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 cheek@usna.edu

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 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 (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 (prak@usna.edu)

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 (prak@usna.edu)

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, trulove@usna.edu, 3-6622

CDR David P. Durkin, MI-243, durkin@usna.edu, 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?