Analytical Chemistry Division

2016

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• CAPT Rob Calhoun• Professor Graham Cheek• Professor Christine Copper• Professor Judith Hartman• Professor Dianne Luning Prak• Professor Dan O’Sullivan• Professor Maria Schroeder• Associate Professor Ron Siefert• Professor Paul Trulove

Electroanalytical Chemistry

CAPT Rob Calhoun, USN, Ph.D.Mi‐237, 3‐6635

calhoun@usna.edu

Electroanalytical chemistry

• Current major project:– Development of a rapid screening technique for new anti‐corrosion coatings for Naval Aviation using scanning electrochemical microscopy (SECM).

– Work will move into screening of additive materials (AM) since they are showing differences from the same alloys when forged.

Experimental Visualization

Coating

5‐20 µm

Aluminum Substrate

Fc+

Fc

0.1V

0.5V to 3.0V

FcMeOHSolution

SECM Tip

Substrate

Soluble oxide?  Ferrocene?

Sample 1.0V 1.5V 1.8V 2.5V

non-chromated primer on anodized Al 0.28 0.28 3.50 10.00

waterborne primer on alodine pretreated Al

0.25 0.25 1.60

chromated primer on alodine pretreated Al

0.28 0.18 0.18

Tip current (nA) at indicated substrate

potential vs. Ag/AgCl

TABLE I

‘Screening of Novel Anti‐Corrosion Coatings by Scanning Electrochemical Microscopy’, Lee, C., Dorriety, W., Hanrhan, R., Calhoun, R., ECS Transactions, 2015 66(30): 65‐71

RESEARCH  INTERESTSProf.  Graham Cheek

Mi 144   36625

Electrochemistry of organic compounds1.   Bio‐electrochemistry of amino acids

2.   Effect of Lewis acids on reaction pathways

3.   Electrochemical fluorination2 F‐ → F2 +  2 e‐

F2 +   RH  → RF  +  HF

Solvents :   Water, ionic liquids,  adiponitrileN

+CF3 SO3 -

Forensic  Applications1.   Soil Characterization :                  X‐Ray Fluorescence2.   Paper / Ink  Characterization :    Raman Spectroscopy 

cysteine tryptophan

RESEARCH  INTERESTS    Prof.  Graham Cheek

SolventspH 7  aqueous bufferNonaqueous solventsIonic  liquids

Use of   NMR,  UV‐VIS ?

Bio‐electrochemistry of amino acids

Effect of metal ions ( Zn2+ ) on electrochemical behavior

http://greenfleet.dodlive.mil/energy/great‐green‐fleet/ Midn 1/C Bridget Lee

Fuel certification program/Office of Naval Research                      Goal:  How does chemical structure impact the physical and chemical properties of fuels? density, viscosity, surface tension, speed of sound, bulk modulus, flash point, enthalpy of combustion, distillation behavior, combustion in diesel engines

Luning Prak, D. J., Jones, M. H., Trulove, P. C., McDaniel, A. M., Dickerson, T., Cowart, J.,  2015, “Physical and Chemical Analysis of Alcohol‐to‐Jet (ATJ) Fuel and Development of Surrogate Fuel Mixtures,” Energy and Fuels, 29, 3760 − 3769.

January 20, 2016: Navy launched Carrier Strike Group out of San Diego powered by mixtures of petroleum‐based and bio‐based fuel. 

Prof. Dianne Luning Prak (prak@usna.edu) & Prof. Paul Trulove

Luning Prak, D.J., Breuer, J.E.T., Rios, E.A., Jedlicka, E.E., O’Sullivan, D.W., “Influence of pH, Temperature, Salinity, and Dissolved Organic Matter on the Photolysis of 2,4,6‐trinitrotoluene in Seawater and Estuary Water,” submitted to Marine Chemistry, Dec. 2015.

How can the photolysis behavior of munitions constituents and algal toxins in be sped up by the addition of photosensitizers:

∙ riboflavin∙ dissolved organic matter?

Unexploded Ordnancein shallow waters

Photolysis of munitions constituents and algal toxins

http://www.SERDP.org Midn 1/C Evelyn Rios

HPLC with autosampler

SUNSHINE LABSolar Simulator Project involves

∙ preparing solutions ∙ using solar simulator∙ analyzing samples with HPLC∙ identifying products solid‐phase extraction, LC/MS

Oxidation of formaldehyde in atmospheric aerosolsProfessor O’Sullivan:

Examine the oxidation kinetics of formaldehyde as a source of formic acid:• In aqueous solutions with compositions 

similar to aerosols• H2CO oxidation is thought to be 

dominated by gas phase chemistry• Examine aqueous oxidation as a function 

of pH, ionic composition, and various oxidants

• O3, H2O2 and metal catalysis

Atmospheric aerosols:• Life time 4 to 7 days• Size 0.01 to 10 m• Large surface area• Experience a number of 

hydration and dehydration cycles.

Figure from the Leibniz‐Institute for Tropospheric Chemistry

Professor Schroeder’s Research Interests

Harold Edgerton, photographer

‐ Improved Polymer Coatings for:‐ Military Transport (Humvees)‐ Body Armor‐ Hazardous Material Transport‐ Transparent Armor

‐ Education Research/Laboratory Development‐ Understanding Plebe learning‐ Experiments in support of 

Chemistry of Cooking course  or ILProjectile hitting elastomer 

at > 500 mph

Motivation for Coatings Research• To understand the mechanisms of impact protection of polymer‐coated surfaces

projectiles hittingelastomers at           high speed

protection         no protection

• To understand temp effects (Tg)• To improve armor protection

Polymer synthesis, characterization, processing

Engineering, physical and mechanical testing

Materials Science Ballistic testing

Basic research with military applicationsCurrent Research Student

John Chamberlain, ’15Research Collaboration:

Naval Research Laboratory (NRL) 

Another Research AreaUnderstanding How Plebes Learn

Midn 1/C Stephanie Moore

• Educational Research Study• Selected topics (spectroscopy, 

laboratory concepts)• What helps plebes learn and retain 

complex chemistry topics?• Can the lab be used better to teach 

concepts?  (MORE labs)• How can we develop better 

“transfer” in students?• Can “molecular‐level” thinking help 

reinforce concepts?

Demo Midn Moore developed – hope to publish it

Ron SiefertAssociate Professor

3‐6336 (office), Mi‐243 (office), Mi‐240 (lab)

Iron in Marine Aerosols

Vehicle NH3 Emissions Agricultural NH3 Emissions

Current Project / Development of Nanoporous Sorbent Materials for “Lab on a Chip”

Deposition of Nutrients to Surface Waters

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 Ammonia & Nitrate 

Measurements in the Chesapeake Bay 

Enhanced Detection of Explosives and Related Compounds

OBJECTIVE: Develop organosilicas as sorbents applicable to the preconcentration of nitroenergeticsand perchlorates for enhancement of in situ detection techniquesAPPROACH: Characterize the binding characteristics (e.g., selectivity, capacity, kinetics) of imprinted PMOs for nitroenergetics and perchlorate propellants. Use of HPLC and IC.

Nanoporous Photocatalysts for Decontamination of Nerve Agents

Lab on a ChipMicrofluidic devices using electro‐osmotic flow.

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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.

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 polymers.

N N

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+

CH3COO−

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, in-situ medical applications

Producing natural materials with dramatically enhanced mechanical propertiesEnabling tuneable natural material properties with high spatial resolution Facilitating the integration of functional solid materials with electrical, magnetic and optical properties into natural fibermatrices MAIN ACHIEVEMENTS

Investigated the ionic properties of fiber welding solvents and the impacts of biopolymer on themStudied the optimization of Inkjet printing of biopolymers from ionic liquid solventsPrepared nanoscale bimetallic catalysts in natural polymer materials and used them to fabricate a catalytic membrane via natural fiber welding Developed natural fiber welded antimicrobial biopolymer and metal oxide coatings on cellulose substratesDemonstrated a continuous fiber welding process that significantly improves the mechanical properties of treated yarns

Department of Chemistry

Biopolymer Properties

19

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 80Cotton 6-7 6-11 0.3-0.7 1.50 5-15Kevlar 49 2.5 124 2.8 1.44 15Steel 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

Inkjet Printing with Ionic Liquid “Inks”

Movie Obtained from Wikipedia http://en.wikipedia.org/wiki/Micro_PiezoDimatix Materials Printer

Printing Ionic Liquid @ 70 °C

3 mm

3 mm

500 µm

500 µm

Ionic Liquid Printed on Cotton Paper

MIDN Audrey Head

Department of Chemistry

Integration of Chitin and Chitosan into Cellulose Surfaces

21

• Chitin most abundant biopolymer after cellulose− Similar in structure to cellulose− Can be harvested from waste materials (i.e. shrimp shells)− Chitosan generated from Chitin by deacetytalation

• Chitin and Chitosan have desirable properties− Antimicrobial− Metal complexation/absortion

MIDN Molly Chandler*

MIDN Robert Nolan**Lt. Robert Russell – Lead Research Advisor

Department of Chemistry

GFP E. coli Testing of NFW Chitin on Cotton Cloth

No Welding

500 μm

IL & 0.5% chitin

500 μm

No Welding

500 μm

IL & 0.5% chitin

500 μm

• Con-Focal Fluorescence (CFM) Images of Untreated and NFW Chitin on Aida Cotton Cloth

• Modified Version of *ASTM (E2722-09) ‒ Standard test method for the

screening assessment of antimicrobial activity in fabric and air filter media

• Welding done for 120 min at R.T. Samples coated with 4×105

cells/mL GFP E. Coli w/ agar, 72 hrs growth.

408 nm 488 nm

Department of Chemistry23

Use of Ionic Liquids to Fabricate Biopolymer Composite Materials

Knitted Electrochemical Capacitors for Smart Textiles*

*Collaboration with Drexel University

Bamboo (0.54 mg/cm)

MIDN Katie Ryall

Department of Chemistry

+ + +

Yarn Separator

Yarn Electrode

Yarn Electrode

Knitted Linen/Bamboo/Viscose Capacitors!

24

Department of Chemistry

Questions?