| Contact antimicrobial coatings with poly-alkylammonium compositions have been a subject of increasing interest in part because of the contribution of biocide release coatings to antibiotic resistance. Herein, a concept for antimicrobial coatings is developed based on thermodynamically driven surface concentration of soft block side chains. The concept incorporates structural and compositional guidance from naturally occurring antimicrobial proteins and achieves compositional economy via a polymer surface modifier (PSM). For this purpose, polyurethanes having P[AB] co-polyoxetane soft blocks, where A is a surface active (fluorous) or PEG-like side chain and B represents a desired function (alkylammonium) were prepared. Specifically, poly(2,2-substituted-1,3-propylene oxide) ran-co-telechelics with bromobutoxymethyl (-CH2O(CH2)4Br) and either trifluoroethoxymethyl (3FOx, -CH2OCH2CF 3)) or PEG-like (2-(2-methoxyethoxy)ethoxy)methyl (ME2Ox, (-CH 2(OCH2CH2)2OCH3)) side chains were prepared via cationic ring opening polymerization. Characterization utilized 1H NMR spectroscopy, temperature modulated differential scanning calorimetry (MDSC) and thermogravimetric analysis (TGA). Molecular weights (M n) by 1H NMR end group analysis were ∼6000-8000g/mole. Bromobutoxymethyl groups were completely substituted with N,N-dimethylalkyl amines to obtain alkylammonium co-telechelics. Two alkyl ammonium chain lengths, six carbons (C6) and twelve carbons (C12) were used. T gs of bromobutoxymethyl co-telechelics were -68°C and -48°C for ME2Ox and 3FOx, respectively. Tgs remained low after amine substitution. Alkylammonium co-telechelics decomposed at 220-230°C regenerating amine. Telechelics were incorporated into polyurethanes (PUs) having 4,4'-(methylene bis (p-cyclohexyl isocyanate) (H12MDI) and butanediol (BD) as the hard block (30wt%). Characterization by 1H NMR, GPC, MDSC and TGA is described. From DSC data, using the Fox equation, the weight fraction of pure soft block in the soft block domain (w1) was very high (0.96-0.99) for polyurethanes with fluorous soft blocks, while soft blocks with PEG-like side chains were phase mixed (w1 = 0.73-0.75). To our knowledge, this is the first time that a polycationic telechelic has been incorporated into a polyurethane. By using X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR-IR) spectroscopy, dynamic contact angle (DCA) analysis, sessile drop measurement, and Tapping Mode Atomic Force Microscopy (TM-AFM), surface properties of polyurethanes were examined. These polyurethanes were co-processed with base polyurethanes to modify surfaces. Surface concentration of 2 wt% P[AB]-polyurethanes was studied by using the same surface characterization methods. Surface concentration of semifluorinated and alkylammonium side chains (C6 and C12) was observed. Miscibility of PEG-like side chains resulted in weak concentration of short alkyl ammonium side chains (C6). However, longer alkylammonium side chains (C12) can "self-chaperone" and surface concentrate better compared to shorter side chain analogs. For biocidal testing, aerosol and touch tests were designed and implemented. Coatings were tested for zone of inhibition. The polyurethanes were first tested as 100 wt% coatings and found to be highly effective against both Gram(-) (Pseudomonas aeruginosa, Escherichia coli) and Gram(+) (Staphylococcus aureus) bacteria. Polyurethane modified surfaces (2 wt%) were tested against aerosol challenges of the same bacteria strains. The 2 wt% PSM with soft block containing trifluoroethoxy ( A, 89 mol%) and C12 alkylammonium (B, 11mol%) side chains gave the highest biocidal effectiveness against all bacteria strains in 30 min (100% kill, 3.6-4.4 log reduction). |
