67th
Intercollegiate
Student
Chemists’ Convention
Saturday, April 5, 2003
Mendel Hall
Villanova University
Villanova, Pennsylvania
Organized by the Villanova University
Department of Chemistry
1
Sponsors
We wish to thank the following companies without whose
kind contributions, this year’s convention would not have
been possible.
American Chemical Society, Philadelphia Section
Centocor, Inc.
Cephalon, Inc.
Silvestri Lecture Series
Wyeth Pharmaceutical
2
Draw the molecule depicted by the 1H NMR spectra on the
cover of this booklet (the molecule’s infrared spectra and 13C
chemical shifts are given below) and win a prize!
Additional Spectral Information to 1H Spectra on Cover
-IR and 13C NMR-
13
C NMR-: 20-s, 24-s, 30-s, 36-s, 46-s, 54-s, 128-s, & 172-s (relative to
CHCl3).
The molecular formula of this molecule is C14H18O6N2.

Simply draw the molecule on the index card provided at
registration and turn it in when you attend lunch at the Italian
Kitchen in Dougherty Hall.

In case of more than one correct answer, winner will be selected
randomly!
3
Foreword
The Department of Chemistry at Villanova University welcomes you to the 67 th
Annual Intercollegiate Student Chemist Convention.
The inaugural ISC Convention was held in 1936 under the guidance of Professor
B. Meldrum of Haverford College. Eleven charter member institutions participated
in the first convention which included representatives from Bryn Mawr College,
Dickinson College, Drexel Institute of Technology, Gettysburg College, Haverford
College, Johns Hopkins University, Lafayette College, Swarthmore College,
Temple University, the University of Pennsylvania, and Ursinus College. Since
that time, a number of institutions have joined the fold. With the exception of one
year during World War II, chemistry undergraduates from institutions in
Delaware, New Jersey, New York, Maryland, and Pennsylvania have met for the
past 66 years to discuss their research. The ISC Convention is one of the oldest,
continuously meeting annual convention of its type in the US and we, the
Department of Chemistry at Villanova University, are proud to host this year’s
meeting.
This year’s convention is represented by 12 institutions with 38 students
presenting their progress in research.
Thank you for your participation!
Organizing Committee:
Dr. Joseph Bausch, Dr. Willam Birdsall, Dr. Eduard Casillas, Dr. Robert Giuliano,
Dr. Scott Kassel, Dr. Brian Ohta, Dr. Robert Reczkowski, Dr. Barry Selinsky, Dr.
Kathleen Thrush, Dr. Deanna Zubris
Staff Participants:
Mrs. Nancy Proud, Mrs. Joan Davis
And last, but in no way least,
Graduate & Undergraduate Volunteers:
Mr. Carl Kaub, Ms. Nancy Ata, Mr. Chris DeFeo, Ms. Lauren DellaGreca, Mr.
Chris Jones, Ms. Gina Bartolomeo, Ms. Adrienne Kline, Ms. Kathleen Spencer,
Mr. Michael Berlinger, Ms. Meghan Klaric, Mr. Jeffrey Schubert, Mr. Kevin
Wiacek, Ms. Jennie DiLemmo, Ms. Liz Hauser, Ms. Peggy Greene, Ms. Emily
Ma, Ms. Karen Chiang, Mr. Henry Gannon, Ms. Emily Cushnie, Mr. Michael
Giuliano
4
Table of Contents

Sponsors
1

Schedule of Events
5

Presentation Schedule
6

Plenary Lecturer
7

ISCC Presentation Guidelines
8

Analytical/Physical Chemistry Presentation & Abstracts
9-12

Biochemistry I Presentation & Abstracts
13-16

Biochemistry II Presentation & Abstracts
17-20

Inorganic Chemistry Presentation & Abstracts
21-24

Organic Chemistry I Presentation & Abstracts
25-28

Organic Chemistry II Presentation & Abstracts
29-32

Judges
33

Attendees
34-36

Last Year’s Winners
37

Map of Villanova Campus
38
5
Schedule of Events
8:00-8:45 a.m.
Registration
Mendel Hall Lobby
8:30-8:45 a.m.
Judges’ Meeting
Mendel, Rm G08
8:45-9:00 a.m.
Opening Remarks/Bob Giuliano
Mendel, Rm 101
Greeting/Father Kail Ellis
Dean of Arts & Sciences,
Villanova University
9:00-12:00 p.m.
Mendel, Rm 101
Presentation of Papers

Analytical Chemistry
Mendel, Rm 115

Biochemistry I
Mendel, Rm 213

Biochemistry II
Mendel, Rm 256

Inorganic Chemistry
Mendel, Rm 154

Organic Chemistry I
Mendel, Rm 258

Organic Chemistry II
Mendel, Rm 260
11:40-12:00 p.m.
Business Meeting*
Mendel, Rm 213
12:30-1:30 p.m.
Lunch Buffet
Dougherty Hall,
Italian Kitchen
1:45-2:15 p.m.
2:20-2:50 p.m.
Plenary Lecture
Dr. Bruce E. Maryanoff
Presentation of Awards
Connelly Center Cinema
Connelly Center Cinema
* For the Business Meeting, at least one faculty member and one student from
each participating institution should attend this meeting.
Presentation Schedule
Room
9:00 - 9:20
9:20 - 9:40
9:40 - 10:00
10:00 - 10:20
10:20 - 10:40
10:40 - 11:00
11:00 - 11:20
115
Analytical
Myers
F&M
Norey
Muhlenberg
Sievering
Bucknell
Break
213
Biochemistry I
Wiles
Hood
Kenfu
IUP
Gehman
LVC
Break
256
Biochemistry II
Patri
Ursinus
Ewing
Hood
Wibowo
IUP
Break
154
Inorganic
Terzian
F&M
Bushey
LVC
Marks
Ursinus
Break
258
Organic I
Shimp
VU
Hoch
Ursinus
Steinbacher
F&M
Break
260
Organic II
Adedeji
Temple
Valentin
VU
Dempsey
Haverford
Break
Kelly
Ursinus
Kreischer
Bloomsburg
Vaughn
Hood
DeFeo
VU
Klim
Ursinus
O'Connor
Haverford
Kim
Haverford
Manges
IUP
Eller
UDel
Nathan
Muhlenberg
Fedors
F&M
Crecca
Bloomsburg
Birk
UDel
Baker
IUP
Micalizzi
VU
Thuma
UDel
Smith
Temple
Coleman
Ursinus
Cummings
VU
Hespell
F&M
11:20 - 11:40
11:40 - 12:00
Business Meeting
Plenary Speaker: Dr. Bruce E. Maryanoff, Ph.D.
Dr. Bruce E. Maryanoff was born in Philadelphia, Pennsylvania, and grew up there. He
earned a B.S. degree in chemistry from Drexel University in Philadelphia (1969) and continued at
Drexel to earn his Ph.D. degree in organic chemistry (1972) with Prof. Robert Hutchins. After
postdoctoral studies for two years at Princeton University with Prof. Kurt Mislow, he joined McNeil
Laboratories. He advanced through the ranks of the scientific ladder in McNeil Laboratories,
McNeil Pharmaceutical, and the Janssen Research Foundation (all Johnson & Johnson
companies) to Distinguished Research Fellow, the highest scientific-ladder position in the
company. Dr. Maryanoff became a part of the R. W. Johnson Pharmaceutical Research Institute
in 1990 and Johnson & Johnson Pharmaceutical Research & Development (J&JPRD) in 2001.
From 1976 to 1992, he principally worked on therapeutic agents for the treatment of disorders of
the central nervous system (CNS); in 1992, he moved to the field of cardiovascular research.
Presently, he is a Distinguished Research Fellow and Co-Leader of the Vascular Research Team
in the J&JPRD.
During his 28-year tenure with Johnson & Johnson companies, Dr. Maryanoff has made
numerous contributions to areas of chemical research including: heterocyclic chemistry (e.g.,
pyrroles, isoquinolines, indoles, and imidazoles); boron-based reducing agents; N-acyliminium ion
cyclizations; affinity labels for the opiate receptor; stereochemistry and mechanism of the Wittig
olefination reaction; carbohydrate and nucleoside chemistry; peptides and peptidomimetics. Over
the past 10 years, he has worked mainly in the following drug discovery areas: thrombin
inhibitors, fibrinogen receptor (GPIIb/IIIa) antagonists, antagonists for protease-activated
receptors, and vasopressin receptor antagonists. Dr. Maryanoff discovered TOPAMAX ®
topiramate, a unique sugar sulfamate drug that is marketed worldwide for the treatment of
epilepsy and is under development for other therapeutic indications. He has published ca. 200
scientific papers, is an inventor on 56 U.S. patents (issued or pending), has presented ca. 115
invited lectures at universities and scientific conferences, and was the inaugural editor of the book
series Advances in Medicinal Chemistry.
Dr. Maryanoff was twice a recipient of J&J's prestigious Philip B. Hofmann Research
Scientist Award (1978, 1987). In 1997, he was honored with the Johnson Medal for Research
and Development, the highest award in J&J, for his contributions to the discovery and
development of TOPAMAX®. In 1984 he received the Philadelphia Section Award of the
American Chemical Society (ACS), in 2000 he received a Heroes of Chemistry 2000 Award from
the ACS, and in 2003 he received the ACS Award in Industrial Chemistry. Dr. Maryanoff has
been honored by Drexel University as a notable alumnus with several awards, including election
to the Drexel Alumni 100 Club. He was elected Fellow of the Royal Society of Chemistry and the
American Association for the Advancement of Science.
Dr. Maryanoff has served professionally in numerous capacities, including: the Editorial
Advisory Boards of seven chemistry journals; a four-year term on the Advisory Board of the
Petroleum Research Fund of the ACS, a four-year term on the Medicinal Chemistry Study
Section of the National Institutes of Health; several years as member of the Board of Directors of
the ACS Philadelphia Section; Chair of the Philadelphia Organic Chemists’ Club; and Chairman
of the 1989 Gordon Research Conference on Organic Reactions and Processes. Also, he has
organized/chaired several symposia at ACS national and regional meetings.
8
ISCC Presentation Guidelines
Judges will evaluate student presentations using the guidelines described for
each of the five evaluation categories listed below and will select 1st and 2nd
place award winners in each division.
Scoring System
The guidelines for, and the maximum number of points to be awarded in each
evaluation category are as follows:
Maximum
Points
30
15
15
20
20
Evaluation Category
Presentation: Judges will evaluate the overall effectiveness of
the presentation, including organization of the material, the
quality of the oral delivery itself, poise shown by the speaker, the
clarity of the explanations, and the appropriate use of visual aids.
Violations of the time limit will incur penalties.*
Research Project: Judges will evaluate the relevance of the
project, including the case that is made for carrying out the work,
and the potential contribution of the project to the field of
chemistry.
Design of Investigation: Judges will evaluate the overall
experimental design, including the appropriate use of
experimental techniques, the creativity of the approach taken,
and the completeness of the experimental investigation.
Interpretation of Data & Conclusions: Judges will assess the
efficiency and clarity of the presentation of the experimental data,
the accuracy and completeness of the data analysis, and the
strength of the conclusions drawn.
Response to Questions: Consideration will be given to the
student’s ability to answer correctly and concisely any questions
asked. Each student will be asked 2 or more questions.
* The time limit for presentations is 12 minutes, and each speaker will be alerted
when one minute remains in their talk. A question period of 4 minutes will follow
each presentation. The remaining 4 minute period can be used for changing
rooms to hear talks in other sessions.
9
Analytical Chemistry Session
Mendel 115
Time
Speaker, Affiliation, Title
9:00 a.m.
Adam S. Myers, Franklin and Marshall University
“Glass analysis in a tetrafluoromethane glow discharge”
9:20 a.m.
Erica L. Norey, Muhlenberg College and Winterthur
Museum
“Authentication of Schimmel Woodcarvings”
9:40 a.m.
Jennifer Sievering, Bucknell University
“Effects of electrophoretic stacking on in-column mixing
and reaction in capillary electrophoresis”
10:00 a.m.
BREAK
10:20 a.m.
Brendan Kelly, Ursinus College
“Determination of Anesthetic Activity and Blood
Concentration of Alcohols in Goldfish and Eigenmannia
Virescens”
10:40 a.m.
Nathan Kreischer, Bloomsburg University
“Optimization of a Fluorescent Gel Slice Assay”
11:00 a.m.
Caitlin Vaughn, Hood College
“The Application of Chlorophyll Fluorescence as a
Measure of Algal Growth”
10
Glass analysis in a tetrafluoromethane glow discharge
Author: Adam S. Myers
Professor: Kenneth R. Hess
Type of Support: Hackman Scholars Program
School: Franklin and Marshall College
Project Duration: Summer 2002
Low pressure rare gas discharges have found application in the analytical community as
efficient atom sources for atomic spectroscopy and elemental mass spectrometry by directly
atomizing electrically conducting samples through physical sputtering. However, non-conducting
samples such as glasses and ceramics pose difficulties for analysis by glow discharge methods
because they cannot sustain a discharge. As an alternative to physical sputtering, the chemical
reactivity of certain gases such as tetrafluoromethane may be exploited to create atomic
populations through chemical etching. Specifically, investigations of adding 1%
tetrafluoromethane to an argon or neon gas plasma were completed. Previous results employing
x-ray fluorescence analysis of unique cathode surface deposits showed the addition of CF 4 to
liberate and redeposit atoms from an insulating ceramic (Macor) shield that was in the plasma
environment. These preliminary studies indicated the potential for the reactive gas to create
atomic populations from a non-conducting sample, and the goal of this project is to attempt to
implement chemical etching for the analysis of a National Institute of Standards glass sample
held in the plasma. A scanning electron microscope (SEM) stage was positioned in the discharge
to collect liberated material through redeposition. Material was collected from the discharge, and
the material exhibits glass-like characteristics under the SEM with a measurable electric
resistance. Analyses of the material by dissolving in acid followed by inductively coupled plasma
atomic emission spectroscopy were also attempted. These experiments provide a potential
method for the evaluation of relative erosion rates in the plasma, and may provide further insight
into the nature and cause of the observed surface effects in a tetrafluoromethane/argon plasma.
Authentication of Schimmel Woodcarvings
Author: Erica L. Norey
School: Muhlenberg College and Winterthur Museum
Professor: Dr. Marsha R. Baar and Ms. Janice Carlson
Project Duration: 8 weeks
Type of Support: Muhlenberg Undergraduate Summer Research Grant
Wilhelm Schimmel was a German immigrant who arrived in Cumberland County, PA
circa the 1860s and supported himself by bartering small wooden carvings for food, lodging, and
alcohol. Although his work was not greatly appreciated in the late nineteenth century, today his
woodcarvings of eagles, parrots, roosters, and squirrels have sold for tens of thousands of
dollars. Therefore the need for improved scholarship on the materials used by Schimmel is
essential for the authentication of sculptures.
Six sculptures within the Winterthur Museum’s collection attributed to Schimmel provided
the necessary reference scholarship. These 6 eagles were visually examined in both white and
UV light, by XRF and SEM-EDS to determine the pigments used, and by micro-FTIR and GC-MS
to identify binding media. Schimmel’s woodcarvings had a gesso preparation layer, were
varnished, and were painted with lead-based pigments. Stylistically his sculptures were squat,
deeply crosshatched, possessed parrot-like beaks and sharply defined toes.
My research involved the investigation of three additional woodcarvings, a rooster and
two eagles, tentatively attributed to Schimmel within the Winterthur collection. Rooster #65.1856
had some stylistic discrepancies but all materials were found consistent. Eagle #59.2340
although stylistically consistent, sustained extensive modern repairs to the paint and adhesives.
Eagle #59.2350 although stylistically similar, was not pigmented and was carved from better
quality wood.
11
Effects of electrophoretic stacking on in-column mixing and reaction in
capillary electrophoresis
Author: Jennifer Sievering
Professor: Dr. Timothy Strein
School: Bucknell University
It has been previously shown that nanoliter volumes of creatinine and picrate (Jaffe
Reaction) can be electrophoretically mixed in a capillary electrophoresis column to form a doubly
anionic Janovski complex having a strong absorbance at ~500 nm. Using electrophoretically
mediated microanalysis (EMMA), this chemistry has been applied to the analysis of clinical blood
and urine samples for the detection of creatinine. However, one drawback of the EMMA approach
is relatively poor detection sensitivity. This presentation will include discussion of recent attempts
to increase sensitivity via electrophoretic stacking and/or in-line multiple mixing steps.
Electrophoretic stacking of ions can result in a localized zone of high concentration, thus lowering
the detection limit for that ion. Results of the addition of varied identity and concentration of
inorganic salts to the reactant and buffer zones will be presented. In addition, the affect of rapid
polarity switching on reaction efficiency will also be described. Combining the effects of product
stacking and increased reaction efficiency should dramatically enhance the sensitivity of this
methodology.
Determination of Anesthetic Activity and Blood Concentration of Alcohols in Goldfish and
Eigenmannia Virescens
Author: Brendan Kelly
School: Ursinus College
Professor: Dr. Eric Williamsen
Project Duration: One summer and a semester (not including current semester)
Type of Support: HHMI, Camille and Henry Dreyfus Foundation, VanSant Fund of Ursinus
College
Brendan Kelly, Layali Eshqaidef, Tim D’Andrea, and Eric J. Williamsen. Department of Chemistry,
Ursinus College; 601 E. Main St.; Collegeville, PA 19426-1000.
Although anesthetics have effectively been used for many years, the molecular mechanism of
anesthesia is not well-understood, due in part to the diversity of compounds that lead to
anesthesia. One class of compounds that serve as anesthetics is alcohols. Goldfish and the
weakly electric fish Eigenmannia virescens have been exposed to saturated 1-alkanols from 1ethanol to 1-dodecanol for 1.0 to 20.0 min, and the anesthetic activity and blood concentration for
these compounds have been measured. Anesthetic activity was measured by observing the flip
time for goldfish and decrease in electric organ discharge (EOD) frequency for Eigenmannia, and
the blood concentration has been determined by gas chromatography/mass spectroscopy
(GC/MS). Measurements made on both types of fish show that the blood concentration and
anesthetic activity increase with exposure up to1-decanol, after which a decrease is observed.
Although differences in the magnitude of the effect occur between gold fish and Eigenmannia,
blood concentrations for both fish are higher than the concentration in the bathing solution for
longer chained alcohols. These results are of interest in the study of anesthesia and transport of
compounds through fish gills.
12
Optimization of a Fluorescent Gel Slice Assay
Author: Nathan Kreischer
Professor: Dr. Michael Pugh
School: Bloomsburg University
Project Duration: Fall 2002-Spring 2003
The kinetic parameters of two chymotrypsin substrates, N-Succinyl-Ala-Ala-Pro-Phe-7-Amido-4methylcoumarin and N-Succinyl-Ala-Ala-Phe-7-Amido-4-methylcoumarin were investigated by
fluorescent analysis and used to determine the optimum substrate for use in a gel slice detection
method. N-Succinyl-Ala-Ala-Pro-Phe-7-Amido-4-methylcoumarin yielded kinetic values of 5.1 x
10-6 M, 2.1 s-1, and 4.1 x 106 M-1s-1, and N-Succinyl-Ala-Ala-Phe-7-Amido-4-methylcoumarin
yielded values of 2.3 x 10-5 M, 4.6 x 10-1 s-1, and 2.0 x 104 M-1s-1 for Km, Kcat, and the specificity
constant, respectively. These results were compared to literature values of similar substrates
whose kinetic parameters were determined by spectrophotometric analysis. The optimum
substrate, N-Succinyl-Ala-Ala-Pro-Phe-7-Amido-4-methylcoumarin was used to detect
chymotrypsin in a Brewer and Ashworth pH 4.3 -Alanine tube gel system in amounts as low as
50 ng. Amounts ranging from 1 ug to 25 ug of chymotrypsin exhibit a linear correlation between
the nanomoles of product and the amount of chymotrypsin added to the gel. Further analysis will
be conducted to optimize the assay for the detection of chymotrypsin in lower amounts in this
system and others to show the versatility of this method.
The Application of Chlorophyll Fluorescence as a Measure of Algal Growth
Author: Caitlin Vaughn
School: Hood College
Professor: Dr. Drew Ferrier
Project Duration: Fall Semester 2002
Type of Support: Hood College Biology Department
Chlorophyll fluorescence can be a valuable tool for the determination of algal growth by cell
density. When a chlorophyll a molecule in the thylakoid membrane absorbs a photon, an electron
is raised from a ground state to an unstable excited state. In order to minimize the lifetime of this
excited state, the electron falls back down to ground state, giving off a photon; this afterglow is
called fluorescence. This principle has many applications, including the use of in vivo
fluorescence of chlorophyll as a measure for algal growth and cell density. The implications of
this are important, especially with respect to possible inhibitory allelopathic compounds. Barley
straw has been known to control freshwater algal blooms for decades, but not much is
understood concerning its effects on estuarine and marine algal species. To facilitate
experiments with these species, the principle of chlorophyll fluorescence was put to the test,
using a microplate-reader to take relative fluorescence measurements. The subsequent
microbioassay that was developed is currently being expanded for use with fractionated barley
straw extract in the hope of identifying the compound or group of compounds responsible for algal
growth inhibition.
13
Biochemistry Session I
Mendel 213
Time
Speaker, Affiliation, Title
9:00 a.m.
Christopher J. Wiles, Hood College
“The Identification and Biochemical Action of
Phytoalexin Extracted from Soybean”
9:20 a.m.
Abera Kenfu, Indiana University of Pennsylvania
“Two-hybrid analysis for detection of proteins
interacting with mouse growth hormone binding protein”
9:40 a.m.
Jennifer L. Gehman, Lebanon Valley College
“A Strategy for Cloning and Expression of E. coli GMP
Synthetase Mutants”
10:00 a.m.
BREAK
10:20 a.m.
Christopher DeFeo, Villanova University
“The Use of Receptor Chimeras to Understand the Nterminus of VR-1”
10:40 a.m.
Joseph Klim, Ursinus College
“Effects of Fluazifop and Fluoroacetate on Root
Exudates Involved in the Germination of the Parasitic
Weed Striga”
11:00 a.m.
Catherine O’Connor, Haverford College
“EF-hand Containing Proteins: Characterizing Their
Structure by the “Cut and Paste” Method”
11:40 a.m.
* Business Meeting
* For the Business Meeting, at least one faculty member and one student from
each participating institution should attend this meeting.
14
The Identification and Biochemical Action of Phytoalexin Extracted from Soybean
Author: Christopher J. Wiles
Professor: Dr. Sharon Smith
Type of Support: USDA ARS FDWSRU
School: Hood College
Project Duration: January-May 2003
The ability to induce microbial resistance in plants is of agricultural and economic significance.
Resistance in some plants is correlated to the production of low molecular weight phenolic
compounds collectively known as phytoalexins. Phytoalexins are thought to act by interfering
with plasma membrane function. In the case of soybean (Glycine max), the phytoalexin of our
interest has been previously identified as glyceollin. The production of glyceollin and its isomers
may confer resistance to many microbial infections, potentially including the fungal pathogen
Phakopsora pachyrhizi Sydow, which causes soybean rust. It is hypothesized that plants may be
screened for disease resistance by identifying the production of specific phytoalexins such as
glyceollin. Methods of identification and quantitation may include HPLC, UV-Vis spectroscopy,
and GC-MS. These techniques may allow for the further identification of resistance traits in
soybean and other plants.
Two-hybrid analysis for detection of proteins interacting with mouse growth hormone
binding protein
Author: Abera Kenfu
School: Indiana University of Pennsylvania
Professor: Dr. Southard
Type of Support: MERCK /AAAS Undergraduate Science Research Program
“Two-Hybrid Screening for GHBP-Interacting Proteins”
Protein-protein interactions are important to many cellular processes including DNA replication,
transcription, and translation. In this experiment we use two-hybrid screening to detect proteinprotein interactions. Previous studies indicate that growth hormone binding protein (GHBP)
associate with liver cell membranes by interacting with an unknown protein in the cells
membrane. In our experiment, we attempt to identify liver cell proteins that are able to interact
with growth hormone binding protein (GHBP) and that could signify the membrane protein that is
responsible for association of GHBP with the membrane. In the study we introduce plasmids
containing DNA for GHBP and for liver proteins into E. coli. Cells will be screened under
conditions where growth will occur only if GHBP interacts with a liver cell protein.
15
A Strategy for Cloning and Expression of E. coli GMP Synthetase Mutants
Author: Jennifer L. Gehman
Professor: Dr. Walter A. Patton
Type of Support: NIH R15 Grant
School: Lebanon Valley College
Project Duration: One year
E. coli guanosine-5’-monophosphate synthetase (GMPS) utilizes glutamine, XMP and ATP to
catalyze the formation of GMP. As the terminal enzyme in the de novo pathway for guanine
nucleotide synthesis, GMPS is a logical target for chemotherapeutic and immunosuppressive
therapies. To investigate the XMP- and ATP-binding sites in the carboxy-terminal domain of
GMPS, we are using site-directed mutagenesis to generate GMPS point-mutants. Concurrently,
we set-out to develop a cloning system for the generation of our mutants as fusion proteins, thus,
providing us with the capability to purify our mutant proteins from GMPS that is native to the
protein expression host. The strategy used for generating mutant GMPS constructs as well as
the cloning of our constructs into the Intein expression system will be discussed. Initial kinetic
characterization of WT-GMPS expressed and purified using this system shows we have
generated a system that will allow affinity purification of our mutants away from endogenous
GMPS, without affecting the integrity of the recombinant protein.
O
O
N
HN
O
O
HO
Glutamate
AMP + PPi
H2N
OH
XMP
N
N
O
O
GMP
Synthetase
N
HN
N
N
H
O
HO P O
OH
Glutamine
ATP
HO P O
OH
HO
OH
GMP
The Use of Receptor Chimeras to Understand the N-terminus of VR-1
Author: Christopher De Feo
Professor: Dr. Joseph Rucker
Type of Support: HHMI
School: Villanova University
Project Duration: Summer 2001-Spring 2003
Vanilloid receptor subtype 1 (VR1) is a protein found on the surface of neurons that are
responsible for pain response. VR1 is activated by several different stimuli including noxious heat
(>43° C), low pH, and in particular, the vanilloid capsaicin, the active ingredient in ‘hot’ chili
peppers. When capsaicin or other vanilloid compounds bind to VR1, a cation channel is
activated, which allows calcium and other cations into the cell. Cation influx into the cell causes a
change in the cell potential and presumably plays a role in pain transduction. A similar receptor,
vanilloid receptor-like protein 1(VRL-1), only shows responsiveness to noxious heat (>52° C).The
function of the N-terminus of VR1 was examined by the construction of two receptor chimeras.
The chimeras were made by exchanging the N-termini of VR1 and of VRL-1. Using a
fluorescence-based calcium influx assay, the activation of VR1 and the chimeras could be
followed and it was determined that the body of VR1, rather than the N-terminus, was necessary
for activation by capsaicin binding. Dose-response studies suggest that VR1 and CD1 have
similar affinity to capsaicin, while CD1’s calcium permeability appears to be reduced. The
reduced permeability of calcium through CD1 made it difficult to quantify an EC 50 value for
comparison with VR1 data. Preliminary studies suggest that they are similar 317 +/-21 nM for
VR1 versus 356 +/- 156nM for CD1. Expression levels were also compared qualitatively using
western blot analysis and it seems that both proteins were expressed equally.
16
Effects of Fluazifop and Fluoroacetate on Root Exudates Involved in the Germination of
the Parasitic Weed Striga
Author: Joseph Klim
School: Ursinus College
Professor: Thomas Ruttledge
Project Duration: 3 semesters
Type of Support: HHMI, VanSant Fund of Ursinus College, Staiger Fund of Ursinus College
The first step involved in parasitism by the weed Striga is germination as a direct response to
stimulants exuded by the roots of a host plant such as Sorghum. One of multiple stimulants
exuded by Sorghum is the labile hydroquinone SXSg. A structurally similar compound also
exuded by the host root, resorcinol, does not cause germination but rather acts as an antioxidant
to stabilize SXSg in the soil. Earlier studies by Fate, et al. suggested that these two structurally
similar compounds share the same biosynthetic pathway. However, based on differences in fatty
acid side chain saturation between SXSg and resorcinol found by Erikson, et al. and the
differential effects of the chemical inhibitors fluoroacetate and fluazifop on the relative
abundances of the two compounds in the root exudates as determined by GC/MS presented in
this study, we would suggest that it is unlikely that these two compounds share the same
biosynthetic pathway as suggested by Fate, et al.
EF-hand Containing Proteins: Characterizing Their Structure by the “Cut and Paste”
Method
Author: Catherine O’Conor
School: Haverford College
Professor: Karin Akerfeldt
Project Duration: May 2002-May 2003
Type of Support: Haverford College, HHMI, NSF
Calcium ions, and thus calcium-binding proteins, are important in a variety of cellular functions.
One important class of calcium-binding proteins contains EF-hands. This helix-loop-helix motif
binds calcium, allowing the protein to function as either a sensor or a buffer of this ion. In an
effort to determine the domain organization of a protein containing six EF-hands, Calbindin D28k,
a “cut and mix” method was employed by Linse, Åkerfeldt et al. in 19971. This experiment
showed all six EF-hands to associate, forming a single globular domain. In order to further
evaluate this “cut and mix” method, the experiment was repeated on two EF-hand-containing
proteins of known structure, Calmodulin and the Sarcoplasmic Calcium Binding Protein (SARC).
These proteins both contain four EF-hands, yet have very distinct domain organizations. This
method successfully proved the structure of Calmodulin, yet the results from SARC were
inconclusive. In order to improve on these results, the experiment on SARC is currently being
repeated, this time synthesizing the same sequences but containing the hydrophobic tail of the Cterminal EF-hand and the connecting loops. The four segments, 40 to 46 amino acid residues
long, have been synthesized by solid-phase methods, and we are currently in the process of
purifying them, along with carrying out some initial biophysical measurements.
1Linse,
S., Thulin, E., Gifford, L.K., Radzewsky, D., Hagan, J., Wilk, R.R., Åkerfeldt, K.S. (1997).
Domain Organization of calbindin D28k as determined from the association of six synthetic Efhand fragments. Protein Science 6, 2385-2396.
17
18
Biochemistry Session II
Mendel 256
Time
Speaker, Affiliation, Title
9:00 a.m.
Rahul Patri, Ursinus College
“GC-MS Analysis of SXSg-DMDS Adducts in order to
Analyze the location of the Double Bonds in the Fatty
Acid Tails of Sorghum Root Exudates”
9:20 a.m.
Laura Ewing, Hood College
“Real Time RT-PCR analysis of gene expression
during the first 14 days post inoculation of the
soybean rust fungus, Phakopsora pachyrhizi”
9:40 a.m.
Ardian Soca Wibowo, Indiana University of
Pennsylvania
“Ultradian Rhythms of Paramecium”
10:00 a.m.
BREAK
10:20 a.m.
Hyemin Kim, Haverford College
“Synthesis Toward a Templated Alamethicin Ion
Channel”
10:40 a.m.
Sherri Manges, Indiana University of Pennsylvania
“In Vitro Translation Products of Tomato Mosaic Virus
RNA and Real Time Polymerase Chain Reaction
(PCR) Analysis”
11:00 a.m.
Christopher J. Eller, University of Delaware
“Structural Analysis of Pseudouridine Synthesis by
Circular Dichroism ”
19
GC-MS Analysis of SXSg-DMDS Adducts in order to Analyze the location of the Double
Bonds in the Fatty Acid Tails of Sorghum Root Exudates
Author: Rahul Patri
School: Ursinus College
Professor: Dr. Thomas Ruttledge
Project Duration: 2 semesters
Type of Support: HHMI, Staiger Fund of Ursinus College, Vansant Fund of Ursinus College
Striga asiatica is a parasitic angiosperm that is stimulated by the germination
stimulants produced by Sorghum hosts. SXSg (dihydrogsorgoleones) with one,
two, or three units of unsaturation in their fatty acid chain which, are produced as
root exudates from Sorghum plants have been discovered to act as germination
stimulants. SXSg-Dimethyl disulfide (DMDS) adducts have been produced in
order to elucidate the exact position of double bonds as the adducts preferentially
cleave at the double bond sites when analyzed through GC-MS. Since the
hydroxyl groups of the SXSg are highly unstable and reactive during the reaction
with DMDS, they had to be derivatized. First, the SXSg was derivatized using
BSTFA (Silation). Since the mass of the derivative was greater than the high end
of GC-MS and due to low efficiency, another mode of derivatization had to be
chosen. Thus, the hydroxyl groups of the SXSg were methylated with the aid of
NaH/CH3I (THF).
Real Time RT-PCR analysis of gene expression during the first 14 days post inoculation of
the soybean rust fungus, Phakopsora pachyrhizi
Author: Laura Ewing
School: Hood College, Frederick, MD
Professor: Sharron Smith, Ph.D., Whitaker Prof. of Chemistry, Hood College, Frederick, MD
On-site Supervisors: Reid D. Frederick, Ph.D., Research Molecular Biologist, USDA-ARS
Foreign Disease-Weed Science Research Unit, Fort Detrick, MD and Martha-Lucia Posada,
Ph.D., Computational Biologist, DOE Joint Genome Institute, Walnut Creek, CA
Soybean rust, caused by the fungus Phakopsora pachyrhizi, is responsible for significant losses
of soybean crop in Africa, Asia, Australia and South America. If it enters the continental United
States it could decrease yields in southeastern states. An understanding of early pathogen-host
interactions between P. pachyrhizi and soybean is crucial for development of strategies to
prevent and combat soybean rust. In this study, Real Time RT-PCR was used to examine the
expression of five putative genes: heat-induced catalase, ATP-binding cassette (ABC)
transporter, plasma membrane (H+) ATPase and  and -tubulin obtained from an EST library of
P. pachyrhizi germinating spores (Posada and Frederick, manuscript in preparation). Primers
and fluorogenic probes were designed for each of the five genes and used to determine their
relative levels of expression in germinating spores and infected leaf tissue at 1,2,4,6,8,10,12,14
days post inoculation (dpi). Gene expression was monitored using the threshold cycle (C T) which
is the first cycle in which a significant increase in normalized Reporter (R n) is detected. All five
genes showed similar expression patterns during the first 14 dpi. Expression levels of the genes
change during the course of infection; however, the variation is likely due to increasing fungal
growth. Current studies are being conducted using in vitro transcription to produce RNA template
for generating standard curves which can be used to quantify the amount of original transcript at
each time point. The relative expression of the heat-induced catalase, ABC transporter and
ATPase genes will be normalized against the two constitutive genes,  and -tubulin.
20
Ultradian Rhythms of Paramecium
Author: Ardian Soca Wibowo
School: Indiana University of Pennsylvania
Professor: Dr. Hinrichsen
Project Duration: Semester and a half (about 6 months)
Type of Support: Merck/AAAS Undergraduate Research Program
The research studies the response of Paramecium, a protozoon, to various inputs into its
environment. Specifically, lithium, caffeine and BHQ were introduced into the Paramecium
environment to see how they effect the normal ultradian swimming rhythms of these protozooans.
These substances are known to effect their inositol cycle, which regulates calcium processes,
which in turn have influence on ion channels and ciliary beating, thus disrupting the normative
ultradian swimming rhythms.
Paramecium normally swims with a regular ultradian rhythm. The pattern is like a wave
oscillation with intervals forward swimming, and intervals when the cells undergo avoidance
reactions, swimming backwards. The cilia turn 180 degrees to allow the cell to swim backwards
to avoid obstacles. These avoidance reactions require intake of calcium to perform the backward
ciliary beating. The role of calcium is important to understanding how lithium is able to disrupt
this process.
Ultimately, it is widely accepted that lithium is involved in the inhibition of inositol
monophospatase (IMPase) in the inositol cycle. Lithium consequently depletes inositol and stops
the calcium cycle involved in ciliary beating. However, it’s still uncertain how exactly lithium
disrupts the IMPase in the cycle, and to what extent. The major part of the research explores
how lithium affects the ultradian rhythms of paramecium. Another aspect is to create mutants
that will tolerate higher levels of lithium and to determine if adding more lithium to these mutants
will still affect them in the same way as normal paramecium cells would be affected.
Synthesis Toward a Templated Alamethicin Ion Channel
Author: Hyemin Kim
Professor: Dr. Karen Åkerfeldt
School: Haverford College
Ion channel proteins are crucial in communicating between cells and regulating cellular
behavior. To mimic the natural ion channels and study their conductance properties an attempt is
being made at synthesizing a simplified model. Alamethicin is a naturally occurring peptide that
forms ion channels when incorporate into lipid bilayers. The problem is that it forms channels of
different size. In order to freeze out one size, we are attempting to attach the alamethicin peptide
to a cyclic template, -cyclodextrin. We will describe the synthesis of the cyclodextrin template in
which all six primary hydroxyl groups have been functionalized in order to be coupled to the
peptide. In this construct, all secondary hydroxyl groups have also been protected as methyl
ethers. The details of the synthetic route will be presented.
21
IN VITRO TRANSLATION PRODUCTS OF TOMATO MOSAIC VIRUS RNA AND REAL TIME
POLYMERASE CHAIN REACTION (PCR) ANALYSIS
Author: Sherri Manges
School: Indiana University of Pennsylvania
Professor: Dr. N. Bharathan
Project Duration: 6 months
Type of Support: MERCK/AAAS Undergraduate Research Program
Tomato Mosaic Virus (ToMV) is an important virus that infects the forest ecosystem and several
agricultural crops, such as the tomato. In an attempt to characterize the virus and develop
sensitive detection techniques, ToMV RNA was translated from purified virions in the rabbit
reticulocyte lystae (RRL) system, using tRNA-mediated biotin labeling (Amersham). Proteins of
various sizes were produced, but only two polypeptides, of 17,800 and 14,400 daltons were
immunoprecipitated with polyclonal antibodies, which are produced against ToMV. The RRL
products, translated in the absence and presence of dithiothreitol (DTT), were compared for
proteolytic processing. Results indicate that there is no appreciable change in the ToMV’s RNA
translation products, with or without the DTT, suggesting very little or no cleaving into smaller
proteins during incubation with DTT. In an attempt to characterize the ToMV RNA, Real-Time
PCR was performed incorporating an intercalating dye SYBR GreenR. The designed primers
were identical to bases 5349-5370 (5’-GAGTGCGGGCTACTGC CCTTTG) and complementary
to bases 6367-6384 (5’- TGGGCCCCAACCGGGGGT). Temperature profiles, growth curves, and
melting curves were used to monitor the PCR amplification. The gel analysis of the PCR products
revealed 800 base pairs (bp) and 600 bp fragments intrinsic to the coat-protein gene of ToMV.
Structural Analysis of Pseudouridine Synthesis by Circular Dichroism
Author: Christopher J. Eller
School: University of Delaware
Professor: Eugene G. Mueller
Project Duration: June 2002 - May 2003
Type of Support: Howard Hughes Medical Institute, UD Undergraduate Research Program
The pseudouridine synthases catalyze the isomerization of uridine to pseudouridine in RNA. The
E. coli pseudouridine synthase TruB catalyzes the isomerization of a uridine in the T-arm stem
loop (TSL) of tRNA to pseudouridine. In addition to an absolutely conserved aspartate, three
families of pseudouridine synthases share highly conserved lysine and proline residues (K19 and
P20 in TruB) [Koonin, E. V. Nucleic Acids Res., 1996, 24:2411-2415]. The catalytic activity of
P20G TruB is comparable to that of wild-type TruB. Surprisingly, the CD spectrum of P20G TruB
is of significantly reduced intensity, suggesting a substantial loss of secondary structure in 50 mM
phosphate buffer, containing ammonium chloride (100 mM), pH 7.5. The CD spectrum intensity
does not increase upon the addition of excess substrate, suggesting that the enzyme does not
refold in the presence of substrate. The CD spectra of P20G TruB and wild-type TruB are
equivalent however, if ammonium chloride is replaced with sodium fluoride, suggesting that
sodium or fluoride ion stabilizes P20G TruB. E. coli TruB- mutants are at a selective
disadvantage to wild-type E. coli, but transformation of these cells with the gene for the
catalytically inactive D48C TruB reverses this growth effect [Gutgsell, et al., RNA, 2000, 6:18701881]. A 17-mer RNA substrate, corresponding to the TSL, undergoes two thermal transitions
when subject to thermal denaturation. The melting temperature of the first transition increases in
the presence of D48C TruB, suggesting that the pseudouridine synthases might serve as RNA
chaperones.
22
Inorganic Chemistry
Mendel 154
Time
Speaker, Affiliation, Title
9:00 a.m.
James Terzain, Franklin and Marshall College
“Intramolecular Coordination in Organosilanes”
9:20 a.m.
Jared Bushey, Lebanon Valley College
“Integral Equation Theory for Counterion Interactions in
Associating Polymer”
9:40 a.m.
Brian C. Marks, Ursinus College
“An Investigation of the Mechanism of the Sodium
Borohydride Reduction of Benzil”
10:00 a.m.
BREAK
10:20 a.m.
Jared J. Nathan, Muhlenberg College
“Development of an Asymmetric Intermolecular Heck
Reaction”
10:40 a.m.
Nathan Fedors, Franklin & Marshall College
“The Synthesis of Transition Metal Apatites”
11:00 a.m.
Christina Crecca, Bloomsburg University
“Computational Investigation of Geometric Effects on
the Spectra of Vanadyl Complexes”
11:20 a.m.
Denise A. Birk, University of Delaware
“Synthesis and Characterization of Irontris(pyrazolyl)borate complexes”
11:40 a.m.
Thomas A. Baker, Indiana University of Pennsylvania
“The effect of polarity on hydrogen bond energies
involving imidazole”
23
Intramolecular Coordination in Organosilanes
Author: James Terzian
Professor: Claude H. Yoder
Type of Support: PRF
School: Franklin and Marshall College
Project Duration: one year
Numerous penta- and hexa-coordinated organosilicon species achieve intramolecular
coordination via a ligand containing either an aryl, amide, or ester functionality. The present
research attempts to discover if aliphatic ligands containing an amino functionality can coordinate
intramolecularly to silicon. Thus far, the following compounds have been prepared and
characterized: MeSi(O(CH2)2NMe2)3, Me2Si(O(CH2)2NMe2)2, Ph2SiClN((CH2)3NMe2)2,
PhSiCl2N((CH2)3NMe2)2, (t-bu)2Si(OTf)N((CH2)3NMe2)2, and EtO3SiN((CH2)3NMe2)2 .
NMR spectroscopy confirms that none of these novel organosilicon species exhibit intramolecular
coordination between the nitrogen heteroatom located on the aliphatic ligand and silicon. The
syntheses of F3Si derivatives containing the N((CH2)3NMe2)2 substituent will be pursued and the
effect of the nature of the ligand on intramolecular coordination will be discussed.
Integral Equation Theory for Counterion Interactions in Associating Polymer Melts
Author: Jared Bushey
Professor: Kathleen Kolbet
Type of Support: Institutional
School: Lebanon Valley College
Project Duration: 1 year
Microscopic polymer integral equation theory (PRISM) is used to investigate the effects of
counterions on the structure and clustering of telechelic ionomer melts. The counterions are
modeled as hard spheres with strong attractions to the ionic groups on the polymer chain in
addition to repulsions to each other. A variety of intermolecular potentials are used to describe
the interactions. The varying effects of the potentials on the microdomain clustering, effective
composition, and structure factors are explored.
An Investigation of the Mechanism of the Sodium Borohydride Reduction of Benzil
Author: Brian C. Marks
Professor: Dr. Victor Tortorelli
Type of Support: institutional funds
School: Ursinus College
Project Duration: 7 months
The reduction of benzil by sodium borohydride is a common undergraduate laboratory
experiment, but the mechanism has not been well understood. In the reduction of benzil, a
mixture of stereoisomeric diols are produced: (1R,2S)-hydrobenzoin (meso),
(1R,2R)-hydrobenzoin, and (1S,2S)-hydrobenzoin. It was determined that the reduction of benzil
favors the meso diastereoisomer. Sodium borodeuteride was used in the reduction of benzoin to
produce monodeuterated hydrobenzoin and benzil to produce dideuterated hydrobenzoin. Benzil
was then reduced with an equimolar ratio of NaBH4:NaBD4, and the analysis of the products
offered insight into the mechanism of this reaction. All products were characterized by FT-IR, 1H
NMR, and 13C NMR spectroscopy, as well as GC/MS, which required silylation of the products.
Analysis of our data will allow us to make some conclusions about the mechanism of this
reaction.
24
Development of an Asymmetric Intermolecular Heck Reaction
Author: Jared J. Nathan
Professor: Charles E. Russell
Type of Support: Departmental
School: Muhlenberg College
Project Duration: Academic year
The Heck reaction of aryl halides with allylic alcohols is catalyzed by palladium(0) and gives arylsubstituted carbonyl compounds.
Our goal is to apply this to symmetrical alkene diols such as cis-2-buten-1,4-diol (1) in an
enantioselective reaction using a chiral ligand. The products obtained would be useful
intermediates in natural products synthesis. The initially formed hydroxy aldehyde (2) cyclizes to
give the lactol (3). Oxidation with PCC gives the lactone (4).
OH
Ar
X
+
OH
Pd(0) cat.
CH2 CH CH CH2
O
OH
CH2 CH CH2 CH
O
H2C
L
PCC
O
H2C
CH CH2
Ar
2
1
OH
Ar
3
O
CH CH2
Ar
4
The Synthesis of Transition Metal Apatites
Author: Nathan Fedors
Professor: Claude Yoder
Type of Support: PRF
School: Franklin & Marshall College
Project Duration: one year
The limits on metallic cations able to form apatitic structures have been reported but the presence
of literature preparations of first-row transition metal hydroxyapatites, specifically zinc, copper and
manganese, casts doubt on these cation size limitations. We report on our attempts to prepare
these compounds. A new synthetic preparation has been developed to prepare lead and calcium
apatites: Pb5(PO4)3Cl, Pb5(PO4)3Br, Pb5(PO4)3F and Ca5(PO4)3Cl from metal halides and
(CH3O)3PO. The products have been identified with X-ray diffraction and ICP spectrometry.
Computational Investigation of Geometric Effects on the Spectra of Vanadyl Complexes
Author: Christina Crecca
Professor: Wayne Anderson
Type of Support:
School: Bloomsburg University
Project Duration: 3 semesters
Oxovanadium (IV), vanadyl, complexes are known to exist in square pyramidal, nearly trigonal
bipyramidal, and cis or trans octahedral geometries. To date, factors influencing these
geometrical preferences and the spectroscopic changes that occur upon change of geometry are
not well understood. In fact different spectroscopic techniques sometimes suggest different
geometries.
In order to gain a basic understanding of the effect of geometry on IR, UV-visible, and
photoelectron spectra of such systems, we have carried out density functional theory calculations
on a series of small vanadyl complexes. Results of calculated UV-visible and photoelectron
spectra as a function of geometry will be presented. Implications of these small complex
calculations on larger vanadyl complexes will be discussed.
25
Synthesis and Characterization of Iron-tris(pyrazolyl)borate complexes
Author: Denise A. Birk
Professor: Klaus H. Theopold
Type of Support: DOE Grant ER14273
School: University of Delaware
Project Duration: July 2002 – Present
Cobalt-tris(3-t-butyl-5-methylpyrazolyl)borate (Tp') complexes have been known for over a
decade and remain a focus of the Theopold group's research today. However, iron complexes
analogous to these cobalt systems have been a recent topic of interest. In particular, comparison
of a Tp'-iron superoxo complex with its well-known cobalt analogue could yield valuable
information about trends in reactivity and may provide a route to oxygenation catalysis. This
complex is being synthesized via an iron(I)-dinitrogen compound which is still being
characterized. This talk will discuss the synthesis and characterization of the supposed dinitrogen
complex and its precursor, Tp'FeI.
The effect of polarity on hydrogen bond energies involving imidazole
Author: Thomas A. Baker
School: Indiana University of Pennsylvania
Professor: Dr. Ronald F. See Project Duration: 10 months
Type of Support: Merck/AAAS Undergraduate Research Program
The effects of a polar medium on the energies of hydrogen bonds involving imidazole were
investigated by molecular orbital calculations at the B3LYP/6-31G* level. A hydrogen bond from
imidazole to Fe-bound O2 may be an important factor in the stabilization of O2, relative to CO, in
the active site of myoglobin. The gas-phase hydrogen bond energy in the complex
im•••Fe(por)(im)(L) was calculated to be 37 kJ/mol when L = O 2, and about 18 kJ/mol when L =
CO or NO; this difference in gas-phase hydrogen bond stabilization energy (~19 kJ/mol) is too
large for the observed effect of the protein on ligand binding. However, gas-phase calculations
may not be entirely realistic for the active site of a protein. SCI-PCM is a technique that allows the
effect of a polar medium to be included in a molecular orbital calculation. Unfortunately, SCI-PCM
did not work for metals, so H2O, (NH2)O and SO were used in place of the Fe-bound O2. It was
found that, with all three acceptors, the hydrogen bond energy decreased with increasing polarity
of the calculation. The implications of these results for ligand stabilization in myoglobin will also
be discussed.
26
Organic Chemistry Session I
Mendel 258
Time
Speaker, Affiliation, Title
9:00 a.m.
Heidi Shimp, Villanova University
“A Nazarov Approach to 4,5-Disubstituted
Cyclopentanone: A Route to Helminthosporal”
9:20 a.m.
Jessica Hoch, Ursinus College
“The study of Phenylketene trimers”
9:40 a.m.
Jeremy L. Steinbacher, Franklin & Marshall
“Towards the Synthesis of Pleiadene-Cored
Dendrimers”
10:00 a.m.
BREAK
10:20 a.m.
Douglas Micalizzi, Villanova University
“Synthetic Studies of the Polyketomycin Disaccharide”
10:40 a.m.
Benjamin A. Thuma, University of Delaware
“Synthesis of -methylcarbonyl-4, 5-dimethoxy-tetralone from 4,5-dimethoxyl-indenone via BF3 .OEt2
mediated ring expansion.”
11:00 a.m.
Traci Smith, Temple University
“Pyridone Chemistry and Photoreactivity”
27
A Nazarov Approach to 4,5-Disubstituted Cyclopentanone: A Route to Helminthosporal
Author: Heidi Shimp
Professor: Dr. Eduard Casillas
School: Villanova University
The purpose of this project is the total synthesis of the natural product helminthosporol.
Helminthosporol is a phytotoxin which has been found to be an inhibitor of Acyl-CoA cholesterol
acyltransferase (ACAT). Inhibition of ACAT has strong potential to reduce the absorption of
dietary cholesterol. The multi-step synthesis highlights several essential reactions such as a silyldirected Nazarov cyclization as well as a Darzens condensation of a 4,5 disubstituted
cyclopentenone. The recently optimized Nazarov approach also marks a branch point at which
analogs of helminthosporol may be pursued. After synthesis of helminthosporol and its analogs is
complete, measurements of the ACAT inhibition of these molecules will be studied.
O
OH
O
OBz
Helminthosporol
The Study of Phenylketene Trimers
Author: Jessica Hoch
Professor: Dr. Ronald Hess
School: Ursinus College
Project Duration: One year
Arylketenes, such as phenylketene, are produced from the reaction of arylacetyl chloride with
triethylamine in refluxing ether. These highly reactive molecules rapidly form dimmers, then
trimers which can be isolated as solids from ethereal solutions. This synthesis has been
extended to para-substituted phenylketenes and several of these trimers have been prepared.
This paper describes our attempts to synthesize trimers of m- and o- substituted phenylketene,
presently unknown.
These arylketene trimers can undergo catalytic hydrogenation to form “dihydrodimers” and
2,4-diarylcyclobutenone. This reaction was studied, comparing the behavior of phenylketene
trimer with that of its para-substituted relatives.
28
Towards the Synthesis of Pleiadene-Cored Dendrimers
Author: Jeremy L. Steinbacher
Professor: Marcus W. Thomsen
Type of Support: Internal college grants
School: Franklin & Marshall College
Project Duration: 6 months
Various aromatic species can be used as core molecules for dendritic systems that facilitate the
funneling of energy towards the core. Methyl benzoate-terminating linkages have been prepared
for use as branches in a convergent approach to the synthesis of quinizarin-cored dendrimers. In
addition, the potential of other polyaromatic species, such as substituted pleiadenes, to be used
as dendrimer core molecules has been investigated. The dendrimers have been characterized by
infrared spectrscopy and NMR.
Synthetic Studies of the Polyketomycin Disaccharide
Author: Douglas Micalizzi
School: Villanova University
Professor: Dr. Robert Giuliano
Project Duration: one year
Type of Support:
ACS-PRF Type B Grant, Howard Hughes Medical Institute,
Villanova University Chemistry Department
Polyketomycin is an anthracylcine antibiotic that contains an unusual disaccharide consisting of
D-amicetose and L-axenose attached by an -1,4 glycosidic linkage. The disaccharide of
polyketomycin is thought to be important to the drug’s function and transport through cell
membranes. Synthesis of this disaccharide has not been reported and is an important step in
structure-activity studies as well as in development of routes to polyketomycin analogs. The
goals of this project are to develop a synthesis of suitable monosaccharides for the construction
of the polyketomycin disaccharide, and also to explore the -glycosylation of amicetose.
The Polyketomycin Disaccharide:
H3C
H3C
OH
O
O
O
OR
D -amicetose
HO CH3
L-ax enos e
29
Synthesis of -methylcarbonyl-4, 5-dimethoxy--tetralone from 4,5-dimethoxyl-indenone
via BF3 .OEt2 mediated ring expansion
Author: Benjamin A. Thuma
Professor: Dr. Douglass F. Taber
School: University of Delaware
Project Duration: 1 Month
Abstract: Synthesis of -methylcarbonyl-4, 5-dimethoxy--tetralone from
4,5-dimethoxyl-indenone via BF3 .OEt2 mediated ring expansion.
A one or two step synthesis of the intermediate -methylcarbonyl-4, 5-dimethoxy-tetralone would improve the overall yield of the (-) - morphine synthesis. It has been reported
that -ketoesters were formed by BF3 .OEt2 mediated reaction as ethyl diazoacetate with
ketones. We examined the question of regioselectivity of that reaction with the hopes of
producing the desired -tetralone. In fact, the insertion was highly selective, although it did not
give the tetralone we desired.
Pyridone Chemistry and Photoreactivity
Author: Traci Smith
Professor: Dr. Scott Sieburth
School: Temple University
Project Duration: Fall 2002-Spring 2003
A chlorinated trans dimer will be generated from N-butyl-2-pyridone. First, the N-butyl-2-pyridone
was made from 2-hydroxypyridine with a 39% yield. The reaction was completed again with a
65% yield. The N-butyl-2-pyridone was taken and immersed in methanol and placed under UV
light for one week. Beginning reactions yielded around 2%. Various techniques have been used
to create and increase in the resulting yield. By varying the amounts of methanol and trans dimer
used the crystalline product will either stay in solution or form the crystals. The resulting
compound was a crystalline trans dimer and a liquid cis dimer. The trans dimer was isolated from
the cis product by vacuum filtration with hexane and ethyl acetate. A saturated chlorine solution
will be used to chlorinate the trans product.
30
Organic Chemistry Session II
Mendel 260
Time
Speaker, Affiliation, Title
9:00 a.m.
Adedamola Adedeji, Temple University
“Regioselective Synthesis of N-alkyl pyridones”
9:20 a.m.
Valerie Valentin, Villanova University
“Synthesis of Glycal Derivatives of Trideoxy Sugars”
9:40 a.m.
Logan Dempsey, Haverford College
“Synthesis and Characterization of a Porphyrin Dimer
System”
10:00 a.m.
BREAK
10:20 a.m.
Jeffrey Coleman, Ursinus College
“Preparation of Sorghum Seed Germination Stimulant
Polyketide Precursors”
10:40 a.m.
Christopher Cummings, Villanova University
“Synthesis of Vinyl Glycosides and Their Cyclopropyl
Derivatives”
11:00 a.m.
Jennifer L. Hespell, Franklin & Marshall
“Synthesis of substituted pleiadenediones”
31
Regioselective Synthesis of N-alkyl Pyridones
Author: Adedamola Adedeji
Professor: Prof. Scott Sieburth
School: Temple University
The Regioselective synthesis of N-alkyl pyridones can be facilitated of 2-hydroxypyridones with
phenyl halides. The synthesis are high yielding with the photochemistry been taken into
consideration.
Synthesis of Glycal Derivatives of Trideoxy Sugars
Author: Valerie Valentin
School: Villanova University
Professor: Dr. Robert Giuliano
Project Duration: six months
Type of Support: Petroleum Research Fund of the American Chemical Society,
Villanova University Chemistry Department
The trideoxy sugars amicetose and rhodinose occur in oligosaccharide components of several
antibiotics including axenomycin, polyketomycin, and landomycin. Synthesis of these
oligosaccharides requires access to glycosyl donors for these trideoxy sugars. A versatile
intermediate that has found wide application in the synthesis of oligosaccharides is the "glycal,"
also known as a 1,2-anhydro sugars. Structures of glycals of D-amicetose ( D-amicetal) and Lrhodinose (L-rhodinal) are shown below. Glycals can be used as glycosyl donors
CH3
O
O
D-amicetal
HO
CH3
L-rhodinal
HO
themselves, or converted to a variety of other glycosyl donors. We have been investigating the
use of iodo ester derivatives for use in the Roush glycosylation.
32
Synthesis and Characterization of a Porphyrin Dimer System
Author: Logan Dempsey
School: Haverford College
Professor: Suzanne Amador-Kane, Julio de Paula and Karin Åkerfeldt
Project Duration: Ongoing
Type of Support: Packard Foundation Grant
Chlorophylls are pigments found in plants that act as antennaes to absorb photons from sunlight
and pass their energy on to the reaction center where it is converted to chemical energy. W e are
attempting to utilize the natural light-harvesting abilities of porphyrins, biomolecules closely
related to chlorophylls, to create nanodevices capable of energy and electron transfer. We will
describe the design and synthesis of a Self-Assembled Monolayer (SAM) system in which
tetraphenylporphyrin (TPP) is covalently bound to a gold surface via a thiol terminated linker. A
synthetic route is proposed for attaching an alykl thiol linker to monoaminotetraphenylporphyrin
(maTPP). Methods for physical characterization of the system are also proposed. We will also
present the synthesis of a porphyrin dimer system, in which two porphyrins are linked to each
other via a disulfide bond. The characterization of the system using techniques such as circular
dichroism and UV-Vis spectroscopy will also be discussed.
Preparation of Sorghum Seed Germination Stimulant Polyketide Precursors
Author: Jeffrey Coleman
Professor: Dr. Thomas Ruttledge
School: Ursinus College
Project Duration: 8/2002 – 5/2003
Striga asiatica is an extremely dangerous hemiparasite that attacks monocotyledons such as
maize, sorghum, rice and millet. Germination of Striga seeds requires special conditions which
are culminated with exposure to several host and non-host derived root exudates, or germination
stimulants, specifically sorgoleone and its hydroquinone derivative, dihydrosorgoleone (SXSg).
Recent evidence points to both of these compounds as performing key roles in the inception of
Striga germination. We focus on a novel synthetic approach for preparing sorghum seed
germination stimulant polyketide precursors for use in determination of the germination stimulant
biosynthetic pathway. Synthesis begins with protection of the carbonyl carbon in chloroacetone
by forming an acetal via ethylene glycol and concentrated acid. 2-bromonaphthalene is
converted to a Grignard reagent and, in a successive reaction, linked to chloroacetone via an Sn2
mechanism in which Cl- is evolved from the alpha-position. Further modification includes a Birchtype reduction of the aromatic rings by Li at –6.0 oC in order to obtain a species in which the
double bonds remain unconjugated. Cleavage of the rings with O 3 should yield the desired
polyketide, which will be made membrane-permeable with the addition of a N-acetylcysteamine
(NAC) thioester. Biochemical studies will incorporate these polyketide precursor molecules into
germinating sorghum seeds in an effort to successfully elucidate the germination stimulant
biosynthetic pathway.
33
Synthesis of Vinyl Glycosides and Their Cyclopropyl Derivatives
Author: Christopher Cummings
School: Villanova University
Professor: Dr. Robert Giuliano
Project Duration: six months
Type of Support: ACS-PRF Type B Grant, Corixa, Inc., Villanova Chemistry Department
An ongoing area of interest in our laboratory is the development of methods for the synthesis of
oligosaccharides, such as the disaccharides found in the polyketomycin and axenomycin
antibiotics. Oligosaccharide synthesis typically involves the coupling of a glycosyl donor and a
glycosyl acceptor. The goal of this research is to synthesize novel types of glycosyl donors,
cyclopropyl glycosides, and determine if they will undergo coupling to an acceptor under
conditions of activation with a Lewis acid. The synthesis of the cyclopropyl glycosides and initial
attempts at coupling reactions will be described.
OH
ROH 2C
ROH 2C
RO
RO
O
RO
RO
ROH 2C
RO
RO
O
O
R'
CH2
O
RO
RO
RO
vinyl glyc oside
acc eptor
O
R'
cyc lopropyl
gly coside
O
acc eptor
Synthesis of substituted pleiadenediones
Author: Jennifer L. Hespell
School: Franklin & Marshall College
Professor: Marcus W. Thomsen
Project Duration: 1 year
Type of Support: Schappell Scholar, Internal college grant
Friedel-Crafts acylation, as used to synthesize quinizarins, has been used to produce various
substituted pleiadenediones. Examples of synthesized pleiadenediones include 1,6dihydroxypleiadene-7,12-dione and 8,9,10,11-tetrafluoro-1,6-dihydroxypleiadene-7,12-dione;
8,9,10,11-tetrachloro-1,6-dihydroxypleiadene-7,12-dione trial results are pending. Products have
potential uses as core molecules in dendrimer syntheses.
34
Judges
We wish to thank the following people for donating their time as judges for ISCC.
Judge
Affiliation
Section
Marshall Fishman
USDA ARS
Analytical/Physical
John Wójcik
Villanova University
Analytical/Physical
Dittmar Wulff
DC Scientific
Analytical/Physical
Kurt Moyer
Sanofi-Synthelabo
Biochemistry I
Elizabeth Ottinger
Swarthmore College
Biochemistry I
Victoria Robinson
UMDNJ
Biochemistry I
Sharon Haynie
DuPont
Biochemistry II
Walter Patton
Lebanon Valley College Biochemistry II
Mary Ann Mascelli Centocor
Biochemistry II
Michael Abrams
Atofina Chemicals
Inorganic
Cindy Kepler
Bloomsburg University
Inorganic
Jennifer Petoff
Rohm and Haas
Inorganic
Deanna Zubris
Villanova University
Inorganic
Erica Martin
Rohm and Haas
Organic I
Cynthia Parrish
Glaxo Smith Kline
Organic I
John Williams
Temple University
Organic I
J. Kent Barbay
Johnson & Johnson
Organic II
Linda Casillas
Glaxo Smith Kline
Organic II
Roger Murray
St. Joseph’s University
Organic II
35
2003 ISCC Attendee List
(*indicates student presenting research)
Bloomsburg University
*Christina Crecca
*Nathan Kreischer
Alicia Campbell
Justin Steen
Amy Risen
Bethany Hueholt
Jennifer Wasilisin
John Horoshock
April Lumpkin
Josh Spragle
Tony Fabian
Dr. Cindy Kepler
Dr. Michael Pugh
Dr. Wayne Anderson
Dr. Christopher Hallen
Bucknell University
*Jennifer Sievering
Elizabethtown College
Michael Santillo
Samantha Uliana
Dr. Charles Schaeffer
Franklin and Marshall College
*Nathan Fedors
*Adam S. Myers
*James Terzain
*Jeremy L. Steinbacher
*Jennifer L. Hespell
Natalie Flora
Haverford College
*Catherine O’Connor
*Logan Dempsey
*Hyemin Kim
Dr. Claude Yoder
Dr. Marcus Thomsen
Dr. Ken Hess
36
Hood College
*Caitlin Vaughn
*Christopher J. Wiles
*Laura Ewing
Leah Giambarresi
Dr. Kevin Bennett
Indiana University of Pennsylvania
Abera Kenfu
Ardian Soca Wibowo
Sherri Manges
Thomas A. Baker
Lebanon Valley College
*Jennifer L. Gehman
*Jared Bushey
Dr. Walter A. Patton
Muhlenberg College
*Erica L. Norey
*Jared J. Nathan
Dr. Charles Russell
Dr. Marlon Smith
Temple University
*Traci Smith
*Adedamola Adedeji
University of Delaware
*Christopher J. Eller
*Denise A. Birk
*Benjamin A. Thuma
Dr. Harold White
37
Ursinus College
*Brendan Kelly
*Joseph Klim
*Rahul Patri
*Brian C. Marks
*Jessica Hoch
*Jeffrey Coleman
Dr. Andrew C. Price
Villanova University
*Christopher Cummings
*Christopher DeFeo
*Douglas Micalizzi
*Heidi Shimp
*Valerie Valentin
Mr. Carl Kaub
Ms. Nancy Ata
Ms. Lauren DellaGreca
Mr. Chris Jones
Ms. Gina Bartolomeo
Ms. Adrienne Kline
Ms. Kathleen Spencer
Mr. Michael Berlinger
Ms. Meghan Klaric
Mr. Jeffrey Schubert
Mr. Kevin Wiacek
Ms. Jennie DiLemmo
Ms. Liz Hauser
Ms. Peggy Greene
Ms. Emily Ma
Ms. Karen Chiang
Mr. Henry Gannon
Ms. Emily Cushnie
Mr. Michael Giuliano
Dr. Joseph Bausch
Dr. Willam Birdsall
Dr. Eduard Casillas
Dr. Robert Giuliano
Dr. Scott Kassel
Dr. Brian Ohta
Dr. Robert Reczkowski
Dr. Barry Selinsky
Dr. Kathleen Thrush
Dr. Deanna Zubris
38
Last Year’s ISCC Winners
Analytical Chemistry I
1st:
Mark B. Rowand (Franklin and Marshall College)
2nd: Katie L. Shearer (Ursinus College)
Analytical Chemistry II
1st:
Andrew Vincent (Ursinus College)
2nd: Michele Jablonski (University of Delaware)
Biochemistry
1st:
Shannon McDonald (Hood College)
2nd: Layali Eshgaidef (Ursinus College)
Inorganic Chemistry I
1st:
C. Adam Samuelson (Gettysburg)
2nd: Michael D. Werner (Villanova University)
Inorganic Chemistry II
1st:
Kevin Wiacek (Villanova University)
2nd: Alan Silverstein (Ursinus College)
Organic Chemistry I
1st: Valerie Dzubeck (University of Delaware)
nd
2 : William H. Pitcock (Lebanon Valley College)
Organic Chemistry II
1st:
Kristine Nolin (University of Delaware)
Olszewski (University of Delaware)
2nd:
Physical Chemistry
1st:
2nd:
Cheri Faust (Ursinus College)
Christine Crecca (Bloomsburg)
39