NDSU Receives $2M for Pancreatic Cancer Research

Dr. Guodong Liu will work on the research team.

Dr. DK Srivastava is a co-PI on the NIH COBRE grant.

NDSU has received a $2M research grant to establish a Center of Biomedical Research Excellence focussed on pancreatic cancer. Profs. Sanku Malik (Pharmaceutical Sciences) and DK Srivastava (Chemistry and Biochemistry) are leading up the effort. Associate professor, Guodong Liu from the Department of Chemistry and Biochemistry will also participate on the research team.

Reported today in the Fargo Forum

FARGO — North Dakota State University has received a $2 million grant to establish a center to study pancreatic cancer, members of the North Dakota congressional delegation announced Wednesday.

The Center for Diagnostic and Therapeutic Strategies in Pancreatic Cancer will be in NDSU’s department of pharmaceutical sciences, Hoeven’s release said.

“This significant federal funding will allow NDSU pharmaceutical sciences researchers to advance cutting-edge science, which will help the medical community improve diagnosis and therapies for pancreatic cancer down the road,” Sen. Heidi Heitkamp said in a news release.

The funds will go toward pharmacology, physiology and biological chemistry research, Rep. Kevin Cramer said in a news release.

NDSU chemistry faculty receives funding to study sustainable chemistry

Jayaraman_Sivaguru_2011Jayaraman Sivaguru, North Dakota State University James A. Meier Jr. Professor of chemistry and biochemistry, has received a three-year, $440,000 award (CHE-1465075) from the National Science Foundation to develop environmentally benign, green strategies for performing chemical reactions with light. These projects are significant in the Department’s research focus area in sustainability and materials chemistry.

The funding also provides research opportunities to graduate and undergraduate students. The research program in Sivaguru’s group focuses on using light for atropselective photochemical reactions. These reactions initiated by light producing molecules that are chiral, which have two non-superimposable mirror images, and make only one of the two possible forms—a single enantiomer.

“Harnessing the power of light to synthesize chiral compounds with high stereoselectivity during light-induced transformations is very challenging. Our proposed methodology has the ability to provide an opportunity to develop sustainable strategies with minimal impact on the environment,” said Sivaguru.

Based on the National Science Foundation funding, his research group will evaluate the use of visible and ultraviolet light to synthesize complex molecules that are enantiomerically pure. One of the research goals is to gain a fundamental understanding of interaction of light with atropisomeric photoreactive substrates. That is coupled with an intricate control over molecular reactivity, dynamics and non-bonding interactions to enhance stereoselectivity in the photoproducts.

“The project also provides students an opportunity to learn modern chemical methods that are utilized for synthesizing compounds with minimal environmental impact,” added Sivaguru. With this most recent funding, students involved in these investigations will learn both traditional techniques to characterize and evaluate asymmetric induction during enantiospecific phototransformations and modern spectroscopic methods and characterization techniques to assess excited state reactivity.

Through the research, area high school students receive opportunities in PICNICS, or Parents Involvement with Children, Nurturing Intellectual Curiosity in Science. Top area high school students conduct research each summer alongside graduate students and postdoctoral fellows at NDSU. Sivaguru developed the PICNICS program as an outreach component in an earlier National Science Foundation CAREER award. PICNICS engages high school students and their parents to learn more about recent science and technology advancements and to encourage high school students to consider science as a career path. The program has trained 42 high school students since 2007.

The most recent National Science Foundation award is a renewal grant for the proposal titled “Manipulating photochemical reactivity through restricted bond rotations.” Sivaguru previously received funding through CHE-1213880 and CAREER-CHE-0748525.

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Graduate student receives ASBMB award

Minfei Su, a doctoral student in Dr. Sangita Sinha’s lab in the Department of Chemistry and Biochemistry, was chosen to receive an ASBMB 2015 Best Thematic Poster Award. Her poster entitled “Targeting the γ-Herpesvirus Bcl-2–Mediated Inhibition of Autophagy and Apoptosis”attracted extensive attention in the Molecular Mechanisms of Infection and Immunity posters section during the 2015 annual meeting of the American Society of Biochemistry and Molecular Biology. In this study, Minfei and her coauthors designed a peptide to selectively bind to a γ-herpesvirus protein, to abrogate it mediated down regulation of autophagy, which is a very important intracellular degradation pathway that has a wide variety of physiological and pathophysiological roles including protecting cells from pathogens. Such selective inhibitors are important for understanding the role of γ-herpesvirus proteins in viral reactivation and oncogenic transformation of host cells. This workis now published in the Journal of Biological Chemistry: (http://www.jbc.org/content/early/2014/01/17/jbc.M113.515361). In addition to this award, Minfei’s research achievements have led to several recent honors and awards including the ND EPSCoR Doctoral Dissertation Fellowship, ASBMB 2015 Graduate/Postdoctoral Travel Award and CSM Graduate Student Travel Grant.

Biochemistry graduate students receive Doctoral Dissertation Fellowships

Minfei Su and Yang Mei, doctoral students in the laboratory of Dr. Sangita Sinha, an associate professor in the Department of Chemistry and Biochemistry, have been chosen to receive ND EPSCoR Doctoral Dissertation Assistantship (DDA). Ms. Mei and Ms. Su are among the five graduate students at NDSU awarded the DDA for the 2014-2016 academic years.

Dr. Sinha’s laboratory focuses on obtaining a structure-based understanding of the autophagy pathway, an essential cellular homeostasis pathway, using a combination of biophysics, bioinformatics, biochemistry, molecular biology methods and cellular assays. “This research in structural biology with Dr. Sinha is a first in North Dakota and they are producing cutting edge science that will put NDSU on the map.” as Dr. Greg Cook, the chair of chemistry and biochemistry, said in the endorsement letter.

Ms. Mei’s research focuses on elucidating the structure-based mechanism of Beclin 1, a key autophagy protein, and its interactions with various other important autophagy proteins and interactions partners including Bcl-2, AMBRA1 and ATG14. Beclin 1 is implicated in numerous diseases including cancer, neurodegenerative diseases and innate immune defenses against viruses. This information may enable the design of therapeutics to specifically up-regulate or down-regulate autophagy levels in the cell.

Ms. Su’s DDA proposal focuses on Beclin 2, a recently identified homolog of Beclin 1 that is important for degradation of G-protein coupled receptors via autophagy and in regulating metabolism and obesity. Ms. Su’s work will elucidate the structure of the Beclin 2 coiled-coil domain (CCD), and help understand the interaction of the Beclin 2 CCD and Atg14 CCD. The detailed information obtained from this proposal will help identify Beclin 2 residues important for interacting with Atg14 that will allow selective inhibition or activation of Beclin 2-regulated autophagy.

The DDAs provide a 21-month stipend of $1620 per month, enabling Ms. Su and Ms. Mei to dedicate their time exclusively to dissertation research. $2,000 is awarded for research supplies and to support each student’s attendance at the 2015 Annual Meeting of the American Crystallographic Association in Philadelphia, PA.

Assistant professor receives National Science Foundation Award

An NDSU faculty member has received $890,900 from the National Science Foundation (NSF) to support her research and educational programs at NDSU.

Sangita Sinha, assistant professor of chemistry and biochemistry has received a four year award from the NSF Division of Molecular and Cellular Biosciences. Currently, this is the only investigator-initiated NSF MCB award in the state of North Dakota.

Sinha determines the atomic resolution structure of proteins using X-ray crystallography in order to understand how different proteins perform their biological function. A detailed understanding of a protein’s structure is essential to understanding its mechanism, and is a central concept in Biochemistry. The Sinha laboratory, the first macromolecular crystallography laboratory in ND, combines X-ray crystallography, the most powerful method of protein structure determination, with multiple complementary biophysical, biochemical, molecular biology and cellular methods to obtain a comprehensive structure-based understanding of protein function.

The goal of the NSF grant is to understand the structure and mechanism of a protein called Beclin 1, which is a key component of the autophagy pathway.

Autophagy is an essential pathway responsible for the removal of unwanted or harmful cellular components to enable nutrient recycling. Autophagy occurs in all eukaryotic organisms, ranging from yeast to humans. Beclin 1 and autophagy are required for a range of critical organismal processes including embryonic development, tissue differentiation, cell-growth and surviving external and internal stressors such as free radicals and pathogens. Dysfunction of human Beclin 1 has been implicated in a wide range of human health issues including embryonic fatalities and developmental defects; reduced longevity; neurodegenerative diseases, especially Alzheimer’s disease; cancer; heart failure; and stroke. Many viruses such as herpesviruses, HIV and the influenza virus encode proteins that bind Beclin 1 to block autophagy, allowing the viral infection to continue. This underscores the importance of Beclin 1 and autophagy for our innate immune defenses. Thus, differential modulation of Beclin 1-mediated autophagy is a promising therapeutic target for diverse diseases.

Key work done by Sinha and coworkers has delineated the domain architecture, detailed structure and conformational flexibility of this protein. Beclin 1 appears to be a protein interaction hub as it binds to over twenty diverse cellular or viral proteins. Research in the Sinha lab is providing important insight into how this protein interacts with so many partners, by resolving the dynamics of Beclin 1 conformational flexibility and establishing the role of selected binding motifs. A structure-based mechanistic understanding of Beclin 1 function is key to understanding the role of Beclin 1 in various diseases, and eventually to designing therapeutics targeting Beclin 1 function to treat these diseases.

Yang Mei, a graduate student in the Sinha laboratory has been a key contributor to this research. In the future this research will involve a postdoctoral fellow, and several other graduate and undergraduate students.

Additionally, funds are provided for the creation of a new 3-credit, graduate-level course at NDSU (BIOC 600), to provide high school STEM teachers across the upper Midwest with a unique professional development opportunity. The objective of the course is educate high school teachers in the principles of biomolecular structure, and also provide them with pedagogical tools and resources to disseminate this information to their students. Ultimately, this will impact hundreds of students, far beyond the 4-year period funded by this grant. BIOC 600 is being offered for the first time as part of the North Dakota State University Distance and Continuing Education’s summer 2015 professional development program.

The research is funded by Award No. 1413525 from the NSF.

Sinha earned a doctorate in biochemistry and molecular biology from Purdue University. She then worked as a Howard Hughes Medical Institute research associate at University of Texas Southwestern Medical Center. She started as faculty in the department of Internal Medicine at University of Texas Southwestern Medical Center before moving to NDSU.


NDSU Scientists Create Artificial Enzymes

Enzymes do amazing things and are Nature’s ultimate catalysts to carry out the chemical reactions of life. They are very complex and not easily duplicated in the lab. A big scientific question is: How does one develop a small molecule catalyst that can carry out the functions of a biological enzyme? Recently, Scientist from NDSU’s Department of Chemistry and Biochemistry have made headway in this direction. A recent paper by University Distinguished Professor Mukund Sibi, postdoctoral research fellow Jun Deng and graduate student Gaoyuan Ma in the journal Angewante Chemie International Edition, is turning heads and making an impact. The paper was featured by the journal as a cover article.

Kinetic resolution is a means of differentiating two enantiomers (left and right handed molecules) in a racemic mixture. In kinetic resolution, two enantiomers react with different reaction rates in a chemical reaction with a chiral catalyst or a reagent, resulting in an enantioenriched sample of the less reactive enantiomer. In the biology world, enzymes do these types of reactions on a routine basis.  Organic chemists have adapted enzymes such as lipases to carry out kinetic resolutions.  There are several drawbacks for the use of native enzymes in organic reactions: (1) ready availability in pure form, (2) high molecular weight, (3) limited solubility in organic solvents, and (4) stability to degradation.  Thus there is significant interest in the development of small organic molecules or organocatalysts that can mimic enzymes.

The paper by Ma, Deng and Sibi details the use of novel fluxionally chiral dimethylaminopyridine (DMAP) organocatalysts.  DMAP’s are superbases and form reactive intermediates with anhydrides in situ which can resolve racemic secondary alcohols and axially chiral birayls (atropisomers, handedness from rotation about a single bond). Chiral dihydroxy biaryl derivatives are used extensively as ligands for stereoselective reactions. Thus development of catalysts that can resolve a variety of biaryls efficiently is significant. In organic chemistry, the efficiency of a catalyst to carry out kinetic resolution is denoted by an s factor, the higher the number the better it is. There is only one example of chiral DMAP catalyzed acylative kinetic resolution of 1,1’-binaphthyl derivatives proceeding with only modest selectivities (s = 1-4). The Sibi group has designed useful templates, ligands, and additives that use fluxional groups to control and/or enhance stereoselectivity in a variety of asymmetric transformations. Fluxional substituents are groups that undergo inversion rapidly, for example, a nitrogen with three substituents. A day-to-day analogy is the behavior of an umbrella on a windy day.  A key feature of this strategy is that the size of the fluxional substituent can be varied readily and easily. Using this novel concept, several chiral DMAP catalysts containing fluxional chirality have been prepared. These catalysts were found to be highly efficient in promoting kinetic resolution of sec-alcohols and axially chiral binols. Biaryl substrates were resolved with s factors of up to 51 by using the new catalyst system. The selectivities obtained for resolution of biaryl compounds are better than previously reported asymmetric acylation catalysts. These results clearly demonstrate the novelty and utility of the chiral DMAP catalysts.

Research on the Prairies – All you wanted to know about Chlorite Dismutase

Participating in an REU program was definitely an experience I was looking forward to as a chemistry major.  After all, what better way to glimpse life as a graduate student conducting new and exciting research at an advanced level than to have the opportunity to work in a research group alongside graduate students conducting new and exciting research at an advanced level?  I was a little concerned during the application process since the chance to tour the lab and meet in person with the professor is definitely worth doing if at all possible, and while the program I was most interested in happened to be just across the river from my home institution, my current institution for the semester (the National University of Ireland in Galway) happened to be just across the ocean.  Luckily, Skype works quite well for transcending geographical and temporal hurdles, and, as can probably be surmised, I eventually found myself spending quite a lot of time on the Fargo side of the Red River.

The Rodgers group is one that sort of creates a niche of its own.  The molecule heme is a running theme in all of the ongoing projects and is examined using multiple spectroscopic techniques including UV-Visible and resonance Raman, the latter of which is laser-based.  Heme is an aromatic structure that contains an iron center surrounded by a porphyrin ring with characterizing substituents.  It is a prevalent cofactor and plays a role in a broad spectrum of proteins.  This includes hemoglobin, which is responsible for oxygen transport (among other functions) and is what lends blood its red color.The metal component of heme coupled with its role with so many different proteins and biological processes results in the research falling under not solely inorganic or biochemistry but an amalgamation of the two dubbed bioinorganic chemistry.

The all-important cofactor, heme b

The same type of heme found in hemoglobin (heme b) is also found in my focus for the summer, a very unique group of bacterial and archael enzymes called chlorite dismutases (Cld).  What sets this superfamily of proteins apart is their ability to decompose chlorite (ClO2) into chloride (Cl) and oxygen (O2).  The capacity to produce O2 is recognized in only a few characterized enzymes.  Another more familiar example would be photosynthesis with photosystem II.Chlorite dismutases also become very significant in their potential for bioremediation.  ClO2 and other chloro-oxyanions like perchlorate (ClO4), chlorate (ClO3), and hypochlorite (ClO) present quite the environmental and health hazards due to their ubiquitous use as herbicides, explosives, and industrial bleaching agents.  In fact, the EPA categorizes ClO2 as one of the top ten pollutants in drinking water, and the health hazard it presents generally targets children in the forms of neonatal jaundice and childhood anemia.ClO2 can also disproportionate in acidic conditions into ClO, otherwise known as household bleach, and cause some pretty nasty chemistry.  Consequently, an enzyme that not only produces oxygen but detoxifies the environment certainly merits a look.

The mechanism of Cld is currently under investigation, and the goal of the study is to fully detail the relationship between the function of the enzyme and the structure of the enzyme.  Below is a proposed mechanism for how it goes about the decomposition.4  ClO2 enters the active site of the protein and attacks the iron center.  An oxygen is left behind as the molecule releases as ClO.  ClO reorients and forms a peroxy or oxygen-oxygen bond before coming off as O2 and Cl.   While there is evidence for the initial steps of the mechanism, full confirmation has yet to be achieved.  This is partly because, as of yet, none of the intermediates hang around long enough to be isolated.

  In order to conduct experiments on our proteins, we first needed to have them.  This involved a week-long process of culturing, inducing protein expression, harvesting, freezing (via liquid nitrogen, always fun), ultrasonication, and purification via column chromatography that, ideally, would end with milligrams of new, shiny (not literally) protein to work with.  Of course, as my graduate student mentor Zach Geeraerts and I found out, protein preps can sometimes be generously described as problematic.  While it may have delayed our timeline a bit, it was always a good exercise in reasoning what the problem was, testing and confirming that it was indeed the problem, and altering the procedure to reflect the new information.  Considering that research is often breaking new ground in its field, being able to nail down that process is invaluable.

A column filled with resin used for purifying protein.  Much protein was sacrificed to appease the column deities. 

 We worked with two strains of Cld.  One was a soil bacteria by the name of Dechloromonas aromatica and the other was Klebsiella pneumoniae.  The experiments, once they got under way, dealt with activity measurements and nitric oxide adducts.  The former involves measuring how much O2 is produced by the enzyme when introduced to a ClO2 solution.  The probe we use has a ruthenium complex in its tip that, when excited by an LED, luminesces.  When O2 is present, that luminescence signal undergoes Stern-Volmer quenching, and the signal from the probe decreases.  The more O2 produced, the lower the signal, and the higher the enzyme’s activity.

On the left is the activity assay for the Klebsiella.  The right is for Dechloromonas.  From the steepness of the curve, one can see that Dechloromonas has a higher activity.

The nitric oxide (NO) adducts involved coordinating or bonding NO to the iron center in order to emulate the chemistry of potential intermediates.  Through UV-Visible spectroscopy, we were able to confirm that we had made both the {FeNO}6 form its reduced form {FeNO}7.  The next step would be to use resonance Raman spectroscopy to explore the positioning of the NO in the active site, where the electron density is, and what the hydrogen bonding environment is like.  As I will be continuing in the Rodgers lab, I will have the pleasure of seeing how these experiments play out during the semester.


1.  Streit, B.; Blanc, B.; Lukat-Rodgers, G.S.; Rodgers, K.R.; DuBois, J.L. J. Am. Chem. Soc. 2010, 16, 5711-5724.

2.  Hofbauer, S.; Schaffner, I.; Furtmüller, P.G.; Oblinger, C. Biotechnol. J. 2014, 9, 461-473.

3.  Streit, B.; DuBois, J.L. Biochemistry. 2008, 19, 5271-5280.

4.  Lee, A.Q.; Streit, B.R.; Zdilla, M.J.; Abu-Omar, M.M.; DuBois, J.L. Proc. Natl. Acad. Sci. USA 2008, 105, 15654-15659.


Research on the Prairie – Plastic from Plants

by Charles Good

Elementary school was a great time in my life. I walked the four blocks from our home in south central Pennsylvania to Lititz Elementary School with my mom and our yellow lab, Elsa. I played kickball and Four Square during recess. I performed in our school play. Through this blur of young excitement, learning and building, I remember a few key moments. One of them was my introduction to good storytelling.  I was in second grade, and my teacher, Mrs. Sitler, invited Mrs. Clarke (mother to one of my classmates) to perform for the class. While I don’t remember any of the stories she told, I remember the way she told them. Her voice had a distinctly deep timbre and her hands danced as she told us her stories. She came to our class for one year; the next year, there was no time for telling stories as the mountains of science, history, math, and language began piling up.

My time here in Fargo has been similar in many ways. Certainly, there has been so much to learn, to do, to experience. It’s been a blur of meeting new people, figuring out a new area, and learning how to cook. It’s been the training wheels for a hopeful research scientist. Most importantly, however, my experience has helped me tell a good story.

Like most stories, mine has a beginning. I’ve had the privilege of working in the Sibi Group under the direction of my fearless leader and Ph.D. hopeful, Eric Serum. I plugged into an existing project on the topic of biomass monomer synthesis. Essentially, I’ve been making the building blocks for polymers like plastics, polyurethanes, nylons, etc. using plant matter instead of petroleum as a starting material. Currently, about 96% of organic chemicals are made from petroleum (1). This is a real problem for three reasons: 1) fossil fuels are finite and are predicted to run out in the next few decades; 2) fossil fuel consumption leads to CO2 emissions, which continues to cause climate change; 3) fossil fuel resources are distributed unevenly throughout the world, which will continue to induce political tensions (2). Because organic chemicals are prolific in today’s industrial lifestyle, these issues are not trivial. In that vein, I am helping to developing alternatives to petroleum.

Currently, biomass is the only renewable resource that is large enough to do that (3). Furthermore, it has two important answers to petroleum: 1) biomass crops can be grown annually; 2) biomass is considered carbon neutral because the carbon dioxide emissions released during combustion are consumed during the growth of new crops (4). Of course, there are some drawbacks. Biomass is still more expensive than petroleum, and the ethical debate over food vs. fuel (is growing crops for fuel instead of food a good idea when so many are starving in this world?) rages on. Some crops, such as switchgrass and elephant grass, grow on marginal land while still remaining abundant sources of plant mass, which has helped ease this debate. Still, the benefits for biomass appear to be getting better with time.

The middle of my story involves actually working with the carboxylic acids that are derived from biomass resources. My goal was to make the nitrile, which can then be transformed to the amine, which is used to make polymers. Traditionally, amines are made from the amide using lithium aluminum hydride (LAH). However, LAH is pyrophoric (ignites on exposure to air), making it a highly dangerous chemical. LAH can be avoided by making the nitrile, then using a green method to form an amine.

There are well-known methods to make amides from carboxylic acids and nitriles from amides. At the beginning of the summer, the idea was to apply these methods to the new biomass carboxylic acids. There were two criteria that I followed: 1) the reactions remained relatively inexpensive so they could later be applied at a larger scale; 2) the chemicals had minimal environmental impact. Unfortunately, publications were much easier read than effectively implemented.

This is where my story in lab strays from the story that I’ll present at the Research Symposium. My story in lab was an almost utter failure. For example, it took me almost 7 weeks to make the amide. In the meantime, I explored many methods to make the nitrile from the amide, starting with a recently published method using a chemical called MSFTA. This process actually worked really well…unfortunately, MSTFA is really expensive. When the reaction makes about 1 gram of product, $30 of MSFTFA is used. Scalable? Not so much. Then I moved on to a reaction that looked fantastic on paper. Cost was low and the reagents remained relatively benign, but it only worked for one type of starting material and not the biomass material. So it was back to the drawing board after 7+ weeks. Instead of working with complex biomass starting materials, I explored converting 5 simple amides to nitriles using 4 established methods. That way, I could create a map of sorts to determine the most effective method to extrapolate to the complex biomass amides. With that map in hand, I applied the best way to make 2,5-furandicarbonitrile. This reaction is currently running.

The story I’ll tell at the Research Symposium might sound a little bit backwards from that of the lab. The beginning of my story will remain the same – how important biomass is for organic chemistry and the goal of avoiding LAH. However, my map will come next. I’ll talk about how my map led me to choose an appropriate method for making 2,5-furandicarbonitrile (among other chemicals). Then I’ll focus on the challenges of biomass – how they are different from the simple amides from the map. That’s it. Maybe I’ll gloss over how I finally managed to make those biomass amides after 7+ weeks, but likely, that would only be for someone who asks about that specific process. That’s because failure doesn’t make a great story.

Two weeks ago, I was in crisis mode because I didn’t have any results to put on my poster. It was then that I began to plan out what story I wanted to tell about my work this summer, and soon, I could see what blocks I needed to fill in. Now, my story has little successes. I did make nitriles from (some of) the simple amides, and I really improved on the process of making amides from biomass. My story is short and probably won’t be remembered by very many people. But I’ll always remember how it was crafted, how the pieces came together at the last minute. Maybe in my future as a scientist, my stories will be told over and over again to young and old alike. For now, I’ll remember Mrs. Clarke and my fantastic 10 weeks at NDSU.

Research on the Prairie – Organic Electronics

Materials for Organic Electronics: Thiophene-based Low Bandgap Polymers by Claire Buysse

If you had asked me what I wanted to do with my chemistry degree a year ago, I wouldn’t have known.  Even six months ago, I wasn’t completely sure where I was headed.  I suppose that part of this uncertainty came from growing up in Marshall, a small town in southwest Minnesota which did not exactly provide me with much exposure to the broad range of careers I could pursue with chemistry.  Nonetheless, I loved my hometown and took full advantage of the college chemistry courses my high school offered.  I enjoyed and excelled in these courses, which led me to attend CSB/SJU last year and to take advantage of their up and coming chemistry program.  It was at the College of St. Benedict that I discovered my passion for environmental topics and particularly my interest in solar energy.  As a result of the encouragement and support of the chemistry faculty at CSB/SJU, I applied for this REU program – and I got in!  I was so excited at the chance to do research this summer at North Dakota State University and I knew it would be an invaluable experience for me.  Through this program, my eyes have been opened to all the opportunities that are available to me and I can truthfully say that it has been a phenomenal summer so far.

This summer, I am working in the Department of Chemistry at NDSU as a part of the Research on the Prairies REU program.  I spend my time in the Rasmussen Research Lab under the supervision of Dr. Seth Rasmussen and graduate student Trent Anderson (pictured right).  The focus of my lab group is on the creation of useful low bandgap polymers that have a variety of potential applications.  The polymers of particular interest to us utilize conjugation and fused-ring systems, in addition to a number of other interrelated factors, to achieve low bandgap energies.  This lower energy between valence and conduction bands (which closely corresponds to the HOMO-LUMO energy difference) allows the polymers to adopt electronic properties which mimic those of inorganic semiconductors.  As a result, these organic materials have the potential to act in place of the inorganic electronic materials that are commonly used today.  In particular, low bandgap polymers have been studied for use in organic solar cells (OPVs), organic light-emitting diodes (OLEDs), electrochromic devices, field-effect transistors, and more.  Recently, these “flexible electronics” have attracted much attention for their low production costs and processibility.  This new line of organic polymers also shows promise as a more sustainable source of electronic materials.

The chemical foundation for many of the low bandgap polymers in the Rasmussen Lab is thiophene, utilized for its versatility and ease of synthetic modification.  Additionally, thiophene is an undesirable component of petroleum, which is typically removed during processing.  The acquisition of the thiophene starting material from petroleum waste offers promise for a relatively sustainable (and essentially renewable) source of electronic material.  In the early stages of my summer research experience, I used thiophene as the starting  material in the synthesis of 2,3-dihexylthieno[3,4-b]pyrazine (later abbreviated as TP), which I completed in conjunction with my graduate student mentor.  This synthesis involved a series of reactions and purification steps where I got the chance to apply many of the laboratory techniques I had worked with at St. Ben’s, in addition to learning some new techniques as well.  Some of these included distillation, column chromatography, thin-layer chromatography, recrystallization, and extraction.  Although the synthesis of TP has been well-established, completing this synthesis successfully gave me the chance to familiarize myself with the lab and to gradually increase my level of independence on the project.

The second part of my summer research experience dealt with the creation of a novel synthesis for a dimer of the TP I had synthesized and the 4-bromo-2,1,3-benzothiadiazole (or BTD)  that my graduate student mentor had prepared.  The first step towards this synthesis was the isolation of TP with a trimethylstannyl group bound in the 5 position, for which the synthesis had been previously recorded but an isolation of the compound was not attempted, likely due to instability and easy degradation.  I completed this reaction a number of times and earned yields varying from 40-70%.  At this point, my summer research experience was winding down and time constraints did not allow me to continue with my synthesis.  As a result, future plans for this project in the Rasmussen group include the coupling of this compound with the brominated BTD to create the asymmetrical dimer as shown in the reaction below.  Ideally, the electronic properties of this dimer would be characterized and the potential for a polymeric form of this dimer to be used as an organic electronic material evaluated.

Working in the Rasmussen Lab this summer has been an amazing experience for me and I am so glad that I have had this opportunity.  I got the chance to work with some great people in the lab, and it turned out that one of them (Eric Uzelac, pictured here) went to St. John’s University with my brother and lived on the same freshman dorm floor!  Spending ten weeks in Fargo for this program has definitely been a positive experience for me, both in and out of the laboratory.  It was a blast to hang out with the other REU students, and a few of us even discovered a new hobby together at the climbing wall on campus.  Ultimately, I’ve had a great time here at NDSU as a part of the Research on the Prairies program and I have discovered quite a bit about my interests in chemistry, too.  I have a much better idea of where I’m headed in the future (grad school!) and what I want to do.  So if you asked me what I want to do with my chemistry degree today, I’d know exactly the answer to give you.