Thymine Polymers Amy S. Cannon, Ph.D. Center for Green Chemistry University of Massachusetts Lowell.
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Transcript of 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
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
O N
N
CH3
H
H
O
Photodimerization Site
TripleH-BondingSite
Derivatization Site pKa ~ 9
-Stacking Site
Polymerization Site
Vinylbenzyl Thymine
+ + + + + + + + + + + + + + + + + + + + + +
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.
Applications
• Photoresist polymers• Controlled release• Hair and fabric toning and shaping• Templated Conductive polymers • Antimicrobial surfaces
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