Analytical Chemistry Division
2019
Analytical Chemistry
• Not JUST titrations!
Fro
m t
he
Am
eri
can
Ch
em
ical
So
ciet
y (A
CS)
“Analytical chemistry is the art and science of determining what matter is and how much of it exists.In 2012 (salary survey data), analytical chemistry was the most popular field of work for ACS chemists.”
“Analytical chemists use their knowledge of chemistry, instrumentation, computers, and statistics to solve problems in almost all areas of chemistry and for all kinds of industries.”
Analytical Chemistry
• Not JUST titrations!
• We’re doing research in topics as diverse as better batteries, labs-on-chips, forensics, explosives detection and degradation, biofuels analysis, and creating new materials.
• 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
• Professor Graham Cheek
• Professor Christine Copper
• CDR Dave Durkin
• Professor Dianne Luning Prak
• LCDR Doug Marks
• Professor Maria Schroeder
• Associate Professor Ron Siefert
• Professor Paul Trulove
RESEARCH INTERESTSProf. Graham Cheek
Mi 144 36625 [email protected]
Electrochemistry of organic compounds
Bio-electrochemistry of amino acids
Cyclic and Square-Wave VoltammetrySpectroscopic Techniques (NMR, MALDI)
Solvents : Water, non-aqueous solvents, ionic liquidsN
+CF3 SO3 -
Forensic Applications
1. Soil Characterization : X-Ray Fluorescence2. Paper / Ink Characterization : Raman Spectroscopy
cysteine tryptophan
RESEARCH INTERESTS Prof. Graham Cheek
SolventspH 5, 7 aqueous buffersNonaqueous solventsIonic liquids
Use of NMR, MALDI ?
Bio-electrochemistry of amino acids
Effect of metal ions ( Zn2+ ) on electrochemical behavior,
especially for “zinc fingers” !
RESEARCH INTERESTS Prof. Graham Cheek
Bio-electrochemistry of amino acids
Wikipedia, “Zinc Fingers,” accessed 11 February 2018
Interaction of Zn2+ and possibly other ionswith cysteine and histidine side groups in proteins
CHEEK, Graham T., Professor, and WOROSZ, Matthew A., MIDN, “Electrochemical Studies of L-Cysteine,”ECS Trans., 2016, 72(27), pp. 1-8. doi:10.1149/07227.0001ecst
Prof Christine [email protected]
Michelson 265
Development of Separation and Detection Methods for Forensic Analysis
Capillary Electrophoresis (CE)
*Separation is achieved based on different rates of migration of charged species in an applied electric field.
• 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
Capillary Electrophoresis can be used to detect…
• Explosives in seawater, sand, and soil
• 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 (Deglau and Gosney) are working on analyzing dyes in fibers that could be residues at a crime scene.
http://greenfleet.dodlive.mil/energy/great-green-fleet
Fuel certification program/Office of Naval Research
Prof. Dianne Luning Prak ([email protected])
January 2016Navy launched Carrier Strike Group out of San Diego powered by mixtures of petroleum-based and bio-based fuel.
Sept 2016
Successful test flight of EA-18G Growler
on 100% CHCJ fuel at Naval Air Station
Patuxent River, MD (Lt. Cmdr. Bradley
Fairfax, project officer & test pilot)
http://www.navy.mil/submit/display.asp?story_id=96702
http://www.explainthatstuff.com/diesel-engines.html
4-Stroke diesel engine
Fuel Compression by pressure pulsedepends on bulk modulus = r c2
Spray behavior depends on Density, viscosity, surface tension
Fuel certification program/Office of Naval Research Chemical composition, physical properties & combustion of bio-based and petroleum-based fuels
Goal: How does chemical structure impact the physical and chemical properties of fuels?
· density · viscosity · enthalpy of combustion· speed of sound · bulk modulus · flash point· surface tension · flash point · distillation behavior· enthalpy of vaporization · combustion in diesel engines
Prof. Dianne Luning Prak ([email protected])
Example student publicationsLuning Prak, D. J., Fries, J. M., Gober, R. T.; Vozka, P., Kilaz, G., Johnson, T. R., Graft, S. L., Trulove, P. C., Cowart, J. S. Densities, Viscosities, Speeds of Sound, Bulk Moduli, Surface Tensions, and Flash Points of Quarternary Mixtures of n-Dodecane (1), n-Butylcyclohexane (2), n-Butylbenzene (3), and 2,2,4,4,6,8,8-Heptamethylnonane (4) at 0.1 MPa as Potential Surrogate Mixtures for Military Jet Fuel, JP-5, submitted to Journal of Chemical and Engineering Data
Luning Prak, D. J., Graft, S., Johnson, T., Cowart, J. S., Trulove, P., 2018. Density, Viscosity, Speed of Sound, Bulk Modulus, Surface Tension, and Flash Point of Binary Mixtures of n-Hexylbenzene (1) or n-Butylbenzene (1) in 2,2,4,6,6-Pentamethylheptane (2) or 2,2,4,4,6,8,8-Heptamethylnonane (2) at 0.1 MPa, J. Chem. Eng. Data, 63, 3503–3519.
Rochelle GoberJulia Fries
Professor Schroeder’s Research Interests
Harold Edgerton, photographer
- Improved Polymer Coatings for:- Military Transport (Humvees)- Body Armor- Hazardous Material Transport- Transparent Armor
- Laboratory Development- Experiments in support of IL or
Chemistry of Cooking course- Chemical Education Research
- Analyzing Plebe Chemistry Curriculum Changes
Projectile hitting elastomer at > 500 mph
PDMS
• Previous Experiments developed by Students (used in IL)• Analysis of Foods by Atomic Absorption Spectroscopy (Tony Ferro, ’05)
Determination of Iron in Total Cereal by Flame AA
• Synthesis and Characterization of Polymer Networks (Colin Browning, ‘03)PDMS Networks, GluepSwelling, Tensile StrengthViscosity, Crosslinking
• Current Project• Determination of Heavy Metals in Hyperaccumulator Plants by XRF
Laboratory Development
1/C NicoleSarao
Flame AA
XRF
Rascio, Plant Science 2011, 180, 169-181 http://www.horiba.com
https://www.youtube.com/watch?v=-Kwau5l7AeMhttps://www.thestudentroom.co.uk/showthread.php?t=1589126
http://lab-training.com/2013/05/08/introduction-to-aas-component-parts/
• A few years ago, a pilot study on the use of an Atoms First curriculum in Plebe Chemistry was tested
• Research students involved in analyzing data
Chemical Education Research
Olivia Bair, ’18 1/C Clare Suess 1/C Bianca Roach
• Need further analysis (coding of student responses, statistical analysis, method development) before publication – focus on particulate-nature of matter
• Work in collaboration with Prof. Dillner, Prof. Teichert, Dr. Thomas
Prof. Ron SiefertAssociate Professor
3-6336 (office), Mi-237 (office), Mi-240 (lab)
Iron in Marine Aerosols
Vehicle NH3 Emissions
Agricultural NH3 Emissions
2016-2017 Project – Nanotubes & Their Applications
Deposition of Nutrients to Surface Waters
Novel Sorbents (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
Pas
t P
roje
cts
Chesapeake Bay Ammonia & Nitrate Measurements
OBJECTIVE: Investigate the ability of nanotubes to encapsulate and stabilize biomacromolecules. Possible applications include: drug delivery, and as a method to protect biomacromolecules from thermal and chemical stresses.
OBJECTIVE: Investigate the ability of nanotubes to encapsulate and stabilize biomacromolecules. Possible applications include: drug delivery, and as a method to protect biomacromolecules
from thermal and chemical stresses.
APPROACH: Use model systems to study the ability of the
nanotubes to protect and stabilize biomacromolecules.
- Method development: Choosing enzymes & substrates- Encapsulation of enzymes in nanotubes
- Protein assays
- Substrates that result in products that fluoresce at appropriate wavelengths
- Performing studies investigating the stability of encapsulated enzymes to thermal and chemical stresses
Current studies using lithocholic acid (LCA) nanotubes & chymotrypsin.
Nanotubes & Their Applications
Analysis of Explosives - Capillary Electrophoresis
MIDN Cody Mendelow (2018-2019)
• Micellar electrokinetic chromatography (MEKC) – allows for separation of neutral molecules in an electric field by adding surfactant micelles to the separation buffer.
• Simultaneous analysis of hydrophilic and hydrophobic analytes
• On-line pre-concentration to improve detection limits
10 15 20 25 30 35 40
TIme (Minutes)
100 mAU
EOF Marker
1,3,5-TNB
TNT 2,4-DNT
2-Am-4,6-DNT
Department of Chemistry
The USNA Ionic Liquids Team
20
CDR Dave Durkin Dr. Patrick Fahey
Dr. Ashlee AielloDr. Tyler CosbyMIDN Christian HoffmanMIDN Robert Chung
Prof. Paul Trulove
Department of Chemistry
QU
AN
TIT
AT
IVE
IM
PA
CT
Advanced Functional Biopolymer MaterialsProf. Paul C. Trulove, MI-248, [email protected], 3-6622
CDR David P. Durkin, MI-243, [email protected], 3-6635
STA
TU
S Q
UO
EN
D-O
F-P
HA
SE
GO
AL
NE
W I
NS
IGH
TS
Natural PolymersNatural 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 to nonexistant.
Ionic Liquids SolventsWe 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 polymer materials.
Develop multi-functional natural
materials and coatings with
unique electronic, catalytic,
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, in-situ medical
applications
Producing natural materials
with dramatically enhanced
mechanical properties
Enabling tuneable natural
material properties with high
spatial resolution
Integrating functional micro- or
nano-materials with catalytic,
electrical, magnetic and optical
properties into natural fiber
matrices
MAIN ACHIEVEMENTS
Discovered new classes of welding Ionic liquids,
including polymerizable & non-aromatic cations
Developed operational NFW Pd-In catalyst reactor to
remove nitrates from contaminated drinking water
Evaluated novel functional biocomposites containing
Ag nanoparticles (surface enhanced Raman) and Pd-
Fe nanomagnets (catalysis and/or EMI shielding)
Studied enhanced thermal stability of fiber-welded
materials containing silane-modified nanocellulose
Investigated apparent superionicty of ionic welding
solvents containing co-solvent & biopolymer
Determined impact of ionic liquid contaminants on
nanoparticle catalyst structure and reactivity
Establishing AFM methods to quantitatively measure
physical property changes to fiber-welded materials.
Ag Nanoparticle-Linen
for enhanced RamanNFW Si-nanocellulose
improves thermal
stability
Discovered New
Classes of Ionic
Liquids Capable of
Welding
Department of Chemistry
Biopolymer Properties
22
Fiber Elongation
at Failure
(%)
Modulus
(GPa)
Strength
(GPa)
Density
(g/cm3)
Energy to
Break (J/g)
Dragline Spider Silk
(Nephila clavipes)
10-40 1-30 0.3-1.8 1.35 30-125
Silkworm Cocoon
Silk (Bombyx mori)
15-35 5 0.6 1.45 70
Nylon 66 18 5 0.88 1.14 80
Cotton 6-7 6-11 0.3-0.7 1.50 5-15
Kevlar 49 2.5 124 2.8 1.44 15
Steel 8 200 2 13.0 2
D.L. Kaplan, S.J. Lombardi, W. Muller, S. Fossey, in Biomaterials: Novel Materials from Biological Sources (Ed: Byrom D.), Stockton Press, New York 1991.
Department of Chemistry
“Natural Fiber Welding”
++ +
+++
+
+ ++
+
+
+
+
+
+
+
+
+
+
++
+
+
+
+
+
+
¯
¯
¯¯
¯
¯
¯
¯
¯
¯
¯
¯
¯
¯
¯¯
¯ ¯ ¯
¯
¯
¯¯
¯¯¯
¯
¯
Heated
60 min
Natural Fibers Welded Fibers
add
Ionic
Liquid
remove
Ionic
Liquid
Controlled Application of
ILs Opens Up the Fiber
Structure to Enable
Physical and Chemical
Modification
L. M. Haverhals, H C. De Long, W. M Reichert, P. C. Trulove,
“Natural Fiber Welding,” US patent 8,202,379; L. M. Haverhals,
et al, Cellulose, 19, 13 – 22 (2012).; L. M. Haverhals, et al,
Macromolecular Materials & Engineering, 295 (5), 425 – 430
(2010)
Department of Chemistry
Applications of NFW
• Improve Natural Material Properties
• Controlled Fabrication of Novel Composites
Integrate Small Molecules
Merge Functional Polymers
Entrap Functional Solids
Department of Chemistry25
Use of Ionic Liquids to Fabricate
Biopolymer Composite Materials
Knitted Electrochemical Capacitors for Smart Textiles*
*Collaboration with Drexel University
Bamboo (0.54 mg/cm)
Department of Chemistry
+ + +
Yarn
Separator
Yarn
Electrode
Yarn
Electrode
Knitted Linen/Bamboo/Viscose Capacitors!
26
Department of Chemistry
MIDN Robert Chung
27
Application of Polymerizable Ionic Liquids to NFW
Polymerization of Ionic Liquid
used in Welding
Department of Chemistry28
AFM Analysis of Welded Biopolymer Materials
MIDN Christian Hoffman
Welded Yarns
Welded Yarns Cross
Section
Questions?