Thymine Polymers Amy S. Cannon, Ph.D. Center for Green Chemistry University of Massachusetts Lowell.

Thymine Polymers

Amy S. Cannon, Ph.D.Center for Green Chemistry

University of Massachusetts Lowell

Green Chemistryand

Sustainable Materials

Molecular Recognitionand

Self-Assembly

NonCovalent Derivatization

Bioinspired Polymers

Ambient Metal Oxide Semiconductors

Medicinal Chemistry

Educational Research

Reaction Design

                              Chemistry au Naturel Chemists aim to mimic natural systems with the hope of developing more-efficient chemical processes that are alsoless harmful to the environment.

February 12 2005

NN

H3C

O

H O

NN

CH3

O

HO

NNO

H O

NN O

HO

H3C CH3

+

UV Light

Po

lymer

Chain

Polym

er C

hain

Po

lymer

Chain

Polym

er

Cha

in

Bioinspired Photopolymers

Pustular Psoriasis

PUVA Phototherapy

Psoriasis – What’s Happening?

Normal Psoriatic

NN

H3C O

H

ON

N

H NH

N

N

O

H

HH

O

CH2

H H

PO

O O

NN

N

ON

N

O N

N

O

H

H

OH H

PO O

H2C

O

HH

NHH

H

H

CH2

O

H

CH2

O

OP

O

P OO

H

H

H

H

O

O

H

H

H

H

OO

-

-

-

-

Thymine in DNA

Thymine in DNA

CHN

CC C

H

N

O

O

H3C

O

H

H

O

H

3'

H

CH2

O

P O-O

O

H

H HH

CH2

O

5'

CHN

CC C

H

N

O

O

H3C

UV light

CHN

CC CH

N

O

O

H3C

O

H

H

O

H

'3

H

H2C

O

P O-O

O

H

H H H

H2C

O

'5

CHN

CC C

H

N

O

O

H3C

*Diagram taken from Principles of Biochemistry, 2nd Edition, Horton, et al.

Photodimerization of Thymine in DNA

Physiological repair mechanisms

O N

N

CH3

H

H

O

Photodimerization Site

TripleH-BondingSite

Derivatization Site pKa ~ 9

-Stacking Site

Polymerization Site

Vinylbenzyl Thymine

N

N

CH3

O

H

R

n m

O

N

N

CH3

O

H

O OCH3

n m

O

Styrene Methacrylate

Organic Soluble Polymers

Cationic Anionic

N

N

CH3

O

H

n m

O

NR

R R

+ Cl-

N

N

CH3

O

H

SO3

n m

O

-

Na+

Water Soluble Polymers

+ + + + + + + + + + + + + + + + + + + + + +

OHN

N

OH

O3S_

OHN

N

OH

O3S_

OHN

N

OH

O3S_

Acid Alizarin Violet N

S

N

NN

_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

Cl-

+

S

N

NN

Cl-

+

S

N

NN

Cl-

+

S

N

NN

Cl-

+

Methylene Blue

Electrostatic Affinity

Kiarie, C.; Bianchini, J.; Trakhtenberg, S.; Warner, J.C. Methylene Blue Adsorption on Thymine Based Polyvinylphenylsulfonate Films J. Macromol. Sci. A, 2005, 42(11), 1489-1496

Food Color Dyes

N

N

- O3S

NaO3S

SO3Na

+

FD&C Blue No. 1

N N

SO3 -

NaO3S

SO3Na

OH

+

FD&C Green No. 3

ONa

I

I

O

COONa

I

I

O

FD&C Red No. 3

NaO3S

OH

N

N

H3CO SO3Na

FD&C Red No. 40

FD&C Yellow No. 6

FD&C Yellow No. 5

SO3Na

HO N

N

SO3Na

COONa

HO

N

N

SO3Na

NN

H3C

O

H O

NN

CH3

O

HO

NNO

H O

NN O

HO

H3C CH3

UV Light

Polymer Crosslinking

PCT Int. Appl. WO 9,729,405. August 14, 1997.US Patent 5,705,312. January 6, 1998.

US Patent 5,708,106. January 13, 1998.US Patent 5,741,630. April 21, 1998.US Patent 5,750,463. May 12, 1998.US Patent 5,750,464. May 12, 1998.

N

N

H3C

O

H O

N

N

CH3

O

HO

N

NO

H O

N

N O

HO

H3CCH3 +

DNA Photolyase

DN

A C

ha

in

DN

A C

hain

DN

A C

hain

DN

A C

ha

in

APPLICATION: Enzymatic Reversal

“Enzymatic Reversal of Polymeric Thymine Photocrosslinking with E. coli DNA Photolyase” Whitfield, Justin; Morelli, Alessandra and Warner, John C., J. Macr. Sci. 2005 A42 1541-1546.

"Methods of solubilizing and recycling biodegradable polymers containing photoreactive moieties using irradiation", Warner, John C.; Morelli, Alessandra; Ku, Man-Ching U.S. Pat. Appl. Publ. 2003, 4 pp. US 2003224497.

(a) (b)

SEM of photoresist film showing region of removal at (a) 1000X and (b) 40X

Applications

• Photoresist polymers• Controlled release• Hair and fabric toning and shaping• Templated Conductive polymers • Antimicrobial surfaces

Conventional Photoresists

Polymerization

Acrylates and Acrylamides… Trapped Residues

Environmentally Benign Photoresists

Nontoxic, Water Soluble… No “Trapped” Reactants

Crosslink

APPLICATION: Photoresists

Kindstrand, L.L. Warner, J.C. Thymine-containing styrene polymers as environmentally benign photoresists in Biopolymers, Volume 9, Eds.: S. Matsumura and A. Steinbuechel Wiley-VCH Verlag GmbH, Weinheim, Germany 2003, pp 165-174

Warner, J. C. Environmentally Benign Photopolymers Based on DNA Mimics ARCHIPOL 2005: III Argentine-Chilean Polymer Symposium, Cordoba, Argentina, December 4-7, 2005, 13.

Trakhtenberg, S.; Warner, J. C.; Nagarajana, Ramaswamy; Bruno, Ferdinando F.; Samuelson, Lynne A.; Kumar, Jayant Spectroscopic and Microscopic Analysis of Photocrosslinked Vinylbenzylthymine (VBT) Copolymers for Photoresist Applications Chem. Mater. 2006 In Press..

0 50 100 150 200 250 300 350 4000.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50A

bsor

ba

nce

exposure dose (mJ/cm2)

polymer absorption intensity at 222 nm before irradiation polymer absorption intensity at 222 nm after irradiation

and washing adsorbed dye absorption intensity at 639 nm

Irradiation Response

Yu, C.; Trakhtenberg, S.; Cain, T. E.; Warner, J. C. Effect of Dye Additives on Photodimerization of Thymine Pendant Groups in Water-Soluble Photoresist Polymers Journal of Polymers and the Environment. 2006 In Press.

Applications

• Photoresist polymers• Controlled release• Hair and fabric toning and shaping• Templated Conductive polymers • Antimicrobial surfaces

1

2

3

PET Film

25% PVA, 75% VBT, 2 micron10% PVA, 90% VBT, 2 micron

48% PVA, 48% VBT, 4% Dye 2 micron

APPLICATION: Controlled Release

time time

Wavelength (nm)600 610 620 630 640 650

Abso

rban

ce (A

U)

0.05

0.1

0.15

0.2

0.25

0.3

0.35

635

Time

510152025

30

Seconds of immersionin water.

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0 5 10

Diffusion Rate as a function of UV Exposure

UV Exposure (Min)

Ab

sorb

ance

Applications

• Photoresist polymers• Controlled release• Hair and fabric toning and shaping• Templated Conductive polymers • Antimicrobial surfaces

APPLICATION: Hair and Fabric Curling and Toning

“Photoreactive Polymers and Devices for use in Hair Treatments”, Cannon, Amy S.; Raudys, Jennifer; Undurti, Arundhati; Warner, John C. PCT Int. Appl. 2004, 23pp WO 2004058187.

Applications

• Photoresist polymers• Controlled release• Hair and fabric toning and shaping• Templated Conductive polymers • Antimicrobial surfaces

Enzyme Horseradish Peroxidase + Aniline

APPLICATION: Templated Conductive Polymers

“Photocrosslinked Immobilization of Polyelectrolytes for Enzymatic Construction of Conductive Nanocomposites” Trakhtenberg, Sofia; Hangun-Balkir, Yelda; Warner, John C.; Bruno, Ferdinando; Kumar, Jayant; Nagarajan, Ramaswamy; Samuelson, Lynne A. J. Am. Chem. Soc. 2005 127, 9100-9104

300 400 500 600 700 800 900 10000.00

0.25

0.50

0.75

1.00

1.25

1.50

1.750.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

BpH

10 5

Ab

sorb

an

ce

Wavelength (nm)

ApH

10 5

Ab

sorb

an

ce

1 cm

“Photocrosslinked Immobilization of Polyelectrolytes for Enzymatic Construction of Conductive Nanocomposites” Trakhtenberg, Sofia; Hangun-Balkir, Yelda; Warner, John C.; Bruno, Ferdinando; Kumar, Jayant; Nagarajan, Ramaswamy; Samuelson, Lynne A. J. Am. Chem. Soc. 2005 127, 9100-9104

Applications

• Photoresist polymers• Controlled release• Hair and fabric toning and shaping• Templated Conductive polymers • Antimicrobial surfaces

APPLICATION: Antimicrobial surfaces

E- Coli Bacterial growth

Control plate : no polymer Coated plate : no bacterial growth

El-Hayek, R.; Warner, J. C. Bacteriostatic Polymer Film Immobilization J. Bio. Mat. Res. 2006 In Press..

“Immobilized Antimicrobial Films”, El-Hayek, Rami; Mullin, Steve; Warner, John C. Patent Disclosure Filed with UML CVIP 2005.

• Structural integrity of polymers•Biodegradable/renewable polymers

• Enzymatic reversal – extremophiles• Textiles

Current and Future Directions

Acknowledgements

Jason BianchiniKevin DyeRami El HayekLaura IngallsCecilia KiarieJustin Whitfield

Funding:SAPPIToxics Use Reduction Institute

Dr. Roger BoggsDr. Yelda Hangun-BalkirDr. Jayant KumarDr. Ramaswamy NagarajanDr. Kei SaitoDr. Lynne SamuelsonDr. Sofia TrakhtenbergDr. John Warner