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Functional Conducting Polymers via Thiol-ene Chemistry.

Feldman KE, Martin DC - Biosensors (Basel) (2012)

Bottom Line: We demonstrate here that thiol-ene chemistry can be used to provide side-chain functionalized monomers based on 3,4-propylenedioxythiophene (ProDOT) containing ionic, neutral, hydrophobic, and hydrophilic side chains.These monomers were polymerized either chemically or electro-chemically to give soluble materials or conductive films, respectively.This strategy provides for facile tuning of the solubility, film surface chemistry, and film morphology of this class of conducting polymers.

View Article: PubMed Central - PubMed

Affiliation: Department of Materials Science and Engineering, University of Delaware, Newark, DE 19716, USA. katiefeldman0@gmail.com.

ABSTRACT
We demonstrate here that thiol-ene chemistry can be used to provide side-chain functionalized monomers based on 3,4-propylenedioxythiophene (ProDOT) containing ionic, neutral, hydrophobic, and hydrophilic side chains. All reactions gave high yields and purification could generally be accomplished through precipitation. These monomers were polymerized either chemically or electro-chemically to give soluble materials or conductive films, respectively. This strategy provides for facile tuning of the solubility, film surface chemistry, and film morphology of this class of conducting polymers.

No MeSH data available.


FTIR spectra of electrochemically deposited films. Deposition solutions contained a total monomer concentration of 50 mM and either 100% ProDOT, 90% ProDOT + 10% functionalized ProDOT, or 80% ProDOT + 20% functionalized ProDOT. (A) Full spectra and (B) fingerprint region of ProDOT-CO2H-containing films; (C) full spectra and (D) fingerprint region of ProDOT-NH2-containing films.
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biosensors-02-00305-f001: FTIR spectra of electrochemically deposited films. Deposition solutions contained a total monomer concentration of 50 mM and either 100% ProDOT, 90% ProDOT + 10% functionalized ProDOT, or 80% ProDOT + 20% functionalized ProDOT. (A) Full spectra and (B) fingerprint region of ProDOT-CO2H-containing films; (C) full spectra and (D) fingerprint region of ProDOT-NH2-containing films.

Mentions: Several of the functional monomers were tested for their ability to be electrochemically polymerized. This strategy allows for conformal films to be generated on conductive substrates while tuning the surface chemistry through the side chain functionality. The monomers chosen for electrochemical polymerization included ProDOT-CO2H, ProDOT-NH2, and ProDOT-glycerol. Although deposition of films of pure functional monomer was found to be difficult, each could be co-deposited with non-functionalized 3,4-propylenedioxythiophene (ProDOT) at levels up to 20 mol% (functional monomer fraction in deposition solution). FTIR spectra of the deposited films clearly demonstrate the incorporation of functional monomer; Figure 1 shows such data for films deposited from solutions containing 0, 10, and 20 mol% ProDOT-CO2H. The spectra show peaks at 1,640 cm–1 (C=O stretch) and 3,415 cm–1 (OH stretch) characteristic of the carboxylic acid containing monomer. Baseline subtraction of the region between 2,000 and 650 cm–1 and normalization to the peak at 1,060 cm–1 (C–O stretch from dioxypropylene ring; intensity should be insensitive to oxidation state of polymer) demonstrates that more functional monomer is incorporated into the film with an increase in the relative concentration in the deposition solution, since the intensity of the carbonyl stretch increases. Similarly, films deposited from solutions containing ProDOT-NH2 show peaks at 1,632 cm–1 (N–H bend) and 3,450 cm–1 (N–H stretch) that increase in intensity with an increase in functional monomer content in the deposition solution. No distinguishing peaks were seen in films containing ProDOT-glycerol or ProDOT-SO3Na. Changes in hydrophilicy also indicate that functional monomer was incorporated into the films. With 20 mol% comonomer in the deposition solution, both ProDOT-CO2H and ProDOT-NH2 containing films showed a decrease in static water contact angle from 59° to 43° as compared to pure ProDOT films, while 20 mol% ProDOT-glycerol solutions produced films with contact angles of 50° (although changes in film morphology as shown below can also affect contact angles). Data could not be obtained for films containing ProDOT-SO3Na because they were immediately wetted and swollen by the water droplets.


Functional Conducting Polymers via Thiol-ene Chemistry.

Feldman KE, Martin DC - Biosensors (Basel) (2012)

FTIR spectra of electrochemically deposited films. Deposition solutions contained a total monomer concentration of 50 mM and either 100% ProDOT, 90% ProDOT + 10% functionalized ProDOT, or 80% ProDOT + 20% functionalized ProDOT. (A) Full spectra and (B) fingerprint region of ProDOT-CO2H-containing films; (C) full spectra and (D) fingerprint region of ProDOT-NH2-containing films.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
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getmorefigures.php?uid=PMC4263549&req=5

biosensors-02-00305-f001: FTIR spectra of electrochemically deposited films. Deposition solutions contained a total monomer concentration of 50 mM and either 100% ProDOT, 90% ProDOT + 10% functionalized ProDOT, or 80% ProDOT + 20% functionalized ProDOT. (A) Full spectra and (B) fingerprint region of ProDOT-CO2H-containing films; (C) full spectra and (D) fingerprint region of ProDOT-NH2-containing films.
Mentions: Several of the functional monomers were tested for their ability to be electrochemically polymerized. This strategy allows for conformal films to be generated on conductive substrates while tuning the surface chemistry through the side chain functionality. The monomers chosen for electrochemical polymerization included ProDOT-CO2H, ProDOT-NH2, and ProDOT-glycerol. Although deposition of films of pure functional monomer was found to be difficult, each could be co-deposited with non-functionalized 3,4-propylenedioxythiophene (ProDOT) at levels up to 20 mol% (functional monomer fraction in deposition solution). FTIR spectra of the deposited films clearly demonstrate the incorporation of functional monomer; Figure 1 shows such data for films deposited from solutions containing 0, 10, and 20 mol% ProDOT-CO2H. The spectra show peaks at 1,640 cm–1 (C=O stretch) and 3,415 cm–1 (OH stretch) characteristic of the carboxylic acid containing monomer. Baseline subtraction of the region between 2,000 and 650 cm–1 and normalization to the peak at 1,060 cm–1 (C–O stretch from dioxypropylene ring; intensity should be insensitive to oxidation state of polymer) demonstrates that more functional monomer is incorporated into the film with an increase in the relative concentration in the deposition solution, since the intensity of the carbonyl stretch increases. Similarly, films deposited from solutions containing ProDOT-NH2 show peaks at 1,632 cm–1 (N–H bend) and 3,450 cm–1 (N–H stretch) that increase in intensity with an increase in functional monomer content in the deposition solution. No distinguishing peaks were seen in films containing ProDOT-glycerol or ProDOT-SO3Na. Changes in hydrophilicy also indicate that functional monomer was incorporated into the films. With 20 mol% comonomer in the deposition solution, both ProDOT-CO2H and ProDOT-NH2 containing films showed a decrease in static water contact angle from 59° to 43° as compared to pure ProDOT films, while 20 mol% ProDOT-glycerol solutions produced films with contact angles of 50° (although changes in film morphology as shown below can also affect contact angles). Data could not be obtained for films containing ProDOT-SO3Na because they were immediately wetted and swollen by the water droplets.

Bottom Line: We demonstrate here that thiol-ene chemistry can be used to provide side-chain functionalized monomers based on 3,4-propylenedioxythiophene (ProDOT) containing ionic, neutral, hydrophobic, and hydrophilic side chains.These monomers were polymerized either chemically or electro-chemically to give soluble materials or conductive films, respectively.This strategy provides for facile tuning of the solubility, film surface chemistry, and film morphology of this class of conducting polymers.

View Article: PubMed Central - PubMed

Affiliation: Department of Materials Science and Engineering, University of Delaware, Newark, DE 19716, USA. katiefeldman0@gmail.com.

ABSTRACT
We demonstrate here that thiol-ene chemistry can be used to provide side-chain functionalized monomers based on 3,4-propylenedioxythiophene (ProDOT) containing ionic, neutral, hydrophobic, and hydrophilic side chains. All reactions gave high yields and purification could generally be accomplished through precipitation. These monomers were polymerized either chemically or electro-chemically to give soluble materials or conductive films, respectively. This strategy provides for facile tuning of the solubility, film surface chemistry, and film morphology of this class of conducting polymers.

No MeSH data available.