Kansas State University Department of Chemistry

1
Kansas State UniversityDepartment of Chemistry
This presentation will provide you with
information about some of the many different
research topics that we offer. Feel free to take
a virtual trip through our Department (use the
slide show option) and do not hesitate to contact
us if you have any questions or comments. Prof.
Aakeröy aakeroy_at_ksu.edu or 785-532 6096
2
Going to graduate School?
3
You can make new molecules...
4
...or study their properties.
5
Several focus areas
Asymmetric catalysis
Bioanalytical chemistry and chemical sensors
Biophysical chemistry
Drug design in theory and practice
Materials science and nanotechnology
Structure and bonding
Supramolecular chemistry and crystal engineering
6
Analytical and physical chemistry
Electronic structure
Biological sensors
Chemical separation
Quantum chemistry
Ultrasensitive microscopy
Biophysical chemistry
Single-molecule spectroscopy
7
Professor Christine AikensQuantum chemistry
Application of electronic structure methods to
Nanoparticles Nanostructured materials Complex
intermetallics Quasicrystals
To investigate
Design and programming of efficient algorithms
in the GAMESS program
Optical properties Interparticle
interactions Growth mechanisms
8
Nanostructured Materials
Self-assembly of colloidal crystals

• Control over assembly of nanoparticles is primary
  obstacle to bottom-up construction of novel
  materials and devices
• Goals
• Understand the interactions between nanoscale
  building blocks
• Achieve control over these interactions
• Elucidate how certain types of interactions lead
  to specific target structures

Binary nanoparticle superlattices
Murray, C. B. et al. Science 1995, 270, 1335.
Shevchenko, E. V. et al. Nature 2006, 439, 55.
Aikens Group
9
Complex Intermetallics

• Complex intermetallic icosahedral alloys
• Excellent long-range order but no periodicity
• How do these structures form?
• Cluster-by-cluster
• Atom-by-atom
• Goals
• Explain stability of gas-phase clusters
• Determine structural motifs in these clusters
• Examine the atom-by-atom growth mechanism in
  order to determine its viability

icosahedral Zn-Mg-Dy
Aikens Group
10
Professor Viktor ChikanPhysical Chemistry and
Material Chemistry
Research Interest Physical chemistry of
nanostructures- optical, electrical properties
and thermodynamics of doped quantum confined
semiconductor systems
Synthesis of Doped Nanostructures Controlling the
conductivity (carrier density, carrier mobility)
in quantum confined semiconductor devices is
important for future applications. We are
developing synthetic methods of creating doped
quantum dots. In addition, we are interested in
doping intrinsically anisotropic (such as GaSe
quantum dots) and extrinsically anisotropic
quantum confined systems (e.g. CdSe quantum rods).
11
Time-domain Terahertz Spectroscopy of Doped
Nanostructures
Measuring the conductivity of the doped
nanostructures is challenging because of the
difficulty to connecting them to external
circuitry. Terahertz radiation generated by an
ultrafast laser provides a convenient way to
measure the frequency dependant complex
conductivity of the doped nanostructures.
1 THz 300 µm 33 cm-1 4.1 meV
12
Ultrafast Carrier Dynamics (Time-resolved
Terahertz Spectroscopy)
While Time-domain Terahertz Spectroscopy offers a
way to probe the equilibrium conductivity of the
doped system, Time-resolved Terahertz
Spectroscopy provides a way to measure the
transient conductivity in doped quantum dots, p-n
junctions and 3D quantum Wells.
13
Professor Christopher CulbertsonBioanalytical
Chemistry - Separations, Microfluidics,
and Cell Analysis
We are interested in developing new separation
and sample handling components for microfluidic
(Lab-on-a-Chip) devices and then using these
devices to solve interesting bioanalytical
problems.
These devices may facilitate 1) the early
diagnosis and successful treatment of diseases
like cancer, and 2) a better understanding how
complex organisms develop from single cells.
14
Prof. Christopher Culbertson
Buffer
Sample
Waste
SW
High Efficiency Separations
5.08 cm
Single Cell Analysis
15
Professor Dan HigginsAnalytical Chemistry,
Materials Chemistry, Optical Microscopy
and Spectroscopy
Single Molecule Spectroscopy
Near-field Scanning Optical Microscopy (NSOM)
16
1. High Resolution Optical Microscopy Studies of
Liquid-Crystal/Polymer Composites
Multiphoton Excited Fluorescence Microscopy
Conventional Fluorescence
Two Photon Excitation
Near-Field Optical Microscopy
125 µm
Optical
Fiber
Aluminu
m
100 nm
l

Near Field
ltlt
(
5 nm)
Sample
Far Field
Funding NSF-CHE/DMR ONR Photovoltaics
Detector
Higgins Group
17
2.Polymer/LC Composites Order LC Droplet Arrays
andPhotorefractive Materials
NSOM Imaging Photorefractive LCs
Multiphoton Excited Fluorescence Hexagonal LC
Droplet Arrays
Topography
Birefringence
Fluorescence
Asymmetric Laser Beam Diffraction
2 µm
Hall and, Higgins, J. Phys. Chem, in press.
Luther, Springer, Higgins, Chem. Mater., 2001,
13, 2281.
Higgins Group
18
3. Organic PhotovoltaicsSelf-Assembly of New
Solar Cell Materials
Dye/Polymer Composites
Domain Organization
C12-PDI
Higgins Group
Higgins Group
19
Professor Takashi Ito Analytical Chemistry
(Chemical Sensing), Electrochemistry, Nanoporous
Materials, Nano/microfluidics

• Our Research Interests
• Design, synthesize and characterize novel
  nanoporous materials with uniform pore
  morphologies.
• Clarify molecular-level mass- and
  charge-transport within the nanopores.
• Develop sensing devices and catalysts for
  chemical and biological targets of medical and
  environmental interests.

20
Preparation and Characterization of Nanoporous
Materials
Design and prepare monolithic materials
comprising an array of self-organized cylindrical
nanopores with uniform pore sizes.
Characterize the properties of nanopores using
electrochemical, spectroscopic and microscopic
techniques.
1) T. Ito, A. A. Audi, G. P. Dible Anal. Chem.
2006, 78, 7048. 2) Y. Li, H. C. Maire, T. Ito
Langmuir 2007, 23, 12771. 3) Y. Li, T. Ito
Langmuir 2008, 24, 8959. 4) H. C. Maire, S.
Ibrahim, Y. Li, T. Ito Polymer 2009, 50,
2273. 5) D. M. N. T. Perera, T. Ito Analyst 2010,
135, 172. 6) F. Li, R. Diaz, T. Ito RSC Advances
2011, in press. 7) S. Ibrahim, S. Nagasaka, D. S.
Moore, D. A. Higgins, T. Ito Analyst, submitted.
21
Applications of Nanoporous Materials
2. Chemical Sensing
1. Fundamental Studies on Mass-Transport within
Nanopores
1) Y. Li, T. Ito Anal. Chem. 2009, 81, 851. 2) S.
Ibrahim, T. Ito Langmuir 2010, 26, 2119. 3) T.
Ito, I. Grabowska, S. Ibrahim Trends Anal. Chem.
2010, 29, 225. 4) D. M. N. T Perera, B. Pandey,
T. Ito Langmuir 2011, 27, 11111. 5) B. Pandey, K.
H. Tran Ba, Y. Li, R. Diaz, T. Ito Electrochim.
Acta 2011, in press.
1) K. H. Tran Ba, T. A. Everett, T. Ito, D. A.
Higgins Phys. Chem. Chem. Phys. 2011, 13,
1827. 2) A. W. Kirkeminde, T. Torres, T. Ito, D.
A. Higgins J. Phys. Chem. B submitted.
22
Professor Jun LiAnalytical Chemistry and
Materials Chemistry
Research Interest The growth and characterization
of nanowire materials (carbon nanotubes/nanofibers
, inorganic semiconducting or metal nanowires),
the fabrication and integration of nanowire
materials into solid-state micro/nano- devices,
and the development of novel nanodevices
(particular electronic devices) for analytical
and biomedical applications.
Goal Our goal is to develop new biosensors and
nanobiotechnologies for environmental, security,
and biomedical applications through the
innovation in nanomaterials growth and device
integration and collaboration with industries and
government agencies.
Plasma Enhanced Chemical Vapor Deposition
23
Nanotechnology Platforms Based on Vertically
Aligned Nanowires
Electrical
Mechanical
Ultrasensitve Nucleic Acid Detection
Electrical
Biomimetic Dry Adhesives
MWCNT/CNF
Electrical
Electrical
Thermal Mechanical
Inorganic Nanowires
Ultrasensitive Immunosensor
Electronic
Nanoscale IC Interconnects
Vertical Nanoelectronics and nanophotonics
Neural Electrical Interface
Thermal Interface Materials
24
Fabrication of Carbon Nanofiber Nanoelectrode
Arrays for Biosensing
As-grown CNF arrays
Inlaid CNF arrays in SiO2
Micro- patterned
2 mm
30 dies on a 4 wafer
Nano- patterned
5 mm
A 3x3 microelectrode
carbon nanofiber arrays on each microelectrode
Non- patterned
J. Li, et al, Nanoletters, 3(5), 597-602
(2003). J. Li, et al, Appl. Phys. Lett., 82(15),
2491 (2003). J. Koehne, et al., Clinic. Chem.
5010, 1886 (2004).
500 nm
25
Professor Ryszard Jankowiak Physical,
biophysical, and analytical chemistry
Photosynthesis Research
Cancer Research
26
Photosynthesis Research
Solar energy driven primary events of
photosynthesis molecular electronics
The primary events of interest are excitation
energy transfer and charge separation, both of
which involve arrays of interacting chlorophyll
molecules and other cofactors that are held in
strategic positions by protein scaffolding.
27
Cancer Research
Understanding the activity of carcinogens,
structure of DNA adducts, and development of
advanced biomonitoring techniques for cancer
risk assessment

• Develop novel methods/devices for screening
  estrogen-derived DNA adducts, conjugates, and
  metabolites in human samples
• immunoaffinity biosensor columns with imaging
  capabilities
• innovative MAb-based biosensors on glass,
  polymer, and/or silicon wafer substrates with
  multiple addressable patches on the surface
  designed and built for detection of CEQ-derived
  biomarkers  

Detection will be based on a novel
first-come-first-served approach and
fluorescence based imaging. Human samples to be
studied include urine, serum, and tissue
extracts obtained from human breast and prostate
cancer patients
28
Professor Paul SmithBiophysical chemistry
Co-solvent effects on peptides and proteins.
Modeling of opioid peptides and their receptors.
Computer simulation of the structure and dynamics
of peptides, proteins and nucleic acids.
29
The general focus of the group is the study of
the effects of solvent and cosolvents on the
structure and dynamics of biomolecules in
solution. Our main tool is molecular dynamics
simulations which are used to provide atomic
level detail concerning the properties of these
molecules. Our current research is focused in
several areas Cosolvent Effects on Peptides and
Proteins Why do urea and gdmcl denature
proteins? How does trifluoroethanol induce helix
structure? What does the denatured state of a
protein look like? Opioid peptides and
delta-opioid receptor modeling What does the
delat-opioid receptor look like? What is the
active conformation of receptor agonists? What
is the conformational change of the receptor on
activation? Improved force field parameters
How can we improve our ideas of how
atoms/molecules interact?
30
Opioid peptides and delta-opioid receptor
modeling Opioids are small peptides that play a
major role in our response to pain. The design of
improved and non addictive new pain killing drugs
depends on an understanding of the interaction
between opioids and their receptor. The exact
site of opioid peptide binding to the receptor is
unknown. We have recently developed a model for
the delta-opioid receptor (see right) which can
be used to probe the interactions between
potential drug molecules and the receptor.
By simulating the conformational preferences of
known delta-opioid receptor agonists one can
speculate on the bioactive conformation of the
peptides required for receptor activation (see
left for Deltorphin I).
31
Inorganic and materials chemistry
Organometallic chemistry
New catalysts
Molecular magnets
Nanoparticles
Zeolite mimics
Environmental protection
Supramolecular chemistry
32
Professor Christer AakeröySupramolecular
synthesis and structural chemistry
Fundamental crystal engineering
Design of functional solids
Supramolecular synthesis
Molecular sociology
33
Interactions between molecules control...
Key steps in supramolecular synthesis
the bouquet of wine,...
the ability of a drug to block an enzyme,...
and the formation of thunder clouds.
34
1. Supramolecular inorganic chemistry (NSF
support)
Porous materials and nanoparticles.
2. Supramolecular organic chemistry (NSF support)
Molecular capsules
Ternary co-crystals
3. Pharmaceutical chemistry (Industry Support)
Why compounds fail or slow down in development
We have shown that co-crystals of anti-cancer
agents can improve properties such as solubility.
Aqueous solubility of the drug can be modulated!
The solubility can be increased or decreased
compared to that of the drug itself.
35
Professor Ken KlabundeInorganic and materials
chemistry
Adsorption Properties of Nanoscale Metal Oxide
Particles
Organometallic Chemistry
Magnetic Properties of Nanoscale Fe Particles
Materials Science and Nanoscale Particles
36
1. Nano-sizing Causes Changes In
Color Crystal shape Conductivity Magnetism Melting
Points Chemical Reactivity Light Absorption
2. Uses and Potential Uses of Nanomaterials/Devic
es
Sun Screen Drug Delivery Immunological
Labeling DNA Recognition Computers Information
Storage Book Preservation Harder
Metals Environmental Remediation Refrigeration Sol
ar Cells Catalysts Better Batteries Burn
Treatments Softer Ceramics Air Purification Water
Purification Smart Magnetic Fluids Self-Cleaning
Windows Homeland Security
and Paints
37
(No Transcript)
38
Professor Chris LevyOrganometallic chemistry and
catalysis
Our primary interests are the development of new
stereospecific catalysts for organic
transformations and polymerizations and the
investigation of organometallic structure and
mechanism.
We are creating new helical transition metal
catalysts for the following asymmetric
transformations
39
Some new helical complexes and their structures.
40
Professor Eric Maattaeam_at_ksu.eduSynthetic
Inorganic and Materials Chemistry
Polyoxometalate clusters
Multinuclear NMR studies
Metal-ligand multiple bonds
Transition metal catalysis
Hybrid materials
really big molecules
41
A couple of our favorites . . .
A soluble polystyrene incorporating a
redox-active polyoxometalate cluster
A nitrido-polyoxometalate
(OsVIN)P2W17O617-
42
Organic and biological chemistry
Total synthesis
Proteins and peptides
Anti-cancer drugs
Host-guest chemistry
Ferroelastic materials
Regioselective catalysis
43
Professor Stefan BossmannOrganic and Physical
Chemistry, Materials Chemistry
Molecular Machines
44
Professor Stefan BossmannOrganic and Physical
Chemistry, Materials Chemistry
Porin-Transport Assays
MspA-Nanopore
Artificial Nanomembrane
45
Professor Stefan BossmannOrganic and Physical
Chemistry, Materials Chemistry
Gated Devices and Nanotransistors Using Ruthenium
Polypyridines and Photochromic Switches Linked to
MspA
MspA Porin Isolated from Mycobacterium smegmatis
46
Professor Mark HollingsworthPhysical-Organic and
Solid-State Organic Chemistry
47
Probing the elastic properties of materials -
studies of ferroelastic and ferroelectric domain
switching
Domain switching is an important phenomenon in
technological devices, but it also can be used as
a tool to understand how elastic properties of
crystals are affected by internal molecular
structures, impurities and defect structures.
As a complement to SWBXT, birefringence mapping
using the Metripol microscope gives both
indicatrix orientation (upper) and optical
retardation (lower) and reveals disorder both
within and between domains, especially at
boundaries that show epitaxial mismatches.
after stress
before stress
2,10-Undecanedione/urea crystals contain
ferroelastically distorted domains that are
twinned across two types of boundaries to give as
many as twelve sectors.
Synchrotron white beam X-ray topography (SWBXT)
images taken before and after stress
for crystals containing 10 (top), 14 (middle)
and 18 2-undecanone (bottom) show that
impurities unpin stressed defect sites and make
domain switching reversible.
Pure crystals of this material undergo
irreversible (plastic) domain reorientation
(above), but 2-undecanone impurities can make
this process elastic. (See videos on the next
page.)
By generating a large series of ferroelastic
inclusion compounds that are closely related to
each other, and then comparing domain switching
in these crystals as a function of impurities, it
is possible to show that the impurities control
the dynamics and reversibility of domain
switching by breaking up cooperative hydrogen
bonding networks and unpinning stressed sites in
these crystals.
48
Ferroelectric domain switching in
inclusion compounds of tetra-t-butylcalix4arene
In an electric field, the guests rotate about the
pseudo-fourfold axis of the host
Host structure
Which of the above guests could
show ferroelectric domain switching?
49
Professor Duy H. HuaSynthesis and
Bio-evaluation of Natural and Unnatural Products,
Design of Enzyme Inhibitors, and Syntheses of
Beltenes and Nanomaterials
Anti-cancer agents targeting Gap junction
intercellular communication
Development of new stereo-selective reactions
Synthesis of nanogels for selective drug delivery
50
Duy H. Hua
Two major research projects are being carried out
in our group, and they are synthesis, mechanism,
and bioevaluation of biologically active
compounds and syntheses and applications of
beltenes and nanomaterials.
Surface Plasmon Resonance of Ab and CP2
Releasing of blood vessel
Gap junction channel and PQ1
51
Duy H. Hua
1H-15N-HSQC spectrum of Ab40 peptide
52
Professor Ping Li Chemical Biology/Bioorganic
Chemistry
Research Interests Use synthetic organic
chemistry and molecular biology as major tools to
study and manipulate biologically important
enzymes/proteins. Currently, I have four projects
in my lab.
53
1. Studies of ghrelin acylation by ghrelin
O-acyltransferse (GOAT). GOAT was recently
discovered1-2 as a potential drug target for
curing obesity. We will investigate its molecular
mechanisms and design effective inhibitors to it.
1. Gutierrez, J. A. Solenberg, P. J. Perkins,
D. R. Willency, J. A. Knierman, M. D. Jin, Z.
Witcher, D. R. Luo, S. Onyia, J. E. Hale, J.
E. Proc. Natl. Acad. Sci. USA 2008, 105, 6320. 2.
Yang, J. Brown, M. S. Liang, G. Grishin, N.
V. Goldstein, J. L. Cell 2008, 132, 387.
2. Mechanistic studies of polyhydroxy-
alkonate (PHA) biosynthesis. Biodegradable
plastic PHAs can substitute oil-based plastics
that are non-biodegradable. Our ultimate goal is
to understand mechanisms of proteins involved in
PHA biosynthesis and to engineer them to produce
PHAs in an economically competitive fashion,
which will help to protect our environment and
save energy.
Commercial products made of PHA
54
3. Investigation of peptidoglycan glycosyl-
transferases (PGTs) in peptidoglycan
biosynthesis. PGT catalyze the final step of
polymerizing Lipid II to form the nascent
bacterial wall. Because their function is unique
and essential for bacterial survival, PGTs have
been the major target of clinically used
antibiotics. Our goals are to understand the
mechanism of substrate recognition by PGTs, to
develop a model that can predict interactions
between PGTs and substrate, and to design novel
inhibitors to PGTs.
4. Site-specific protein labeling using SNAP
tag. Selective labeling of proteins has become an
essential tool to visualize and characterize
biological activities inside living cells. The
SNAP tag was first introduced by Kai Johnsson
using a human O6-alkylguanine-DNA
alkyltransferase (hAGT), which transfers the
alkyl group from its substrate,
O6-alkylguanine-DNA to one of its cysteine
residues. Our goals are to develop novel small
molecule probes for specific labeling and apply
this technology for detection of protein-protein
interactions.
55
Dr. Sundeep Rayat
Organic and Biological Chemistry
RESEARCH INTERESTS We will investigate problems
at the interface of chemistry and biology by a
combination of chemical, biochemical and
computational methods.
Our laboratory will focus on two main projects

• We will study the deamination of catecholamine
  neurotransmitters under nitrosative stress as a
  novel potential pathway of neurodegeneration in
  Parkinsons Disease.
• We will synthesize enyne-carbodiimide based
  prodrugs for cancer therapy and test their
  ability to cause cytotoxicity in human cancer
  cell lines.

56
Neurodegeneration in Parkinsons Disease
Dopamine and norepinephrine are the catecholamine
neurotransmitters in brain areas concerned with
movement, emotional behavior, arousal, reward,
and regulation of sleep and mood.
Parkinsons disease (PD) is caused by the
selective and progressive degeneration of
dopamine and norepinephrine-containing neurons as
a result of oxidative stress. Reactive nitrogen
species (NOx) can deaminate the primary amino
group of these neurotransmitters and cause
oxidative stress.
We will study the nitrosative deamination of
catecholamine neurotransmitters to form the
diazonium ions 1 and their subsequent adduct
formation 2 with various biomolecules such as DNA
and proteins in vitro and in vivo.
57
Masked Enyne-Carbodiimides Prodrugs for
Chemotherapy
Enyne-carbodiimides are highly reactive towards
biological nucleophiles which restricts their use
as potent DNA cleaving agents.
We will synthesize the enyne-carbodiimide
prodrugs 4 in which the carbodiimide
functionality will be masked in a
tetrazolin-5-thione ring structure. 4 will be
selectively irradiated in the target tissue to
generate carbodiimides 1 that will cyclize to
form biradicals 2 or 3. The biradicals so
formed can abstract hydrogen atoms from the
sugar-phosphate backbone of the DNA resulting in
strand scission and ultimately in cytotoxicity.
58
A few more reasons to consider Graduate studies
in Chemistry at Kansas State

• Competitive stipends.
• An expanding and well-funded Department.
• First-rate research in inorganic, organic,
  physical, analytical, materials, and biological
  chemistry.
• Friendly and helpful staff and faculty.
• Our graduate students have successful careers
  (see next few pages for some examples)!

59
Dr. Destin Leinen Ph. D. 2000 Pantex, Amarillo
Dr. Keith Lorimer Ph. D. 2001 Aptuit, West
Lafayette
Dr. Min Zou Ph. D. 2002 Aldrich Chemicals, St.
Louis
Dr. Michelle Smith Ph. D. 2009 York University, UK
60
Dr. Brock Levin Ph. D. 2005 Patent Specialist,
St. Louis
Dr. Nate Schultheiss Ph. D. 2007 Haliburton,
Houston.
Dr. Joaquin Urbina Ph. D. 2005 Assistant
Professor University of Belize
61
Five most recent graduates from the Klabunde
group
David Heroux (Ph. D. 2004) Assistant Professor,
U. of Maine
Gavine Medine (Ph. D. 2004) Baker-Petrolite Oil
Co.
Dmytro Demydou (Ph. D. 2006) Research Assist.
Prof., U. of Arkansas
Al Smetana (Ph. D. 2006) Wright-Patterson Air
Force Base
Johanna Haggstrom(Ph. D. 2007) Haliburton Co.
62
Hewlett-Packard Research Center
Post-doc at UC Santa Barbara
Research Scientist, Boreskov Catalysis Institute,
Russia
63
We also have a beautiful Campus..
Student Union
Anderson Hall
The Art Museum
The Farrel library
The Hale library
64
...with over 20,000 students,...
65
many of them in Chemistry.
66
KSU is located in Manhattan...
67
in the Flint Hills, North-East Kansas.
68
If you need more information about Chemistry at
Kansas State or if you want to receive an
application package.
Contact Prof. Christer Aakeröy
(aakeroy_at_ksu.edu) or Mary Dooley
(mldooley_at_ksu.edu)
69
Welcome to Kansas State!
http//www.ksu.edu/chem/