to Saccharin, a sweetener. Over the course of the 10 weeks, over 80 experiments were carried out using different acids and solvents using both carboxylic acids and benzamides. In order to determine if a cocrystal was present, an Infrared spectrum was run on both the pure samples (of the acid and saccharin), which would essentially give a fingerprint of the crystal structure. If a cocrystal was present, shifts in the peak would be observed. In these experiments, only three different carboxylic acids cocrystallized with saccharin, and one (so far) of the 11 benzamides used. Further research would be appropriate to know the cocrystallization properties of Saccharin.

O3Synthesis of Imidazoline Scaffolds as Proteasome Inhibitors

and their Role as Anti-Inflammatory AgentsTeri Lansdell, Lauren Azevedo, Adam Mosey, Jake Ludwig, Dillon Cogan,

Michael Kuszpit, Daljinder Kahlon, and Jetze Tepe

Michigan State University

Here we present the synthesis and activity of unique imidazoline scaffolds as proteasome inhibitors. These imidazolines have been previously reported to inhibit the transcription of pro-inflammatory cytokines by targeting the NF-κB signaling pathway. Inhibition of these cytokines is particularly important in the prevention of certain inflammatory disorders, including rheumatoid arthritis (RA). By modulation of the proteasome by these inhibitors, the inactive NF-κB is not liberated from its inhibitory subunit, disrupting nuclear translocation and preventing subsequent translation of the pro-inflammatory cytokines. A structural activity relationship (SAR) has been conducted for the proteasome inhibitors in this study with variance at the 1, 2, 4, and 5 positions of the imidazoline ring. A key feature in the synthesis of these imidazolines lies in the diastereoselectivity of the trans aromatic groups at the 4 and 5 positions.

O4Kinetic Studies of ε-Caprolactone Polymerizations with

Aluminum-Salen CatalystsYvonne DePorre, Maria Miranda, William B. Tolman

Michigan State University, and University of Minnesota

Three structurally similar Aluminum-Salen complexes were synthesized, differing only in their electronic substituents (-NO2, -Br, and –OMe). These complexes are an example of the many catalysts used for cyclic ester polymerizations. PLA (polylactic acid) is a renewable and biodegradable polymer that is primarily used for food containers. Caprolactone, although not renewable, polymerizes by the same mechanism, so it can be used a model for cyclic ester polymerization. Previous studies of similar catalysts were conflicting; in some catalysts electron-withdrawing groups increased the rate but for others the rate decreased. Previous studies provided no insight into the rates of mechanistic steps, only the overall rate of polymerization. Therefore, monomer concentration was increased to approximately 2M, which expanded the rate law to follow Michaelis-Menten kinetics. Polymerizations were monitored at various temperatures by 1H-NMR and the data was analyzed to determine the rates of the insertion and coordination steps independently.

O5Efforts Towards the Synthesis of Amino-substituted

β-iodo N-alkenyl PyridonesMitchell Groenenboom, John Lagrand, Emily Rhude, Dr. Carolyn E. Anderson

Calvin College

The N-alkyl pyridone motif is synthetically important given its presence in natural products and pharmacologically important structures. We have shown that O-propargyloxypyridines can be transformed into β-iodo N-alkenyl pyridones in the presence of lithium iodide and oxygen. By incorporating a nitrogen substituent, additional targets of biological interest may be accessible. As such, protected amino alcohols 1 have been targeted for incorporation into O-propargyloxypyridines 2. The synthesis of the requisite amino alcohols and efforts to improve the coupling will be reported along with progress towards the synthesis of N-alkenyl pyridones 3.

O6Development of Colletoic Acid Derivatives as Potential

11β-Hydroxysteroid Dehydrogenase Type 1 InhibitorsLindsey Karp, Katsuhiko Mitachi, Taotao Ling, Fatima Rivas

University of Michigan

Colletoic acid is a novel acorane sesquiterpenoid isolated from the fungus Colletotrichum gloeosporioides in 2008. Colletoic acid was shown to selectively inhibit 11β-Hydroxysteroid Dehydrogenase Type 1 (11β-HSD1) with an IC50 value of 13 nM, making it an attractive probe with which to study this enzyme. Prior studies have demonstrated that selective inhibition of 11β-HSD1 is a potential therapeutic target for the treatment of metabolic syndrome. Herein, new derivatives of colletoic acid are presented using a synthetic strategy established in the Rivas laboratory for the core of colletoic acid. Development of novel and more selective inhibitors will allow us to study the mechanism of binding of this natural product to 11β-HSD1. Thus, the scalable core framework of colletoic acid can be derivitized to generate a small-focus library for structure-activity-relationship (SAR) studies.

O7SAR Optimization of an Imidazoline Scaffold

Jake Ludwig, Dilion Cogan, Theresa Lansdell, Lauren Azevedo, Jetze Tepe

Michigan State University

Protein degradation is a fundamental biological event that is essential for the regulation of intracellular processes. The 26S proteasome is a multi subunit enzyme responsible for protein degradation. The 26S proteasome consists of a 20S subunit and a 19S subunit. The 20S subunit is responsible for catalyzing peptide bond cleavage, and the 19S subunit is responsible for various regulatory processes such as the recognition, unfolding, and translocation of peptide substrates. The regulation of protein degradation by the proteasome plays an important role in many cellular signaling cascades, and this reason makes it an important therapeutic target for the treatment of many diseases and conditions including cancer. Tumor growth is dependant on proteasome-responsive intracellular processes and therefore proteasome inhibition can have a large impact on the growth of a tumor. Proteasome inhibition is the standard method for the treatment of cancers such as multiple myeloma (MM) and mantle cell lymphoma (MCL). Bortezomib is a clinically used proteasome inhibitor that slows the progression of both cancers to a median survival rate of around 3 years. Bortezomib, along with all other reported proteasome inhibitors, bind in the catalytic site of the 20S proteasome through a competitive type mechanism. The imidazoline scaffold discovered by the Tepe group inhibits the proteasome through a non-competitive allosteric mechanism. My research involves the structure activity relationship (SAR) of this imidazoline scaffold to yield nanomolar proteasome inhibitors.

The synthesis of the imidazoline scaffold is achieved through a 1,3-dipolar cycloaddition of an oxazolone with an imine. Oxazolones are created by treating an N-acylated amino acid with an anhydride such as TFAA or a carbodiimide such as EDCI. The oxazolone is then treated with a Lewis acid, such as TMSCl, to form the 1,3-dipolar intermediate referred to as a münchnone. When this münchnone intermediate is generated in the presence of an imine, a [3+2] cycloaddition occurs to afford an imidazoline in a diasteroselective fashion. The imidazoline scaffold that has been optimized in the Tepe lab via an SAR study is shown here.

The 1,3-dipolar cycloaddition yields a racemic mixture of the bioactive diasteromer shown above, in which the phenyl rings are trans to each other. My research involved the synthesis of new compounds in which the group denoted “R” in the graphic above was modified. These new compounds were then tested for their potency as proteaseome inhibitors, and new functional groups were chosen based on the potency of previous compounds.

O8Towards Improved Characterization of

Precisely-defined Dendrimer-ligand ConjugatesAndrew W. Phillips, Casey A. Dougherty, Mark M. Banaszak Holl

University of Michigan – Ann Arbor

Nanoparticles, such as generation 5 (G5) poly(amido amine) (PAMAM) dendrimers, conjugated with small molecule ligands, such as dyes, drugs, targeting ligands, and solubilizing agents, have become popular for drug delivery and imaging research. However, dendrimer conjugations result in a Poisson distribution of small molecules on the nanoparticle, creating a heterogeneous sample. To avoid these distributions, reversed-phase high-performance liquid chromatography (RP-HPLC) can be used to obtain a precise number of small molecules per dendrimer. In this research, monofluorinated cyclooctyne linkers (MFCO) are first conjugated to a dendrimer, producing a ligand distribution, and then RP-HPLC is used to separate the conjugates into homogenous fractions of defined numbers of linkers. Fluorine (19F) nuclear magnetic resonance (NMR) spectroscopy will be used as an additional characterization technique to verify the precise number of linkers on dendrimers. To further functionalize the dendrimer, we then conjugated azide containing ligands using strain-promoted alkyne-azide cycloaddition (SPAAC), which works to maintain a precise number of ligands. Using azidocoumarin pro-dyes and poly(ethylene glycol) conjugated (PEGylated) azidocoumarins, the precise number of ligands can be further verified by measuring the fluorescence before and after the click reaction, as azidocoumarins exhibit a marked increase in fluorescence after undergoing cycloaddition.

Figure 1. Example click reaction between G5-conjugated MFCO and 3-azidocoumarin pro-dye.  When the fluorescence-quenching azide forms the 1,3-triazole ring, there is a marked increase in fluorescence.

O9Synthesis of Cyclic Guanidines via

Pd-Catalyzed Carboamination ReactionsBlane Zavesky, John P. Wolfe*

University of Michigan – Ann Arbor

Five-membered cyclic guanidines have been synthesized in good yields via a palladium catalyzed carboamination reaction between acyclic N-allyl guanidines and aryl iodides. A variety of aryl iodides, ranging in electronic properties, have been coupled using this methodology. Given the wide array of biological activity attributed to guanidine containing natural products, ongoing research is focused on employing this methodology to aid in the synthesis of more complex cyclic guanidines.

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P1Understanding and Controlling the Mechanistics of

Nanocrystal Cation ExchangeMelika H. Fini and Prashant K. Jain

University of Illinois at Urbana-Champaign

The doping of semiconductors is a vital process in the electronics industry. This process, while well characterized and understood at the bulk scale, is still in its infancy with regard to nanostructures. Cation exchange is one form of doping nanostructures that allows for many distinct outcomes, from dopant incorporation to heterostructures with two unique compositions. However, creating these structures reproducibly and deterministically requires an understanding of the mechanism by which the exchange takes place. Still unanswered is the fundamental question of how the nanocrystals in a cation exchange actually do the exchange: one by one completely, cation by cation, or simply stochastically. Two different experiments were designed to investigate the nanocrystal exchange process.

In the first experiment, the cation exchange between silver nitrate (AgNO3, dissolved in methanol) and cadmium selenide (CdSe) was done in several steps, and the absorbance and fluorescent intensity were measured at each step. These measurements were used as indicators for the quenching effect of silver on CdSe and the presence of CdSe in samples. Since the silver nitrate was dissolved in methanol, and methanol has a significant quenching effect on the samples, a control sample of methanol was included in the experiment in order to evaluate the exact quenching effect of silver.

The second experiment involved the same cation exchange; however, in this experiment, the silver nitrate was introduced by gradually adding droplets of silver nitrate in one sample and by bulk introduction in the second sample. This experiment was designed to investigate the diffusion dependence of the cation exchange. It was found that nanocrystal (NC) exchange is most likely NC by NC, at least in the case of CdSe with Ag+. This implies that the cation exchange process may be nucleated in a single nanocrystal, followed by growth of the new phase. This in turn suggests that optimum conditions could be created to control the exchange of each nanocrystal, rather than converting a nanocrystal completely. In addition, the result of this experiment shows that gradual addition of silver nitrate can be used to study diffusion dependence of the cation exchange.

The results of this study can help with understanding cation exchange reactions, to enable accurate control of exchange of each nanocrystal when designing complex nanoheterostructures.

P2Photodegradation of

Poly(methyl Methacrylate) Films with Polystyrene CapsWilliam O. Hutson, Sanjay M. Prakadan, and Steven J. Sibener

The James Franck Institute and The University of Chicago,

Multilayered polymer films are of great fundamental and technical importance due to their current and future use in applications such as lightweight electronics, energy efficient devices, lenses with tunable optical properties, and especially as protective permeation barriers in packaging. In this presentation we will show our preliminary results on the photodegradation of these systems due to illumination by deep UV light, specifically poly(methyl) methacrylate (PMMA) films capped by thin nanoscale overlayers of polystyrene (PS). The kinetics and morphological changes induced in PMMA films exposed to UV light are well understood [J. Phys. Chem. A 2011, 115, 3736-45]. Norrish type I ester side chain reactions form diffusive and volatile methyl formate radicals. Our study aims to understand how the rate of mass loss was affected by the diffusion of these species through a PS capping layer. PS was chosen as the capping polymer because its resistance to photodegradation is well understood [Plasmas and Polymers 2002, 7, 185-205], and its transparency allows light to affect the buried PMMA film. This system was additionally chosen as a simplified alternative to PS-b-PMMA diblock, a copolymer whose unique surface properties are of importance to nanolithography. We obtain kinetic information by quartz crystal microbalance, directly giving information on mass loss from the film, allowing us to identify time-varying changes during illumination. We observe physical changes to the system by inspecting the films before and after exposure with atomic force microscopy (AFM). Results showed that the presence of a PS capping layer affected the rate of mass loss of the film. Characterization by AFM shows little damage to the PS film, suggesting that mass loss is the result of the interaction between light and the PMMA film underneath with the subsequent diffusion and evaporation of molecular photoproducts. It was found that the rate of mass loss decreased when the PMMA film was capped versus when the PMMA film was not capped. Observations also revealed local and isolated pores on the PS film after degradation, approximately 30 nm in size. Since PS is highly resistant to photodegradation, these pores are likely due to structural changes in the PMMA film that influence the structure of the overlayer.

P3Reduction Potential Shift in

Cytochrome c Peroxidase Mutants D79K and D267KBrianna M. Jackman,  Garett M. MacLean,  Justine M. Travis, and Cory M. DiCarlo

Grand Valley State University

Required methodology modifications were determined for the growth and purification of single site mutants of Horse Heart Cytochrome c Peroxidase (CcP) E267K, D79K, and E118K. Two main changes required included significant modification of chromatography conditions and adaptation required by reduced protein expression efficiency in the Escherichia coli bacterial expression system used to obtain these protein mutants.  Crystallization was accomplished in each case following method modification, although crystal size ultimately proved suboptimal for x-ray crystallographic structural determination.  Further alteration of the method required six-histidine tagging of the protein sequence followed by affinity chromatography for post expression purification.  Expression of the six-histidine protein resulted in measurement of the pH 7.0 reduction potential for the D79K and D267K forms.

P4Studies of Iron (III) Complexes with

Ab Initio Hartree-Fock MethodsAlexis C. Konja, Jonathan E. Stevens

University of Detroit Mercy

Synthetic chemists have considerable interest in coordination chemistry, specifically in highly multi-dentate ligand-metal complexes. Potential uses of such materials could be in real world solutions for the remediation of polluted water or in distant future regarding molecular switches and computing devices. This research is part of a collaborative effort to make, characterize, and examine a series of multi-dentate ligands and the metal complexes they can form. Our current work models small “model ligands” ligands and their complexes. Our collaborators, the Benvenuto group at the University of Detroit Mercy, attempt to synthesize complexes of particular model ligands. Calculations involve small simple ‘model’ ligands similar to the multi-dentate ligands the Benvenuto group seeks to synthesize. Calculations optimize ligand structures and ligand-iron complexes with the Hartree-Fock and density functional methods and a 6-31G(d) basis set. The structures of these model compounds and complexes are presented and discussed.

P5Pressure Broadening Coefficient Measurements by a

High-precision Near Infrared Absorption SpectrometerTrent Mazer, Stephanie Pierson, Dr. George McBane, Dr. Stephanie Schaertel

Grand Valley State University

The quantitative study of the response of spectral line shapes to gas pressure is a powerful method of understanding energy transfer during molecular collisions. Here we describe progress in the development of a diode-laser-based apparatus that can measure a molecular parameter that describes the width of a spectral absorption lines as a function of pressure. This parameter, the pressure broadening coefficient (PBC) is specific to molecule/collider gas/spectral line combinations. We have focused on the 0 to 3 overtone of CO with N2 as the collider gas. This poster will focus on two recent improvements to the apparatus: improvement of our protocol for etalon fringe triggering of the apparatus, and exploration of a broader range of pressures than we had before.

P6Plasmon-Enhanced Fluorescence for Super-Resolution

Single-Molecule ImagingCourtney N. Talicska, Jessica E. Donehue, Esther Wertz, and Julie S. Biteen

University of Michigan

Single-molecule fluorescence microscopy is a powerful technique for imaging position, structure, and dynamics below the standard diffraction limit of light. In this imaging method, isolated fluorophores are localized with nanometer-scale accuracy in a standard optical microscope, and image resolution improves with increasing number of detected photons. This dependence of super-resolution imaging on the properties of the fluorescent emitters has fueled a quest for brighter fluorophores, and we are interested in creating universal substrates for increasing the intensity and photostability of fluorescent labels in bioimaging applications. Our approach makes use of the enhanced electromagnetic field about resonantly excited gold nanoparticles. The free electrons present in metal nanoparticles are confined to the small particle volume and oscillate upon laser excitation. At resonance, the electrons oscillate collectively in phase, leading to an enhanced electric field in the area around the particle. Interestingly, this ‘particle-plasmon’ results in enhancement of the photophysical properties of nearby fluorophores.

We have coupled organic dyes and fluorescent proteins to gold nanoparticles created by colloidal chemistry, metal film annealing, and electron-beam lithography. Single-molecule investigations of the fluorescent emitters show improved emission intensity, radiative decay rate, and photobleaching quantum yield in multiple systems. To better characterize the process, which depends sensitively on the distance between the gold surface and our fluorophores, we are investigating this spacing with carefully regulated spacer layers. We have deposited ultra-smooth polyelectrolyte films layer-by-layer with spin coating to monitor the effect of spacing of the fluorescent protein, mCherry, and the organic dye, Cy3, from gold nanoisland films. We have characterized the multi-layer spacers by atomic force microscopy and found a correlation between the spacer thickness and the surface roughness, and we are currently investigating the relationship between fluorescence enhancement and spacer thickness. Our preliminary results for these bio-compatible platforms indicate that plasmon enhancement is a promising method for improving the resolution in bioimaging applications.

Previous Years Poster Session Award Winners

2011Inorganic/Analytical ChemistryLyndsey Reynolds (Albion College)

Organic ChemistryVictoria Garza (Ohio State University)

Physical ChemistryHector Figueroa (Eastern Michigan University) Patrick Louden (Grand Valley State University) Kristen Zuraski (Michigan State University)

Thinking about going to grad school?www.chemistry.msu.edu/graduate/apply.cfm

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