Novel photosensitive carbon dioxide based polycarbonate derivatives and method for preparation of photo-antimicrobial polycarbonate-bioplasticizer composites and their use

Abstract

The present invention refers to a novel photosensitive polycarbonate carbon dioxide based polycarbonate derivatives and a process for preparing polycarbonate-based photo antimicrobial composite materials from carbon dioxide, epoxides, tetrapyrrolic macrocycles types and a natural-based plasticizer and their use. The method of the present invention is a straightforward preparation process involving only two to four sequential steps, in which the first step proceeds with the use of a single substance as reaction catalyst and photosensitizing agent; additionally, the composite materials are non-harmful and potentially biodegradable.

Description

DESCRIPTIONNOVEL PHOTOSENSITIVE CARBON DIOXIDE BASED POLYCARBONATE DERIVATIVES AND METHOD FOR PREPARATION OF PHOTO-ANTIMICROBIAL POLYCARBONATE-BIOPLASTICIZER COMPOSITES AND THEIR USETechnical FieldThe present invention relates novel photosensitive polycarbonate carbon dioxide based polycarbonate derivatives and a process for preparing polycarbonate-based photo antimicrobial composite materials from carbon dioxide, epoxides, tetrapyrrolic macrocycles types and a natural-based plasticizer and their use.Summary of the inventionMost plastic materials used in our day-to-day life are derived from fossil fuels, which bring economic and environmental issues, such as the economic dependence on oil producing countries, the persistence of plastics in the environment and the atmospheric pollution associated with plastic incineration. In particular, polycarbonate plastics, which are commonly used in the manufacture of glazing materials, face shields and medical devices, are usually prepared through environmentally harmful synthetic processes, involving highly toxic reagents (such as phosgene) and additives. In addition to environmental concerns, infectious diseases caused by multi-drug resistant (MDR) microorganisms are a huge global health problem, which also engage environment and economical concerns, due to the use of conventional plastics in life support medical devices and the patients' long-term stays in health care units. In addition, the Covid-19 pandemic brought new and heightened concerns regarding the transmission of microorganisms and contagious infections at commercial surfaces and hospital facilities.Aiming to contribute to the mitigation of these environmental and public health problems, the present invention relates to a sustainable process to prepare photo-antimicrobial polycarbonate-based plastic materials, developed through a green strategy based on the copolymerization of renewable, abundant, cheap and non-toxic carbon dioxide with epoxides, catalysed by metal complexes of tetrapyrrolic macrocycle type molecules, which are simultaneously used as photosensitizer agents, followed by addition of a bioplasticizer derivative in variable ratios to produce composites with distinct physical / mechanical properties and different potential uses.The first step of the process is the copolymerization reaction between carbon dioxide and differently functionalized epoxides, namely, but not exclusively, vinyl functionalized epoxides in the presence of a metal complex of tetrapyrrolic macrocycles type, in particular but not exclusively, metalloporphyrins or metallophthalocyanines, which have simultaneous applications as catalyst and photo-antimicrobial molecule.In the following step, solutions of photosensitive polycarbonate, with variable concentrations, are mixed with a bioplasticizer, namely, but not exclusively, glycerol; poly-(R)-3- hydroxybutyrate or a cellulose derivative, to produce photo-antimicrobial composite materials. Different formulations, varying the relative polycarbonate / bioplasticizer derivative ratios, are created to modulate the physical / mechanical properties of the composites in terms of resistance, hardness and elasticity properties, thus expanding their potential use into a wide range of applications.Background of the inventionThe development of photosensitive materials from bio-based renewable feedstocks, able to promote the photodynamic inactivation (PDI) of microorganisms by the action of an appropriate photosensitizer and selected light source is described in scientific literature.1'22Regarding the development of photosensitive polymers for application in the photoinactivation of microorganisms, binding of curcumin to poly(vinyl pyrrolidone) (PVP) has been reported for inactivation of Gram-positive and Gram-negative bacteria.23This photosensitive polymer, upon irradiation with 33,8 J / cm2led to an efficient inactivation of S. aureus (> 6 logic) after 5 minutes of incubation. The study also reveals that longer incubation times lead to less phototoxicity, due to degradation of the photosensitizer. In another report, curcumin ester and ether synthetic derivatives have been incorporated in polyfvinyl chloride) (PVC), serving both as bioplasticizers and photosensitizers. The resulting photosensitive materials promoted S. aureus photoinactivation (> 6 log io) with just 23,5 J / cm2.24Covalent immobilization of curcumin onto polyfvinyl chloride) (PVC) endotracheal tubes has been carried out through nucleophilic substitution reaction of PVC chlorine atoms. These modified endotracheal tubes were able to promote the inactivation of S. aureus, P. aeruginosa and E. coli biofilms using a PDI approach with 50 J / cm2light irradiation.25In this study, it was possible to observe the inactivation of up to 95% for Gram-positive and up to 73% for Gramnegative bacteria.Two different strategies were reported to prepare porphyrin-based poly(2- hydroxyethylmethacrylate) polymers, namely PHEMA-Porph and PHEMA-co-Porph.26PHEMA- Porph was obtained in situ by non-covalent incorporation of the porphyrin molecule inside the polymeric matrix during the free radical polymerization of 2-hydroxyethyl methacrylate (HEMA). PHEMA-co-Porph was prepared through covalent coupling reaction between the methacrylated-porphyrin and HEMA, through a free radical co-polymerization reaction. Both materials showed fluorescent properties, good photostability and ability to form singlet oxygen. Regarding the evaluation of photodynamic inactivation (PDI) both materials were reused up to at least three times, without significant loss of effectiveness, being PHEMA-co- Porph the most active material.The synthesis of antibacterial material based on cellulose (TTPropP-Cel), has been reported through a "Click-Chemistry" approach between an acetylenic porphyrin derivative (TTPropP)and cellulose functionalized with azide units.27In this study, it was possible to observe that, under visible light irradiation, the synthesized material has antibacterial activity against E. coli and S. aureus.More recently, polylactic acid (PLA) appeared as a sustainable alternative to petroleum-based polymers,28-31including the use of silver and chitosan to prepare PLA-based antimicrobial surfaces.32'34It was reported the antimicrobial activityof PLA / carvacrol-based materials for food packaging and biomedical applications.35,36Other promising polymeric materials are those based on polycarbonates using CO2 as renewable starting material.37'41The preparation of CO2-based cationic polycarbonate / polyacrylonitrile nanofibers has also been reported, showing an optimal fibrous microstructure for antibacterial applications.42These poly(vinylcyclohexene carbonates) (PVCHCs) were used as precursors to prepare cationic PVCHCs (CPVCHCs) via thiol-ene click chemistry functionalization. They were able to obtain CPVCHC-43 with a tertiary amine density of 43% relative to the backbone with a significant antibacterial activity against S. aureus. Blending CPVCHC-43 with polyacrylonitrile (PAN), CPVCHC / PAN nanofiber meshes (NFMs) have been successfully prepared by electrospinning and the further quaternization treatment enhance the antibacterial ability. Moreover, an excellent biocompatibility of the quaternized NFMs was reported.42However, to date, there are no reports on the preparation of photosensitizer-polycarbonate- bioplasticizer composites or their use as photo-antimicrobial materials.Advantages of the inventionThe present invention relates to a sustainable method for preparing photosensitive polycarbonate-based composite materials, through a green strategy, using carbon dioxide as a renewable, abundant, cheap and relatively non-toxic reagent.The method of the present invention is a straightforward preparation process involving only two to four sequential steps, in which the first step proceeds with the use of a single substance as reaction catalyst and photosensitizing agent; additionally, the composite materials are nonharmful and potentially biodegradable.The process of the present invention avoids the use of harmful reagents, such as phosgene, and toxic plasticizers, such as phthalates and is a circular economy process of valorisation and release of carbon dioxide after biodegradation.Brief Description of the DrawingsThese and other features are to be easily understood by the accompanying drawings, which should be taken as examples only and are not to be considered as limiting the scope of thepresent invention.In a preferred embodiment of the invention:Figure 1 represents the synthesis reaction scheme of photosensitive polycarbonate derivatives (PCn-PSn: PCi-PSn; PC2-PSn; PCs-PSn and PC4-PSn), wherein PCn is a polycarbonate and PSn is a photosensitizer. The scheme also describes the synthesis of photosensitive polycarbonate-bioplasticizer composites films (PCn-PSn-BPn), wherein BPnis a bioplasticizer.Figure 2 representsNMR spectrum of photosensitive polycarbonate PC1-PS1.Figure 3 represents13C NMR spectrum of photosensitive polycarbonate PCi-PSi.Figure 4 represents UV-Vis spectrum of photosensitive polycarbonate PCi-PSi.Figure 5 represents thermogravimetric analysis (TGA) of photosensitive polycarbonate PCi- PSi.Figure 6 represents differential scanning calorimetry (DSC) analysis of photosensitive polycarbonate PCi-PSi.Figure 7 represents Fourier-transform infrared (FTIR) spectrum of photosensitive polycarbonate PCi-PSi.Figure 8 represents scanning electron microscope (SEM) images of photosensitive polycarbonate PCi-PSi.Figure 9 representsNMR spectrum of photosensitive polycarbonate PC2-PS1.Figure 10 represents UV-Vis spectrum of photosensitive polycarbonate PC2-PS1.Figure 11 representsNMR spectrum of photosensitive polycarbonate PC3-PS1.Figure 12 represents UV-Vis spectrum of photosensitive polycarbonate PC3-PS1.Figure 13 represents thermogravimetric analysis (TGA) of photosensitive polycarbonate PC3- PSi.Figure 14 represents differential scanning calorimetry (DSC) analysis of photosensitive polycarbonate PC3-PS1.Figure 15 represents Fourier-transform infrared (FTIR) spectrum of photosensitive polycarbonate PC3-PS1.Figure 16 represents scanning electron microscope (SEM) images of photosensitive polycarbonate PC3-PS1.Figure 17 represents thermogravimetric analysis (TGA) of photosensitive polycarbonate PC4-PSi.Figure 18 represents differential scanning calorimetry (DSC)analysis of photosensitive polycarbonate PC4-PS1.Figure 19 represents Fourier-transform infrared (FTIR) spectrum of photosensitive polycarbonate PC4-PS1.Figure 20 represents UV-Vis spectrum of polycarbonate-ethyl cellulose biocomposite film PCi-PSi(25)-BPi(75).Figure 21 represents stress-strain curve of polycarbonate-ethyl cellulose biocomposite film PCi-PSi(25)-BPi(75).Figure 22 represents in vitro S. aureus antibacterial photoinactivation studies with photosensitive polycarbonate PC1-PS1 and photosensitive polycarbonate PC3-PS1. "X" denotes complete inactivation of the bacterial inoculum (7 log CFU bacterial reduction).Detailed description of the inventionAs can be clear to a person skilled in the art, the application of the principles described herein is not limited to the embodiments shown. Possible changes that can occur in the present invention, defined in number, remain within the scope of the present invention.Additionally, although some embodiments present multiple new features, and as can be seen throughout this document, all features can be independent and it is not essential that all be used in a single embodiment.Additionally, the embodiments described herein are merely examples of the effect intended with the present invention, so other ways known from the state of the art to achieve the same technical effect are equally applicable for other embodiments.Terms not specifically defined herein should be given the meanings that would be given to them by one of skill in the art in light of the disclosure and the context. For example, the expressions "solution" and "dissolved" or "solved" according to the present invention should be understood in its broadest meaning and include all kind of mixture of solid in a liquid medium such as true solutions, dispersions and the like, unless otherwise stated.Furthermore, it should be noted that the chemical species explicitly mentioned should not be understood to be limited to the specific described species but those skilled in the art know the equivalent compounds having a similar or comparable effect or reaction which should be within the present scope of protection.The object of the present invention is a process for preparing photosensitive antimicrobial polycarbonate-based composite materials from carbon dioxide, epoxides, metal complexes oftetrapyrrolic macrocycles type and a bioplasticizer.The first step of the process is the copolymerization reaction between carbon dioxide, with pressure of preferably 10 to 80 bar, more preferably 10-40 bar, and vinyl functionalized epoxides, namely, but not exclusively, 4-vinyl epoxide, in the presence or absence of organic solvent, a co-catalyst, namely, but not exclusively, bis(triphenylphosphine)iminium chloride (PPNCI); tetrabutylammonium chloride (TBAC); tetrabutylammonium bromide (TBAB); tetrabutylammonium iodide (TBAI) or 4-dimethylaminopyridine(DMAP), and a transition metal complexes of tetrapyrrolic macrocycles types, in particular, but not exclusively, metalloporphyrins or metallophthalocyanines, simultaneously used as catalyst and antimicrobial photosensitizer molecule, at temperature from preferably 50 to 120 °C, more preferably 50 to 80 °C (scheme I).Scheme IFormula I wherein, m can vary between 8 and 178;PSn is a metal complex tetrapyrrolic macrocyle type according to formula A:PS n =Formula A wherein,X is either a N atom or C-Y and Y is a H atom or aryl group;M is a transition metal, namely, but not exclusively: Al; Cr, Mn; Fe; Co; Ni; Cu or Zn.And wherein, the metal complex of tetrapyrrolic macrocycles type PSn can be a metallophthalocyanine according to the formula B or can be a metalloporphyrin according to the formula C:M is a transition metal, namely, but not exclusively: Al; Cr, Mn; Fe; Co; Ni; Cu or Zn.Table 1 - Non-limiting other polycarbonate-photosensitizer derivates composites.PCl-PSnPC1-PS1PC1-PS2PC1-PS3PC1-PS4PC1-PS5PCi-PSePC1-PS7PCi-PSsPC1-PS9The resulting vinyl-functionalized polycarbonate-photosensitizer composites (PCi-PSn) have the following general formula I:( PCl-PSn)Formula I wherein, m can vary between 8 and 178; andPS n =( PS1-PS2 ) ( PS3-PS9 )Formula B Formula C wherein,PSn can be a metallophthalocyanine according to formula B, wherein R' is an alkyl group between 1 and 12 carbon atoms (PSi) or an aryl moiety (PS2); andM is a transition metal, namely, but not exclusively: Al; Ni; Cu or Zn;Or PSn can be a metalloporphyrin according to formula C, wherein Ar is a 4- trifluoromethylphenyl (PS3); 2,6-dichlorophenyl (PS4); pentafluorophenyl (PSs); 3- trifluoromethylphenyl (PSe); 2-trifluoromethylphenyl (PS7); 2,6-difluorophenyl (PSs) or 2,6- dibromophenyl (PS9) group; andM is a transition metal, namely but not exclusively: Al; Cr; Mn; Fe or Co.Another object of the present invention is the synthesis of photosensitive polycarbonate composites (PCn-PSn) according to the general formula II:Formula II wherein:R is either: ethyl; 1,2-dibromoethyl; 3-oxopropyl or 3-hydroxypropyl; andPSn can be a metallophthalocyanine according to formula B, wherein R' is an alkyl group comprising between 1 and 12 carbon atoms (PSi) or an aryl moiety (PS2), andM is a transition metal, namely, but not exclusively: Al; Ni; Cu or ZnFormula B Formula COr PSn can be a metalloporphyrin according to formula C, wherein Ar is a 4- trifluoromethylphenyl (PS3); 2,6-dichlorophenyl (PS4); pentafluorophenyl (PSs); 3- trifluoromethylphenyl (PSe); 2-trifluoromethylphenyl (PS7); 2,6-difluorophenyl (PSs); or 2,6- dibromophenyl (PS9) group; andM is a transition metal, namely, but not exclusively: Al; Cr; Mn; Fe or Co.The synthesis of polycarbonate-photosensitizer composites (PCn-PSn) according to formula II is shown in scheme II.In the synthesis of polycarbonate-photosensitizer composites (PCn-PSn) according to formula II, the vinyl functional group of vinyl-functionalized polycarbonate polymers (PCi-PSn) is chemically transformed either through: i) reaction with Br? solution in organic solvent, namely but not exclusively, carbon tetrachloride or chloroform obtaining photosensitive (1,2-dibromoethyl)- functionalized polycarbonates (PC2-PSn), and subsequent nucleophilic substitution reactions; ii) reaction with a 1 : 1 mixture of CO / H2 (hydroformylation), in the presence of catalyst CAT1 dicarbonyl(acetylacetonato)rhodium(I) (Rh(acac)(CO)2) and a phosphineligand, namely but not exclusively, (9,9-dimethyl-9H-xanthene-4,5- diyl)bis(diphenylphosphane) (xantphos)43in an organic solvent, namely, but not exclusively, toluene or tetra hydrofuran, obtaining photosensitive (3-oxopropyl)- functionalized polycarbonates (PCs-PSn); ill) hydrogenation of the photosensitive (3-oxopropyl)-functionalized polycarbonates (PCs-PSn) in the presence of catalyst CAT2 1-hydroxytetraphenylcyclopentadienyl- (tetraphenyl-2,4-cyclopentadien-l-one)-p-hydrotetracarbonyldiruthenium(II) (Shvo's complex)44in an organic solvent and a 1 : 1 mixture of CO / H2 obtaining (3- hydroxypropyl)-functionalized polycarbonates (PC4-PSn); iv) other addition reactions.Table 2 - Non-limiting other polycarbonate-photosensitizer composites.Process to produce polvcarbonate-photosensitizer composites (PCn-PSn) :Photosensitive vinyl-functionalized polycarbonate composite derivatives (PCi-PSn) were synthesized by placing the desired amount of tetrapyrrolic macrocycle catalyst / photosensitizer (PSn) and a selected nucleophile co-catalyst inside a stainless-steel autoclave, which was left under vacuum for 1-3 h, at 50 °C-120 °C. Then, the vinyl epoxide (2-10 ml), was inserted into the autoclave via cannula. The autoclave was then pressurized with 10-80 bar CO2 and the reaction proceeded at the selected temperature (50-120 °C). After 18-36 h, the autoclave was cooled and slowly depressurized. The reaction crude was evaporated, and the residue was dried under vacuum. Then, the solid was washed with organic solvents, filtered and dried under vacuum, yielding the photosensitive vinyl- functionalized polycarbonate composites (PCi-PSn).Photosensitive (l,2-dibromoethyl)-functionalized polycarbonates (PC2-PSn) were synthesized by dissolving photosensitive vinyl-functionalized polycarbonate polymers (PCi-PSn) in a minimal amount of organic solvent and left in agitation. Then, a solution of Br2 5% (w / w) in organic solvent, preferably, carbon tetrachloride or chloroform, was added dropwise. The mixture was then washed with sodium thiosulfate and the organic phase was extracted with organic solvent. Finally, the organic phase was dried with a drying agent, and the solvent was evaporated. The material was dried under vacuum, yielding the photosensitive (1,2- dibromoethyl)-functionalized polycarbonates (PC2-PSn).Photosensitive (3-oxopropyl)-functionalized polycarbonates (PCs-PSn) were synthesized by mixing a selected transition metal catalyst precursor and a selected phosphine ligand with photosensitive vinyl-functionalized polycarbonate polymers (PCi-PSn) in a stainless-steel autoclave, which was purged with three cycles of vacuum and an equimolar mixture of CO / H2 (syngas). Then, the organic solvent was added, via cannula, into the autoclave, which was pressurized with the desired pressure of syngas (10-80 bar). The reaction was conducted for 5-24 hours, with stirring, preferably between 50 °C-120 °C. At the end, the reactor was cooled to room temperature and depressurized. The reaction crude was evaporated, and the residue was dried under vacuum, yielding the photosensitive (3-oxopropyl)-functionalized polycarbonates (PCs-PSn).Photosensitive (3-hydroxypropyl)-functionalized polycarbonates (PC4-PSn) was synthesized by mixing a selected transition metal-based catalyst, namely, but not exclusively, ruthenium catalyst and the photosensitive (3-oxopropyl)-functionalized polycarbonates (PCs-PSn) in a stainless-steel autoclave, which was purged with three cycles of vacuum and an equimolar mixture of syngas. Then, the organic solvent was added, via cannula, into the autoclave, which was pressurized with the desired pressure of syngas and heated, preferably between 50 °C-120 °C, and stirred for 6-36 hours. Then, the autoclave was cooled, and the pressurewas released. The reaction crude was evaporated, and the residue was dried under vacuum, yielding the desired photosensitive (3-hydroxypropyl)-functionalized polycarbonates (PC4- PSn).The resulting polycarbonate-photosensitizer composites (PCn-PSn) were characterized by UV- Vis, NMR, TGA, DSC, FTIR and GPC.Another object of the present invention is the process for preparing photosensitive polycarbonate-bioplasticizer composites (PCn-PSn-BPn) according to formula III wherein a bioplasticizer (BPn) is added to a solution of photosensitive polycarbonates (PCn-PSn) according to formula II, in an organic solvent. Formulations containing polycarbonate / bioplasticizer from 5 to 95% (w / w). These formulation lead to the polycarbonate-photosensitizer-bioplasticizer composites films (PCn-PSn-BPn) with the general formula III:Scheme III(PCn-PSn-BPn)Formula IIFormula III wherein: m can vary between 8 and 178;R is either: ethyl; vinyl; 1,2-dibromoethyl; 3-oxopropyl or 3-hydroxypropyl; andwherein,PSn can be a metallophthalocyanine according to formula B, wherein R' is an alkyl group between 1 and 12 carbon atoms (PSi) or an aryl moiety (PS2); andM is a transition metal, namely, but not exclusively: Al; Ni; Cu or Zn; orPSn can be a metalloporphyrin according to formula C, wherein Ar is a 4-trifluoromethylphenyl (PS3); 2,6-dichlorophenyl(PS4); pentafluorophenyl (PSs); 3-trifluoromethylphenyl(PS6); 2- trifluoromethylphenyl (PS7); 2,6-difluorophenyl(PSs) or 2,6-dibromophenyl (PS9) group; and M is a transition metal, namely but not exclusively: Al; Cr; Mn; Fe or Co.BPnis a bioplasticizer, namely, but not exclusively, glycerol; poly-(R)-3-hydroxybutyrate or a cellulose derivative according to the formula IV:Formula IV wherein:R' is either: a methyl (BPi); ethyl (BP2); acetyl (BP3); hydroxyethyl (BP4); 2-hydroxypropyl(BPs) or carboxymethyl (BPe) groups; andP is between 200 and 7000.The photosensitive polycarbonate (PCn-PSn) according to formula II, previously obtained, is dissolved in an organic solvent, namely but not exclusively, anisole; p-cymene or 2- methyltetra hydrofuran and the bioplasticizer (BPn), namely but not exclusively, glycerol; poly- (R)-3-hydroxybutyrate or cellulose derivative, is slowly added between from 5 to 95% (w / w). The mixture is heated between 20 to 80 °C; more preferably 25 to 80 °C; even more preferably 25 to 50 °C; more precisely between 30 to 50 °C on a stirring hot-plate, until a viscous solution is observed, and the polycarbonate-photosensitizer-bioplasticizer films are obtained by namely, but not exclusively, solvent casting techniques; compression moulding; injection moulding; extrusion; blow moulding; thermoforming or foam moulding.The resulting polycarbonate-photosensitizer-bioplasticizer (PCn-PSn-BPn) composites films were characterized by UV-Vis and mechanical tensile strength tests.The chemical structure of the different bioplasticizer, namely, but not exclusively, glycerol; poly-(R)-3-hydroxybutyrate or cellulose derivatives, and the relative percentage of polycarbonate / bioplasticizer derivative provide a wide range of composites with distinct physical / mechanical properties, in terms of resistance, hardness and elasticity.Another object of the present invention is the modulation of physical / mechanical properties of the polycarbonate-photosensitizer-bioplasticizer composites in terms of resistance, hardness and elasticity properties, thus expanding their potential use in to a wide range of applications, namely, but not exclusively, in the manufacturing and their antimicrobial photo-decontamination of objects selected from, namely, but not exclusively: containers, packaging films / wrappers, garbage bags, pens and chairs.Additionally, polycarbonate-photosensitizer-bioplasticizer (PCn-PSn-BPn) composite films can be used in the manufacturing of photo-antimicrobial healthcare and medical devices, comprises, namely, but not exclusively, catheters, endotracheal tubes, stethoscopes, protection glasses and face shields.In addition, polycarbonate-photosensitizer (PCn-PSn) and polycarbonate-photosensitizer- bioplasticizer (PCn-PSn-BPn) composites can be used as photo-antimicrobial varnishes and protection films for hospital surfaces and equipment, namely, but not exclusively, computers and laptop touch screens, desks and stretchers.Additionally, in the presence of light with appropriate wavelength, polycarbonate- photosensitizer derivatives (PCn-PSn) and polycarbonate-photosensitizer-bioplasticizer (PCn- PSn-BPn) composite films can be applied in antimicrobial photodynamic inactivation (aPDI), namely, but not exclusively, in photo-decontamination of hospital surfaces and equipment and in photo-decontamination of medical devices.The photodynamic antimicrobial inactivation (aPDI) method comprises the following steps: i) The selected polycarbonate-photosensitizer composite (PCn-PSn) is dissolved in a compatible organic solvent. Aliquots from this solution are taken and placed into the wells of a polypropylene round bottom 96-well plate, followed by solvent evaporation; ii) Then, the previously prepared bacterial inoculum is added and the wells are irradiated with a LED lamp with a selected power preferably 10-100 mW / cm2, more preferably of 10-80 mW / cm2white or red radiation (300 - 700 nm). Distilled water is added to each well to homogenize the medium and the aliquots are plated in Petri dishes with MH agar. After incubation, the surviving CFU / mL were counted and compared with the control (absence of polycarbonate-photosensitizer (PCn-PSn) composite).The same antimicrobial inactivation procedure can be carried out directly with the photosensitive polycarbonate-bioplasticizer composites films (PCn-PSn-BPn), by cutting a circular section of the film (diameter = 6 to 7 mm), which is inserted into the bottom of a propylene round bottom 96-well plate.Embodiments of the inventionThis invention is further illustrated by the following non-limiting examples.Example 1: Preparation of PCi-PSiExample 1 illustrates the wide range of photosensitive 4-vinylcyclohexane polycarbonates (PCi-PSn) that can be synthesized by a procedure characterized by the absence of solvent, where l,2-epoxy-4-vinylcyclohexene and carbon dioxide (CO2), are employed as starting materials, metal complexes of tetra pyrrol ic macrocycles are used as catalyst / photosensitizer (PSn) (5 to 15% (m / m)) and a phosphine iminium halide or quaternary ammonium salt is used as co-catalyst.In one preparation, the catalyst / photosensitizer 2(3), 9(10), 16(17), 23(24)-tetrakis(4-tert- butylphenoxy) phthalocyaninato chloride aluminium (III)45(PSi) (0,5 mol%) and the cocatalyst bis(triphenylphosphine)iminium chloride (PPNCI) (0,07 mol%) were placed in a glass beaker, inside the autoclave and it was left in vacuum for approximately 3 h, preferably at 80 °C. Then, l,2-epoxy-4-vinylcyclohexene (4 ml), previously dried over alumina, was inserted into the autoclave via cannula. The autoclave was then pressurized with CO2 (40 bar) and the reaction proceeded at 80 °C. After 24 h, the autoclave was cooled and slowly depressurized. The reaction crude was evaporated, and the residue was dried in vacuum at 100 °C for 5 h. Then, the solid was washed with n-hexane, filtered and dried under vacuum at 100 °C for 12 h. The photosensitive polycarbonate (PC1-PS1) was obtained in 89% isolated yield (4,64 g), calculated from the mass of the isolated product relative to the weighted mass of epoxide and CO2. The CO2 content (%) was calculated fromTH NMR data by the integral ratio between copolymer carbonate linkages (6 = 4,64 ppm) with respect to the ether linkage signals (6 = 3,57 ppm). The polycarbonate-photosensitizer composites were characterized by UV-Vis, NMR, TGA, DSC, FTIR and GPC. The characterization data of the isolated product is presented in Figures 2 to 8.TH NMR (400 MHz, CDCI3): 6 (ppm): 5,83-5,67 (m, 1H), 5,16-4.94 (m, 2H), 4,93-4,73 (m, 2H) 2,43 (br s, 1H), 1,97-1,41 (m, 6H).13C NMR (100 MHz, CDCI3): 6 (ppm): 153,4; 141,7; 73,4; 39,2; 35,0; 31,7; 29,5; 26,2; 25,4. UV-Vis (nm): 685, 617, 363.Example 2: Preparation of PC2-PS1Example 2 illustrates the wide range of photosensitive 4-(l,2-dibromoethyl) cyclohexane polycarbonates (PC2-PSn) that can be synthesized by a procedure which consists on the addition of Br2 in organic solvent, preferably, carbon tetrachloride solution (5%) to photosensitive vinyl-functionalized polycarbonate polymers (PCi-PSn).In one preparation the (PC1-PS1) (250 mg, 1,5 mmol) was dissolved in a minimal amount of carbon tetrachloride and left under stirring. Then, 5,7 ml of the solution of Br2 in carbon tetrachloride (5%) was added dropwise using a burette until a colour change was observed in the solution. The mixture was then washed with sodium thiosulfate and the organic phase was extracted with dichloromethane. Finally, the organic phase was dried with sodium sulphate, and the solvent was evaporated. The material was dried under vacuum and the photosensitive polycarbonate (PC2-PS1) was obtained in 89% yield (0,69 g). The polycarbonate-photosensitizer composites were characterized by UV-Vis, NMR, TGA, DSC, FTIR and GPC. The characterization data of the isolated product is presented in Figures 9 and 10.TH NMR (400 MHz, CDCI3): 6 (ppm): 4,97-4,84 (m, 4H), 4,20 (s, 3H), 3,85-3,67 (m, 5H), 2,35-2,31 (m, 3H), 1,99-1,52 (m, 18H). UV-Vis (nm): 683, 617, 362.Example 3: Preparation of PC3-PS1Example 3 illustrates the wide range of photosensitive 4-(3-oxopropyl)cyclohexane polycarbonates (PCs-PSn) that can be synthesized by a procedure which consists on the rhodium-catalyzed hydroformylation of photosensitive vinyl-functionalized polycarbonate polymers (PCi-PSn), using a rhodium catalyst, a phosphine ligand in an organic solvent, preferably toluene or tetrahydrofuran, and a 1: 1 mixture of CO / H2 (syngas).In one preparation Rh(acac)(CO)2 (2,58 mg, 0,01 mmol), xantphos43( 29 mg, 0,05 mmol) and (PC1-PS1) (840,95 mg, 5 mmol) were placed in a glass-lined stainless-steel autoclave, which was purged with three cycles of vacuum and an equimolar mixture of CO / H2. Then, 10 ml of toluene were added, via cannula, into the autoclave, which was pressurized with 20 bar of syngas. The reaction was conducted for 5 hours, upon stirring at 80 °C. At the end, the reactor was cooled to room temperature and depressurized. The reaction crude was evaporated, and the residue was dried under vacuum at 80 °C overnight. The photosensitive polycarbonate (PC3-PS1) was obtained in 44% yield (0,37 g). The polycarbonate- photosensitizer composites were characterized by UV-Vis, NMR, TGA, DSC, FTIR and GPC. The characterization data of the isolated product is presented in Figures 11 to 16.TH NMR (400 MHz, CDCI3): 6 (ppm): 9,71 (s, 1H), 4,86-4,66 (m, 2H), 2,41 (s, 1H), 1,80-1,50 (m, 10H). UV-Vis (nm): 687, 620, 364.Example 4: Preparation of PC4-PS1Example 4 illustrates the wide range of photosensitive 4-(3-hydroxypropyl)cyclohexane polycarbonates (PC4-PSn) that can be synthesized by a procedure which consists in the hydroformylation-hydrogenation of photosensitive 4-(3-oxopropyl)cyclohexane polycarbonates (PCs-PSn), using a ruthenium catalyst in an organic solvent and a 1: 1 mixture of CO / H2 (syngas).In one preparation, Shvo's complex44(11 mg, 0,01 mmol) and PC3-PS1 (50 mg, 0,40 mmol) were placed in a glass-lined stainless-steel autoclave, which was purged with three cycles of vacuum and an equimolar mixture of CO / H2. Then 5 ml of toluene were added, via cannula, into the autoclave, which was pressurized with 20 bar of syngas and heated to 120 °C with stirring. After 4 h, the autoclave was cooled and the pressure was released. The reaction crude was evaporated, and the residue was dried under vacuum at 80 °C overnight. The photosensitive polycarbonate (PC4-PS1) was obtained in 46% yield (0,23 g). The characterization data of the isolated product is presented in Figures 17 to 19.Example 5: Preparation of PCi-PSi-BPiExample 5 illustrates the wide range of polycarbonate-photosensitizer-bioplasticizer composite (PCn-PSn-BPn) that can be synthesized by a procedure where different percentages of bioplasticizer (BPn) are added to a solution of photosensitive polycarbonate (PCn-PSn) in anorganic solvent, preferably, but not exclusively, anisole, p-cymene or 2- methyltetra hyd rofu ra n .In one preparation, (PC1-PS1) (125 mg, 25% m / m) is dissolved in anisole (5 ml) and a solution of ethyl cellulose (BPi) (375 mg, 75% m / m) in organic solvent, preferably anisole, is slowly added. The mixture is heated to 50 °C on a stirring hot-plate, until a viscous solution is observed, and the polycarbonate-ethyl cellulose biocomposite film PCi-PSi(25)-BPi(75) was obtained by solvent casting techniques. Its characterization data is presented in Figures 20 and 21. UV-Vis (nm): 682, 615, 363. Tension at maximum strength (oM) = 9,4 MPa. Elongation at breaking tension (etB) = 2,9%.Example 6: Antibacterial studies of oolvcarbonate-ohotosensitizer composites PCn-PSiExample 6 illustrates the wide range of in vitro antibacterial photoinactivation assays of polycarbonate-photosensitizer composites (PCn-PSn).In one preparation, (PCi-PSi) or (PC3-PS1) composites was tested in in vitro antibacterial photoinactivation assays that were performed with aqueous solutions of Staphylococcus aureus American Type Culture Collection (ATCC) 29213 bacteria. PC1-PS1 or PC3-PS1 composites was dissolved in acetone (83 mg / mL), from which 40 pL aliquots are taken and placed in wells of a plate 96 polypropylene round bottom wells, followed by solvent evaporation. Then, the previously prepared bacterial inoculum is added and the wells are irradiated with a LED lamp with a power of 20 mW / cm2of red radiation (660±20 nm). Distilled water is added to each well to homogenize the medium and the aliquots are plated in Petri dishes with MH agar. After incubation, the surviving CFU / mL were counted and compared with the control (in absence of polycarbonate-photosensitizer composite). A total bacteria inactivation was obtained, with up to 7 logic CFU reduction, using a total light dose of 49 J / cm2(Figure 22).Measurement methods:NMR SpectroscopyTH and13C NMR spectra were recorded in CDCI3 on a Bruker DRX 400 spectrometer, operating at 400,13 MHz forTH and 100,61 MHz for13C. Chemical shifts forTH and13C are expressed in ppm, relatively to a TMS as internal standard, or relatively to residual peaks, present in the deuterated solvents used, CDCI3 or DMSO-ds.High performance size exclusion chromatography (HPSEC)High performance size exclusion chromatography (HPSEC) was performed, using a Viscotek (ViscotekTDAmax) with a differential viscometer (DV), right-angle laser-light scattering (RALLS, Viscotek), and refractive index (Rl)detectors. The column set was composed by a PL 10 mm guard column followed by one MIXED-E PLgel column and one MIXED-C PLgel column.Previously filtered THF was used as an eluent at a flow rate of 1,0 miymin at 30 °C. The samples were filtered through a polytetrafluoroethylene (PTFE) membrane with 0,2 mm pore before injection and the system was calibrated with narrow PS standards. The MnSEC and E> of the synthesized polymers were determined by using a conventional calibration (OmniSEC software version: 5,0).UV-VIS SoectroscoovUV-Visible spectra were obtained on a Shimadzu 2100 spectrophotometer, using glass cells with an optical path of 1 cm. To determine the absorptivity coefficient (e), the Beer-Lambert Law was used, which establishes a linear relationship between the absorbance of a sample (Abs) and the respective concentration (c), molar absorptivity coefficient (e) and length of the optical path (I), given by Equation 1:Abs = e c I (Equation 1)For each determination, a mother solution containing ~1 mg to ~2 mg of compound was prepared, from which between 6 and 8 daughter solutions were prepared per dilution, with concentrations between 10-5 and 10-7 M (Abs= 0,1 to 1,0). A linear adjustment was made to the concentration and respective absorbance data set according to the least squares' method, using Origin 2018.Fluorescence SpectroscopyQuantum fluorescence yields were determined by the absolute method, using a Hamamatsu Quantaurus-QY model C113347-11 fluorimeter. For this, sample solutions prepared in dichloromethane with an absorbance of approximately 0,05 were used and the samples were excited at their maximum absorption wavelength (415 nm).Singlet Oxygen Quantum YieldsThe determination of the quantum yield of singlet oxygen (OA) was carried out using a comparative method by detecting the phosphorescence of singlet oxygen at 1270 nm. For this, an Applied Photophysics LKS.60 lightning photolysis spectrometer was used, consisting of a Nd-YAG Spectra- Physics Quanta Ray GCR-130 laser, a Hewlett Packard Infinium oscilloscope and a cooled Hamamatsu R5509-42 photomultiplier as detector, to 193K by liquid nitrogen. As a reference, phenalenone was used (<DAphenalenone(chloroform) = 0,98). Solutions of each sample and the reference were prepared satisfying the condition Abs ~0,2 at 355 nm. Each of the solutions was subjected to about 10 excitation experiments at 355 nm, using different relative laser intensities, and the respective decays of singlet oxygen phosphorescence emission were recorded. For each decay obtained, a mono-exponential decay function was adjusted, where the pre-exponential factor (FP.exp) was recorded for each laser intensity, which is directly related to the amount ofTO2 generated. To the FP.exp dataset as a function of laser intensity, a linear regression was fitted using the method of leastsquares. Once the pre-exponential factor (FP.exp) lines were obtained as a function of the laser energy for the samples and reference, the singlet oxygen yield of the samples ( A,a) was determined from equation 5,2 which relates the slopes of the lines obtained for the reference (Sref) and sample (Sa) with their <DA and absorbances (Abs).Thermogravimetrv (TG)The thermogravimetric studies were carried out in a Perkin-Elmer equipment, model STA 6000 connected to a cooling bath (cooling liquid: water-ethylene glycol 1: 1, at a temperature of 15 °C) made by Julabo, model F12. The samples were placed in alumina crucibles and analysed in the temperature range between 25 °C and 600 °C with a heating rate of 10 °C / min.Differential scanning calorimetry (DSC)DSC tests were performed using a power compensated differential scanning calorimeter.Perkin-Elmer, model DSC7, with a branded circulation bath MGW Lauda as a cooling system (coolant: water-ethylene glycol 1 : 1, at -20°C). Nitrogen was used as purge gas with a flow of 20 ml / min. In each analysis, 2 to 4 mg of sample was weighed and then placed in 50 pL aluminum capsules with holes and covered with a 0,1 mm thick aluminum cap, both from Perkin-Elmer. As a reference, an empty capsule was used. For each sample, heating was carried out from 25 to 200 °C, with a scanning speed of 8=10 °C / min.Scanning electron microscopy (SEM)SEM analyses were carried out in a Zeiss-GEMINI II FESEM operated at an accelerating voltage of 2 kV, using a secondary electron detector. Samples analysed by SEM were covered with a gold monomeric layer by Physical Vapor Deposition (PVD).Fourier-transformed infrared Spectroscopy (FTIR)The solid-state infrared spectroscopy studies were carried out using an infrared spectrophotometer with Fourier transform from Thermo Scientific, model Nicolet 380 FT-IR, with an ATR module, model Orbit Diamond from the same brand. 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Claims

CLAIMS1. Photosensitive carbon dioxide-based polycarbonate-bioplasticizer composites (PCn-PSn-BPn) according to the general formula III:Formula III wherein, m can vary between 8 and 178;R is either: vinyl; ethyl; 1,2-dibromoethyl; 3-oxopropyl or 3-hydroxypropylBPn is a bioplasticizerPSn is a metal complex of tetrapyrrolic macrocycle type according to formula A:Formula A wherein,X is either a N atom or C-Y and Y is a H atom or aryl group, M is either Al; Cr; Mn; Fe; Co; Ni; Cu or Zn.

2. A process for preparing photosensitive vinyl-functionalized polycarbonate composites (PCi- PSn) according to the formula I characterized by comprising a copolymerization reaction between carbon dioxide, with pressure from 10-80 bar, and vinyl functionalized epoxides in the presence or absence of organic solvent, a co-catalyst and a transition metal complex of tetrapyrrolic macrocycles type (PSn), according to the formula A, simultaneously used as catalyst and antimicrobial photosensitizer molecule, at temperature from 50 to 120 °C:Formula I wherein, m can vary between 8 and 178;PSn is a metal complex of tetrapyrrolic macrocycle type according to formula A:Formula A wherein,X is either a N atom or C-Y and Y is a H atom or aryl group, M is either Al; Cr; Mn; Fe; Co; Ni; Cu or Zn.

3. Process according with the claim 2 wherein the metal complex of tetrapyrrolic macrocycles type PSn is a metallophthalocyanine according to the formula B:Formula B wherein,R' is an alkyl group comprising between 1 and 12 carbon atoms or an aryl moiety, and M is Al; Ni; Cu or Zn; or the tetrapyrrolic macrocycle type PSn is a metalloporphyrin according to the formula C:Formula C wherein,Ar is a 4-trifluoromethylphenyl; 2,6-dichlorophenyl; pentafluorophenyl; 3-trifluoromethylphenyl;2-trifluoromethylphenyl; 2,6-difluorophenyl or 2,6-dibromophenyl group; andM is Al; Cr; Mn; Fe or Co.

4. Process according with the claims 2 to 3 wherein the co-catalyst is bis(triphenylphosphine)iminium chloride (PPNCI); tetrabutylammonium chloride (TBAC); tetrabutylammonium bromide (TBAB); tetrabutylammonium iodide (TBAI) or 4- dimethylaminopyridine (DMAP).

5. Process according with the claims 2 to 4 characterized in that the reaction is carried out at a pressure between 10 and 40 bar.

6. Process according with the claims 2 to 5 characterized in that the reaction is carried out at a temperature between 50 and 80°C.

7. A process for preparing photosensitive (1,2-dibromoethyl)- functionalized polycarbonate composites (PC2-PSn) according to the formula II, characterized by comprising the reaction of the vinyl-functionalized polycarbonate derivatives (PCi-PSn) according to the formula I with a Br2 solution in an organic solvent:Formula I Formula I I wherein, m can vary between 8 and 178;R is 1,2-dibromoethyl;PSn is a metal complex of tetrapyrrolic macrocycle type according to the formula B:Formula B wherein,R' is an alkyl group comprising between 1 and 12 carbon atoms or an aryl moiety, and M is Al; Ni; Cu or Zn; or the tetrapyrrolic macrocycle type PSn is a metalloporphyrin according to the formula C:Formula C wherein,Ar is a 4-trifluoromethylphenyl; 2,6-dichlorophenyl; pentafluorophenyl; 3-trifluoromethylphenyl; 2-trifluoromethylphenyl; 2,6-difluorophenyl or 2,6-dibromophenyl group; andM is Al; Cr; Mn; Fe or Co.

8. Process according with the previous claim wherein the organic solvent is carbon tetrachloride or chloroform.

9. A process for preparing photosensitive (3-oxopropyl)- functionalized polycarbonate composites (PCs-PSn) according to the formula II, characterized by comprising the catalytic hydroformylation of vinyl-functionalized polycarbonate polymers (PCi-PSn) according to the formula I using a catalyst and a ligand in an organic solvent, and a 1 : 1 mixture of CO / H2, with pressure between 10 and 50 bar, at temperature from 50 to 120 °C:Formula I Formula I I wherein, m can vary between 8 and 178;R is 3-oxopropyl;PSn is a metal complex of tetrapyrrolic macrocycle type according to the formula B:Formula B wherein:R' is an alkyl group comprising between 1 and 12 carbon atoms or an aryl moiety, and M is Al; Ni; Cu or Zn; or the tetrapyrrolic macrocycle type PSn is a metalloporphyrin according to the formula C:Formula C wherein:Ar is a 4-trifluoromethylphenyl; 2,6-dichlorophenyl; pentafluorophenyl; 3-trifluoromethylphenyl;2-trifluoromethylphenyl; 2,6-difluorophenyl or 2,6-dibromophenyl group; andM is Al; Cr; Mn; Fe or Co.

10. Process according with the claim 9 wherein the catalyst is a rhodium complex.

11. Process according with the claim 10 wherein the rhodium complex is dicarbonyl(acetylacetonato) rhodium(I).

12. Process according with the claims 9 to 11 wherein the ligand is a phosphine ligand.

13. Process according with the claim 12 wherein the phosphine ligand is 9,9-dimethyl-9H- xanthene-4,5-diyl)bis(diphenylphosphane (xantphos).

14. Process according with the claims 9 to 13 wherein the organic solvent is toluene or tetra hydrofuran.

15. A process for preparing photosensitive (3-hydroxypropyl)- functionalized polycarbonate composites (PC4-PSn), characterized by comprising the hydrogenation of the photosensitive (3-oxopropyl)-functionalized polycarbonate derivatives (PCs-PSn) according to the formula II, using a catalyst in an organic solvent, and a 1 : 1 mixture of CO / H2, with pressure between 10 and 50 bFormula I I PC4-PSnwherein: m can vary between 8 and 178;R in formula (II) is 3-oxopropyl and R in formula PC4-PSn is 3-hydroxypropyl;PSn is a metal complex of tetrapyrrolic macrocycle type according to the formula B:Formula Bwherein:R' is an alkyl group comprising between 1 and 12 carbon atoms or an aryl moiety, and M is Al; Ni; Cu or Zn; or the tetrapyrrolic macrocycle type PSn is a metalloporphyrin according to the formula C:Formula C wherein:Ar is a 4-trifluoromethylphenyl; 3-trifluoromethylphenyl; 2-trifluoromethylphenyl; 2,6- difluorophenyl; 2,6-dichlorophenyl; 2,6-dibromophenyl or pentafluorophenyl group, andM is Al; Cr; Mn; Fe or Co.

16. Process according with the claim 15 wherein the catalyst is a ruthenium catalyst.

17. Process according with the claim 16 wherein the ruthenium catalyst is 1- hydroxytetraphenylcyclopentadienyl-(tetraphenyl-2,4-cyclopentadien-l-one)-p- hydrotetracarbonyldiruthenium(II) (Shvo's complex).

18. Process according with the claims 15 to 17 wherein the organic solvent is toluene.

19. A process for preparing polycarbonate-photosensitizer-bioplasticizer (PCn-PSn-BPn) composites films according to the formula III, wherein a bioplasticizer is added to a solution of photosensitive polycarbonate (PCn-PSn) according to formula II in an organic solvent at temperature from 20 to 80 °C:Formula I I Formula I I Iwherein: m can vary between 8 and 178;R is either: ethyl; vinyl; 1,2-dibromoethyl; 3-oxopropyl or 3-hydroxypropylBPn is a bioplasticizer;PSn is a metal complex of tetrapyrrolic macrocycle type according to the formula B:Formula B wherein:R' is an alkyl group comprising between 1 and 12 carbon atoms or an aryl moiety, and M is Al; Ni; Cu or Zn; or the tetrapyrrolic macrocycle type PSn is a metalloporphyrin according to the formula C:Formula C wherein:Ar is a 4-trifluoromethylphenyl; 3-trifluoromethylphenyl; 2-trifluoromethylphenyl; 2,6- difluorophenyl; 2,6-dichlorophenyl; 2,6-dibromophenyl or pentafluorophenyl group, andM is Al; Cr; Mn; Fe or Co.

20. Process according with the claim 19 wherein the bioplasticizer is glycerol; poly-( / ?)-3- hydroxybutyrate or is a cellulose derivative.

21. Process according with the claim 20 wherein cellulose derivative is according to the formula IV:Formula IV wherein:R' is either: methyl; ethyl; acetyl; hydroxyethyl; 2-hydroxypropyl or carboxymethyl groups;P is between 200 and 7000.

22. Process according with the claims 19 to 21 wherein the organic solvent is anisole; p-cymene or 2- methyltetra hydrofuran.

23. Process for preparation of photosensitive polycarbonate-bioplasticizer composites films according with the claim 19 wherein the process further a step selected from: solvent casting techniques; compression moulding; injection moulding; extrusion; blow moulding; thermoforming or foam moulding.

24. Use of the photosensitive polycarbonate-bioplasticizer composites claimed in claim 1 in the photodynamic inactivation of microorganisms.

25. Use of the photosensitive polycarbonate-bioplasticizer composites according to the claim 1, in antimicrobial photo-decontamination of medical devices; hospital surfaces and equipment.

26. Use of the photosensitive polycarbonate-bioplasticizer composites according to the previous claim wherein medical devices comprises catheters, endotracheal tubes, stethoscopes, protection glasses and face shields.

27. Use of the photosensitive polycarbonate-bioplasticizer composites according to the claim 25 wherein hospital surfaces and equipment comprises desks, stretchers, computers and laptop touch screens.

28. Use of the photosensitive polycarbonate-bioplasticizer composites claimed in claim 1 in the manufacture and their antimicrobial photo-decontamination of objects selected from: pens, chairs, containers, packaging films / wrappers and garbage bags.

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