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Analytical Chemistry Division
2014
Analytical Chemistry
• Not JUST titrations!
• We’re doing research in topics as diverse as
better batteries, labs-on-chips, forensics,
explosives detection and degradation, and
better body armor.
• We use almost every instrument you’ve seen
plus some.
• Two of the departments’ scanning probe
instruments are in the Analytical Division.
Analytical Chemistry Members
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CDR Rob Calhoun
Professor Graham Cheek
Professor Christine Copper
Professor Judith Hartman
Associate Professor Dianne Luning Prak
Professor Dan O’Sullivan
Professor Maria Schroeder
Associate Professor Ron Siefert
Professor Paul Trulove
RESEARCH INTERESTS
Prof. G. Cheek
Mi 144 36625
Electrochemistry of organic compounds
1. Effect of Lewis acids on reaction pathways
2. Bio-electrochemistry of amino acids
3. Kolbe reaction
RCOO- - 1 e- → RCOO.
RCOO. → R. + CO2
2 R. → R2
Solvents : Ionic liquids, water, acetonitrile
N
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Forensic Applications
1. Soil Characterization :
X-Ray Fluorescence
2. Paper / Ink Characterization : Raman Spectroscopy
CF3 SO3 -
RESEARCH INTERESTS
Prof. G. Cheek
Effect of Lewis acids on organic reactions
Use of NMR, UV-VIS ?
+ Yb(TfO)3
N
+
Ionic liquid
BMPY TfO
CF3 SO3 -
Bio-electrochemistry of amino acids
also dipeptides ?
- 2 e- 2 H+
cysteine
cystine
Development of Separation and Detection
Methods for Environmentally
Important Molecules
Prof Christine Copper
ccopper@usna.edu
Michelson 265
project will also include collaboration with scientists at the
Naval Research Laboratory, Washington, D.C. or at Drexel University
Capillary Electrophoresis (CE)
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CE was first used in the early 1980’s.
Reasonably high sensitivity (ppm or ppb)
Short separation time (<5 min)
Small Sample Volume (nanoliters)
Can be done on a microchip device instead
of in a column
*Separation is achieved based on different rates of migration of
charged species in an applied electric field.
Instrumentation
CE instrument is in MI 264.
This automated instrument
can run samples when you
are not there!
Capillary Electrophoresis can be used to detect…
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Explosives in seawater
Poisons in beverages
Ozone in submarine atmospheres
Nerve agents in atmospheres
Polyaromatic hydrocarbons in environmental samples
Carbon monoxide poisoning in blood
Illicit drugs in urine
Current students:
Micala Migneault
and Clay Aronica
Assoc. Prof. Dianne Luning Prak (prak@usna.edu) & Prof. Paul Trulove
July 19-20, 2012 demonstration successfully evaluated the performance of
“drop in replacement” advanced biofuel [50-50 mixtures of biofuel (made from
used cooking oil and algae) and petroleum-based marine diesel or aviation fuel. ]
http://greenfleet.dodlive.mil/energy/great-green-fleet/
Midn 1/C Sarah Alexandre
Fuel certification program/Office of Naval Research
Goal: Analysis and testing of alternative fuels: density, viscosity, surface tension, speed of
sound, bulk modulus, flash point, enthalpy of combustion (bomb calorimetry)
Luning Prak, D. J., Alexandre, S. M., Cowart, J. S., Trulove, P.C., “Density, Viscosity, Speed of Sound, Bulk
Modulus, Surface Tension, and Flash Point of Binary Mixtures of N-Dodecane with 2,2,4,6,6Pentamethylheptane or 2,2,4,4,6,8,8-Heptamethylnonane” submitted to J. Chem. Eng. Data, 1/14
Photolysis of munitions constituents
Unexploded Ordnance
in shallow waters
How does the photolysis behavior of
munitions constituents in marine
systems differ from that in fresh
water systems?
· salinity
· nitrate
· dissolved organic matter
http://www.SERDP.org
Midn 1/C James Breuer
SUNSHINE LAB
Solar Simulator
HPLC with
autosampler
Project involves
· preparing solutions
· using solar simulator
· analyzing samples with HPLC
· identifying products
solid-phase extraction,
LC/MS
Luning Prak, D.J., Milewski, E.A., Jedlicka, E.E., Kersey, A.J., O’Sullivan, D.W., 2013, “Influence of pH, Temperature,
Salinity, and Dissolved Organic Matter on the Photolysis of 2,4-dinitrotoluene and 2,6-dinitrotoluene in Seawater,”
Marine Chemistry, 157, 233-241.
Professor Schroeder’s Research Interests
Harold Edgerton, photographer
- Improved Polymer Coatings for:
- Military Transport (Humvees)
- Body Armor
- Hazardous Material Transport (DTRA)
- Transparent Armor (ARL)
- Laboratory Development:
- Experiments in support of Chemistry of
Cooking course
- Experiments for the IL courses
Projectile hitting elastomer at > 500 mph
Motivation for Coatings Research
• To understand the mechanisms  Polymer synthesis,
of impact protection of
characterization,
polymer-coated surfaces
processing
projectiles hitting  Engineering,
physical and
elastomers at
high speed
mechanical testing
protection
no protection
 Materials Science
• To understand temp effects (Tg)  Ballistic testing
• To utilize nanoparticles
 Basic research with
military
• To improve armor protection
applications
Continuing Student Project (DTRA)
Protective Coatings for Hazardous Material Transport
Current Research Student
1/C Philip Solt
North Dakota
Dec 31, 2013
Train Derailment – Lac-Megantic, Quebec
74 train cars containing crude oil
42 persons killed, 30 buildings destroyed
July 6, 2013
Research Collaboration:
Naval Research Laboratory (NRL)
Defense Threat Reduction Agency (DTRA)
Ron Siefert
Associate Professor
3-6336 (office), Mi-243 (office), Mi-240 (lab)
Current Projects / Development of Nanoporous Sorbent Materials
Novel Sorbents (PMOs: periodic mesoporous organisilicas)
-For Analysis of Nitroenergetics (i.e, explosives)
-For Analysis of Perchlorates (used as propellants)
-As a substrate for catalysts to destroy contaminants
Past
Projects
Vehicle NH3 Emissions
Agricultural
NH3 Emissions
Measurements in the
Chesapeake Bay
Iron in Marine Aerosols
Deposition of Nutrients to Surface Waters
Enhanced Detection of Explosives and
Related Compounds
Nanoporous Photocatalysts for
Decontamination of Nerve Agents
Lab on a Chip
Microfluidic devices using electro-osmotic flow.
OBJECTIVE: Develop organosilicas as sorbents
applicable to the preconcentration of nitroenergetics
and perchlorates for enhancement of in situ detection
techniques
APPROACH: Characterize the binding characteristics
(e.g., selectivity, capacity, kinetics) of imprinted PMOs
for nitroenergetics and perchlorate propellants. Use of
HPLC and IC.
Current Impact
Producing natural materials with
dramatically enhanced mechanical
properties
Enabling tuneable natural material
properties with high spatial
resolution
Facilitating the integration of
functional solid materials with
electrical, magnetic and optical
properties into natural fiber
matrices
Natural Polymers
Natural polymers are renewable
materials that have many
attractive properties. Some
natural silks have strength and
toughness comparable to the best
synthetic polymers.
The ability to modify and tailor the
shape and properties of natural
polymers is limited.
N
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R
CH3COO−
MAIN ACHIEVEMENTS
N
R''
R'
Ionic Liquids Solvents
We have shown that ionic liquids
are powerful solvents for the
dissolution and processing of a
wide variety of natural polymers.
The solvating ability of ionic
liquids provides a powerful tool for
the modification and processing of
natural polymers.
Department of Chemistry
Investigated the impact co-solvent properties
on the natural fiber welding process
Demonstrated Inkjet printing of ionic liquids on
natural fiber substrates
Utilized Laser heating to spatially control the
welding of natural fiber substrates
Developed a continuous fiber welding process
to coat yarns with functional solid materials
Evaluated the electrochemical and knitting
properties of yarn based supercapacitors
Studied incorporation of fire retardant materials
in natural yarns via fiber welding
Research Goals
Develop multi-functional natural
materials and coatings with unique
electronic, optical, and sensing
properties for Air Force and DoD
relevant applications in areas such
as ballistic protection, energy
storage, microelectronics, stealth,
laser eye protection, optical
computing, chem./bio sensing, in17
situ medical applications
Control of Natural Fiber Welding Using
Inkjet Printing of Ionic Liquids
piezoelectric
inkjet
thermal
inkjet
Movies Obtained
from Wikipedia
Department
of Chemistry
http://en.wikipedia.org/wiki/Micro_Piezo
– Rhodamine/Ionic Liquid
– Substrate
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Laser Induced Natural Fiber Welding
Laser
Ionic
Liquid
Natural
Fiber
Substrate
Use a Laser to Spatially Control the Welding
of Ionic Liquid Coated Cotton Paper
 CNC 40 W CO2 laser with raster and/or vector operation
Department ofbyChemistry
Full Spectrum Laser (www.fslaser.com)
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Use of Ionic Liquids to Fabricate
Biopolymer Composite Materials
Knitted Electrochemical Capacitors for Smart Textiles*
Bamboo (0.54 mg/cm)
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Department of Chemistry
*Collaboration with Drexel University
Knitted Linen/Bamboo/Viscose Capacitors!
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Yarn
Electrode
Yarn
Separator
Yarn
Electrode
Department of Chemistry
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Questions?