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Antimicrobial activity of polysiloxane coatings containing quaternary ammonium-functionalized polyhedral oligomeric silsesquioxane

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Abstract

An array of quaternary ammonium functionalized-polyhedral oligomeric silsesquioxane (Q-POSS) compounds with different alkyl chain lengths and counter ions were synthesized using a two-step process. First, octasilane POSS was functionalized with dimethylamino groups by hydrosilylation with allyldimethylamine. Next, partial quaternization of the tertiaryamino-functional POSS was achieved using an alkyl halide to produce the Q-POSS. Alkyl chain length of the Q-POSS compounds varied from –C12H25 to –C18H37 and the counter ions varied between chlorine, bromine, and iodine. Moisture-cured polysiloxane coatings were prepared by dispersing Q-POSS molecules into a solution blend of silanol-terminated polydimethylsiloxane, methylacetoxysilane, and a catalyst. To evaluate the utility of the Q-POSS molecules as a broad-spectrum antimicrobial additive, the antimicrobial activity of the coatings toward the Gram-negative bacterium, Escherichia coli, the Gram-positive bacterium, Staphylococcus aureus, and the opportunistic fungal pathogen, Candida albicans, was determined using an agar plating method. The results obtained showed that both the composition of the Q-POSS and the composition of the polysiloxane matrix affected antimicrobial properties. Compositions were identified that inhibited the growth of all three microorganisms on the coating surface. Surface Raman spectroscopic analysis was performed on selected set of coatings to understand the relative concentration of Q-POSS molecules at the coating surface.

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Acknowledgment

The authors acknowledge financial support from the Office of Naval Research under grants N00014-05-1-0822 and N00014-06-1-0952.

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Authors and Affiliations

  1. The Center for Nanoscale Science and Engineering, North Dakota State University, 1805 Research Park Drive, Fargo, ND, 58102, USA

    Partha Majumdar, Jie He, Elizabeth Lee, Alekhya Kallam, Nathan Gubbins, Shane J. Stafslien, Justin Daniels & Bret J. Chisholm

  2. Department of Coatings and Polymeric Materials, North Dakota State University, 1735 Research Park Drive, Fargo, ND, 58102, USA

    Bret J. Chisholm

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  1. Partha Majumdar
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  2. Jie He
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Correspondence to Partha Majumdar.

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This paper was presented at the 2009 CoatingsTech Conference, sponsored by NPCA/FSCT, April 28–29, 2009, in Indianapolis, IN.

Appendix 1: Synthesis details for Q-POSS compounds

Appendix 1: Synthesis details for Q-POSS compounds

Synthesis of tertiaryamino-functional POSS

In a 100-mL round-bottom flask equipped with a nitrogen inlet, condenser, and temperature controller, 2.00 g of octasilane POSS (1.96 mmol) and 1.75 g of allyldimethylamine (20.55 mmol) were dissolved in 50 mL of THF. Once dissolved, 180 μL of Karstedt’s catalyst was added to the reaction mixture and the reaction mixture was refluxed for 48 h. Completion of the reaction was confirmed using proton nuclear magnetic resonance spectroscopy (1H NMR) by observing the disappearance of the Si–H peak at δ 4.7 ppm. After completion of the hydrosilylation reaction, excess allyldimethylamine was removed under reduced pressure. Allydimethylamine removal was confirmed by the absence of the 1H NMR (in CDCl3) peaks at δ 5.72 ppm (–N–CH2–CH=) and 5.01 ppm (−N−CH2−CH=CH 2 ). 29Si NMR displayed a singlet at δ 14.9 ppm, corresponding to the M-type silicon, and another singlet at δ −107.3 ppm, corresponding to the Q-type silicon of the POSS core. The presence of only two singlets in the 29Si NMR spectrum confirmed that the cubic structure of POSS remained intact during the reaction. 1H NMR (in CDCl3) peaks are: δ 0.02–0.03 ppm (Si–CH 3 ), δ 0.45–0.48 ppm [Si–CH 2 –CH2–CH2–N and Si–CH(CH3)–CH2–N], δ 0.88 ppm [Si–CH(CH 3 )–CH2–N], δ 1.39 ppm (Si–CH2–CH 2 –CH2–N), and δ 2.09–2.22 ppm [−CH 2 –N(CH 3 )2]. The proportion of α-isomer was 20%.

Synthesis of Q-POSS (octadecyldimethylammoniumiodide-POSS, Q-18-I)

In a 20-mL glass vial containing a magnetic stir bar, 2.00 g of the tertiaryamino-functional POSS (9.4 × 10−3 moles of tertiary amine functional groups) was mixed with 1.43 g of 1-iodooctadecane (3.76 × 10−3 moles) and the quaternization reaction was carried out at 50°C for 48 h. A substantial increase in viscosity was observed as a result of the reaction. Using 1H NMR (in CDCl3), new peaks appeared at δ 3.53 ppm (–N+–CH 2 –) and 3.27 ppm [(–N+–(CH 3 )2] due to quaternization. 1H NMR (in CDCl3) peaks are: δ 0.01–0.09 ppm (Si–CH 3 ), δ 0.45–0.55 ppm [Si–CH 2 –CH2–CH2–N+, Si–CH(CH3)–CH2–N+, Si–CH 2 –CH2–CH2–N, and Si–CH(CH3)–CH2–N], δ 0.86 ppm [–(CH2)17–CH 3 ], δ 0.93 ppm [Si–CH(CH 3 )–CH2–N+ and Si–CH(CH 3 )–CH2–N], δ 1.22 ppm [–CH2–CH2–(CH 2 )15–CH3], δ 1.38 ppm (Si–CH2–CH 2 –CH2–N and Si–CH2–CH 2 –CH2–N+), δ 1.71 ppm [N+–CH2–CH 2 –(CH2)15–CH3], δ 2.09–2.22 ppm [–CH 2 –N(CH 3 )2], δ 3.27 ppm [(–N+–(CH 3 )2], and δ 3.53 ppm (–N+–CH 2 –). The extent of quaternization was 34.3 mol%. The Q-POSS was diluted with THF to produce 5 and 50 wt% solution.

Synthesis of Q-POSS (hexadecyldimethylammoniumiodide-POSS, Q-16-I)

In a 20-mL glass vial containing a magnetic stir bar, 2.00 g of the tertiaryamino-functional POSS (9.4 × 10−3 moles of tertiary amine functional groups) was mixed with 1.32 g of 1-iodohexadecane (3.76 × 10−3 moles) and the quaternization reaction was carried out at 50°C for 48 h. A substantial increase in viscosity was observed as a result of the reaction. Using 1H NMR (in CDCl3), new peaks appeared at δ 3.54 ppm (–N+–CH 2 –) and 3.28 ppm [(–N+–(CH 3 )2] due to quaternization. 1H NMR (in CDCl3) peaks are: δ 0.03–0.11 ppm (Si–CH 3 ), δ 0.44–0.56 ppm [Si–CH 2 –CH2–CH2–N+, Si–CH(CH3)–CH2–N+, Si–CH 2 –CH2–CH2–N, and Si–CH(CH3)–CH2–N], δ 0.85 ppm [–(CH2)15–CH 3 ], δ 0.93 ppm [Si–CH(CH 3 )–CH2–N+ and Si–CH(CH 3 )–CH2–N], δ 1.23 ppm [–CH2–CH2–(CH 2 )13–CH3], δ 1.38 ppm (Si–CH2–CH 2 –CH2–N and Si–CH2–CH 2 –CH2–N+), δ 1.72 ppm [N+–CH2–CH 2 –(CH2)13–CH3], δ 2.09–2.22 ppm [–CH 2 –N(CH 3 )2], δ 3.28 ppm [(–N+–(CH 3 )2], and δ 3.54 ppm (–N+–CH 2 –). The extent of quaternization was 37.3 mol%. The Q-POSS was diluted with THF to produce 5 and 50 wt% solution.

Synthesis of Q-POSS (dodecyldimethylammoniumiodide-POSS, Q-12-I)

In a 20-mL glass vial containing a magnetic stir bar, 2.00 g of the tertiaryamino-functional POSS (9.4 × 10−3 moles of tertiary amine functional groups) was mixed with 1.11 g of 1-iodododecane (3.76 × 10−3 moles) and the quaternization reaction was carried out at 50°C for 48 h. A substantial increase in viscosity was observed as a result of the reaction. Using 1H NMR (in CDCl3), new peaks appeared at δ 3.51 ppm (–N+–CH 2 –) and 3.25 ppm [(–N+–(CH 3 )2] due to quaternization. 1H NMR (in CDCl3) peaks are: δ 0.03–0.08 ppm (Si–CH 3 ), δ 0.44–0.53 ppm [Si–CH 2 –CH2–CH2–N+, Si–CH(CH3)–CH2–N+, Si–CH 2 –CH2–CH2–N, and Si–CH(CH3)–CH2–N], δ 0.82 ppm [–(CH2)11–CH 3 ], δ 0.93 ppm [Si–CH(CH 3 )–CH2–N+ and Si–CH(CH 3 )–CH2–N], δ 1.20 ppm [–CH2–CH2–(CH 2 )9–CH3], δ 1.38 ppm (Si–CH2–CH 2 –CH2–N and Si–CH2–CH 2 –CH2–N+), δ 1.69 ppm [N+–CH2–CH 2 –(CH2)13–CH3], δ 2.09–2.22 ppm [–CH 2 –N(CH 3 )2], δ 3.25 ppm [(–N+–(CH 3 )2], and δ 3.51 ppm (–N+–CH 2 –). The extent of quaternization was 34.3 mol%. The Q-POSS was diluted with THF to produce 5 and 50 wt% solution.

Synthesis of Q-POSS (octadecyldimethylammoniumbromide-POSS Q-18-Br)

In a 20-mL glass vial containing a magnetic stir bar, 2.00 g of the tertiaryamino-functional POSS (9.4 × 10−3 moles of tertiary amine functional groups) was mixed with 1.26 g of 1-bromooctadecane (3.76 × 10−3 moles) and the quaternization reaction was carried out at 50°C for 48 h. A substantial increase in viscosity was observed as a result of the reaction. Using 1H NMR (in CDCl3), new peaks appeared at δ 3.53 ppm (–N+–CH 2 –) and 3.30 ppm [(–N+–(CH 3 )2] due to quaternization. 1H NMR (in CDCl3) peaks are: δ 0.03–0.11 ppm (Si–CH 3 ), δ 0.45–0.56 ppm [Si–CH 2 –CH2–CH2–N+, Si–CH(CH3)–CH2–N+, Si–CH 2 –CH2–CH2–N, and Si–CH(CH3)–CH2–N], δ 0.85 ppm [–(CH2)17–CH 3 ], δ 0.96 ppm [Si–CH(CH 3 )–CH2–N+ and Si–CH(CH 3 )–CH2–N], δ 1.23 ppm [–CH2–CH2–(CH 2 )15–CH3], δ 1.45 ppm (Si–CH2–CH 2 –CH2–N and Si–CH2–CH 2 –CH2–N+), δ 1.68 ppm [N+–CH2–CH 2 –(CH2)15–CH3], δ 2.09–2.22 ppm [–CH 2 –N(CH 3 )2], δ 3.30 ppm [(–N+–(CH 3 )2], and δ 3.53 ppm (–N+–CH 2 –). The extent of quaternization was 27.2 mol%. The Q-POSS was diluted with THF to produce 5 and 50 wt% solution.

Synthesis of Q-POSS (hexadecyldimethylammoniumbromide-POSS, Q-16-Br)

In a 20-mL glass vial containing a magnetic stir bar, 2.00 g of the tertiaryamino-functional POSS (9.4 × 10−3 moles of tertiary amine functional groups) was mixed with 1.15 g of 1-bromohexadecane (3.76 × 10−3 moles) and the quaternization reaction was carried out at 50°C for 48 h. A substantial increase in viscosity was observed as a result of the reaction. Using 1H NMR (in CDCl3), new peaks appeared at δ 3.52 ppm (–N+–CH 2 –) and 3.28 ppm [(–N+–(CH 3 )2] due to quaternization. 1H NMR (in CDCl3) peaks are: δ 0.03–0.10 ppm (Si–CH 3 ), δ 0.44–0.55 ppm [Si–CH 2 –CH2–CH2–N+, Si–CH(CH3)–CH2–N+, Si–CH 2 –CH2–CH2–N, and Si–CH(CH3)–CH2–N], δ 0.84 ppm [–(CH2)15–CH 3 ], δ 0.95 ppm [Si–CH(CH 3 )–CH2–N+ and Si–CH(CH 3 )–CH2–N], δ 1.21 ppm [–CH2–CH2–(CH 2 )13–CH3], δ 1.45 ppm (Si–CH2–CH 2 –CH2–N and Si–CH2–CH 2 –CH2–N+), δ 1.68 ppm [N+–CH2–CH 2 –(CH2)13–CH3], δ 2.09–2.22 ppm [–CH 2 –N(CH 3 )2], δ 3.28 ppm [(–N+–(CH 3 )2], and δ 3.52 ppm (–N+–CH 2 –). The extent of quaternization was 34.5 mol%. The Q-POSS was diluted with THF to produce 5 and 50 wt% solution.

Synthesis of Q-POSS (dodecyldimethylammoniumbromide-POSS Q-12-Br)

In a 20-mL glass vial containing a magnetic stir bar, 2.00 g of the tertiaryamino-functional POSS (9.4 × 10−3 moles of tertiary amine functional groups) was mixed with 0.94 g of 1-bromododecane (3.76 × 10−3 moles) and the quaternization reaction was carried out at 50°C for 48 h. A substantial increase in viscosity was observed as a result of the reaction. Using 1H NMR (in CDCl3), new peaks appeared at δ 3.51 ppm (–N+–CH 2 –) and 3.28 ppm [(–N+–(CH 3 )2] due to quaternization. 1H NMR (in CDCl3) peaks are: δ 0.03–0.09 ppm (Si–CH 3 ), δ 0.44–0.54 ppm [Si–CH 2 –CH2–CH2–N+, Si–CH(CH3)–CH2–N+, Si–CH 2 –CH2–CH2–N, and Si–CH(CH3)–CH2–N], δ 0.83 ppm [–(CH2)11–CH 3 ], δ 0.94 ppm [Si–CH(CH 3 )–CH2–N+ and Si–CH(CH 3 )–CH2–N], δ 1.21 ppm [–CH2–CH2–(CH 2 )9–CH3], δ 1.45 ppm (Si–CH2–CH 2 –CH2–N and Si–CH2–CH 2 –CH2–N+), δ 1.68 ppm [N+–CH2–CH 2 –(CH2)13–CH3], δ 2.09–2.22 ppm [–CH 2 –N(CH 3 )2], δ 3.28 ppm [(–N+–(CH 3 )2], and δ 3.51 ppm (–N+–CH 2 –). The extent of quaternization was 34.4 mol%. The Q-POSS was diluted with THF to produce 5 and 50 wt% solution.

Synthesis of Q-POSS (octadecyldimethylammoniumchloride-POSS, Q-18-Cl)

In a 20-mL glass vial containing a magnetic stir bar, 2.00 g of the tertiaryamino-functional POSS (9.4 × 10−3 moles of tertiary amine functional groups) was mixed with 1.09 g of 1-chlorooctadecane (3.76 × 10−3 moles) and the quaternization reaction was carried out at 110°C for 48 h. A substantial increase in viscosity was observed as a result of the reaction. Using 1H NMR (in CDCl3), new peaks appeared at δ 3.40 ppm (–N+–CH 2 –) and 3.31 ppm [(–N+–(CH 3 )2] due to quaternization. 1H NMR (in CDCl3) peaks are: δ 0.03–0.09 ppm (Si–CH 3 ), δ 0.45–0.54 ppm [Si–CH 2 –CH2–CH2–N+, Si–CH(CH3)–CH2–N+, Si–CH 2 –CH2–CH2–N, and Si–CH(CH3)–CH2–N], δ 0.84 ppm [–(CH2)17–CH 3 ], δ 0.95 ppm [Si–CH(CH 3 )–CH2–N+ and Si–CH(CH 3 )–CH2–N], δ 1.22 ppm [–CH2–CH2–(CH 2 )15–CH3], δ 1.45 ppm (Si–CH2–CH 2 –CH2–N and Si–CH2–CH 2 –CH2–N+), δ 1.67 ppm [N+–CH2–CH 2 –(CH2)15–CH3], δ 2.13–2.22 ppm [–CH 2 –N(CH 3 )2], δ 3.31 ppm [(–N+–(CH 3 )2], and δ 3.40 ppm (–N+–CH 2 –). The extent of quaternization was 27.2 mol%. The Q-POSS was diluted with THF to produce 5 and 50 wt% solution.

Synthesis of Q-POSS (hexadecyldimethylammoniumchloride-POSS, Q-16-Cl)

In a 20-mL glass vial containing a magnetic stir bar, 2.00 g of the tertiaryamino-functional POSS (9.4 × 10−3 moles of tertiary amine functional groups) was mixed with 0.98 g of 1-chlorohexadecane (3.76 × 10−3 moles) and the quaternization reaction was carried out at 110°C for 48 h. A substantial increase in viscosity was observed as a result of the reaction. Using 1H NMR (in CDCl3), new peaks appeared at δ 3.40 ppm (–N+–CH 2 –) and 3.32 ppm [(–N+–(CH 3 )2] due to quaternization. 1H NMR (in CDCl3) peaks are: δ 0.03–0.09 ppm (Si–CH 3 ), δ 0.44–0.53 ppm [Si–CH 2 –CH2–CH2–N+, Si–CH(CH3)–CH2–N+, Si–CH 2 –CH2–CH2–N, and Si–CH(CH3)–CH2–N], δ 0.84 ppm [–(CH2)15–CH 3 ], δ 0.95 ppm [Si–CH(CH 3 )–CH2–N+ and Si–CH(CH 3 )–CH2–N], δ 1.22 ppm [–CH2–CH2–(CH 2 )13–CH3], δ 1.44 ppm (Si–CH2–CH 2 –CH2–N and Si–CH2–CH 2 –CH2–N+), δ 1.67 ppm [N+–CH2–CH 2 –(CH2)13–CH3], δ 2.13–2.22 ppm [–CH 2 –N(CH 3 )2], δ 3.32 ppm [(–N+–(CH 3 )2], and δ 3.40 ppm (–N+–CH 2 –). The extent of quaternization was 28.4 mol%. The Q-POSS was diluted with THF to produce 5 and 50 wt% solution.

Synthesis of Q-POSS (dodecyldimethylammoniumchloride-POSS, Q-12-Cl)

In a 20-mL glass vial containing a magnetic stir bar, 2.00 g of the tertiaryamino-functional POSS (9.4 × 10−3 moles of tertiary amine functional groups) was mixed with 0.94 g of 1-bromododecane (3.76 × 10−3 moles) and the quaternization reaction was carried out at 110°C for 48 h. A substantial increase in viscosity was observed as a result of the reaction. Using 1H NMR (in CDCl3), new peaks appeared at δ 3.40 ppm (–N+–CH 2 –) and 3.32 ppm [(–N+–(CH 3 )2] due to quaternization. 1H NMR (in CDCl3) peaks are: δ 0.03–0.11 ppm (Si–CH 3 ), δ 0.44–0.56 ppm [Si–CH 2 –CH2–CH2–N+, Si–CH(CH3)–CH2–N+, Si–CH 2 –CH2–CH2–N, and Si–CH(CH3)–CH2–N], δ 0.85 ppm [–(CH2)11–CH 3 ], δ 0.96 ppm [Si–CH(CH 3 )–CH2–N+ and Si–CH(CH 3 )–CH2–N], δ 1.22 ppm [–CH2–CH2–(CH 2 )9–CH3], δ 1.43 ppm (Si–CH2–CH 2 –CH2–N and Si–CH2–CH 2 –CH2–N+), δ 1.68 ppm [N+–CH2–CH 2 –(CH2)13–CH3], δ 2.14–2.22 ppm [–CH 2 –N(CH 3 )2], δ 3.32 ppm [(–N+–(CH 3 )2], and δ 3.40 ppm (–N+–CH 2 –). The extent of quaternization was 28.9 mol%. The Q-POSS was diluted with THF to produce 5 and 50 wt% solution.

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Majumdar, P., He, J., Lee, E. et al. Antimicrobial activity of polysiloxane coatings containing quaternary ammonium-functionalized polyhedral oligomeric silsesquioxane. J Coat Technol Res 7, 455–467 (2010). https://doi.org/10.1007/s11998-009-9197-x

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  • DOI: https://doi.org/10.1007/s11998-009-9197-x

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