Patent ID: 12247106

EXAMPLES

Preparation of the Samples

Example 1: Preparation of 3-(4-bromobutoxy)methylsiloxane

A 250 ml three neck round bottomed flask was degassed under high vacuum (1−3mbar) and flushed with argon. Then, 200 μL of Karstedt (2% of Pt in the catalyst, 0.1% mol in the mixture) and toluene (50 mL, dried over molecular sieves) were added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then tetrahydrofuran (18.5 mL, dried over molecular sieves) and allyl bromide (19.8 mL, 97%) were added into the system. Polyhydridomethylsiloxane (14.9 mL, Mn 1900 g/mol) were added dropwise. The mixture was stirred and refluxed at 100° C. inside under inert atmosphere (Ar) until complete conversion of the SiH groups was achieved (the reaction was followed by1H-NMR). The mixture (when necessary) was decolorized by adding activated carbon and an excess of pentane and stirred for 16 h at room temperature. The crude was filtrated trough celite, and the solvents and volatiles were evaporated under vacuum. The obtained product (yield 80-90%) was a colorless, transparent viscous liquid. The molecular weight and structure of the product was confirmed by GPC (Mn=4882 g/mol, PDI 2.190) and NMR spectroscopy.

Example 2: Preparation of (3-(4(polymethylsiloxane)butoxy) pyridinium bromide

A 25 ml two neck round bottomed flask was degassed under high vacuum (1−3mbar) and flushed with argon. Ethanol (5 mL, dried over molecular sieves) and toluene (5 mL, dried over molecular sieves) are added. Halosilated intermediate obtained according to Example 1 is added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then pyridine (1.85 mL, 99%) was added into the system. The mixture was stirred (oil bath temperature: 75° C.) under inert atmosphere (Ar) until complete quaternization was achieved (the reaction was followed by1H-NMR). The solvents and volatiles were evaporated under vacuum. The obtained product (yield 95-100%) was a slightly yellow to yellow, transparent to milky, high viscous, sticky liquid. The molecular weight and structure of the product was confirmed by NMR spectroscopy.

Example 3: Preparation of (3-(4(polymethylsiloxane)pentoxy) pyridinium bromide

The procedure is the same as shown in Example 2. The halosilated intermediate has a 4-bromopentoxy-side-g roup.

Example 4: Preparation of (3-(4(polymethylsiloxane)hexyloxy) pyridnium bromide

The procedure is the same as shown in Example 2. The halosilated intermediate has a 4-bromohexyloxy-side-group.

Example 5: Preparation of (3-(4(polymethylsiloxane)butoxy) 1-methyl-1H-imidazol-3-ium bromide

A 25 ml two neck round bottomed flask was degassed under high vacuum (1−3mbar) and flushed with argon. Ethanol (5 mL, dried over molecular sieves) and toluene (5 mL, dried over molecular sieves) are added. Halosilated intermediate obtained according to Example 1 is added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then 1-methyl-1H-imidazole (1.85 mL, 99%) was added into the system. The mixture was stirred (oil bath temperature: 75° C.) under inert atmosphere (Ar) until complete quaternization was achieved (the reaction was followed by1H-NMR). The solvents and volatiles were evaporated under vacuum. The obtained product (yield 95-100%) was a yellow to orange, transparent to milky, high viscous, sticky liquid. The molecular weight and structure of the product was confirmed by NMR spectroscopy.

Example 6: Preparation of (3-(4(polymethylsiloxane)pentoxy) 1-methyl-1H-imidazol-3-ium bromide

The procedure is the same as shown in Example 5. The halosilated intermediate has a 4-bromopentoxy-side-group.

Example 7: Preparation of (3-(4(polymethylsiloxane)hexyloxy) 1-methyl-1H-imidazol-3-ium bromide

The procedure is the same as shown in Example 5. The halosilated intermediate has a 4-bromohexyloxy-side-group.

Example 8: Preparation of (3-(4(polymethylsiloxane)butoxy) triethylammonium bromide

A 25 ml two neck round bottomed flask was degassed under high vacuum (1−3mbar) and flushed with argon. Ethanol (5 mL, dried over molecular sieves) and toluene (5 mL, dried over molecular sieves) are added. Halosilated intermediate obtained according to Example 1 is added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then triethylamine (3.22 mL) was added into the system. The mixture was stirred (oil bath temperature: 75° C.) under inert atmosphere (Ar) until complete quaternization was achieved (the reaction was followed by1H-NMR). The solvents and volatiles were evaporated under vacuum. The obtained product (yield 95-100%) was a white, high viscous, waxy liquid. The molecular weight and structure of the product was confirmed by NMR spectroscopy.

Example 9: Preparation of (3-(4(polymethylsiloxane)butoxy) trimethylammonium bromide

A 25 ml two neck round bottomed flask was degassed under high vacuum (1−3mbar) and flushed with argon. Tetrahydrofuran (5 mL, dried over molecular sieves) is added. Halosilated intermediate obtained according to Example 1 is added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then trimethylamine (5.32 mL, 28% in water, ca. 4.3 mol/L) was added into the system. The mixture was stirred (oil bath temperature: 75° C.) under inert atmosphere (Ar) until complete quaternization was achieved (the reaction was followed by1H-NMR). The solvents and volatiles were evaporated under vacuum. The obtained product (yield 95-100%) was a white, high viscous, waxy liquid. The molecular weight and structure of the product was confirmed by NMR spectroscopy.

Example 10: Preparation of (3-(4(polymethylsiloxane)butoxy) 1-butyl-1H-imidazol-3-ium bromide

A 25 ml two neck round bottomed flask was degassed under high vacuum (1−3mbar) and flushed with argon. Ethanol (5 mL, dried over molecular sieves) and toluene (5 mL, dried over molecular sieves) are added. Halosilated intermediate obtained according to Example 1 is added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then 1-butyl-1H-imidazole (3.05 mL, 99%) was added into the system. The mixture was stirred (oil bath temperature: 75° C.) under inert atmosphere (Ar) until complete quaternization was achieved (the reaction was followed by1H-NMR). The solvents and volatiles were evaporated under vacuum. The obtained product (yield 95-100%) was a colourless, transparent to milky, viscous, sticky liquid. The molecular weight and structure of the product was confirmed by NMR spectroscopy.

Example 11: Preparation of (3-(4(polymethylsiloxane)pentoxy) 1-butyl-1H-imidazol-3-ium bromide

The procedure is the same as shown in Example 10. The halosilated intermediate has a 4-bromopentoxy-side-group.

Example 12: Preparation of (3-(4(polymethylsiloxane)hexyloxy) 1-butyl-1H-imidazol-3-ium bromide

The procedure is the same as shown in Example 10. The halosilated intermediate has a 4-bromohexyloxy-side-group.

NMR-Spectroscopy:

All NMR measurements were done on a Bruker 300 MHz, 400 MHz and 600 MHz instrument with deuterated DMSO and methanol as solvent. All the samples were measured at room temperature (297 K). The chemical shifts are given in ppm. The calibration of the chemical shifts in 1H spectra was carried out by using the shifts of the deuterated solvents (DMSO-d6, δH 2.49, 39.7; CD3δD, OH 3.31, 49.0).

GPC:

Gel permeation chromatography was carried out using HP1090 II Chromatography with DAD detector (HEWLETT PACKARD) at 40° C. Tetrahydrofuran (THF) was used as an eluent. THF was passed through three PSS SDV gel columns with molecular weight ranges of 102, 103 and 104 g-mol-1 with a flow rate of 0.9 ml·min-1. The calibration of the device was carried out using polystyrene standards.

Antimicrobial Activity Tests

Kirby-Bauer Test (Zone of Inhibition):

The Kirby-Bauer Test is also known as Agar Diffusion Test and can be used for determination of antimicrobial activity in combination with diffusion properties. The utilized strains areAspergillus brasiliensis(ATCC 16404),Staphylococcus aureus(ATCC 6538) andExophiala dermatitidis(isolate). A suspension of the bacterial or fungal strain of interest is spread evenly over the face of a sterile agar plate. The antimicrobial test substrate (preferential liquid aggregation state) is applied to the center of the agar plate onto a small filter paper. The agar plate is incubated for a defined time at a temperature suitable for the test microorganisms. If the test substrate leaches from the filter paper into the agar and it further contains antimicrobial activity, a zone of inhibition is formed around the filter paper. The larger the number in Table 1, the better the antimicrobial effect.

Minimum Inhibitory Concentration (MIC):

The MIC is an antimicrobial testing method to detect the lowest concentration of an antimicrobial agent that prevents visible growth of bacteria or molds. The utilized strains areCandida albicans(ATCC 10231) andStaphylococcus aureus(ATCC 6538). The evaluation is done optically. The antimicrobial activity is given when the solution is still clear. The concentrations appear from a serial dilution.

TABLE 1Test Results of Kirby-Bauer TestZone of Inhibition [mm] (maximum 45 mm)AspergillusStaphylococcusbrasiliensisExophialaaureusSamples(ATCC 16404)dermatitidis(ATCC 6538)DMSO0.00.0n.dBardac ©4.511.412.1Bardac © 1:102.05.38.0Bardac © 1:1001.54.34.5Pyridine0.01.01.0Pyridine 1:100.00.00.0Pyridine 1:1000.00.00.01-methyl-1H-imidazole3.512.36.51-methyl-1H-imidazole0.00.00.01:101-methyl-1H-imidazole0.00.00.01:1001-Butyl-1H-imidazole5.015.011.0Example 21.04.42.0Example 30.06.06.0Example 40.07.06.0Example 54.48.810.5Example 60.06.07.0Example 70.09.07.0Example 103.57.89.9Example 112.88.38.3Example 121.88.38.0

DMSO was the utilized solvent in the test, the amines were utilized in the reaction, and Bardac© is a disinfectant. The numbers such as 1:10 or 1:100 show the dilution ratio.

MIC test results are given in ppm in Table 2.

TABLE 2Test Results of MICStaphylococcus aureusCandida albicans(ATCC 6538)(ATCC 10231)Example 225625Example 5782500Example 10391250Example 1113625Example 1213625