POLYMER CONETWORKS OF POLY(PYRIDINE-(METH)-ACRYLAMIDE) DERIVATIVES- CROSSLINKED BY TRANSITION METAL IONS-AND LINKED BY POLYDIMETHYLSILOXANE DERIVATIVES

Abstract

Metallo supramolecular polymer conetworks (MSMC) of poly[r(alkyl).sub.a-N-(pyridin-s-yl) (meth)-acrylamide moiety].sub.m,n derivatives-complexed to a transition metal cation-linked by poly(dimethylsiloxane).sub.palkyl-(meth)-acrylate moiety derivatives, wherein a is 0 or 1 or 2, p is an integer selected from the group consisting of from 50 to 70 and of from 120 to 180, r is integer of from 0 to 4, and s is an integer of from 2 to 4, and m and n, independently, are integers of from 5 to 11. These MSMC can be used as film or coating on a substrate and are exhibiting self-healing and bacterial anti-adhesion properties.

Claims

1.-20. (canceled)

21. A metallo supramolecular polymer conetworks (MSMC) of poly[r(alkyl).sub.a-N-(pyridin-s-yl) (meth)-acrylamide moiety].sub.m,n derivatives complexed to a transition metal cation-linked by poly(dimethylsiloxane).sub.palkyl-(meth)-acrylate moiety derivatives, wherein a is 0 or 1 or 2, p is an integer selected from the group consisting of from 50 to 70 and of from 120 to 180, r is integer of from 0 to 4, and s is an integer of from 2 to 4, and m and n, independently, are integers of from 5 to 11.

22. The metallo supramolecular polymer conetworks according to claim 21, wherein the (meth)-acrylate moiety derivatives are at least one of acrylate and methacrylate derivatives.

23. The metallo supramolecular polymer conetworks according to claim 21, wherein the transition metal cation is selected form the group consisting of Zinc and Mn cations.

24. The metallo supramolecular polymer conetworks according claim 21, wherein the alkyl groups are at least one selected from the group consisting of methyl, ethyl, propyl and butyl, or mixture thereof.

25. The metallo supramolecular polymer conetworks according to claim 21, wherein the inorganic anion is chloride or nitrate thereof

26. The metallo supramolecular polymer conetworks according claim 21, wherein p is selected from the group consisting of from 60 to 70 and of from 130 to 170, of from 65 to 70 and of from 145 to 160.

27. The metallo supramolecular polymer conetworks according to claim 21, wherein s is 4.

28. A method of preparing a metallo supramolecular polymer conetworks (MSMC) of poly[r(alkyl).sub.a-N-(pyridin-s-yl) (meth)-acrylamide moiety].sub.m,n derivatives complexed to a transition metal cation-linked by poly(dimethylsiloxane).sub.palkyl-(meth)-acrylate moiety derivatives, wherein a is 0 or 1 or 2, p is an integer selected from the group consisting of from 50 to 70 and of from 120 to 180, r is integer of from 0 to 4, and s is an integer of from 2 to 4, and m and n, independently, are integers of from 5 to 11, comprising the following steps of: providing a reaction medium comprising a mixture of (alkyloxy)-(meth)-acrylate moiety derivatives-poly(dimethylsiloxane).sub.p type compounds wherein p is an integer selected from the group consisting of from 50 to 70 and of from 120 to 180 and an active ester of pentafluorophenyl-(meth)acrylate moiety, and performing an UV-initiated polymerization using a photoinitiator, for the obtention of poly[(pentafluorophenyl-(meth)-acrylate moiety].sub.m,n derivatives linked by poly(dimethylsiloxane).sub.palkyl-(meth)-acrylate moiety derivatives; reacting the product obtained in step a) with an r-amino(alkyl).sub.a-N-s(pyridine) for obtaining poly[r-(alkyl).sub.a-N-(pyridin-s-yl) (meth)-acrylamide moiety].sub.m,n derivatives linked by poly(dimethylsiloxane).sub.palkyl-(meth)-acrylate moiety derivatives; complexation of the derivatives obtained in step b) by a transition metal cation in an organic solvent.

29. The method according to claim 28, wherein the (alkyloxy)-(meth)-acrylate moiety derivatives-poly(dimethylsiloxane).sub.p type compounds of step a), are exhibiting viscosity of from 50 to 90 cSt, having a Mn of from about 4000-5000, or 125-250 cSt, having a Mn of from about 8000 to 11 000.

30. The method according to claim 28, wherein the UV-initiated polymerization of step a) is carried out of from 2 to 5 min.

31. The method according to any of claim 28, wherein the amount of the active ester in the mixture is of from 45 wt % to 60 wt %, the amount of the poly(dimethylsiloxane).sub.p moieties in the mixture is of from 40 wt % to 55% wt %, the amount of an organic solvent, is of from 5 to 10 wt %.

32. The method according to claim 28, wherein the amount range of the r-amino(alkyl)a-N-s(pyridine) compound in the reaction medium of step b) is advantageously of from 1.5 molar eq. to 2.6 molar eq. based on the poly[(pentafluorylphenyl-(meth)acrylate moiety].sub.m,n derivatives linked by poly(dimethylsiloxane).sub.palkyl-(meth)acrylate moiety derivatives molar content.

33. The method according claim 28, wherein the amount of transition metal salt is in the range of from 0.03 M/L to 0.05 M/L.

34. A method for preparing a material coated on a substrate, the material comprising a metallo supramolecular polymer conetworks (MSMC) of poly[r(alkyl).sub.a-N-(pyridin-s-yl) (meth)-acrylamide moiety].sub.m,n derivatives complexed to a transition metal cation-linked by poly(dimethylsiloxane).sub.palkyl-(meth)-acrylate moiety derivatives, wherein a is 0 or 1 or 2, p is an integer selected from the group consisting of from 50 to 70 and of from 120 to 180, r is integer of from 0 to 4, and s is an integer of from 2 to 4, and m and n, independently, are integers of from 5 to 11, said method comprising the following of step of: grafting s(trialkyloxy-silyl)alkyl(meth)-acrylate derivatives onto the substrate, providing a reaction medium comprising a mixture of (alkyloxy)-(meth)-acrylate moiety derivatives-poly(dimethylsiloxane).sub.p type compounds wherein p is an integer selected from the group consisting of from 50 to 70 and of from 120 to 180, and an active ester comprising a pentafluorophenyl-(meth)-acrylate moiety and a photoinitiator, contacting said mixture with the functionalized substrate of step 1), performing an UV-initiated polymerization, for the obtention poly[(pentafluorophenyl-(meth)-acrylate moiety]m,n derivatives linked by poly(dimethylsiloxane).sub.palkyl-(meth)-acrylate moiety derivatives bound to the functionalized substrate; reacting the poly[(pentafluorophenyl-(meth)-acrylate moiety]m,n linked by poly(dimethylsiloxane).sub.palkyl-(meth)-acrylate moiety derivatives which are bound to the functionalized substrate, with an r-amino(alkyl)a-N-s(pyridine) for obtaining poly[r-(alkyl).sub.a-N-(pyridin-s-yl) (meth)-acrylamide moiety].sub.m,n derivatives linked by poly(dimethylsiloxane).sub.palkyl-(meth)-acrylate moiety derivatives, bound to the functionalized substrate; complexation of the derivatives obtained in step 3), which are bound to the functionalized substrate, by a transition metal cation in an organic solvent.

35. The method according to claim 34, wherein, in the step 1), the alkyl groups in s(trialkyloxy-silyl)alkyl(meth)-acrylate derivatives are selected from the group consisting of methyl, ethyl, propyl, butyl or mixtures thereof.

36. The method according to claim 34, wherein concentrations of s(trialkyloxy-silyl) alkyl(meth)acrylate derivatives of the step 1) in an organic solvent are comprised in a range of values of from 10 vol % to 30 vol %.

37. The method according to claim 36, wherein the (trialkyloxy-silyl)alkyl(meth)acrylate derivatives are selected from the group consisting of 1-(trimethoxysilyl)methylacrylate, 2-(trimethoxysilyl)ethylacrylate, 3-(trimethoxysilyl)propylacrylate, 1-(trimethoxysilyl)methylmethacrylate, 2-(trimethoxysilyl)ethylmethacrylate, 3-(trimethoxysilyl)propylmethacrylate 1-(triethoxysilyl)methylacrylate, 2-(triethoxysilyl)ethylacrylate, 3-(triethoxysilyl)propylacrylate, 1-(triethoxysilyl)methylmethacrylate, 2-(triethoxysilyl)ethylmethacrylate, 3-(triethoxysilyl)propylmethacrylate, or a mixture thereof.

Description

DRAWINGS

[0094] Other features and advantages of the present invention will be readily understood from the following non limitative examples and drawings:

[0095] FIG. 1 is a schematic three-step synthesis of an MSMC: poly[N-(pyridine-4-yl)(methacrylamide moiety].sub.m,n derivatives, complexed to Zn(II) cations, linked by poly(dimethylsiloxane).sub.p α,ω-propylmethacrylate moiety derivatives (PNP4A-Zn(II)-I-PDMS) (“a” is 0) in accordance with various embodiment of the present disclosure.

[0096] FIG. 2 shows ATM-FTIR spectra of poly[(pentafluorylphenyl-acrylate).sub.6 moiety (PPFPA) linked by poly(dimethylsiloxane).sub.60 α,ω-propyl-methacrylate moiety (PDMS.sub.60)-(PPFAP-I-PDMS.sub.60) and of poly[N-(pyridin-4-yl) acrylamide].sub.6 linked by poly(dimethylsiloxane).sub.60 α,ω-propylmethacrylate (PNP4A-I-PDMS.sub.60) in accordance with various embodiment of the present disclosure.

[0097] FIG. 3 shows a DSC of PPFAP-I-PDMS.sub.60 and PNP4A-I-PDMS.sub.60, PDMS.sub.60 being noted PDMS in accordance with various embodiment of the present disclosure.

[0098] FIG. 4 represents AFM mode images of the cross-section of PPFPA-I-PDMS.sub.60 (FIG. 4a) PNP4A-I-PDMS.sub.60 (FIG. 4b) and (PNP4A-Zn(II)-I-PDMS.sub.60) (FIG. 4c) in accordance with various embodiment of the present disclosure.

[0099] FIG. 5 shows solid state 13C NMR spectra of the PNP4A-I-PDMS.sub.60 and the PNP4A-I-PDMS.sub.60 complexed by ZnCl.sub.2 in accordance with various embodiment of the present disclosure.

[0100] FIG. 6 shows an optical microscopy image of cross-section of scratched free standing polymer film of PNP4A-I-PDMS.sub.60 complexed by ZnCl.sub.2 in accordance with various embodiment of the present disclosure.

[0101] FIG. 7 depicts self-healing of scratches in PNP4A-I-PDMS.sub.60 complexed by ZnCl.sub.2. Optical microscopy images of scratched free standing polymer films (a and c) and of the same sample after 16 hours at 80° C. (b) and 120° C. (d) in accordance with various embodiment of the present disclosure.

[0102] FIG. 8 represents uniaxial tensile tests of PNP4A-I-PDMS.sub.60 complexed by ZnCl.sub.2, and PNP4A-I-PDMS.sub.60 without Zn(II) (dashed lines) at a strain rate of 10 mm min.sup.−1; Pristine samples, samples after scratch damage, and sample after healing of scratches at 120° C. for 16 hours in accordance with various embodiment of the present disclosure.

[0103] FIG. 9 is a schematic three-step synthesis of an MSMC on a functionalized glass substrate: poly[2-ethyl-N-(pyridin-4-yl)]acrylamide].sub.m,n complexed to Zn(II) cations-linked by poly(dimethylsiloxane).sub.p- α,ω-propylmethacrylate (PNP4EA-Zn(II))-I-PDMS) in accordance with various embodiment of the present disclosure.

[0104] FIG. 10 shows transmittance measurements of functionalized glass substrate coated with PPFAP-I-PDMS.sub.130 (PPFAP and PDMS having the same meanings as in FIG. 1 & 2), PNP4EA-I-PDMS.sub.130 (not complexed to Zn(II)), PNP4EA-Zn(II)-I-PDMS.sub.130 in accordance with various embodiment of the present disclosure.

[0105] FIG. 11 are surface AFM height and phase mode images of PPFPA-I-PDMS.sub.130 (a: height and b: phase); PNP4EA-I-PDMS.sub.130 (c: height and d: phase) and PNP4EA-I-PDMS.sub.130 (e: height and f: phase) loaded with ZnCl.sub.2 polymer coatings. (Scale bar: 100 nm) in accordance with various embodiment of the present disclosure.

[0106] FIG. 12 represents volumetric degree of swelling SVol of PNP4EA-I-PDMS.sub.130 and PNP4EA-Zn(II)-I-PDMS.sub.130 polymer conetworks films in various organic solvents and in water. (mean values of n=3 independent measurements, error bars represent SD) in accordance with various embodiment of the present disclosure.

[0107] FIG. 13 are optical microscope images of the PNP4EA-Zn(II)-I-PDMS.sub.130 glass-coated polymer coating of the damaged surfaces (a to d) and after self-healing (e to h) in presence of THF (e), n-hexane (f), 2-propanol (g) and DMF (h) in accordance with various embodiment of the present disclosure.

[0108] FIG. 14 represents the numbers of bacteria present in a glass substrate covered by PNP4EA-Zn(II)-I-PDMS.sub.130 with comparison with uncoated glass in accordance with various embodiment of the present disclosure.

[0109] Properties, features and technical effects of the following examples are not limitative and could be generalized to the inventive concept of the invention.

DETAILED DESCRIPTION

Materials

[0110] All solvents (purity>95%) were purchased from Sigma-Aldrich. Pentafluorophenyl acrylate (purity>95%), 4-Aminopyridine, 4-(2-Aminoethyl)pyridine were purchased from TCI. α,ω-propyloxymethacrylate-terminated poly(dimethylsiloxane).sub.60 (PDMS60, viscosity of 125-250 cSt., Mn (1HNMR)=8400 or α,ω-propyloxymethacrylate-terminated poly(dimethylsiloxane).sub.100 of viscosity of 50-90 cSt, Mn (.sup.1HNMR)=4200) were purchased from ABCR (Germany). Irgacure 651 (2,2-dimethoxy-1,2-diphenylethan-1-one) (99%), 3-(trimethoxysilyl)propyl methacrylate (98%) and ZnCl.sub.2 (≥98%) were purchased from Sigma Aldrich. All reagents were used without further purification unless otherwise noted. Glass slides (76×26 mm and 1 mm thick) were purchased from Carl Roth. Reactants devoted to glass substrate with the MSMC bacterial analysis are given in the Examples.

UV Photopolymerization

[0111] A customized UV conveyor system designed by Novachem and equipped with an UV-C Flood Lamp, fitted with Mercury bulb, with peak emission at 225 nm was used.

Infrared (IR) Spectroscopy

[0112] Attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectra were recorded on a Bruker Tensor 27 spectrometer on the surface of the polymer conetworks. Proteus software was used to collect and analyze the data.

Atomic Force Microscopy (AFM)

[0113] AFM analysis was conducted on a scanning probe microscope MFP3D infinity (Asylum Research, Santa Barbara). Measurements were performed at ambient conditions in tapping mode with a silicon AFM probe AC160TS-R3 (Olympus, Japan) with a force constant of 26 N m−1 and resonance frequency of 300 kHz. Topography was acquired by maintaining the amplitude at the first cantilever resonance constant via the electronic feedback loops. All the nanomechanical measurements of the coating were performed in fast force mapping with 30 nN force setpoint, enabling the recording of topography and a force-curve at each pixels of the 256 pixels×256 pixels images. These measurements were performed using a AC240TS tip (2.4 N/m (Olympus). Tips spring constant and inverse optical lever sensitivities were obtained with the Sadler non-contact. The polystyrene/low density polyethylene (PS/LDPE) (Bruker, Santa Barbara) copolymer was used as the reference, while the LDPE domains were used to calibrate the AFM tip and for the fitting of the force curves. The viscoelastic properties of the surface were determined according to Oliver-Pharr model. The recorded data were fitted according to the parameters determined from the LDPE analysis, and elastic modulus were extracted from of the entire scanned surface.

Optical Microscopy

[0114] The microscopy images were recorded on Nikon Eclipse LV 100 (3×2 Stage Japan) equipped with LU Plan Fluor objectives. 5×/0.15 A WD 18 and 10×/0.30 A WD15 were mainly used. The surfaces of APCNs films were captured using NIS Elements BR 2.30 software with a resolution of 800×600 pixels.

ICP-MS

[0115] The polymer samples were mineralized in microwave oven (Multiwave Pro, Anton Paar, Graz, Austria). 7 mL of nitric acid (HNO.sub.3 for trace analysis min 67%, LGC Standards, Molsheim, France) and 3 mL of H.sub.2O.sub.2 (30% w/w, Suprapur, Merck, VWR International, Leuven, Belgium) were added to 10 mg of the samples and mineralization was performed at 200° C. under high pressure of 30 bars. At the end of the mineralization process, samples were diluted up to 25 mL of ultra-pure water. The samples were then diluted and zinc was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS 7900, Agilent Technologies, Santa Clara, Calif., United States).

Swelling Measurements

[0116] Dry samples of 0.5-2 cm.sup.2 were immersed into THF, hexane, water or DMF overnight. The edge lengths L.sub.i before and after swelling were measured with a ruler and the average volumetric degree of swelling S.sub.vol was subsequently determined from the sample edges (length L) as with n denoting the number of edges.

[00001]$\mathrm{Svol}=\frac{1}{n}\stackrel{n}{\underset{i=1}{.Math.}}\left(\frac{\mathrm{Li},\mathrm{swollen}}{\mathrm{Li},\mathrm{dry}}\right)$

UV-Vis Analysis

[0117] The transmittance of the glass-coated polymer conetwork was measured on Perkin Elmer Lambda 35 UV-visible spectroscopy.

Differential Scanning Calorimetry (DSC)

[0118] DSC traces were recorded on a NETZSCH DSC 240 F1. A heating rate of 20 K min.sup.−1 was set from −170° C. to 200° C. as the temperature range under nitrogen flow. The data was collected and analyzed by NETZSCH Proteus Thermal Analysis software. The glass transition temperatures were determined on the mid-point of the transition for the second heating cycle.

Tensile Tests

[0119] Mechanical tests were performed on Instron (59-67) tensile test machine. The samples were cut into rectangular strips of 5×1 cm2 and gripped using pneumatic clamps. Tests were performed with a strain rate of 10 mm min−1. The Young's moduli for MSMC films were calculated from the slope of the initial linear region of stress-stain curves. Each measurement was repeated at least three times. Mean values and standard deviation are reported.

Elemental Analysis

[0120] Elemental analysis of the polymer conetworks films were performed at Mikroanalytisches Labor Pascher Germany. Different methods were used to measure the content of each element: conductometric detection after combustion was used for carbon; IR-detection after combustion was used for hydrogen; volumetric detection after combustion (according to Dumas) was used for nitrogen and detection by ion-sensitive electrode after Schöniger combustion was used for fluorine.

Bacterial Adhesion Test

[0121] The surfaces comprising MSMC were pre-sterilized by autoclaving at 105° C., a process validated by a preliminary test. Each surface was glued in a 35 mm petri dish with an adhesive (Aqua Silicone, Den Braven, Netherlands) to prevent flotation of the sample.

Preparation of the Bacterial Suspension

[0122] The study was carried out with the strain Escherichia coli SCC1 (E. coli), the culture medium chosen for the study is a non-nutritive medium NaCl (9 g/L). The bacteria stored in the freezer at −80° C. were cultured on D-2 (2 days before experiments) on Luria Broth (LB) agar for obtaining colonies. On D-1 a solution of nutrient medium LB was inoculated with a colony of E. coli. coli and incubated at 30° C., 15 h-20 h.

[0123] On D-0 (the day of the experiment), a new bacterial culture was prepared with 10%-15% of the preculture and incubated for 3 h-5 h at 30° C. This culture was centrifuged at 3500 rpm for 20 min, the pellet of bacteria was resuspended in NaCl (9 g/L) to obtain an OD (optical density) at 600 nm of 0.01.

[0124] The surfaces were incubated in 3-5 mL of the bacterial solution prepared according to the previous protocol for 1 hour at 30° C. and then rinsed 5-10 times in NaCl at 9 g/l before being observed under the LSM800 (Zeiss) right confocal microscope.

[0125] On each surface 10 random areas were imaged and analyzed using FiJi image processing and analysis software. In each of these areas the number of bacteria was determined.

Example 1: Step a): Synthesis of Derivatives of poly[(pentafluorylphenyl)acrylate].SUB.6 .Moiety (PPFPA) Linked by poly(dimethylsiloxane).SUB.60 .α,ω-propylmethacrylate moiety (PDMS).SUB.60.-(PPFPA-I-PDMS.SUB.60.)

[0126] The PPFPA-I-PDMS60 conetwork precursors were synthesized by UV-initiated polymerization in the presence of Irgacure 651 (2,2-dimethoxy-1,2-diphenylethan-1-one. A reaction medium, comprising a mixture containing 51 wt % of pentafluorophenyl acrylate (PFPA) and 48.5 wt % of α,ω-propyloxymethacrylate-terminated poly(dimethylsiloxane).sub.60, was prepared, and further diluted with 10 wt % of THF into which the initiator Irgacure 651 had been dissolved at 0.5 wt % (FIG. 1). A U-shaped 500 μm thick Teflon membrane was tighten between two glass slides covered with a brown polypropylene (PP) tape, forming a mould (not shown). The monomer mixture was filled into the mould and irradiated with UV light during 2.5 min. The resulting freestanding and optically transparent film of ca. 430 μm thick, 7 cm length, and 1.7 cm width, was transferred into a screw cap bottle and washed in THF at 60° C. overnight in order to remove unreacted PFPA and PDMS cross-linker. The content of PPFPA in the polymer was 43 wt % PPFPA as measured by elemental analysis. The FTIR spectrum of the polymer conetwork precursor revealed the characteristic absorption bands of the active ester at 1783 cm.sup.−1 (C═O stretch) and 1571 cm.sup.−1 (the fluorinated aromatic ring stretch) as shown in FIG. 2. DSC analysis of the precursor conetwork revealed two distinct glass transition temperatures at ca. −120° C. and 44° C. They correspond to the PDMS.sub.60 and active ester phases, respectively (FIG. 3). FT-IR measurements: u=2963, 1783, 1665, 1571, 1471, 1451, 1393, 1260, 1078, 990, 860, 795, 702, 623 (cm.sup.−1).

Example 2: Step b): Synthesis of poly[N-(pyridin-4-yl)acrylamide].SUB.6 .(Moiety III), Linked to poly(dimethylsiloxane).SUB.60 .α,ω-propylmethacrylate (Moiety II) (PNP4A-I-PDMS.SUB.60.)

[0127] 4-Aminopyridine (0.176 g-1,868 mmol) was dissolved in 50 mL of THF and the solution was transferred into a screw cap bottle (250 mL). A PPFPA-I-PDMS.sub.60 film (0.416 g-0.747 mmol of PPFPA) was immersed in the solution, and the bottle was placed overnight into glycerol bath heated at 60° C. to yield poly[(N-(pyridin-4-yl)acrylamide)]6-l-poly(dimethylsiloxane).sub.60 methacrylate (PNP4A-I-PDMS.sub.60).

[0128] According to the FTIR spectrum analysis, the peak assigned to the active ester disappeared and was replaced by the amide stretch signal at 1685 cm.sup.−1 and the pyridine ring vibration signal at 1592 cm.sup.−1 (FIG. 2). DSC analysis confirmed the functionalization by revealing a new Tg at 74° C. that can be assigned to the PNP4A phase (FIG. 3). Elemental analysis of nitrogen allowed to determine the concentration of PNP4A corresponding to 18.5 wt % corresponding to ca. 70% of the yield considering the determined content of the activated ester precursor. The higher glass transition temperature of PNP4A arises from stronger π-π interactions inherent to N-heterocyclic aromatic rings. It is worth noting that the Tg of the PDMS.sub.60 phase remained almost unchanged (ca. −118° C.).

[0129] The swelling ability of the polymer conetwork was tested in various organic solvents and water. One of the outstanding features is their ability to swell both in organic solvents and in water, which can be tuned by the composition of the polymer conetwork and its chemical functionality.

[0130] The polymer conetwork films were immersed in THF, a good solvent of the PNP4A and PDMS.sub.60 phases. An average volumetric degree of swelling (SVol) of 2.14±0.14 revealed a good swelling ability of the polymer conetwork in THF (FIG. 4). Immersing the film in n-hexane, a selective solvent of PDMS.sub.60, resulted in lower swelling (Svol=1.48±0.10), because the PNP4A phase did not swell. A slightly lower swelling ability of Svol=1.42±0.06 was determined in DMF, a selective solvent of the PNP4A phase. In contrast, when the films were immersed in water, they revealed a poor swelling ability with only a Svol of 1.07±0.10. Most likely, hydrophobic interactions between N-heterocyclic aromatic groups hindered the swelling of the polyacrylamide phase in water. The phase morphologies of the polymer conetworks was analyzed by AFM phase mode imaging. A contrast between hard and soft phases arising from their difference in energy dissipation is expected. The bulk morphology of the PPFPA-I-PDMS.sub.60 conetworks revealed phase-separated morphologies with interconnected spherical PDMS.sub.60 domains (ca. 10 nm in diameter) that are homogenously dispersed in the PPFPA matrix. The PNP4A-I-PDMS.sub.60 conetworks exhibited roundish PDMS60 domains similar to the morphology of the active ester-based conetworks. In addition, the phase morphologies were imaged on the surface of the synthesized polymer showing similar morphologies to bulk (FIG. 4b).

[0131] FT-IR: u=2962, 1732, 1685, 1592, 1521, 1450, 1412, 1355, 1258, 1169, 1083, 1064, 1011, 863, 792, 687, 661 (cm.sup.−1) Elemental analysis (unit: mass-%) of PNP4A-I-PDMS C 41.3, H 7.4, N 3.5

[0132] Example 3: Step c): Synthesis of MSMC: poly[N-(pyridine-4-yl)] acrylamide].sub.6 Complexed to Zn(II) Cation)] Linked by poly(dimethylsiloxane).sub.60-α,ω propylmethacrylate (PNP4A-Zn(Il)-I-PDMS.sub.60)

[0133] A PNP4A-I-PDMS60 polymer conetwork film (5×1 cm.sup.2) was immersed in 30 mL of THF into which ZnCl.sub.2 had been previously dissolved concentration of which is 0.038 M/L ZnCl.sub.2. The solution was heated to 60° C. overnight. The film was then rinsed in THF, and dried overnight under vacuum. The concentration of Zn(II) in the material was determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analysis to be 4.5±0.1 wt. %. This content corresponds to a molar ratio of PNP4A to Zn(II) close to 2:1. AFM revealed spherical interconnected PDMS.sub.60 domains in a PNP4A-Zn(II) phase (FIG. 4c). The PDMS.sub.60 domains are bigger, and the hydrophilic domains appear thinner than the domains of the metal-free APCN. Thus, the incorporation of metal ions does not change the overall phase morphology of (PNP4A-Zn(II)-I-PDMS.sub.60, but increases the size of hydrophobic domains, while it decreases the size of the hydrophilic domains due to the cross-linking of the PNP4A phase.

[0134] The complexation of Zn(II) ions by poly(N-(pyridin-4-yl)acrylamide) ligands was confirmed by solid-state NMR analysis. As shown in FIG. 5, the characteristic peaks of pyridine were shifted at 154 ppm CH(2), 148 ppm CH(4) and 128 ppm CH(3) for the PNP4A-I-PDMS.sub.60 conetwork, while for the polymer conetwork loaded with Zn(II) only two signals shifted at 152 CH (2 and 4) ppm and 130 ppm CH(3) were observed. As the pyridine carbon signals are the most impacted by the coordination bond between the aromatic nitrogen and Zn(II), one my conclude that Zn(II) ions are complexed solely by poly(N-(pyridin-4-yl)acrylamide) ligands. FT-IR: u=2962, 1732, 1684, 1615, 1521, 1450, 1412, 1355, 1258, 1169, 1083, 1064, 1011, 863, 792, 687, 661 (cm.sup.−1).

Example 4: Self-Healing Properties of MSMC Compound of Example 3

[0135] To demonstrate the self-healing ability of the MSMC of Example 3, the surface of sample was scratched using a scalpel leading to 10±3 μm scratch width and approximately 100 μm deep, representing approximately 25% of the polymer film thickness (FIG. 6). Then, the sample was placed in an oven and heated to 80° C. for 16 hours. Healing of the scratch was monitored by optical microscopy (FIG. 7). Under these conditions, the scratch closed but did not heal completely. However, when the temperature was increased to 120° C., the healing effect improved. The entire scratch healed, even though one could still observe a scar at the scratched area.

Example 5: Self-Healing Properties of MSMC Compound of Example 3 with Regard to Mechanical Properties

[0136] Another possibility to assess the self-healing of materials is to measure the recovery of their mechanical properties after damage and healing. To this end, tensile tests of polymer films were carried out (FIG. 8). A Young Modulus (E′) of 132±30 MPa with a tensile strength of 7.4±1.3 MPa and a strain at break of 0.31±0.04 were measured at a strain rate of 10 mm min−1 for PNP4A-I-PDMS.sub.60 loaded/complexed with ZnCl.sub.2. For comparison, the PNP4A-I-PDMS without Zn(II) exhibited a lower E′ of 25±5 MPa and a higher strain at break of 0.5, but a lower tensile strength (4.5±0.5 MPa). Thus, non-covalent cross-linking of the polymer conetwork by Zn(II) made it stiffer and strengthened it. Applying a scratch along the entire width of the strip and oriented perpendicular to the uniaxial deformation on the surface of PNP4A-I-PDMS.sub.60 films loaded with ZnCl.sub.2 reduced their mechanical properties. Polymer films broke into two parts at strain of only 0.07±0.02 (FIG. 8). Heating of scratched samples to 120° C. for 16 hours led to a strain at break of 0.25±0.03 i.e., self-heling of the scratches resulted in 80±8% recovery of strain at break. It should be noted that the polymers are covalently cross-linked in addition to the non-covalent crosslinks by the Zn(II) complexes. To demonstrate that the healing of the scratches is due to the reformation of non-covalent supramolecular crosslinks, scratches were applied on the surface of the polymer conetwork PNP4A-I-PDMS60 films that do not contain Zn(II). Tensile tests analysis revealed that heating the damaged sample at 120° C. for 16 hours did not improve the strain unlike the film loaded with Zn(II) as shown in FIG. 8 (dotted lines).

[0137] Additional examples relate the synthesis of PNP4EA-I-PDMS polymer conetworks loaded with ZnCl.sub.2 grafted of a glass substrate, in reference to FIG. 9. The steps of preparing the MSMC of the invention grafted on said substrate essentially include same steps as of examples 1-3.

Example 6: Steps 1-2)): Synthesis of Derivatives of poly[(pentafluorophenyl)acrylate].SUB.10 .Moiety Linked by poly(dimethylsiloxane).SUB.130 .α,ω-propylmethacrylate Moiety (PPFPA-I-PDMS.SUB.130.)

[0138] Glass slides (2.6×3 cm.sup.2) were immersed into Piranha solution (concentrated H.sub.2SO.sub.4/30% H.sub.2O.sub.2, 3:2, v:v) for 30 min, rinsed with water and ethanol, and dried in the oven at 55° C. for 15 min. The glass slides were then transferred in 5 mL solution of dry toluene containing 20 vol % concentration of 3-(trimethoxysilyl)propylmethacrylate. The reaction took place in a tightly closed screw cap bottle for 16 hours at room temperature. The glass slide was washed with toluene and ethanol and dried under vacuum.

[0139] The preparation of the glass-coated polymer consisted in preparing a mixture containing 55% wt of pentafluorophenyl acrylate (PFPA) and 45 wt % of α,ω-propyloxymethacrylate-terminated poly(dimethylsiloxane).sub.130, further diluted with 10 wt % of THF into which the initiator Irgacure 651 had been dissolved at 0.5 wt %. 100 μL of the solution was casted onto the functionalized glass substrate. A glass slide covered with a PP TESA tape was placed on top of the monomer solution and tightly sealed using the binder clips (not shown). The coating was irradiated under UV light for 2.5 min from each side of the glass slide. After removing the top slide, the coated glass slide was placed in THF overnight at room temperature to extract unreacted monomers. ATR-FTIR: u=2963, 1785, 1519, 1259, 1078, 993, 863, 788, 702 (cm.sup.−1).

Example 7: Step 3): Synthesis of Derivatives of poly[2-ethyl-N-(pyridin-4-yl)]acrylamide].SUB.10 .Linked by poly(dimethylsiloxane).SUB.130.-α,ω propylmethacrylate (PNP4EA-I-PDMS.SUB.130.) Covalently Attached to a Glass Substrate

[0140] The PPFPA-I-PDMS130 coating covalently attached onto the glass slide (2.6×3 cm.sup.2) was immersed in 10 mL of THF containing 4-(2-ethylamino)pyridine (0.010 g, 0.082 mmol). The screw cap bottle (50 mL) was placed in an oven heated at 60° C. for 4 hours. After the reaction, the coating was transferred into THF and heated at 60° C. for 2 hours to extract the residue of pentafluorophenol. The coating was then dried under vacuum before analysis. ATR-FTIR: u=3260, 3049, 2962, 1658, 1604, 1556, 1443, 1416, 1400, 1084, 1005, 865, 788, 701 (cm.sup.−1).

[0141] According to the FTIR spectrum analysis, the peak assigned to the active ester disappeared after the reaction and was replaced by the amide stretch signal at 1658 cm.sup.−1 and the pyridine ring vibration signal at 1604 cm.sup.−1 (FIG. 10). The transmittance of the polymer coating following the functionalization of pyridine ligand was measured and reached 90% (FIG. 2), indicating that the nanostructured morphologies remained unaltered, that was confirmed by AFM analysis (FIG. 11). The expected contrast between hard and soft phases, arising from their difference in energy dissipation, was evidenced. The bulk morphology of the PPFPA-I-PDMS.sub.130 conetworks revealed phase-separated morphologies with interconnected spherical PDMS.sub.130 domains (ca. 25 nm in diameter) that are homogenously dispersed in the PPFPA matrix (FIG. 11 a-b). The PNP4EA-I-PDMS conetworks exhibited roundish PDMS.sub.130 domains of 28 nm±2 nm in diameter with the same morphology of the active ester-based conetworks (FIG. 11 c-d). To determine the thickness of the polymer coating, the surface of the coating was scratched using a scalpel, and the scratched area was analysed by AFM, with a thickness of approximately 5 μm.

[0142] The PNP4EA-I-PDMS.sub.130 polymer conetworks films were immersed in THF, a good solvent of the PNP4EA and PDMS.sub.130 phases. An average volumetric degree of swelling (SVol) of 4.84±0.24 revealed a good swelling ability of the polymer conetwork in THF (FIG. 12). The films were immersed in 2-propanol, a selective solvent of PNP4EA phase with an average volumetric degree swelling of 4.4±0.06, in the same range as the one measured in THF. Immersing the film in n-hexane, a selective solvent of PDMS, resulted in much lower swelling (Svol=2.01±0.36), because the PNP4EA phase did not swell. Similarly, a lower swelling ability of Svol=2.03±0.21 was determined in dimethylformamide (DMF), a selective solvent of the PNP4EA phase. In contrast, when the films were immersed in water, they revealed a poor swelling ability with an Svol of only 1.03±0.11. Most likely, hydrophobic interactions between N-heterocyclic aromatic groups hindered the swelling of the polyacrylamide phase in water.

Example 8: Step 4): Complexation of Derivatives of Example 7 by ZnCl.SUB.2.: Obtention of PNP4EA-ZnCl.SUB.2.-I-PDMS.SUB.130 .Bound to the Functionalized Glass Substrate

[0143] The glass coated polymer (2.6×3 cm.sup.2 and 5 μm thick) conetwork of Example 7 was immersed in THF (10 mL) containing 0.5 10.sup.−3 g/mL of ZnCl.sub.2, and the solution was heated at 60° C. for 4 hours. The film was then rinsed in THF, and dried under vacuum overnight. The concentration of Zn(II) corresponding to 8.5±0.1 wt % was determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) by detaching the coating from the glass slide. The loading of metal complexes resulted in a slight decrease of transmittance from 90 to 80% in the visible range, and was assigned to the absorption of the PNP4EA-Zn(II) complexes embedded in the bulk of the coating (FIG. 10). AFM surface analysis revealed spherical interconnected PDMS130 domains in a PNP4EA-Zn(II) phase (FIG. 11 e-f). The PDMS.sub.130 domains are smaller, and the hydrophilic domains appear larger than the domains without Zn(II). Thus, the complexation of compound of Example 7 by Zn(II) into the PNP4EA-ZnCl.sub.2-I-PDMS.sub.130 decreased the size of hydrophobic domains (ca. 15 nm in diameter) due to the cross-linking of the PNP4EA phases by Zn(II).

[0144] The loading of ZnCl.sub.2 into the polymer conetwork film (Example 7) reduced the swelling ability of the polymer conetwork due to the cross-links formed by the metal complexes within the PNP4EA phase. The average volumetric degree of swelling decreased down to 1.94±0.28 and 1.29±0.21 for THF and 2-propanol, respectively. The difference in swelling was assigned to a higher solubility of PDMS130 in THF than 2-propanol. When the polymer conetwork film was immersed in n-hexane, the swelling ability of the film was not affected (SVol=2.20±0.01) because n-hexane does not expand the PNP4EA phase in which the PNP4EA-Zn(II) complexes are localized. In DMF, the SVol of 1.46±0.1 was determined. The slight decrease of the swelling property compared to THF and 2-propanol arises from the fact that DMF is a selective solvent for the PNP4EA phase and a good ligand for metal ions. Therefore, loading Zn(II) ions slightly reduced the swelling property. In water, no improvement in the swelling ability was observed since the interactions between N-heterocyclic aromatic groups prevail over ionic interactions in water.

Example 9: Scratch-Healing Properties of PNP4EA-ZnCl.SUB.2.-I-PDMS.SUB.130 .Covalently Attached to the Glass Substrate

[0145] The impact of the zinc cation on the surface property of the coating was assessed by AFM analysis. The loading of zinc cations into the polymer conetwork coating of Example 7 strengthened the network and thus improved the overall mechanical property of the coating. To highlight this effect, AFM analysis was performed using the friction force microscope (FFM) to determine the lateral forces that are acting between the AFM tip and the surface to be analyzed. The elastic modulus of the PNP4EA-I-PDMS130 surface was determined according to the Oliver-Pharr model and by using a copolymer based on polystyrene and low-density polyethylene (LDPE) as the reference for the calibration. The elastic modulus of the surface of the polymer coating was estimated at 14.01±0.6 MPa and the loading of Zn(II) ions strengthened the polymer conetwork by improving the elastic modulus to 26.27±2.00 MPa.

[0146] The scratch-healing property of the synthesized glass-coated polymers was tested on a polymer conetwork of PNP4EA-Zn(II)-I-PDMS.sub.130. The surface of the sample was scratched using a scalpel to form a 15 μm scratch width, and the scratch-healing property was verified by the optical microscope (FIG. 13 a-d). The extent of the scratch healing was tested by placing the scratched polymer coating in an oven heated to 80° C. No healing effect was observed at 80° C. even after 24 hours, due to the densely cross-linked polymer network that inhibited the mobility of the polymer chains needed for the healing ability. Therefore, the swelling property of the MSMC in organic solvent was exploited to improve the self-healing property. THF was tested as a non-selective solvent of the two phases, by dropping the solvent onto the scratched surface of the coating. The glass-coated polymer was then placed in an oven heated to 65° C. for two hours. Optical microscope images evidenced the healing effect, even though one could still observe a scar on the scratched area. (FIG. 13-e). On the other hand, no healing was observed for n-hexane solvent due to the collapse of the PNP4EA phase, which inhibited the healing property of the scratch. (FIG. 13-f) Therefore a selective solvent is used in the PNP4EA phases in order to improve the swelling of the supramolecularly cross-linked phases. 2-propanol and DMF, which are the selective solvents for the PNP4EA phases, were tested. To this end, 2-propanol was dropped on to the damaged surface before the coating was placed in an oven heated to 80° C. and optical microscopy images evidenced the healing of the scratch (FIG. 13-g). DMF was also tested and because of its higher boiling point, the healing temperature was set to 150° C. to avoid any remaining solvent in the polymer film after healing. Optical images confirmed the successful scratch-healing of the coating induced by the swelling effect of DMF. (FIG. 13-h) Despite the lower volumetric degree of swelling of the overall polymer conetwork film in DMF and 2-propanol measured at room temperature, the ability to selectively swell the PNP4EA phase at higher temperature enables the healing effect.

[0147] According to the invention transparent scratch-healing coating from metallo-supramolecular polymer conetworks is successfully prepared. The combination of their swelling property in organic solvent with the reversible interactions of metal complexes offers a self-healing coating with a robust mechanical property. These materials could be used for a protective coating, taking into account that the metal complexes embedded in the polymer matrix (MSMC) can widen the scope of the application towards conductive coatings, catalytic active surfaces or even for antifouling surfaces via the release of metal ions.

Example 10: Bacterial Anti-Adhesion Behavior of Compound Obtained in Example 3: PNP4A-ZnCl.SUB.2.-I-PDMS.SUB.60 .Bound to the Functionalized Glass Substrate

[0148] The functionalized glass substrate with PNP4A-ZnCl.sub.2-I-PDMS.sub.60 (which was prepared using the protocol of Examples 1-3 with 50 wt % of PFPA and 50 wt % PDMS.sub.60) of was sterilized in an autoclave at about 105°, which was validated by a preliminary test.

[0149] Each glass surface which was glued in a Petri dish of 35 mm owing to a glue (Aqua Silicone; Den Braven, The Netherlands.

[0150] Experiments were carried out with Escherichia coli SCC1 (E.coli) in a culture medium containing NaCl (9 g/L). Frozen Bacteria (−80° C.) were cultured at D-2 (2 days before experiments) on agar Luria Broth (LB) for obtaining bacteria colonies. At D-1, a solution of a LB nutrient medium was inoculated by a E. Coli colony and further incubated at 30° C. during 18 h. At D-0, a new bacteria culture was prepared with 10% of the pre-culture and incubated 4 h at 30° C. This culture was centrifuged at 3500 rpm during 20 min, the bacteria sediment was suspended in NaCl (9 g/L) to obtain an optical density (OD) of 0.01 at 600 nm.

[0151] Glass surfaces with PNP4A-ZnCl.sub.2-I-PDMS.sub.60 were incubated in 4 mL of the bacteria solution as previously prepared during 1 h at 30° C., then washed 8 times in NaCl (9 g/L) before microscope analysis with straight confocal microscope (LSM800- Zeiss). On each surface, 10 random areas were imaged and analyzed with a FiJi software for image treatment. On each area, the number of bacteria was determined.

[0152] Results are depicted in FIG. 14. The results show that the coated glass inhibits the proliferation of bacteria of the coated surface.