Analytical Chemistry Division

2020

Analytical Chemistry

• Not JUST titrations!

Fro

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Am

eri

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Ch

em

ical

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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 cheek@usna.edu

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 Copperccopper@usna.edu

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(prak@usna.edu)

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 (prak@usna.edu)

Professor Schroeder’s Research InterestsOffice: Michelson 244

Email: schroede@usna.edu

- 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

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IVE

IM

PA

CT

Towards Advanced Functional Biopolymer Materials

Paul C. Trulove and David P. Durkin – US Naval Academy

STA

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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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+

+ ++

+

+

+

+

+

+

+

+

+

+

++

+

+

+

+

+

+

¯

¯

¯¯

¯

¯

¯

¯

¯

¯

¯

¯

¯

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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?