Analytical Chemistry Division

2014

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

• CDR Rob Calhoun

• Professor Graham Cheek

• Professor Christine Copper

• Professor Judith Hartman

• Associate Professor Dianne Luning Prak

• Professor Dan O’Sullivan

• Professor Maria Schroeder

• Associate Professor Ron Siefert

• Professor Paul Trulove

RESEARCH INTERESTSProf. G. CheekMi 144 36625

Electrochemistry of organic compounds1. Effect of Lewis acids on reaction pathways2. Bio-electrochemistry of amino acids

3. Kolbe reaction RCOO- - 1 e- RCOO.

RCOO. → R. + CO2

2 R. → R2

Solvents : Ionic liquids, water, acetonitrileN

+CF3 SO3 -

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

RESEARCH INTERESTS Prof. G. Cheek

Effect of Lewis acids on organic reactions

-20

-10

0

10

20

-3-2-1012

Cu

rre

nt,

uA

Potential, V vs Ag / AgCl

+ Yb(TfO)3

Ionic liquid BMPY TfON

+CF3 SO3 -

Use of NMR, UV-VIS ?

Bio-electrochemistry of amino acids

- 2 e-

- 2 H+

cysteine

cystine

also dipeptides ?

Prof Christine Copperccopper@usna.edu

Michelson 265

project will also include collaboration with scientists at the Naval Research Laboratory, Washington, D.C. or at Drexel University

Development of Separation and Detection Methods for Environmentally

Important Molecules

Capillary Electrophoresis (CE)

*Separation is achieved based on different rates of migration of charged species in an applied electric field.

Capillary

Lamp

Inlet Buffer/Sample Injection Outlet Buffer

Data Collection/Storage

vi = uapp E

High Voltage Power +-

DetectorDetector

Electrophoresis

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• 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

Instrumentation

This automated instrument can run samples when you are not there!

CE instrument is in MI 264.

Capillary Electrophoresis can be used to detect…

• Explosives in seawater• 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:Micala Migneault and Clay Aronica

http://greenfleet.dodlive.mil/energy/great-green-fleet/ Midn 1/C Sarah Alexandre

Fuel certification program/Office of Naval Research Goal: Analysis and testing of alternative fuels: density, viscosity, surface tension, speed of sound, bulk modulus, flash point, enthalpy of combustion (bomb calorimetry)

Luning Prak, D. J., Alexandre, S. M., Cowart, J. S., Trulove, P.C., “Density, Viscosity, Speed of Sound, Bulk Modulus, Surface Tension, and Flash Point of Binary Mixtures of N-Dodecane with 2,2,4,6,6-Pentamethylheptane or 2,2,4,4,6,8,8-Heptamethylnonane” submitted to J. Chem. Eng. Data, 1/14

July 19-20, 2012 demonstration successfully evaluated the performance of “drop in replacement” advanced biofuel [50-50 mixtures of biofuel (made from used cooking oil and algae) and petroleum-based marine diesel or aviation fuel. ]

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

Luning Prak, D.J., Milewski, E.A., Jedlicka, E.E., Kersey, A.J., O’Sullivan, D.W., 2013, “Influence of pH, Temperature, Salinity, and Dissolved Organic Matter on the Photolysis of 2,4-dinitrotoluene and 2,6-dinitrotoluene in Seawater,” Marine Chemistry, 157, 233-241.

How does the photolysis behavior of munitions constituents in marine systems differ from that in fresh water systems? · salinity · nitrate · dissolved organic matter

Unexploded Ordnance in shallow waters

Photolysis of munitions constituents

http://www.SERDP.org Midn 1/C James Breuer

HPLC with autosampler

SUNSHINE LABSolar Simulator Project involves

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

Professor Schroeder’s Research Interests

Harold Edgerton, photographer - Improved Polymer Coatings for:

- Military Transport (Humvees)- Body Armor- Hazardous Material Transport (DTRA)- Transparent Armor (ARL)

- Laboratory Development:- Experiments in support of Chemistry of Cooking course- Experiments for the IL courses

Projectile hitting elastomer at > 500 mph

Motivation for Coatings Research• To understand the mechanisms

of impact protection of polymer-coated surfaces

projectiles hitting elastomers at

high speed protection no protection

• To understand temp effects (Tg)• To utilize nanoparticles

• To improve armor protection

Polymer synthesis, characterization, processing

Engineering, physical and mechanical testing

Materials Science Ballistic testing

Basic research with military

applications

Continuing Student Project (DTRA)Protective Coatings for Hazardous Material Transport

Research Collaboration:Naval Research Laboratory (NRL)

Defense Threat Reduction Agency (DTRA)

Train Derailment – Lac-Megantic, Quebec74 train cars containing crude oil42 persons killed, 30 buildings destroyedJuly 6, 2013

Current Research Student1/C Philip Solt

North Dakota Dec 31, 2013

Ron SiefertAssociate Professor

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

Iron in Marine Aerosols

Vehicle NH3 Emissions Agricultural NH3 Emissions

Current Projects / Development of Nanoporous Sorbent Materials

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

ProjectsMeasurements in the Chesapeake Bay

Enhanced Detection of Explosives and Related Compounds

OBJECTIVE: Develop organosilicas as sorbents applicable to the preconcentration of nitroenergetics and 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.

Department of Chemistry

Natural Fiber Welding - Ionic Liquid Facilitated Biopolymer Mobilization and Reorganization

Prof. Paul C. Trulove, MI248, trulove@usna.edu, 3-6622

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IN

SIG

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Research GoalsDevelop 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

MAIN ACHIEVEMENTS· Investigated the impact co-solvent properties on the natural fiber welding process ·Demonstrated Inkjet printing of ionic liquids on natural fiber substrates·Utilized Laser heating to spatially control the welding of natural fiber substrates ·Developed a continuous fiber welding process to coat yarns with functional solid materials·Evaluated the electrochemical and knitting properties of yarn based supercapacitors·Studied incorporation of fire retardant materials in natural yarns via fiber welding

Ionic Liquids Solvents·We 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.

Natural Polymers·Natural 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.

Current Impact·Producing natural materials with dramatically enhanced mechanical properties·Enabling tuneable natural material properties with high spatial resolution ·Facilitating the integration of functional solid materials with electrical, magnetic and optical properties into natural fiber matrices

N N

R'

R R''

+CH3COO−

Natural materials with dramatically enhanced physical and chemical properties

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Department of Chemistry

Control of Natural Fiber Welding Using Inkjet Printing of Ionic Liquids

Movies Obtained from Wikipediahttp://en.wikipedia.org/wiki/Micro_Piezo

piezoelectric inkjet

thermal inkjet

18Yellow – Rhodamine/Ionic LiquidGreen – Substrate

Department of Chemistry

Laser Induced Natural Fiber Welding

CNC 40 W CO2 laser with raster and/or vector operation by Full Spectrum Laser (www.fslaser.com)

Laser

NaturalFiber

Substrate

IonicLiquid AFOSR

Use a Laser to Spatially Control the Welding of Ionic Liquid Coated Cotton Paper

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Department of Chemistry20

Use of Ionic Liquids to Fabricate Biopolymer Composite Materials

Knitted Electrochemical Capacitors for Smart Textiles*

*Collaboration with Drexel University

Bamboo (0.54 mg/cm)

BeforeTreatment

AfterTreatment

Department of Chemistry

+ + +

Yarn Separator

Yarn Electrode

Yarn Electrode

Knitted Linen/Bamboo/Viscose Capacitors!

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separator

VERY FLEXIBLE!

Questions?