Analytical Chemistry Division

2018

Analytical Chemistry• Not JUST titrations!

From

 the Am

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 Che

mical Society (A

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Analytical Chemistry• Not JUST titrations!

From

 the Am

erican

 Che

mical Society (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

• Professor Dianne Luning Prak

• Professor Maria Schroeder

• Associate Professor Ron Siefert

• CDR Julie Spencer

• Professor Paul Trulove

RESEARCH  INTERESTSProf.  Graham Cheek

Mi 144   36625  cheek@usna.edu

Electrochemistry of organic compounds1.   Bio‐electrochemistry of amino acids

Cyclic and Square‐Wave VoltammetrySpectroscopic Techniques (NMR, MALDI)

2.   Effect of Lewis acids on reaction pathwaysKetone Systems

Solvents :   Water, non‐aqueous solvents, ionic liquidsN

+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,  MALDI ?

Bio‐electrochemistry of amino acids

Effect of metal ions ( Zn2+ ) on electrochemical behavior, especially for “zinc fingers” !

RESEARCH  INTERESTS    Prof.  Graham CheekBio‐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.eduMichelson 265

project will also include collaboration with scientists at George Washington University, Washington, D.C.

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. 

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• Current students (Erbach, McDonough, Wieman and 

Barrow) are working on analyzing pen inks (document authentication) and lipsticks (residue 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 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 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.; Ye, S.; McLaughlin, M.; Trulove, P. C.; Cowart, J. S., 2018. Bio‐based Diesel Fuel Analysis and Formulation and Testing of Surrogate Fuel Mixtures, Ind. Eng. Chem. Res., 57,600‐610.

Luning Prak, D. J., Ye, S., McLaughlin, M., Cowart, J. S., Trulove, P., 2017. Density, Viscosity,  Speed of Sound, Bulk Modulus, Surface Tension, and Flash Point of Selected Ternary Mixtures of Butylcyclohexane + a Linear Alkane (Hexadcane or Dodecane) + an Aromatic Compound (Toluene, n‐Butylbenzene, or n‐Hexylbenzene), J. Chem. Engin. Data, 62, 3452–3472. 

Sahara GraftTed Johnson

Prof. Dianne Luning Prak (prak@usna.edu)

Program review: U.C. Davis

Department of Energy Videohttps://betterbuildingssolutioncenter.energy.gov/swap/season-2, Technical video:Energy Research, Start at 1:17 of video

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‐ Analyzing Plebe Chemistry Curriculum 

Changes‐ Experiments in support of Chemistry 

of Cooking course  or IL

Projectile 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 applicationsPast Research Student

John Chamberlain, ’15Research Collaboration:

Naval Research Laboratory (NRL) 

Another Research AreaLaboratory Development for IL

Midn 1/C Lizzie Lee

• Determining the Heavy Metal Uptake in Hyperaccumulator Plants by X‐Ray Fluorescence (XRF)

• XRF specific to metals, simultaneous analysis, direct analysis of solids, nondestructive

• Plants grown in spiked Agar• Would this make an interesting IL experiment?

Rascio, Nicoletta. Plant Science, 2011, 180, 169‐181 http://www.horiba.com/scientific

Ron SiefertAssociate Professor

3‐6336 (office), Mi‐243 (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

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 biomacromoleculesfrom 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.

Analysis of Explosives ‐ Capillary Electrophoresis• 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 40TIme (Minutes)

100 mAU

EOF Marker

1,3,5‐TNB

TNT 2,4‐DNT

2‐Am‐4,6‐DNT

Figure 4. Separation of 4 nitroaromatic compounds.  Background electrolyte is 20 mM Tris, 200 mM Sodium Cholate, 10% v/v MeOH, pH 10.0.  Sample matrix is 180 mM NaCl.  From bottom to top, sample plug lengths are 1.6 cm, 2.4 cm, 4.0 cm, and 6.5 cm.   Separation voltage of 15 kV with and operating current of 43 µAmps.   Capillary is 50 micron i.d., 60 length (50 cm effective length).  

Electroanalytical Chemistry and Surface Science

CDR Julie Spencer, USN, Ph.D.Mi‐230, 3‐6605

jaspence@usna.edu

Electroanalytical chemistry• Corrosion is a major challenge for Naval Aviation and in general – Ongoing research to develop new coatings for better protection and to replace coatings that contain Cr(VI), a carcinogen

Electroanalytical chemistry

• Current major project:– Further 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.

Scanning Electrochemical Microscope (SECM)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., Hanrahan, R., Calhoun, R., ECS Transactions, 2015 66(30): 65‐71

Future Work• Continue previous work on coatings• Begin evaluation of coatings on samples made by additive manufacturing

• Use surface science tools to characterize the coatings – before and after SECM treatment– Scanning Electron Microscope (SEM)– X‐ray Photoelectron Spectroscopy (XPS)

• Look at aspects of corrosion from several different angles

27

http://www.ammrf.org.au/myscope/sem/background/

Scanning Electron Microscope (SEM):  Images and Energy Dispersive Spectroscopy (EDS)

Images

Elemental Composition via EDS (X-

rays)

hν

BE

KE

1s

2s2p

Vacuum Level

hν

EjectedPhotoelectron

54°

Hemispherical Analyzer

Detector

X-ray Source

Lens

(+)

(‐)

Sample EjectedPhotoelectron

BE = hν - KE

X‐ray Photoelectron Spectroscopy (XPS):  Obtaining Chemical Composition from the Surface (~10 nm)

28

Rosenberg et. al., Physical Chemistry Chemical Physics 15.11 (2013): 4002-4015. Wnuk, Joshua. "Electron Beam Induced Deposition: A Surface Science Approach." Order No. 3381524, The Johns Hopkins University,

2009. Ann Arbor: ProQuest. Web. 5 Aug. 2016.

KE = hν - BE

WO3

W(CO)6

What would a research student do?• Learn to use the Scanning Electrochemical Microscope (SECM) and conduct electrochemical experiments

• Learn to use the Scanning Electron Microscope (SEM) and image corrosion samples 

• Possibly travel to Johns Hopkins and observe XPS experiments

• Possibly visit NAVAIR • Possibly attend a meeting:  American Chemical Society, Electrochemical Society…

If this sounds interesting….Contact me or stop by to discuss!

CDR Julie Spencer, USN, Ph.D.Mi‐230, 3‐6605

jaspence@usna.edu

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

R'

R R''

+

CH3COO−

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

32

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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¯¯

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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 NFW• Improve Natural Material Properties• Controlled Fabrication of Novel Composites

Integrate Small MoleculesMerge Functional Polymers Entrap Functional Solids

Department of Chemistry35

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!

36

Department of Chemistry37

Printing and Welding of Ag & Au Nanoparticles

MIDN Saok Park

20 μm

Linen Fiber

50 μm

Linen + Nanoparticles

Dimatix DMP-2800

Department of Chemistry

MIDN Robert Chung

38

Fluorescence Microscopy Evaluation of Welding

Control (untreated) treated 60 min.

Questions?