Supporting Information

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1 Supporting Information UV-curable Contact Active Benzophenone Terminated Quaternary Ammonium Antimicrobials for Applications in Polymer Plastics and Related Devices Lukas Porosa, Alexander Caschera, Joseph Bedard, Amanda Mocella, Evan Ronan, Alan J. Lough, Gideon Wolfaardt and Daniel A. Foucher * Department of Chemistry and Biology, Ryerson University, 350 Victoria Street, Toronto, Ontario, Canada M5B-2K3, daniel.foucher@ryerson.ca Department of Chemistry, University of Toronto, 80 St. George Street, Toronto Ontario, Canada, M5S-3H6, alough@chem.utoronto.ca Stellenbosch University Water Institute Secretariat, Faculty of Natural Science, Stellenbosch Central, Stellenbosch, 7599, South Africa, gmw@sun.ac.za *Corresponding author S-1

2 Table of Contents Experimental S-4 Materials and Instrumental Methods S-4 Antimicrobial Characterization. S-5 Characterization of Antimicrobial Treated Surfaces. S-6 Preparation of Calibration Curve for 5b. S-7 Leachate Analysis of PS UV cured with 5b 1, 2, 3. S-7 Synthesis of QACs 4-7c. S-8 Synthesis of N-(3-(4-benzoylphenyl)propyl)-N,N-dimethyldodecan-1-ammonium bromide 4 S-8 Synthesis of N-(3-(4-benzoylphenyl)propyl)-N,N-dimethyloctadecan-1-aminium chloride 5a S-9 Synthesis of N-(3-(4-benzoylphenyl)propyl)-N,N-dimethyloctadecan-1-aminium bromide 5b S-9 Synthesis of N-(3-(4-benzoylphenyl)propyl)-N,N-dimethyloctadecan-1-aminium iodide 5c S-10 Synthesis of N-(4-(4-benzoylphenyl)butyl)-N,N-dimethyloctadecan-1-aminium chloride 6a S-11 Synthesis of N-(4-(4-benzoylphenyl)butyl)-N,N-dimethyloctadecan-1-aminium bromide 6b S-12 Synthesis of N-(4-(4-benzoylphenyl)butyl)-N,N-dimethyloctadecan-1-aminium iodide 6c S-12 Synthesis of N-(6-(4-benzoylphenyl)hexyl)-N,N-dimethyloctadecan-1-aminium chloride 7a S-13 Synthesis of N-(6-(4-benzoylphenyl)hexyl)-N,N-dimethyloctadecan-1-aminium bromide 7b S-14 Synthesis of N-(6-(4-benzoylphenyl)hexyl)-N,N-dimethyloctadecan-1-aminium iodide 7c S-15 Epifluorescence Microscopy S-16 XPS data S-17 Microbiology Data S-24 ToF-SIMS data S-31 AFM and surface profilometry data S-32 UV-Vis Experimental Data S-36 NMR Spectra S-38 High-resolution Mass Spectrometry Data S-66 S-2

3 Table of Figures Figure S1 Spectroscopic images of polypropylene fabric sample coatings supplemented with dansyl fluorophore S1. S-16 Figure S2 Control CPVC XPS Survey Data. S-17 Figure S3 5b Treated CPVC XPS Survey Data. S-18 Figure S4 Control CPVC Identification XPS data. S-19 Figure S5 Control CPVC Identification XPS data (continued). S-20 Figure S6 5b Treated CPVC Identification XPS data. S-21 Figure S7 5b Treated CPVC Identification XPS data (continued). S-22 Figure S8 Quantification XPS data for control and 5b treated CPVC samples. S-23 Figure S9 Simplified schematic representation of the large drop inoculation (LDI) method. S-24 Figure S10 Tabulated large droplet inoculation (LDI) microbiology data for 4 and 5b. S-25 Figure S11 Graphical representation of Figure S10 Clear Polyvinyl Chloride (CPVC) Arthrobacter sp. (IAI-3). S-26 Figure S12 Graphical representation of Figure S10 Polyvinyl Chloride (PVC) coated with 5b tested against Arthrobacter sp. (IAI-3). S-26 Figure S13 Graphical representation of Figure S10 Polystyrene (PS) coated with 5b tested against Arthrobacter sp. (IAI-3). S-27 Figure S14 Graphical representation of Figure S10 Polyether ether ketone (PEEK) coated with 5b tested against Arthrobacter sp. (IAI-3). S-27 Figure S15 Graphical representation of Figure S10 Clear Polyvinyl Chloride (CPVC) coated with 5b tested against P. aeruginosa. (PAO1). S-28 Figure S16 Graphical representation of Figure S10 Clear Polyvinyl Chloride (CPVC) coated with 5b tested against L. monocytogenes. (Scott A). S-28 Figure S17 Graphical representation of Figure S10 Polystyrene (PS) coated with 4 tested against Arthrobacter sp. S-29 Figure S18 Testing for a leaching zone for uncured 5b coated samples tested against PAO1 (horizontal streak) and IAI-3 (vertical streak). S-30 Figure S19 Negative ion ToF-SIMS imaging of control and 5b coated samples. S-31 Figure S20 AFM imaging of location A of a twice coated PS sample using 5b. S-32 Figure S21 AFM imaging of location B of a twice coated PS using 5b. S-32 Figure S22 AFM imaging of location C of a twice coated PS using 5b. S-33 Figure S23 3D graphical representation using surface profilometry of twice coated PS using 5b. S-34 Figure S24 Mean profile of 5b (2 coating) on PS from Figure S20 (n=51). S-35 Figure S25 Calibration curve for 5b concentrations in the range of 10 to 100 µg ml -1. S-36 Figure S26 UV-Vis spectral data for water rinse solutions (30 ml) of 5b coated on PS. S-36 Figure S27 Quantitative measurement of the amount of unbound compound 5b on PS samples detected in 5 ml of distilled water rinse solution after being spray coated. S-37 Figure S28 1 H NMR (400 MHz, CDCl 3) spectrum of 4. S-38 Figure S29 13 C NMR (101 MHz, CDCl 3) spectrum of 4. S-39 Figure S30 COSY 2D NMR (CDCl 3) spectrum of 4. S-40 Figure S31 HSQC 2D NMR (CDCl 3) spectrum of 4. S-41 Figure S32 1 H NMR (400 MHz, CDCl 3) spectrum of 5a. S-42 S-3

4 Figure S33 13 C NMR (101 MHz, CDCl 3) spectrum of 5a. S-43 Figure S34 1 H NMR (400 MHz, CDCl 3) spectrum of 5b. S-44 Figure S35 13 C NMR (101 MHz, CDCl 3) spectrum of 5b. S-45 Figure S36 COSY 2D NMR (CDCl 3) spectrum of 5b. S-46 Figure S37 HSQC 2D NMR (CDCl 3) spectrum of 5b. S-47 Figure S38 1 H NMR (400 MHz, CDCl 3) spectrum of 5c. S-48 Figure S39 13 C NMR (101 MHz, CDCl 3) spectrum of 5c. S-49 Figure S40 1 H NMR (400 MHz, CDCl 3) spectrum of 6a. S-50 Figure S41 13 C NMR (101 MHz, CDCl 3) spectrum of 6a. S-51 Figure S42 1 H NMR (400 MHz, CDCl 3) spectrum of 6b. S-52 Figure S43 13 C NMR (101 MHz, CDCl 3) spectrum of 6b. S-53 Figure S44 COSY 2D NMR (CDCl 3) spectrum of 6b. S-54 Figure S45 HSQC 2D NMR (CDCl 3) spectrum of 6b. S-55 Figure S46 1 H NMR (400 MHz, CDCl 3) spectrum of 6c. S-56 Figure S47 13 C NMR (101 MHz, CDCl 3) spectrum of 6c. S-57 Figure S48 1 H NMR (400 MHz, CDCl 3) spectrum of 7a. S-58 Figure S49 13 C NMR (101 MHz, CDCl 3) spectrum of 7a. S-59 Figure S50 1 H NMR (400 MHz, CDCl 3) spectrum of 7b. S-60 Figure S51 13 C NMR (101 MHz, CDCl 3) spectrum of 7b. S-61 Figure S52 COSY 2D NMR (CDCl 3) spectrum of 7b. S-62 Figure S53 HSQC 2D NMR (CDCl 3) spectrum of 7b. S-63 Figure S54 1 H NMR (400 MHz, CDCl 3) spectrum of 7c. S-64 Figure S55 13 C NMR (101 MHz, CDCl 3) spectrum of 7c. S-65 Figure S56 - HRMS-ESI TOF of compound 4. S-66 Figure S57 - HRMS-ESI TOF of compound 5a. S-67 Figure S58 - HRMS-ESI TOF of compound 5b. S-68 Figure S59 - HRMS-ESI TOF of compound 5c. S-69 Figure S60 - HRMS-ESI TOF of compound 6a. S-70 Figure S61 - HRMS-ESI TOF of compound 6b. S-71 Figure S62 - HRMS-ESI TOF of compound 6c. S-72 Figure S63 - HRMS-ESI TOF of compound 7a. S-73 Figure S64 - HRMS-ESI TOF of compound 7b. S-74 Figure S65 - HRMS-ESI TOF of compound 7c. S-75 Experimental Materials and Instrumental Methods All reagents and solvents were obtained from commercial sources and used as received unless otherwise indicated. N,N-dimethyldodecylamine was purchased from Alfa and N,N- S-4

5 dimethyloctadecylamine from Acros. Stock plastic (clear) polyvinyl chloride (CPVC) (cat ) and polystyrene (PS) (cat ) was supplied by VWR International, polyvinyl chloride (PVC) sourced from Bow Plastics (cat ), polyether ether ketone (PEEK) sourced from Drake plastics (cat. KT820NT), high density polyethylene (HDPE) sourced from eplastics (cat. HDPENAT0.125SR24X48), and polypropylene (PP) sourced from Special Coatings USA, LLC. The benzophenone alkyl halides (1a-c, 2a-c, 3a-c: Scheme 1) were prepared as previously described by Saettone. 77 Synthesis of propyl-dimethyl(benzoylphenoxy)octadecylammonium bromide 5b was carried out in a Biotage Initiator Microwave Synthesizer (2.45 GHz). The benzophenone functionalized dansyl quaternary ammonium fluorophore, S1, was obtained as previously described. 95 All other experimental details are included in the supplementary section. Antimicrobial Compound Characterization. Nuclear magnetic resonance (NMR) experiments were carried out on a 400 MHz Bruker Avance II Spectrometer using CDCl3. 1 H NMR (400 MHz) and 13 C NMR (100.6 MHz) spectra were referenced to the residual proton and central carbon peak of the solvent. All chemical shifts are given in δ (ppm) relative to the solvent and assigned to atoms on basis of available 2D spectra for each compound. Thin Layer Chromatography (TLC) was carried out on silica gel 60 aluminum backed plates, eluting with the solvent system indicated below for each compound. High resolution mass spectrometry (HRMS) was carried out using electrospray ionization time of flight (ESI-ToF) at the Advanced Instrumentation for Molecular Structure (AIMS) laboratory at the University of Toronto. Melting points were measured in open air using a Fisher Scientific melting point apparatus. A Bruker-Nonius Kappa-CCD diffractometer was used to obtain the X-ray information of the crystal structure of 4 which has been deposited with the Cambridge Crystallographic Data Centre and have been assigned the following deposition number 4: CCDC S-5

6 Characterization of Antimicrobial Treated Surfaces. Advancing water contact angle images of treated and untreated surfaces were taken using a Teli CCD camera equipped with a macro lens, and attached perpendicular to the sample surface. The camera was connected to a monitor using a Sony CMA-D camera adapter. Contact angle measurements were performed using SCA20 contact angle software by Data Physics Corporation. Contact angle experiments performed in accordance with ASTM D7334. X-ray photoelectron spectroscopy (XPS) was performed using a ThermoFisher Scientific K-Alpha and time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed using an IonTOF ToF-SIMS IV at the Ontario Centre for the Characterisation of Advanced Materials (OCCAM), located at the University of Toronto. Atomic force microscopy (AFM) using an Anasys nanoir2 equipped with Contact Mode NIR2 Probes (Resonance frequency 13 ± 4 khz, Spring constant N m -1 ), and surface profilometry using a KLA-Tencor P16+ Surface Profilometer was also performed at OCCAM. AFM data was processed using Gwiddion Coating of plastic test samples, which consisted of 6.25 cm 2 ± 1 cm 2 coupons of each plastic material, was performed via an ESS AD LG electrospray apparatus set to 150 kpa that applied the compound uniformly over the test surfaces. UV curing of benzophenone QAC coated plastics was performed using Novacure spot curing system, set to provide a 300 J UV dose, supplied from a mercury-arc discharge lamp, at a peak intensity of 5000 mw into a reflective curing chamber 2 cm from the light guide source giving a 1.4 W/cm² intensity giving an approximate 32 J cm - ² total dose as measured using an EIT UV Power Puck 2. Epifluorescence microscopy was performed using a Leica MZFLIII fluorescence microscope equipped with a PlanApo 1.0x objective lens and CFP filter set (excitation filter 436/20 nm, barrier filter 480/40 nm). S-6

7 Preparation of Calibration Curve for 5b. A 0.1% (w/v) or 1000 µg/ml stock solution of 5b was prepared by dissolving 100 mg of 5b in 100 ml of distilled water within a volumetric flask. Aliquots of 5 ml of aqueous working solutions ranging from µg ml -1 ( µm) were prepared inside polypropylene screw cap tubes (Sarstedt AG & Co, catalog no , 15 ml capacity) from the freshly prepared stock solution. A calibration curve at 292 nm was prepared by measuring the absorbance within a quartz cuvette (PerkinElmer, Part No. B ) using a single-beam spectrophotometer (Beckman DU530 Spectrophotometer) at 292 nm against a distilled water blank. Molar absorptivity (L mol -1 cm -1 ) for 5b at 292 nm was determined by using the Beer-Lambert equation using averaged concentration and absorbance from all data points. The limit of detection (LOD) was calculated with the following formula, LOD = 3.3 σ / S (4), where σ is the standard deviation of y-intercepts, and S is the slope of the calibration line. 1 Leachate Analysis of PS UV cured with 5b 1, 2, 3. 5b spray and UV cured in singlet 1, duplicate 2 and triplicate 3 onto polystyrene material and untreated polystyrene controls were placed inside polypropylene conical base screw cap tubes (VWR, Cat No , cut into 2 x 2 cm rectangles) containing distilled water (30 ml, Ryerson University, Toronto, Canada) and mechanically stirred using a vortex mixer for 60 seconds (VWR international, Cat no ). UV-VIS absorbance measurements of the washes were made within a quartz cuvette (PerkinElmer, Part No. B ) using a single-beam spectrophotometer (Beckman DU530 Spectrophotometer) between nm against a distilled water blank for leaching measurements. S-7

8 Synthesis of QACs 4-7c. Synthesis of N-(3-(4-benzoylphenyl)propyl)-N,N-dimethyldodecan-1-ammonium bromide 4 In a 500 ml glass vial equipped with a magnetic stir bar, 4-(3- chloropropoxy)benzophenone (1a: g, mmol, 1.0 eq.) was dissolved in EtOAc (70 ml). N,N-dimethyloctadecylamine ( g, 1.00 mmol, 1.0 eq.) was carefully added to the solution before the vial was capped and left to stir in a 100 C sand bath for 48 hours. After removing the magnetic stirrer and allowing the solution to cool to RT, the product precipitated out of solution as a white powder. The excess solvent was poured out, and the product was triturated with another 70 ml of EtOAc to obtain the title compound after further drying under high vacuum. Recovered yield: g (97.2%). A 1% solution of the recovered product (1000mg/100mL) was recrystallized from water over a period of three months by slow evaporation as long, clear needles for X-ray analysis. Mp = C. 1 H NMR (CDCl3, 400 MHz) δ = 7.75 (d, J = 8.8 Hz, 2H, H7), 7.69 (d, J = 7.0 Hz, 2H, H3), 7.53 (t, J = 7.3 Hz, 1H, H1), 7.43 (t, J = 7.5 Hz, 2H, H2), 6.93 (d, J = 8.8 Hz, 2H, H8), 4.19 (t, J = 5.1 Hz 2H, H10), (m, 2H, H12), (m, 2H, H14), 3.40 (s, 6H, H13), (m, 2H, H11), (m, 2H, H15), (m, 18H, H16- H24), 0.83 (t, J = 6.7 Hz, 3H, H25) ppm. 13 C{H} NMR (CDCl3, 101 MHz) δ = (C5), (C9), (C4), (C7), (C1), (C6), (C3), (C2), (C8), 64.6 (C10), 64.5 (C12), 61.2 (C14), 51.6 (C13), 31.9 (C23), (C22-C17 overlap), 26.3 (C16), 23.2 (C11), 22.8 (C23), 22.7 (C24), 14.2 (C25) ppm. HRMS (ESI-TOF) (m/z): [M + - Br] for C30H46BrNO2: calculated ; found S-8

9 Synthesis of N-(3-(4-benzoylphenyl)propyl)-N,N-dimethyloctadecan-1-aminium chloride 5a In a 20 ml glass vial equipped with a magnetic stir bar, 4-(3-chloropropoxy)benzophenone (1a: g, mmol, 1.0 eq.) was dissolved in MeCN (1 ml). N,N-dimethyloctadecylamine (0.298 g, 1.00 mmol, 1.1 eq.) was carefully added to the solution before the vial was capped and left to stir in a 100 C sand bath for 24 hours. After removing the magnetic stirrer and allowing the solution in RT, cold Et2O (4 ml) was then added to the vial for the product to precipitate out of the solution. The excess solvent was evaporated under vacuum, and a crude pale-yellow powder was obtained. Recovered yield: g (77.0%). Mp = C. 1 H NMR (CDCl3, 400 MHz) δ = 7.79 (d, J = 8.7 Hz, 2H, H7), 7.73 (d, J = 7.1 Hz, 2H, H3), 7.56 (t, J = 7.4 Hz, 1H, H1), 7.46 (t, J = 7.5 Hz, 2H, H2), 6.95 (d, J = 8.7 Hz, 2H, H8), 4.22 (t, J = 5.4 Hz, 2H, H10), (m, 2H, H12), (m, 2H, H14), 3.46 (s, 6H, H13), (m, 2H, H11), (m, 2H, H15), (m, 30H, H16-H30 overlap), 0.87 (t, J = 6.8 Hz, 3H, H31) ppm. 13 C{H} NMR (101 MHz, CDCl3) δ = (C5), (C9), (C4), (C7), (C1), (C6), (C3), (C2), (C8), 64.6 (C10+C12 overlap), 61.2 (C14), 51.6 (C13), 32.0 (C29), (C28-C17 overlap), 26.3 (C16), 23.3 (C11), 22.9 (C15), 22.8 (C30), 14.2 (C31) ppm. HRMS (ESI-TOF) (m/z): [M + - Cl] for C36H58ClNO2; calculated , found Synthesis of N-(3-(4-benzoylphenyl)propyl)-N,N-dimethyloctadecan-1-aminium bromide 5b In a 5-10 ml microwave vial equipped with a magnetic stir bar, 4-(3- bromopropoxy)benzophenone (1b: g, 1.93 mmol, 1.0 eq.) was dissolved in MeCN (10 ml). N,N-dimethyloctadecylamine (0.608 g, 2.04 mmol, 1.1 eq.) was carefully added to the solution and the reaction vessel was slightly heated using a heat gun to fully dissolve reactants into the solution. The vial was then capped, placed in the microwave, and with constant stirring run at 150 S-9

10 C for 2 min. The resultant clear mixture was poured into cold Et2O (~10 ml) for the desired product to precipitate out of solution. The product was isolated from excess solvent via decantation then dried under vacuum to yield a white powder. Recovered yield: 1.10 g (93%). Mp = C. UV-Vis (H2O, M to M): λabs max = 292 nm, ε1 = M -1 cm -1 1 H NMR (400 MHz, CDCl3) δ = 7.73 (d, J = 8.8 Hz, 2H, H7), 7.67 (d, J = 7.0 Hz, 2H, H3), 7.51 (t, J = 7.4 Hz, 1H, H1), 7.41 (t, J = 7.5 Hz, 2H, H2), 6.90 (d, J = 8.8 Hz, H8, 2H), 4.17 (t, J = 5.5 Hz, 2H, H10), (m, 2H, H12), (m, 2H, H14), 3.40 (s, 6H, H13), (m, 2H, H11), (m, 2H, H15), (m, 30H, H16-H30 overlap), 0.82 (t, J = 6.8 Hz, 3H, H31) ppm. 13 C{H} NMR (101 MHz, CDCl3) δ = (C5), (C9), (C4), (C7), (C1), (C6), (C3), (C2), (C8), 64.5 (C10+C12 overlap), 61.1 (C14), 51.5 (C13), 31.9 (C29), (C17-C28 overlap), 26.3 (C16), 23.2 (C11), 22.8 (C15), 22.7 (C30), 14.1 (C31) ppm. HRMS (ESI-TOF) (m/z): [M + - Br] for C36H58BrNO2: calculated ; found Synthesis of N-(3-(4-benzoylphenyl)propyl)-N,N-dimethyloctadecan-1-aminium iodide 5c In a 20 ml glass vial equipped with a magnetic stir bar, 4-(3-iodopropoxy)benzophenone (1c: g, mmol, 1.0 eq.) was dissolved in MeCN (1 ml). N,N-dimethyloctadecylamine (0.188 g, mmol, 1.1 eq.) was carefully added to the solution before the vial was capped and left to stir in a 100 C sand bath for 24 hours. After removing the magnetic stirrer and allowing the solution in RT, cold Et2O (4 ml) was then added to the vial for the product to precipitate out of the solution. The excess solvent was evaporated under vacuum, and a crude white powder was obtained. Recovered Yield: g (95.1%). Mp = C. 1 H NMR (CDCl3, 400 MHz) δ = 7.77 (d, J = 8.8 Hz, 2H, H7), 7.71 (d, J = 7.0 Hz, 2H, H3), 7.55 (t, J = 7.4 Hz, 1H, H1), 7.45 (t, J = S-10

11 7.5 Hz, 2H, H2), 6.96 (d, J = 8.8 Hz, 2H, H8), 4.22 (t, J = 5.4 Hz, 2H, H10), (m, 2H, H12), (m, 2H, H14), 3.41 (s, 6H, H13), (m, 2H, H11), (m, 2H, H15), (m, 30H, H16-H30 overlap), 0.85 (t, J = 6.8 Hz, 3H, H31) ppm. 13 C{H} NMR (CDCl3, 101 MHz) δ = (C5), (C9) (C4), (C7), (C1), (C6) (C3), (C2), (C8), (C10), (C12), 61.5 (C14), 51.9 (C13), 32.0 (29), (C28+C17 overlap), 26.3 (C16), 23.4 (C11), 22.9 (C15), 22.8 (C30), 14.2 (C31) ppm. HRMS (ESI-TOF) (m/z): [M + - I] for C36H58INO2; calculated , found Synthesis of N-(4-(4-benzoylphenyl)butyl)-N,N-dimethyloctadecan-1-aminium chloride 6a In a 20 ml glass vial equipped with a magnetic stir bar, 4-(4-chlorobutoxy)benzophenone (2a: g, mmol, 1.0 eq.) was dissolved in MeCN (1 ml). N,N-dimethyloctadecylamine (0.298 g, 1.00 mmol, 1.15 eq.) was carefully added to the solution before the vial was capped and left to stir in a 100 C sand bath for 48 hours. After removing the magnetic stirrer and allowing the solution in RT, cold Et2O (4 ml) was then added to the vial for the product to precipitate out of the solution. The excess solvent was evaporated under vacuum, and a crude pale-yellow waxy solid was obtained. Recovered yield: g (68.5%). Mp = C. 1 H NMR (CDCl3, 400 MHz) δ = 7.62 (d, J = 8.8 Hz, 2H, H3), 7.56 (d, J = 7.0 Hz, 2H, H7), 7.41 (t, J = 7.4 Hz, 1H, H1), 7.31 (t, J = 7.7 Hz, 2H, H2), 6.82 (d, J = 8.8 Hz, 2H, H8), 3.99 (t, J = 5.4 Hz, 2H, H10), (m, 2H, H13), (m, 2H, H15), 3.24 (s, 6H, H14), (m, 4H, H11+H12 overlap), (m, 2H, H16), (m, 30H, H17-H31 overlap), 0.72 (t, J = 6.8 Hz, 3H, H32) ppm. 13 C{H} NMR (101 MHz, CDCl3) δ = (C5), (C9), (C4), (C7), (C1), (C6), (C3), (C2), (C8), 66.8 (C10+C12 overlap), 63.8 (C13), 63.2 S-11

12 (C15), 50.8 (C14), (C17-C31 overlap ), 22.5 (C11), 22.3 (C16), 19.4 (C31), 13.8 (C32) ppm. HRMS (ESI-TOF) (m/z): [M + - Cl] for C37H60ClNO2; calculated , found Synthesis of N-(4-(4-benzoylphenyl)butyl)-N,N-dimethyloctadecan-1-aminium bromide 6b In a 20 ml glass vial equipped with a magnetic stir bar, 4-(3-bromobutoxy)benzophenone (2b: g, mmol, 1.0 eq.) was dissolved in MeCN (1 ml). N,N-dimethyloctadecylamine (0.246 g, mmol, 1.1 eq.) was carefully added to the solution before the vial was capped and left to stir in a 100 C sand bath for 24 hours. After removing the magnetic stirrer and allowing the solution in RT, cold Et2O (4 ml) was then added to the vial for the product to precipitate out of the solution. The excess solvent was evaporated under vacuum, and a crude white powder was obtained. Recovered yield: g (67.9%). Mp = C. 1 H NMR (CDCl3, 400 MHz) δ = 7.81 (d, J = 8.7 Hz, 2H, H7), 7.74 (d, J = 6.9 Hz, 2H, H3), 7.57 (t, J = 8.0 Hz, 1H, H1), 7.47 (t, J = 7.2 Hz, 2H, H2), 6.96 (d, J = 8.7 Hz, 2H, H8), (m, 2H, H10), (m, 2H, H13), (m, 2H, H15) 3.42 (s, 6H, H14), (m, 4H, H11 + H12 overlap), (m, 2H, H16), (m, 30H, H17-H31 overlap), 0.87 (t, J = 6.4 Hz, 3H, H32) ppm. 13 C{H} NMR (CDCl3, 101 MHz) δ = (C5), (C9), (C4), (C7), (C1), (C6), (C3), (C2), (C8), 67.0 (C10+C12 overlap), 64.2 (C13), 63.5 (C15), 51.3 (C14), (C17-C30 overlap), 22.9 (C11), 22.8 (C16), 19.9 (C31), 14.2 (C32) ppm. HRMS (ESI-TOF) (m/z): [M + - Br] for C37H60BrNO2; calculated , found Synthesis of N-(4-(4-benzoylphenyl)butyl)-N,N-dimethyloctadecan-1-aminium iodide 6c In a 20 ml glass vial equipped with a magnetic stir bar, 4-(3-iodobutoxy)benzophenone (2c: g, mmol, 1.0 eq.) was dissolved in MeCN (1 ml). N,N-dimethyloctadecylamine S-12

13 (0.215 g, mmol, 1.1 eq.) was carefully added to the solution before the vial was capped and left to stir in a 100 C sand bath for 24 hours. After removing the magnetic stirrer and allowing the solution in RT, cold Et2O (4 ml) was then added to the vial for the product to precipitate out of the solution. The excess solvent was evaporated under vacuum, and an off-white colored powder was obtained. Recovered Yield: g (46.3%). Mp = C 1 H NMR (CDCl3, 400 MHz) δ = 7.80 (d, J = 8.9 Hz, 2H, H7), 7.74 (d, J = 7.0 Hz, 2H, H7), 7.57 (t, J = 7.4 Hz, 1H, H1), 7.47 (t, J = 7.5 Hz, 2H, H2), 6.99 (d, J = 8.9 Hz, 2H, H8), 4.16 (t, J = 8.9 Hz, 2H, H10), (m, 2H, H13), (m, 2H, H15) 3.39 (s, 6H, H14), (m, 4H, H11+H12 overlap), (m, 2H, H16), (m, 30H, H17-H31 overlap), 0.88 (t, J = 6.8 Hz, 3H, H32) ppm. 13 C{H} NMR (CDCl3, 101 MHz) δ = (C5), (C9), (C4), (C7), (C1), (C6), (C3), (C2), (C8), 67.1 (C10+C12 overlap), 64.6 (C13), 63.9 (C15), 51.6 (C14), (C17-C30), 23.0 (C11), 22.8 (C16), 19.9 (C31), 14.2 (C32) ppm. HRMS (ESI-TOF) (m/z): [M + - I] calculated for C37H60INO2; calculated , found Synthesis of N-(6-(4-benzoylphenyl)hexyl)-N,N-dimethyloctadecan-1-aminium chloride 7a In a 20 ml glass vial equipped with a magnetic stir bar, 4-(3-chlorohexoxy)benzophenone (3a: 250 g, mmol, 1.0 eq.) was dissolved in MeCN (1 ml). N,N-dimethyloctadecylamine (0.258 g, mmol, 1.1 eq.) was carefully added to the solution before the vial was capped and left to stir in a 100 C sand bath for 24 hours. After removing the magnetic stirrer and allowing the solution in RT, cold Et2O (4 ml) was then added to the vial for the product to precipitate out of the solution. The excess solvent was evaporated under vacuum, and a crude pale-yellow powder S-13

14 was obtained. Recovered Yield: g (64.1%). Mp = C. 1 H NMR (CDCl3, 400 MHz) δ = 7.75 (d, J = 8.8 Hz, 2H, H7), 7.69 (d, J = 7.0 Hz, 2H, H3), 7.51 (t, J = 7.4 Hz, 1H, H1), 7.42 (t, J = 7.5 Hz, 2H, H2), 6.90 (d, J = 8.9 Hz, 2H, H8), 3.99 (t, J = 6.2 Hz, H10, 2H), (m, H15, 2H), (m, H17, 2H), 3.35 (s, 6H, H16), (m, 10H, H(11-14, 18) overlap), (m, 30H, H19-H33 overlap), 0.82 (t, J = 6.8 Hz, 3H, H32) ppm. 13 C{H} NMR (CDCl3, 101 MHz) δ = (C5), (C9), (C4), (C7), (C1), (C6), (C3), (C2), (C8), 67.8 (C10), 64.0 (C15), 63.8 (C17), 51.2 (C16), 31.9 (C32), (C20-C31 overlap), 28.8 (C11), 26.3 (C14), 26.0 (C18), 25.7 (C19), (C13), (C12), 22.7 (C33) 14.1 (C34) ppm. HRMS (ESI-TOF) (m/z): [M + - Cl] for C39H64ClNO2; calculated , found Synthesis of N-(6-(4-benzoylphenyl)hexyl)-N,N-dimethyloctadecan-1-aminium bromide 7b In a 20 ml glass vial equipped with a magnetic stir bar, 4-(3-bromohexoxy)benzophenone (3b: g, mmol, 1.0 eq.) was dissolved in MeCN (1 ml). N,N-dimethyloctadecylamine (0.227 g, mmol, 1.1 eq.) was carefully added to the solution before the vial was capped and left to stir in a 100 C sand bath for 24 hours. After removing the magnetic stirrer and allowing the solution in RT, cold Et2O (4 ml) was then added to the vial for the product to precipitate out of the solution. The excess solvent was evaporated under vacuum, and a crude off-white powder was obtained. Yield g (94.1%). Mp = C. 1 H NMR (CDCl3, 400 MHz) δ = 7.80 (d, J = 8.1 Hz, 2H, H7), 7.74 (d, J = 7.6 Hz, 2H, H3), 7.56 (t, J = 6.8 Hz, 1H, H1), 7.46 (t, J = 7.4 Hz, 2H, H2), 6.94 (d, J = 7.8 Hz, 2H, H8), 4.04 (t, J = 6.8 Hz, 2H, H10), (m, 2H, H15), (m, 2H, H17), 3.41 (s, 6H, H16) (m, 10H, H(11-14, 18) overlap), (m, 30H, H19-H33 overlap), 0.87 (t, J = 6.8 Hz, 3H, H34) ppm. 13 C{H} NMR (CDCl3, 101 MHz) δ = S-14

15 (C5), (C9), (C4), (C7), (C1), (C6), (C3), (C2), (C8), 67.7 (C10), 64.1 (C15), 63.8 (C17), 51.2 (C16), 31.9 (C32), (C20-C31 overlap), 28.8 (C11), 26.3 (C14), 26.0 (C18), 25.7 (C19), 22.8 (C13+C12 overlap), 22.7 (C33), 14.1 (C34) ppm. HRMS (ESI-TOF) (m/z): [M + - Br] for C39H64BrNO2; calculated , found Synthesis of N-(6-(4-benzoylphenyl)hexyl)-N,N-dimethyloctadecan-1-aminium iodide 7c In a 20 ml glass vial equipped with a magnetic stir bar, 4-(3-iodohexoxy)benzophenone (3c: g, mmol, 1.0 eq.) was dissolved in MeCN (1 ml). N,N-dimethyloctadecylamine (0.200 g, mmol, 1.1 eq.) was carefully added to the solution before the vial was capped and left to stir in a 100 C sand bath for 24 hours. After removing the magnetic stirrer and allowing the solution in RT, cold Et2O (4 ml) was then added to the vial for the product to precipitate out of the solution. The excess solvent was evaporated under vacuum, and a crude white powder was obtained. Yield g (86.3%). Mp = C. 1 H NMR (CDCl3, 400 MHz) δ = 7.77 (d, J = 8.7 Hz, 2H, H7), 7.72 (d, J = 7.2 Hz, 2H, H3), 7.54 (t, J = 7.4 Hz, 1H, H1), 7.44 (t, J = 7.5 Hz, 2H, H2), 6.93 (d, J = 8.8 Hz, 2H, H8), 4.03 (t, J = 6.2 Hz, 2H, H10), (m, 2H, H15), (m, 2H, H17), 3.35 (s, 6H, H16) (m, 10H, H(11-14, 18) overlap), (m, 30H, H19-H33 overlap), 0.85 (t, J = 6.7 Hz, 3H, H34) ppm. 13 C{H} NMR (CDCl3, 101 MHz) δ = (C5), (C9), (C4), (C7), (C1), (C6), (C3), (C2), (C8), 67.8 (C10) 64.4 (C17), 64.2 (C15), 51.5 (C16), (C23), (C20-C31 overlap), 28.8 (C11), 26.2 (C14), 25.9 (C18), 25.6 (C19) 22.9 (C13) 22.8 (C12), 22.7 (C33), 14.1 (C34). HRMS (ESI-TOF) (m/z): [M + - I] for C39H64INO2; calculated , found S-15

16 Epifluorescence Microscopy N O S O HN N O Br O Figure S1 Spectroscopic images of polypropylene fabric samples under white light (left) and GFP2-filtered UV light (right). Sample coatings of 5b supplemented with dansyl fluorophore S1 (above) appeared to brightly fluoresce when exposed to UV light. S-16

17 XPS data Figure S2 Control CPVC XPS Survey Data. S-17

18 Figure S3 5b Treated CPVC XPS Survey Data. S-18

19 Figure S4 Control CPVC Identification XPS data. S-19

20 Figure S5 Control CPVC Identification XPS data (continued). S-20

21 Figure S6 5b Treated CPVC Identification XPS data. S-21

22 Figure S7 5b Treated CPVC Identification XPS data (continued). S-22

23 Control Compound 5b Element Concentration Sensitivity Element Concentration Sensitivity % Factor % Factor Br3d Br3d C1s C1s Ca2p Ca2p Cl2p Cl2p N1s N1s Na1s Na1s O1s O1s S2p S2p Si2p Si2p Figure S8 Quantification XPS data for control and 5b treated CPVC samples. S-23

24 Microbiology Data Figure S9 Simplified schematic representation of the large drop inoculation (LDI) method. Average Data log(cfu) O Br Inoculum Load Control Treated O N Clear Polyvinyl Chloride (CPVC) 5b 3 Hours ± 0.21 < 1.70 ± 0.00 S-24

25 Arthrobacter sp. (IAI-3) Polyvinyl Chloride (PVC) Arthrobacter sp. (IAI-3) Polystyrene (PS) Arthrobacter sp. (IAI-3) Polyether ether ketone (PEEK) Arthrobacter sp. (IAI-3) Clear Polyvinyl Chloride (CPVC) P. aeruginosa (PAO1) Clear Polyvinyl Chloride (CPVC) L. monocytogenes (Scott A) O 24 Hours 4.83 ± 0.48 < 1.70 ± Hours 6.05 ± 0.52 < 1.70 ± Hours 4.40 ± 0.31 < 1.70 ± Hours 7.47 ± 0.08 < 1.70 ± Hours 7.12 ± 0.03 < 1.70 ± Hours 6.86 ± 0.08 < 1.70 ± Hours 6.44 ± 0.01 < 1.70 ± Hours 6.86 ± 0.55 < 1.70 ± Hours 2.95 ± 1.98 < 1.70 ± Hours 3.71 ± 0.02 < 1.70 ± Hours < 1.71 ± 0.00 < 1.70 ± 0.00 Br O N 4 Polystyrene (PS) Arthrobacter sp. (IAI-3) 3 Hours ± 0.10 < 1.70 ± 0.00 Figure S10 Tabulated large droplet inoculation (LDI) microbiology data. Microbiological testing was performed with triplicate treated (4 and 5b) and untreated controls. The inoculum load represents the quantity of viable cells placed onto each sample material, and was determined concurrently to sample data (± indicates standard deviation n = 3). A value of 1.70 log(cfu) represents the lowest number of detectable cells spot plated onto 3 g L -1 TSA (LOD: 50 cfu, 1 colony in 5 ml undiluted collection fluid). S-25

26 Figure S11 Graphical representation of Figure S10 Clear Polyvinyl Chloride (CPVC) coated with 5b tested against Arthrobacter sp. (IAI-3). Figure S12 Graphical representation of Figure S10 Polyvinyl Chloride (PVC) coated with 5b tested against Arthrobacter sp. (IAI-3). S-26

27 Figure S13 Graphical representation of Figure S10 Polystyrene (PS) coated with 5b tested against Arthrobacter sp. (IAI-3). Figure S14 Graphical representation of Figure S10 Polyether ether ketone (PEEK) coated with 5b tested against Arthrobacter sp. (IAI-3). S-27

28 Figure S15 Graphical representation of Figure S10 Clear Polyvinyl Chloride (CPVC) coated with 5b tested against P. aeruginosa. (PAO1). Figure S16 Graphical representation of Figure S10 Clear Polyvinyl Chloride (CPVC) coated with 5b tested against L. monocytogenes. (Scott A). S-28

29 Figure S17 Graphical representation of Figure S10 Polystyrene (PS) coated with 4 tested against Arthrobacter sp. (IAI-3). S-29

30 Figure S18 Uncured CPVC samples 2 coated with 5b (69.6 µg cm -2 ) compared (bottom) against an uncoated control (top). Absence of a leaching zone was observed for the samples tested against PAO1 (horizontal streak) and IAI-3 (vertical streak). S-30

31 ToF-SIMS data Figure S19 Composite negative ion ToF-SIMS image of µm section of control and 5b treated samples, where lighter parts of the image are representative of more intense signals. Intensity is a function of fragment quantity during analysis. Images correspond to negative ionic fragmentation products of chlorine (Cl - ), bromine (Br - ), ethane (C2H - ), tetracarbonyl ammonium (C4N - ), and hydroxybenzophenone (C13H9O2 - ). S-31

32 AFM and surface profilometry data Figure S20 AFM imaging of location A, found along the separation line between the previously taped (left) and untaped (right) sections of twice coated PS using antimicrobial 5b. Image processed using Gwiddion Figure S21 AFM imaging of location B, found along the separation line between the previously taped (left) and untaped (right) sections of twice coated PS using antimicrobial 5b. Image processed using Gwiddion S-32

33 Figure S22 AFM imaging of location C, found along the separation line between the previously taped (left) and untaped (right) sections of twice coated PS using antimicrobial 5b. Image processed using Gwiddion S-33

34 µm Figure S23 3D graphical representation using surface profilometry of a 0.25 mm 2 area found along the separation line between the previously taped (left) and untaped (right) sections of twice coated PS using antimicrobial 5b. S-34

35 µm L1 L1 R1 R mm 1 StpHt µm TIR 0.92 µm Avg µm Slope Figure S24 Mean profile of 5b (2 coating) on PS from Figure S20 (n = 51). S-35

36 UV-Vis Experimental Data Absorbance at 292 nm y = x R² = Concentration 5b (µg/ml) Figure S25 Calibration curve for 5b concentrations in the range of 10 to 100 µg ml -1. Molar absorptivity (ε1) was found to be L mol -1 cm -1. The limit of detection (LOD) was determined to be µg ml -1 (0.185 µm), while the limit of quantitation was found as µg ml -1 (3.09 µm) based on the standard deviation of the response and the slope Absorbance Wavelength (nm) PS 5b x 0 PS 5b x 1 PS 5b x 2 PS 5b x 3 C18 10 ppm Figure S26 UV-Vis spectral data for water rinse solutions (30 ml) of 5b UV treated in singlet, duplicate and triplicate onto PS (12 cm 2 ), compared against a 10 µg ml -1 (16.2 um, purple) 5b solution. No detectable quaternary ammonium compound at the detection limit of the UV-Vis instrument was released into solution after the aqueous wash protocol employed. S-36

37 Coating Mass/ Area (µg cm -2 ) Uncured UV Cured x1 x2 x3 Coatings/ Polystyrene Sample (4 cm 2 ) Figure S27 Quantitative measurement of the amount of unbound compound 5b on polystyrene samples detected in 5 ml of distilled water rinse solution after being spray coated. Concentrations were calculated using the Beer-Lambert law and determined using UV-vis spectroscopy after washing uncured (blue) and cured (orange) polystyrene samples in the 5 ml rinse solution and measuring the absorbance at the λmax, 292 nm (consistent with the λmax of 5b). S-37

38 NMR Spectra Figure S28 1 H NMR (400 MHz, CDCl3) spectrum of 4. S-38

39 Figure S29 13 C NMR (101 MHz, CDCl3) spectrum of 4. S-39

40 Figure S30 COSY 2D NMR (CDCl3) spectrum of 4. S-40

41 Figure S31 HSQC 2D NMR (CDCl3) spectrum of 4. S-41

42 Figure S32 1 H NMR (400 MHz, CDCl3) spectrum of 5a. S-42

43 Figure S33 13 C NMR (101 MHz, CDCl3) spectrum of 5a. S-43

44 Figure S34 1 H NMR (400 MHz, CDCl3) spectrum of 5b. S-44

45 Figure S35 13 C NMR (101 MHz, CDCl3) spectrum of 5b. S-45

46 Figure S36 COSY 2D NMR (CDCl3) spectrum of 5b. S-46

47 Figure S37 HSQC 2D NMR (CDCl3) spectrum of 5b. S-47

48 Figure S38 1 H NMR (400 MHz, CDCl3) spectrum of 5c. S-48

49 Figure S39 13 C NMR (101 MHz, CDCl3) spectrum of 5c. S-49

50 Figure S40 1 H NMR (400 MHz, CDCl3) spectrum of 6a. S-50

51 Figure S41 13 C NMR (101 MHz, CDCl3) spectrum of 6a. S-51

52 Figure S42 1 H NMR (400 MHz, CDCl3) spectrum of 6b. S-52

53 Figure S43 13 C NMR (101 MHz, CDCl3) spectrum of 6b. S-53

54 Figure S44 COSY 2D NMR (CDCl3) spectrum of 6b. S-54

55 Figure S45 HSQC 2D NMR (CDCl3) spectrum of 6b. S-55

56 Figure S46 1 H NMR (400 MHz, CDCl3) spectrum of 6c. S-56

57 Figure S47 13 C NMR (101 MHz, CDCl3) spectrum of 6c. S-57

58 Figure S48 1 H NMR (400 MHz, CDCl3) spectrum of 7a. S-58

59 Figure S49 13 C NMR (101 MHz, CDCl3) spectrum of 7a. S-59

60 Figure S50 1 H NMR (400 MHz, CDCl3) spectrum of 7b. S-60

61 Figure S51 13 C NMR (101 MHz, CDCl3) spectrum of 7b. S-61

62 Figure S52 COSY 2D NMR (CDCl3) spectrum of 7b. S-62

63 Figure S53 HSQC 2D NMR (CDCl3) spectrum of 7b. S-63

64 Figure S54 1 H NMR (400 MHz, CDCl3) spectrum of 7c. S-64

65 Figure S55 13 C NMR (101 MHz, CDCl3) spectrum of 7c. S-65

66 High-resolution Mass Spectrometry Data Figure S56 - HRMS-ESI TOF of compound 4. S-66

67 Figure S57 - HRMS-ESI TOF of compound 5a. S-67

68 Figure S58 - HRMS-ESI TOF of compound 5b. S-68

69 Figure S59 - HRMS-ESI TOF of compound 5c. S-69

70 Figure S60 - HRMS-ESI TOF of compound 6a. S-70

71 Figure S61 - HRMS-ESI TOF of compound 6b. S-71

72 Figure S62 - HRMS-ESI TOF of compound 6c. S-72

73 Figure S63 - HRMS-ESI TOF of compound 7a. S-73

74 Figure S64 - HRMS-ESI TOF of compound 7b. S-74

75 Figure S65 - HRMS-ESI TOF of compound 7c. References 1. Cui, L.; Puerto, M.; López-Salinas, J. L.; Biswal, S. L.; Hirasaki, G. J. Improved Methylene Blue Two-Phase Titration Method for Determining Cationic Surfactant Concentration in High-Salinity Brine. Anal. Chem. 2016, 86, S-75