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Analytical Chemistry Division
2017
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 Dianne Luning Prak• Professor Dan O’Sullivan• Professor Maria Schroeder• Associate Professor Ron Siefert• CDR Julie Spencer• Professor Paul Trulove
RESEARCH INTERESTSProf. Graham Cheek
Mi 144 36625
Electrochemistry of organic compounds1. Bio‐electrochemistry of amino acids
Cyclic and Square‐Wave VoltammetrySpectroscopic Techniques
2. Effect of Lewis acids on reaction pathwaysKetone Systems
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 5, 7 aqueous buffersNonaqueous solventsIonic liquids
Use of NMR, UV‐VIS ?
Bio‐electrochemistry of amino acids
Effect of metal ions ( Zn2+ ) on electrochemical behavior
Prof Christine [email protected] 265
project will also include collaboration with scientists at the Naval Research Laboratory, Washington, D.C. or at George Washington
University, Washington, D.C.
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, 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
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.
Sept 2016Successful test flight of EA-18G Growleron 100% CHCJ fuel at Naval Air StationPatuxent River, MD (Lt. Cmdr. BradleyFairfax, project officer & test pilot)
http://www.navy.mil/submit/display.asp?story_id=96702
Fuel certification program/Office of Naval Research Chemical composition, physical properties & combustion of bio‐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 ([email protected])
Example student publicationsLuning Prak, D. J., Lee, B. G., Trulove, P. C., Cowart, J. S., 2017, “Density, Viscosity, Speed of Sound, Bulk Modulus, Surface Tension, and Flash Point of Binary Mixtures of Butylbenzene + Linear Alkanes (n‐Decane, n‐Dodecane, n‐Tetradecane, n‐Hexadecane, or n‐Heptadecane) at 0.1 MPa”, Journal of Chemical and Engineering Data, 62, 169−187.
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.
Maggie McLaughlinSonya Ye
Program review: U.C. DavisNext Fall: NPS, Monterey, CA
Prof. Dianne Luning Prak ([email protected])
Program review: U.C. Davis
Next Fall NPS
Monterey, CA
Department of Energy Videohttps://betterbuildingssolutioncenter.energy.gov/swap/season-2, Technical video:Energy Research, Start at 1:17 of video
Ron SiefertAssociate Professor
3‐6336 (office), Mi‐243 (office), Mi‐240 (lab)
Iron in Marine Aerosols
Vehicle NH3 Emissions
Agricultural NH3 Emissions
Current 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
Past
Pro
ject
s
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.
Nanotubes & Their ApplicationsOBJECTIVE: 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.
Nanoporous Photocatalysts for Decontamination of Nerve Agents
Lab on a ChipMicrofluidic devices using electro‐osmotic flow.
RESULTS‐ Chymotrypsin with Proteasome 20S Activity Assay
‐ Able to encapsulate chymotrypsin in LCA nanotubes‐ Able to monitor activity of chymotrypsin by measuring product
fluorescence: λEX = 480‐500 nm & λEX = 480‐500 nm‐ Not in wavelengths where nanotubes scatter light‐ Latest findings show that encapsulation protects enzyme
from thermal stresses compared to free enzyme!
Department of ChemistryQ
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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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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 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 ACHIEVEMENTSInvestigated the nature of the ionic welding solvent and the impacts of co-solvent & biopolymer contentEvaluated the impact of tension on fiber weldingPrepared nanoscale bimetallic catalysts in natural polymer materials and welded them to natural materials to prepare catalytic assembliesStudied the fiber welding of silane modified nanocellulose into natural polymer materialsInvestigating the application of fiber welding to produce novel hair-karatin composite structuresDeveloped welded antimicrobial coatings on cellulose substrates
Fe3O4 Particles in Linen Yarn
Department of Chemistry
Biopolymer Properties
16
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
“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 NFW• Improve Natural Material Properties• Controlled Fabrication of Novel Composites
Integrate Small MoleculesMerge Functional Polymers Entrap Functional Solids
Department of Chemistry19
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!
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Department of Chemistry21
Magnetic Biopolymer Composite Yarns
MIDN Katie Ryall
Fe3O4 Particles in Linen Yarn
Department of Chemistry
MIDN Mary Cate Scully
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Horsehair Biopolymer Composites
Rhino Horn
Rhino Horn Matrix Structure
Horsehair – Silk Composite
Questions?
