analytical chemistry division...analytical chemistry •not just titrations! cs) ^analytical...
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Analytical Chemistry Division
2020
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
• 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 Voltammetry
Spectroscopic Techniques (NMR, MALDI, UV-VIS)
Solvents : Water, non-aqueous solvents, ionic liquidsN
+CF3 SO3 -
Forensic Applications
1. Soil Characterization : X-Ray Fluorescence2. Paper / Ink Characterization : Voltammetry, Raman Spectroscopy
cysteine tryptophan
RESEARCH INTERESTS Prof. Graham Cheek
SolventspH 5, 7 aqueous buffersNonaqueous solvents
Use of NMR, MALDI, UV-VIS
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 other ions such as Bi3+
with 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
Bi(Cys)2
UV-VIS Spectrum
RESEARCH INTERESTS Prof. Graham Cheek
Electrochemical Investigations of Colorants
-1.0
-0.5
0.0
0.5
1.0
-1.50 -1.00 -0.50 0.00 0.50 1.00 1.50
i, μ
A
E, V vs Ag/AgCl
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
-1.50 -1.00 -0.50 0.00 0.50 1.00 1.50
i, μ
A
E, V vs Ag/AgCl
Flair BlueR
BiC Cristal BlueR
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 (Goodwin, Dervishian and King) are working on analyzing dyes and their degradation products in fabrics.
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.
Jay Cooke Michael HamiltonLadavish Dorn
Luning 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, J. Chem. Eng. Data 2019, 64, 1725-1745.
Results GC x GC FIDChemical Composition of JP-5
2.3
Seco
nd
ary
colu
mn
(s)
3.3
4.3
5.3
Primary column (s)
165 2165 4165 6145
Increasing carbon number within category
iso-alkanes linearalkanes
mono-cycloalkanes
di- and tri-cycloalkanes
aromatics
naphthalenes
Navy Jet fuel is a complex mixture of thousands of compounds
Chemical composition, physical properties & combustion of bio-based & petroleum-based fuels
How does chemical structure impact the physical and chemical properties of fuels? · density · viscosity · enthalpy of combustion· speed of sound · bulk modulus · flash point (low flash point compounds)· surface tension · heat capacity · distillation behavior · enthalpy of vaporization · combustion in diesel engines
Use of jet fuels in diesel engines emergency generators/ one-fuel-forward policyWhen will the jet fuels fail to combust? (Look at limitations of Mil Spec)
Flash point: How do structural isomers affect flash point?
Recent submission with studentLuning Prak, D. J.; Foley, M. P.; Dorn, L.; Trulove, P. C.; Cowart, J. S.; Durkin, D. P. Determining the Thermal Properties of the Military Jet Fuel JP-5 and Surrogate Mixtures Using Differential Scanning Calorimetry/Thermal Gravimetric Analysis (DSC-TGA) and DSC Methods,submitted to Energy Fuels, November, 2019.
Prof. Dianne Luning Prak ([email protected])
Professor Schroeder’s Research InterestsOffice: Michelson 244
Email: [email protected]
- Analytical Chemistry, Polymer Chemistry- Laboratory Development
- Experiments in support of IL or Chemistry of Cooking course- Chemistry Education Research (CER)
- Analyzing Plebe Chemistry Curriculum Changes- Studies of the Use of Clickers in Plebe Chemistry for Self-Assessment
A Wordle of the titles of the papers published in U. Chem. Ed. from 1997 – 2004 by Michael Seery.http://michaelseery.com/home/index.php/2011/11/chemistry-education-research-and-practice/
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
• Recent Project• Determination of Heavy Metals in Hyperaccumulator Plants by XRF
Laboratory Development
Nicole Sarao, ‘19
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 conducted. This year, Plebes are using an Atoms-First textbook.
• Research students involved in analyzing data
Chemistry Education Research
Olivia Bair, ’18 Clare Suess, ’19 Bianca Roach, ‘19
• Finishing up analysis and publication • Work in collaboration with Prof. Dillner, Prof. Teichert, Prof. Bunce
1/C Trevor Clark 1/C Sebastian Yocca
Particulate-nature focus
• Current Interest in Plebe Chemistry – Looking at the “Middle Student” – How can we improve their learning?
• Self-Assessment during Class – Clickers• Metacognition (“thinking about your
thinking” or “awareness of how youlearn”)
• Current Study in Plebe Chemistry (SC112), to continue into the fall semester• Treatment (clicker) sections vs Control sections
• Working with both Qualitative and Quantitative data, Statistical Analysis, Coding of Student Responses, Possible Interviews, Development of Clicker Questions
• Collaboration with Prof. Dillner, Prof. Bunce
Chemistry Education Research
Prof. Ron SiefertAssociate Professor
3-6336 (office), Mi-237 (office), Mi-240 (lab)
Iron in Marine AerosolsAgricultural NH3 Emissions
2016-2017 Project – Nanotubes & Their Applications
Deposition of Nutrients to Surface Waters
Novel Sorbents (periodic mesoporous organisilicas)
Nick Hutchinson (2012-2013)
• 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
Lauren Stiff (2016-2017)
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.
Analysis of Explosives - Capillary ElectrophoresisCody 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 analytesOn-line pre-concentration to improve detection limits
Chemistry Evaluation of Printed Inks for Harsh EnvironmentsCollaboration with scientists at Navy Research Laboratory & Air Force Research Laboratory
Additive manufacturing (AM) has found a
wide range of applications in DoD.
Recent AM successes in the USAF, Navy,
and Army include repairs, flight and
submarine critical parts, locally certified
parts, printed armament, AM cast, and the
addition of functionality through AM
Conductive inks are an important
component in the tool set of AM
Conductive inks can be formulated by
blending either nanoparticles or micron
size particles that are highly conductive
such as silver, gold, copper, zinc, or
carbon
Performance in harsh environments will
require enhanced surface adhesion of inks
to the substrates
Ag nanoparticles-functionalization with poly(vinylpyrrolidone) (PVP)
Department of Chemistry
The USNA Ionic Liquids Team
21
MIDN Julia McFarland
CDR Dave Durkin
MIDN Christian Hoffman
Prof. Paul Trulove Dr. Ashlee Aiello Dr. Tyler Cosby
QU
AN
TIT
AT
IVE
IM
PA
CT
Towards Advanced Functional Biopolymer Materials
Paul C. Trulove and David P. Durkin – US Naval Academy
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 nonexistent.
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 & optical
properties into natural fiber
matrices
MAIN ACHIEVEMENTS
Synthesized Fe-Pd nanomagnets in a biomaterial
matrix and measured their magnetic properties.
Evaluated the iconicity of ionic liquid-biopolymer
solutions showing ion pairing & ion mobility are not
significantly impacted by the presence of biopolymer.
Demonstrated > 1000 fold change in the surface area
of welded biomaterials through control of the polarity
of the regeneration solvents.
Developed and applied a Raman spectroscopic
method for evaluating the extent of biopolymer
reorganization due to ionic liquid treatment.
Utilized AFM to measure the impact of fiber welding
on the nanomechanical properties of biomaterials.
Synthesized novel polymerizable ionic liquids and
demonstrated their in-situ polymerization during fiber
welding.
Raman Map of Cellulose
Crystallinity in Welded
Yarn Cross SectionsAFM Modulus Maps of Yarn
Cross Sections
Welded
Yarn
Native
Yarn
5 nm
Fe-Pd
Nano-
magnets
Department of Chemistry
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
Biopolymer Properties
23
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”
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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 Natural Fiber Welding
• Improve Natural Material Properties
• Controlled Fabrication of Novel Composites
Integrate Small Molecules
Merge Functional Polymers
Entrap Functional Solids
Department of ChemistryUntreated MeOH→H2O IPA→B→
CH
H2O→IPA→
B→CH
0.01
0.1
1
10
BE
T S
urf
ace A
rea (
m2/g
)
Untreated Cotton
20 µm
MeOH, Water
20 µm
Water, Isopropyl alcohol,
Butanone, Cyclohexane
20 µm
Isopropyl alcohol,
Butanone, Cyclohexane
20 µm
Untreated MeOH→H2O IPA→B→
CH
H2O→IPA→
B→CH
0.01
0.1
1
10
BE
T S
urf
ace A
rea (
m2/g
)
Untreated MeOH→H2O IPA→B→
CH
H2O→IPA→
B→CH
0.01
0.1
1
10
BE
T S
urf
ace A
rea (
m2/g
)
Untreated MeOH→H2O IPA→B→
CH
H2O→IPA→
B→CH
0.01
0.1
1
10
BE
T S
urf
ace A
rea (
m2/g
)
Morphological Influence of Solvent
Exchange
10×
decrease
1000×
increase
BE
T S
urf
ace A
rea (
m2/g
)
MIDN Julia McFarland
Department of Chemistry27
Application of Polymerizable Ionic Liquids to NFW
Polymerization of Ionic Liquid
used in Welding
MIDN Christian Hoffman
Department of ChemistryDepartment of Chemistry
Fiber Particle
Modified With
Functional
Material**
Incorporation of Functional Materials
via Synthesis with Fiber Particles
Welded Fibers
with Incorporated
Functional
Material
Fiber BundleIonic Liquid
with
Suspended
Fiber Particles &
Solubilized
Polymer
Remove
Ionic
Liquid
Treat –
(Time &
Temperature)
Ionic Liquid
Fiber Particle
**Chemical Modification of
Biopolymer, Encapsulated
Nanoparticles
Department of Chemistry
Synthesis of Functional Nanomaterials in
Fiber Powders
Mill to Powder
& Dry
Add Metal
Nitrates &
Reduce*
Method Used to
Produce Fiber
Impregnated
Nanoparticles
Pd, Cu, In
Pd-Cu
Pd-In
Fe
Fe-Pd
Ag
Au
Catalytic
Magnetic
Optical
*Incipient Wetness Impregnation (IWI) - Fiber powder
impregnated using an aqueous solution containing one
or more of Pd(NO3)2, In(NO3)3, Cu(NO3)2, Fe(NO3)2,
AgNO3, Au(NO3)3. Metal ions then reduced with H2.
Durkin, et al, ACS Sust. Chem & Eng. 4,10, 5511-5522 (2016)
Durkin et al., App. Catal. B., 221, 290-301 (2018)
Aiello, et al, J. Magn. Magn. Mater, 497, 165964 (2019)
Trulove, et al, ECS Trans. 86 287-296 (2018)
Department of Chemistry
Superparamagnetic Fe-Pd NPs in Biopolymer Matrix
• Alloyed nanoparticles (Fe-Pd) form throughout the biopolymer matrix (TEM)
• 5 – 10 nm in size and uniformly distributed (SEM/TEM)
Aiello, Morey, Livi, De Long, ElBidweihy, Trulove, Durkin.
J. Magn. Magn. Mater, 497, 165964 (2019)
Department of Chemistry
Applications and Future Work
EMI Shielding Development
1. Increase metallic loading 23 wt% (up from 6-17 wt%)
2. Examine substrate effects Comparative performance in cotton vs linen
3. Develop welded coatings/structures
4. Evaluate shielding performance
In process
Yarn
Pd-Fe
‘Ink’
Reconstitution Bath
In process*
*establishing collaboration with NAVAIR
Questions?