Department of Chemistry

Brock University
St. Catharines, Ontario
http://www.brocku.ca/chemistry/
 Graduate Opportunities

• MSc – Chemistry
• MSc – Chemical Biotechnology
• PhD – Chemistry
• PhD – Chemical Biotechnology

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 Programme and Admission
Requirements
• Offer graduate programmes leading to a
Master of Science (MSc) and/or Doctor of
Philosophy (PhD) degree
• Require an Hons. BSc degree (≥70%
average)
– May be admitted to the programme with a
qualifying year if not all of the requirements
are met

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 Programme and Admission
Requirements
• Applications can be made at any time
– Formal admission is generally September 1,
January 1, or May 1
• Applications require a recent transcript, an
Application Form, a Statement of Interest
form, and letters from three references
– Forms can be downloaded from the School of
Graduate Studies website
(www.brocku.ca/gradstudies/forms/)

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 Financial Support
• Graduate students receive a research assistantship
and the opportunity to teach in the undergraduate
laboratory programme
– Research assistantship is supplemented by supervisor’s
grants
– Applicants are encouraged to contact the potential
supervisor prior to submitting a formal application
• Brock graduate students are eligible for a host of
internal and external grants to supplement their
stipends

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 The Brock Advantage
Major instrumentation, just as in much
larger universities…

NMR Spectroscopy
(300 MHz and 600 MHz magnets) 6
 The Brock Advantage
Major instrumentation…

Mass spectrometry
(MALDI-TOF, EI, CI, ESI, FAB, GC-MS)
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 The Brock Advantage
Major instrumentation…

EPR
Spectroscopy

Gas
HPLC
Chromatography

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 The Brock Advantage
… with a small school feel

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 The Brock Advantage

• Proximity to major Canadian and US cities:

– Hamilton: ~45 min. by car
– Toronto: ~1.3 hours by car
– Buffalo, NY: ~35 min. by car

• All the advantages of a big city without having to

live in one!
• Major sporting, cultural, and entertainment events
are only a short car/bus trip away
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 The Brock Advantage
• Just a few minutes hike from
the Chemistry Department

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 The Brock Advantage
• In the heart of wine
country
– Wines from many of the
finest wineries in the
country
– Research opportunities
with many local
wineries
– The most extensive
collaboration of this
type in Canada

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Niagara Regional Biosciences
Building

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 It’s Not All Work
• A very social
department
– BBQs, Christmas parties,
etc.
– Even a Chemistry band!

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Research Interests
 Chemistry and Biochemistry of Vitamin-E (Tocopherol),
Mechanism of Lipid Transfer Proteins
Jeffrey Atkinson, Brock University, Chemistry & Biotechnology
jatkin@brocku.ca

Background: HO
 Synthesis and biological evaluation of different
forms of vitamin E O
Results:
 Synthesis of deuterated forms of Vitamin E for a-Tocopherol,phenolic lipophilic antioxidant
biokinetic studies & membrane enzyme modulator
(CD3) D
 Synthesis of fluorescent tocopherols for in vitro
HO D
and in vivo lipid transfer studies
 Synthesis of tocopherol-based P450 inhibitors (D3C) O
 Expression of native and mutant human (CD3)
tocopherol transfer proteins
HO
 Protein structure and function (see Dr. Heather
Gordon)
O
Scientific Uniqueness: Fluorophore
 Combination of organic synthesis, protein
chemistry, and molecular biology
 First creation of molecular tools for analysis of Protein mediated
tocopherol transfer and membrane tocopherol transfer to
biochemistry by fluorescence and from biological and
Impact and Advantages: model membranes can
 Rational molecular approach to vitamin E be followed by FRET &
biochemisty stopped flow
 Strong collaborations with nutritional biochemists fluorescence
and health science researchers around the
world

Human a-Tocopherol Transfer Protein

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 Environmental Analytical Chemistry; Trace Element Analysis

Ian D. Brindle, Brock University, Chemistry & Biotechnology

Dean, Faculty of Mathematics and Science
ibrindle@brocku.ca

Development of analytical
methods for environmental
and other samples. Gas
chromatography/mass
spectrometry and nuclear
magnetic resonance applied
to organometallic species and
to environmental problems.
Trace and ultra-trace Reductant
determination of elements in
complex matrices.
Applications of mass Sample

spectrometry in analytical
chemistry.
Argon

Sample
MSIS™
(Dual Mode Operation) 17
Computationally Directed Asymmetric Catalysis
Travis Dudding, Brock University, Chemistry & Biotechnology
tdudding@brocku.ca
Research Goals:
Research in the Dudding group focuses on the use of
computational theory to gain insight into the mechanistic
origins of stereoselectivity in catalytic asymmetric reactions.
The models derived from these studies are utilized to
guide the development of new stereoselective catalysts and
asymmetric reaction methodologies. Specific reactions
of interest are asymmetric Stetter and aza-Stetter reactions,
Brønsted acid catalyzed asymmetric procedures and
chiral nucleophilic catalyzed annulations.

Significance:
The advent of modern computational chemistry has had a
profound effect on chemists’ understanding of organic reaction
mechanisms. Through computation, chemists are now frequently
able to rationalize or predict the outcome of experiment with a
high level of certainty. In this respect a particularly useful
O
application of computation relates to the modeling of catalytic O
asymmetric methods with the obvious end goal being the use of
theory to design an optimal catalyst for a desired chiral chemical O
O
transformation. The emerging potential of in silico based design H
H

approaches in asymmetric catalysis offers great promise as an O

environmentally friendly alternative for streamlining the discovery O H
process and lessening the demand placed upon chemical resources. H

In this respect the work being conducted in the Dudding group is

Sterically Defined Reaction Pocket
making possible innovative methods grounded both in experiment
and computation which allow for the rapid cost-efficient production
of chiral pharmaceuticals and highly prized chemicals. 18
 Monte Carlo Simulations of Model Antibody Binding Sites
Heather L. Gordon, Brock University, Chemistry & Biotechnology
Antibody binding site:
6 loops on -barrel framework
Monte Carlo simulations employ
random numbers.
95-97% conformations identical
between isolated and assembled loops.
gordonh@brocku.ca
Research Goals:
To understand relationship between
antibody selectivity and specificity and the inherently
flexible antigen binding site.
Methodology:
Use Monte Carlo simulations to sample the
complete conformational distribution of a
model antibody binding site.
Model system:
Abstracted loops
Objective: From crystal structure.
To characterize the conformational change
in the antibody binding site in the presence
and absence of a model antigen.
Results:
Intraloop interactions are more influential
than interloop interactions in determining
peptide loop shape.
Significance: Isolated loop Loop in
Most consistent with view that antibody assembly
binding site displays conformational isomerism:
Antigen binds selectively to a pre-existing
conformation that may not be at the global
minimum in potential energy.
Loop conformational distribution is restricted
when in presence of other loops.
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 Clean Manufacturing of Pharmaceuticals via
Enzymatic and Electrochemical Methods
Tomas Hudlicky, Brock University, Chemistry and Biotechnology
thudlicky@brocku.ca
R R alkaloids
Background:
toluene organic sugars
 Converson of toxic aromatic compounds to chiral OH
dioxygenase chemistry cyclitols
building blocks for use in manufacturing prostaglandins
Results: terpenes
OH
 ”Green” synthesis of functionalized catechols polymers
 Short synthesis of antitumor agents R = alkyl, aryl, halogen oligomers
 Synthesis of carbohydates and oligoinositols
 Electrochemical oxidations and reductions R R Br OH
 Short approach to morphine OH 1. toluene OH
Scientific Uniqueness: dioxygenase
 Biooxidation of aromatics has no chemical 2. electro-
equivalent OH OH
chemistry
 Tandem electrochemistry–enzyme methods are 3. H2O OH
most efficient
OH
 Removal of potential waste products by strategic HO
HO OH
conversion to value-added compounds
HO
Impact: OH
 Concept of Effective Mass Yield O HO
OH O
OH
 One-step synthesis of functionalized NH HO
O NCH3 O OH
catechols
HO
 ”No reagent” synthesis OH O HO OH
OH
HO O
pancratistatin morphine OH
OH
MeO
HO O OH
OH
OH
MeO HO OH L-chiro-4
OMe OH
OH
OMe
combretastatin A-1
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 Synthesis and Study of Molecule-Based Materials
Martin Lemaire, Brock University, Department of Chemistry
martin.lemaire@brocku.ca

Background
• The construction of new materials based on the association of N N
molecular building blocks is a burgeoning area of chemical research. M M
The injection of molecular properties (such as solubility, redox activity, N N
etc.) will endow traditional materials, like magnets, with unusual new
and exciting properties. M N N M
Research Goals N N
N N
1. Synthesis of new “electronically labile” materials: These materials N
feature dynamic molecular structures, and are capable of switching
between two or more different electronic states.
2. Preparation of new families of “single molecule magnets” (SMM’s):
SMM’s are discrete molecules that exhibit similar bulk magnetic N
properties to traditional magnets such as iron!
Methodology N N
N N
• We carry out traditional organic synthesis and coordination chemistry. M M
• Characterization of our molecules is accomplished using standard
methods. Heavy use is made of other exotic techniques, such as SQUID
magnetometry and EPR spectroscopy to probe electronic structures and
magnetic behaviours. N N

Significance/Impact N Co(SQ)(LL) N Co(SQ)(LL)

N
N
Co(CAT)(LL) N
N
Co(CAT)(LL)

• Ultimately we are creating new and useful materials using molecular

precursors—we aim to apply our systems toward the construction of S S S S -T

novel molecule-based electronic devices for use in molecular +T S S S S

computation and as sensory materials—among a number of other

exciting possibilities. (LL)(SQ)Co N (LL)(SQ)Co N
N N (LL)(CAT)Co N (LL)(CAT)Co N
N N

"MAGNETIC" "NON-MAGNETIC"

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 Development of Rigid Chiral N-Heterocyclic
Carbenes Derived from Phenanthrolines
Costa Metallinos, Brock University, Chemistry
metallic@brocku.ca
Background: N-Heterocyclic carbenes (NHCs) with an
Ph Ph
imidazolidine framework can be classified as one i-Pr
of three general structural types: (a) N N Ar Ph
N N Ar N N Ph
Imidazolinylidenes (1) which have a saturated
backbone; (b) unsaturated imidazolylidenes (2), i-Pr
and (c) benzimidazolylidenes (3). There are
1 2 3
comparatively few reports of chiral
benzimidazolylidenes. This can be attributed in
part to limitations imposed by traditional
synthetic routes, which have restricted their NaBH3CN HC(OEt)3
structural diversification. 1 equiv HCl
N N NH HN N N
80 °C
Scientific Uniqueness: Previously we have described a 1,10-phenanthroline Cl
5 6
route to a rigid tetracyclic benzimidazolylidene 4
(7) derived from phenanthroline (4) (Metallinos
et al. Org. Lett. 2004, 6, 3641). The key step in N Cl
0.5 equiv Pd(OAc)2 N
the preparation of this ligand involved a Pd
convenient reduction of the pyridyl rings to make THF, reflux
N Cl N
octahydrophenanthroline (5). We have expanded
this methodology to prepare enantiomerically 7
pure rigid chiral benzimidazolium salt precursors
of benzimidazolylidenes (e.g. 8 and 9). Our
approach to the structural diversification of this H H
sub-class of NHCs holds promise for their future
applications in asymmetric synthesis. N N N N
BF4 H BF4 H
8 9
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 Organometallic and Coordination Chemistry
Georgii Nikonov, Brock University, Chemistry
gnikonov@brocku.ca
Background
• Transition metal (TM) complexes substituted by main group element (MGE) ligands, i.e.
LnM-ERk, often exhibit unusual metal-ligand and ligand-ligand bonding;
• There is a continuing interest in complexes with multiple metal-ligand bonds (silylenes,
phosphinidenes, borylenes etc) and in coordination of multiple E=E bonds to metals
(complexes of disilenes, silenes, silaimines, diphosphenes etc);
• Much of current research is focused on studying nonclassical interligand interactions.
Research Goals
• To develop the chemistry of transition metal hydrides in new ligand environments; I HNR2
• Synthesis, structure and reactivity of TM hydrides and MGE complexes; SiMe2
• Study of nonclassical interligand interactions. Nb H
Methodology SiMe2
• New synthetic strategies to MGE and hydride complexes: I
– reactions of MGE halides with hydrides; R2 = HBut, Et2
– selective functionalization of E-H bonds in complexes;
– E-E coupling reactions on TM complexes;
• X-ray and neutron diffraction, NMR, IR, EPR, DFT calculations. M PMe3 M = Nb or Ta
Results RN PMe3
• Pioneering research on Interligand Hypervalent Interactions +
• New types of Si-H... M agostic complexes HSiC lRR'
• New approaches to diphosphene complexes
• One of the first σ-complexes of the Si-Si bond
Significance/Impact
• New synthetic methodologies
• New insight into the nature of M-L
and L-L bonding

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 Novel Hybrid Organic/Inorganic Molecular
Materials
Melanie Pilkington, Brock University, Chemistry
mpilkington@brocku.ca
Background:
 Inorganic crystal engineering.
 The preparation of magnetic, electronic and optical
materials from molecular building blocks.
Results:
 Synthesis and characterisation of new
tetrathiafulvalene (TTF) building blocks. A New TTF Derivative with Four
 Synthetic strategies for the preparation of Pyridine Binding Sites
functionalised phthalocyanines (Pcs).
 Synthesis, characterisation and study of molecule-
based magnetic materials e.g. high spin clusters, 3-D
networks, 1-D coordination polymers and spin-
crossover compounds. A Novel Fully Conjugated Phenanthroline
Scientific Uniqueness: Appended Phthalocyanine.

 Exploiting the use of metal binding sites as the key

element for the construction of dual property hybrid
materials.
 Target the synergy between the properties of the
inorganic and organic components in each system to
assemble new materials. A High Spin (S = 51/2) [MnII9MoV6]
Impact and Advantages: Molecular Cluster
 Dual property materials with
synergistic properties.
 Development of new electronic,
optical and/or magnetic devices
that will be the cornerstones of
A Three-Dimensional Bimetallic Network
new technology. 1-D Magnetic Coordination Polymer [NbIV{CN)4MnII(H2O)2}2]·2H24
2O
 Novel Approaches to Fundamental Problems in
Computational Chemistry and Physics
Stuart M. Rothstein, Brock University, Chemistry & Physics
Background:
• Chemistry: the factors involved in the
interaction of biomolecules with
themselves, with DNA, and with solvent
are not well understood.
• Physics: one can derive accurate results
from quantum theory by taking
expectation values of operators over the
truly exact electron distribution, not just
an approximate one, contaminated by a
trial function
Results:
 Chemistry: Using sophisicated statistical
methods we developed computer codes
to cluster quantum and classical
molecular dynamics trajectories, and to
visualize the resulting clusters. In
applications
done in collaboration with groups in
Germany, Japan, and Brock, this approach
provided a local description of protein
folding, of non-bonded interactions in
biological systems
(figure), and of high-frequency motions in
proteins, associated with their biological
functioning.
srothste@brocku.ca
Results:
• Physics: quantum Monte Carlo
methods can sample the
unknown exact wavefunction.
We recently discovered how to
sample the unknown exact
probability density as well.
We are applying this methodology
to calculate very accurate estimates
of polarizabilities of chemical
systems.
Scientific Uniqueness: CRP-cAMP-DNA complex.
 Our research has a strong
interdiscipinary flair, drawing
on computational and
theoretical chemistry and much-needed local view of
physics, high-performance bio-molecular interactions.
computing and mathematics Impact and Advantages:
to tackle fundamental problems. • Physics: quantum Monte Carlo
Impact and Advantages: is the most promising approach
• Chemistry: we extract the signal to ab initio electronic structure of
from the noise in biomolecular large molecules.
simulation data better than
standard approaches, and our Group website:
Human arol Transfer Protein
visualizations provide a novel, http://www.brocku.ca/chemistry
/faculty/Rothstein
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 Structure and Function of Photosynthetic Proteins
Electron Spin Resonance Spectroscopy
Art van der Est, Brock University, Chemistry & Biotechnology
avde@brocku.ca
Goals: Photosynthesis
 Better understanding of solar energy
conversion in photosynthetic
organisms
Results:
 Determination of electron transfer rates
D
in Photosystem I using electron spin
HO D
resonance
 Studies of site directed mutants to
(D3C) O
determined the pathway of electron
(CD3)
transfer.
 Computer modelling dynamics (see Dr.
Gordon)
Scientific Advances:
 Development of spin polarization as
effective tool for studying electron
transfer. Electron spin resonance signals
Impact: Photosystem I from photosystem I
 Beginning to unravel the basic
principles of efficient solar energy
conversion
 Strong international collaborations with light
scienctists working in this field P P+A1- P+FX-

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 Carbohydrates, Nucleic Acids, and Bioconjugates
Hongbin (Tony) Yan, Brock University, Chemistry and Biotechnology
tyan@brocku.ca
R1O B
O
O B
O OEt
Background O O
O
• Oligonucleotide synthesis, siRNA synthesis O O
NC P
P NR 2 N
• Glycoconjugates and glycobiology X O B'
• Drug delivery O

Research Goals 2'-Cpep ribonucleoside phosphoramidite Cl

O
• Understanding the chemistry, biochemistry, oligonucleotide phosphate-
and biology of nucleic acids, carbohydrates, phosphorothioate chimeras
and bioconjugates
Research Projects
• Synthesis of oligonucleotide phosphate–phosphorothioate random chimeras
• Solid phase synthesis of oligoribonucleotides/siRNAs using the Cpep chemistry
• Novel siRNA analogues
Applied Biosystem 3400 DNA Synthesizer
• Chemical mimicry of bacterium Pseudomonas aeruginosa surface carbohydrate-binding
proteins – carbohydrate interactions
carbohydrate
Significance
• Methodology for the synthesis of oligoribonucleotides on multi-gram scales
• Understanding lectin–carbohydrate interactions Cationic lipid

• Development of bioconjugates pertinent to human health Neutral lipid

Glycoliposome
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 Organosilicon Chemistry and the Chemistry of
Silicone and Silicone-Modified Materials
Paul Zelisko, Brock University, Chemistry
pzelisko@brocku.ca
• Typically, dibutyltin dilaurate is employed as a catalyst to
bring about the hydrolysis, and subsequent condensation
of silicones to form cross-linked networks in the room
temperature vulcanization (RTV) process. However,
given the interest in silicones as biomaterials, the use of
potentially toxic tin compounds as catalysts can be limit
the use of silicones in such an application. 1.0

Relative proportion of 29Si integral of

0.9
• The goal of this research are: (1) to investigate the
interaction(s) of silicon-based molecules with biological 0.8

phenyltrimethoxysilane
systems; (2) to develop systems where enzymes can be
used to perform chemistry at, or near, silicon in place of 0.7
the more traditional, and somewhat more toxic, metal-
based catalyst systems; and to (3) explore applications 0.6
such as biomaterials, drug delivery devices, sealants,
coatings, and agriculture products to name but a few. 0.5
0.4

O
O 2
Si
3
Si
n O
2
Si
O
Si 1
O 0.3
Si 1 O
3 O
O
TES-PDMS
0.2
Cross-linking

enzyme 2 1 0.1
Spinning 0.0
tin side band
0 2 4 6 8 10
Time (hr)
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 Biotechnology
www.brocku.ca/biotechnology/index.phtml
 Biotechnology Faculty
Chemistry and Biochemistry of Vitamin-E (Tocopherol),
Mechanism of Lipid Transfer Proteins HO
Jeffery Atkinson O
jatkin@brocku.ca
a-Tocopherol,phenolic lipophilic antioxidant
& membrane enzyme modulator

Biology and Molecular Genetics of Insect Pathogenic Fungi

Michael Bidochka
bidochka@brocku.ca

Environmental Analytical Chemistry; Trace Element Analysis

Ian Brindle
Dean, Faculty of Mathematics and Science
ibrindle@brocku.ca
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 Biotechnology Faculty
Photosynthetic Energy Conversion
Doug Bruce
dbruce@brocku.ca

Neurite Outgrowth, Retinoids, and Limb Regeneration

Robert Carlone
rcarlone@brocku.ca

Fungal Genetics
Alan Castle
acastle@brocku.ca

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 Biotechnology Faculty
Plant Cell Factories and Metabolic Engineering for Manufacturing
of Natural Products
Vincenzo DeLuca
vdeluca@brocku.ca

Plant Proteomics and Molecular Pathology

Charles Després
cdespres@brocku.ca

Computationally Directed Asymmetric Catalysis

Travis Dudding
tdudding@brocku.ca

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 Biotechnology Faculty
Antibody binding site:
6 loops on -barrel framework

Monte Carlo Simulations of Model Antibody Binding Sites

Heather Gordon
gordonh@brocku.ca

Development of Bovine Adenoviruses into Helper-Independent Viral Vector(s)

for Applications in Gene Therapy and Recombinant Vaccine
Yousef Haj-Ahmad
yousef@brocku.ca

Clean Manufacturing of Pharmaceuticals via

Enzymatic and Electrochemical Methods
Tomas Hudlicky R R alkaloids
toluene organic sugars
thudlicky@brocku.ca dioxygenase
OH
chemistry cyclitols
prostaglandins
OH terpenes
polymers
R = alkyl, aryl, halogen oligomers 33
 Biotechnology Faculty
Systematics and Ecology of Hematophagous Insects
Fiona Hunter
hunterf@brocku.ca

Volatile Acid Production During Icewine Fermentation

Debra Inglis
dinglis@brocku.ca

Role of Oenological Variables on the Sensory & Chemical

Properties of Wine
Gary Pickering
Chair of Biological Science
gpickeri@brocku.ca
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 Biotechnology Faculty
Viticultural Practices and Their Influences Wine and Juice Quality
Andrew Reynolds
areynold@brocku.ca

Elucidation of Mutagenic Pathways that Corrupt Genetic

Information
Adonis Skandalis
askandal@brocku.ca

Cellular and Molecular Mechanisms Underlying Synaptic Plasticity in the

Nervous System
Gaynor Spencer
gspencer@brocku.ca
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 Biotechnology Faculty
Mitochondrial Function in Experimental Models of Health, Disease, and Aging
Jeff Stuart
jstuart@brocku.ca

Structure and Function of Photosynthetic Proteins

Electron Spin Resonance Spectroscopy
Art van der Est
Chair, Department of Chemistry
avde@brocku.ca

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 For more information visit us at:

www.brocku.ca/chemistry
www.brocku.ca/gradstudies
www.brocku.ca/biotechnology

Application forms for graduate studies:

www.brocku.ca/gradstudies/forms/

Or contact Prof. Stuart Rothstein at:

srothste@brocku.ca
37