Synthesis and Characterization of Hybrid Nanoparticles

for Biomedical and Environmental Remediation

Applications

Soubantika Palchoudhury

Chemical Engineering

University of Tennessee at Chattanooga

6th International Conference and Exhibition on Materials Science and Engineering

9/13/2016

Outline

Platinum Decorated Iron Oxide Nanoparticles for Biomedical Applications

New Materials for Oil Spill Remediation

Motivation

Research

Conclusion

Platinum Decorated Iron Oxide Nanoparticles for

Biomedical Applications

20 nm

Pt nanoparticle

Potential problem: Aggregation of small Pt nanoparticles

Iron oxide support

Motivation

ww

w.u

nig

e.ch

Therapeutic

applications

DNA damage, DNA dissociation,

nanomedicine for antitumor

treatment

Free radical scavenging activity

for oxidative stress disease

OH-

H2O e-

e- H2O2

OH-

Iron Oxide Nanoparticles: Modified “Heat-Up” Method

-4000 -2000 0 2000 4000-60

-40

-20

0

20

40

60

Mo

men

t (e

mu/g

)

Magnetic field (Oe)50 nm

2 nm

Iron oxide Nanoparticle

Phase transfer

Biocompatible ligand: Polyacrylic acid (PAA, Mw 100,000)

Platinum salt: Chloroplatinic acid (H2PtCl6)

Reducing agent: Ultraviolet radiation (UV)

Solvent: Water

Approach for Multiple Pt Attachment: Aqueous Phase

Xu, Y.; Qin, Y.; Palchoudhury, S.; Bao, Y. Water-soluble iron oxide nanoparticles with high stability and

selective surface functionality. Langmuir, 2011, 27, 8990-8997.

Approach for Multiple Pt Attachment: Aqueous Phase

Xu, Y.; Qin, Y.; Palchoudhury, S.; Bao, Y. Water-soluble iron oxide nanoparticles with high stability and

selective surface functionality. Langmuir, 2011, 27, 8990-8997.

100 nm

Pt-Attached Iron Oxide Nanoparticles : Aqueous Phase

2 nm

10 nm

Palchoudhury, S.; Xu, Y.; Goodwin, J.; Bao, Y. Synthesis of multiple platinum attached iron oxide

nanoparticles. J. Mater. Chem. 2011, 21, 3966-3970.

DNA Interaction: Gel Electrophoresis

Control

DNA

NP-DNA

(30 min)Ladder

NP-DNA

(4 h)

Palchoudhury, S.; Xu, Y.; Rushdie, A.; Bao, Y. DNA interaction of multiple Pt attached iron oxide

nanoparticles. IEEE Trans. Magnetics 2013.

20 nm

DNA Interaction: Transmission Electron Microscopy

Palchoudhury, S.; Xu, Y.; Rushdie, A.; Bao, Y. DNA interaction of multiple Pt attached iron oxide

nanoparticles. IEEE Trans. Magnetics 2013.

20 nm

DNA Interaction: Transmission Electron Microscopy

Palchoudhury, S.; Xu, Y.; Rushdie, A.; Bao, Y. DNA interaction of multiple Pt attached iron oxide

nanoparticles. IEEE Trans. Magnetics 2013.

20 nm

Before DNA interaction

Iron oxide

NP

Pt NP

After DNA interaction

20 nm

DNA Interaction of Pt-Attached Iron Oxide

Nanoparticles

Palchoudhury, S.; Xu, Y.; Rushdie, A.; Bao, Y. DNA interaction of multiple Pt attached iron oxide

nanoparticles. IEEE Trans. Magnetics 2013.

Conclusion

Monodisperse and shape-controlled iron oxide nanoparticles using

“modified heat-up” method

Pt-attached iron oxide nanoparticles

Successful demonstration of DNA interaction of Pt-iron oxide

nanoparticles

Future Work: New therapeutics

New Materials for Oil Spill Remediation

0

0.5

1

1.5

2

2.5

3

3.5

200 400 600 800

Absorb

ance

Wavelength (nm)

Oil remaining

Oil

PVP-iron oxide NPs

Oil-water

mixtureFinal treated

water

Oil removal with magnetic nanoparticles

Motivation

Catastrophic oil spills (e.g., Exxon Valdez (1989), MC252 (BP, 2010))

Cause huge environmental concern

Deepwater Horizon Disaster, Nature, Image credit: Daniel

Beltra/Greenpeace; Wikipedia; www.theguardian.com

Motivation

www.theguardian.com

www.cleveland.com

National Geography

Limitations of current oil remediation routes

Hypothesis

Palchoudhury, S.; Lead, J. A facile and cost-effective method for separation of oil-water mixtures using polymer-

coated iron oxide nanoparticles. Environ. Sci. Technol., 2014.

Polyvinylpyrrolidone (PVP)

Hydrophilic iron oxide

nanoparticles Oil spill Clean water

Polyvinylpyrrolidone-Coated Magnetic Nanoparticles

0

5

10

15

20

0 100 200 300 400

PVP-iron oxide NPs

PVP-iron oxide NPs in sea water

Inte

nsity (

%)

Size (d, nm)

76 nm 69 nm

Water-soluble iron oxide nanoparticles synthesized in one-step using “modified polyol method”

Solvent: Triethyleneglycol (TREG)

Capping agent: Polyvinylpyrrolidone (PVP)

Precursor: Iron (III) acetylacetonate

Reaction temperature: 260 °C

PVP

Palchoudhury, S.; Lead, J. A facile and cost-effective method for separation of oil-water mixtures using polymer-

coated iron oxide nanoparticles. Environ. Sci. Technol., 2014.

Analyzing the Oil-Water Separation via UV-vis

Spectroscopy

NPs

magnetically

separated

Magnetic

separation

Oil-water

mixture

0

0.5

1

1.5

2

2.5

3

3.5

200 300 400 500 600 700 800

Ab

sorb

ance

Wavelength (nm)

Oil

Oil

remaining

in water

0

0.5

1

1.5

2

2.5

3

3.5

200 300 400 500 600 700 800

Ab

sorb

ance

Wavelength (nm)

Oil remaining

Oil-water-

NP mixture

Palchoudhury, S.; Lead, J. A facile and cost-effective method for separation of oil-water mixtures using polymer-

coated iron oxide nanoparticles. Environ. Sci. Technol., 2014.

Analyzing the Oil-Water Separation via UV-vis

Spectroscopy

0

0.5

1

1.5

2

2.5

3

3.5

200 300 400 500 600 700 800

Oil recovered

Oil+water+NPs

Oil sample

PVP-iron oxide NPs

Oil remaining

Water

Absorb

ance

Wavelength (nm)

Oil remaining

Oil

PVP-iron oxide NPs

Oil-water

mixture

Oil-water-

NP mixtureNPs

magnetically

separated

Oil

recovered

from NPs

Oil

remaining

in water

Magnetic

separation

Deepwater Horizon oil sample used

Near 100 % oil removal in 12 h

Palchoudhury, S.; Lead, J. A facile and cost-effective method for separation of oil-water mixtures using polymer-

coated iron oxide nanoparticles. Environ. Sci. Technol., 2014.

Oil-Coated Iron Oxide Nanoparticles: Characterization

0

7

14

0 500 1000 1500 2000

PVP-iron oxide NPs

PVP-iron oxide NPs after oil absorption

Inte

nsity (

%)

Size (d, nm)

389 nm69 nm

Palchoudhury, S.; Lead, J. A facile and cost-effective method for separation of oil-water mixtures using polymer-

coated iron oxide nanoparticles. Environ. Sci. Technol., 2014.

Gas Chromatography-Mass Spectroscopy Analysis

50

0.0E0

3.4E6

1.7E6

0

100 %

14 16 18 20 22 24 2610 12 Time

C15

C25

262014 16 18 22 2410 12

C22

C25

50

0

100 %

0.0E0

1.0E6

5.0E5

Time

Crude oil sample Sample after treatment with nanoparticles

Palchoudhury, S.; Lead, J. A facile and cost-effective method for separation of oil-water mixtures using

polymer-coated iron oxide nanoparticles. Environ. Sci. Technol., 2014.

Conclusion

Near 100% separation of BP crude oil-water mixture using PVP-

iron oxide nanoparticles

Nanoparticles absorbed ~178 times their own volume of oil

Easy scale-up, cost-effective, and environment-friendly

Future Work: Practical application in remediation

ACKNOWLEDGEMENTS

Collaborators:

Prof. Arunava Gupta, MINT Center, The University of AlabamaProf. Frank Jones, University of Tennessee ChattanoogaDr. Bryan Ennis, University of Tennessee ChattanoogaDr. Bradley Harris, University of Tennessee ChattanoogaDean Daniel Pack, University of Tennessee Chattanooga

Students

Chemical Engineering Department, UTCCentral Analytical Facility (CAF), UA