Marco Ortenzi | Università degli Studi di Milano - State University of Milan (Italy) (original) (raw)
Papers by Marco Ortenzi
RSC Advances, 2017
Oligoamides based on natural raw materials, l-lysine and l-tartaric acid, were synthesized using ... more Oligoamides based on natural raw materials, l-lysine and l-tartaric acid, were synthesized using one-pot processes. A l-lysine diketopiperazine structure was obtained with good selectivity without protection/deprotection steps.
Royal Society Open Science, 2018
Allyl saccharide/vinyl copolymers were synthesized using renewable feedstocks (α,α′-trehalose and... more Allyl saccharide/vinyl copolymers were synthesized using renewable feedstocks (α,α′-trehalose andd-glucose) to obtain ‘green monomers’. Properly designed synthetic procedures were used to obtain copolymers with high purity and without protection/deprotection steps in agreement with the principles of green chemistry and industrial sustainability. The use of saccharide derivatives as monomers allowed products to be obtained that showed high affinity and compatibility for the cellulosic substrates, like paper or wood, and that were suitable for applications like adhesion or consolidation in the field of cultural heritage. All reaction products were characterized by FT-IR and NMR spectroscopies and SEC analyses, while thermal properties were evaluated by DSC analyses.
Polymers, 2021
Poly(3,4-ethylenedioxythiophene) (PEDOT) plays a key role in the field of electrically conducting... more Poly(3,4-ethylenedioxythiophene) (PEDOT) plays a key role in the field of electrically conducting materials, despite its poor solubility and processability. Various molecules and polymers carrying sulfonic groups can be used to enhance PEDOT’s electrical conductivity. Among all, sulfonated polyarylether sulfone (SPAES), prepared via homogenous synthesis with controlled degree of sulfonation (DS), is a very promising PEDOT doping agent. In this work, PEDOT was synthesized via high-concentration solvent-based emulsion polymerization using 1% w/w of SPAES with different DS as dopant. It was found that the PEDOT:SPAESs obtained have improved solubility in the chosen reaction solvents, i.e., N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone and, for the first time, the role of doping agent, DS and polymerization solvents were investigated analyzing the electrical properties of SPAESs and PEDOT:SPAES samples and studying the different morphology of ...
Journal of Hazardous Materials
Polymers
Despite the poor photochemical stability of capsules walls, polyacrylate is one of the most succe... more Despite the poor photochemical stability of capsules walls, polyacrylate is one of the most successful polymers for microencapsulation. To improve polyacrylate performance, the combined use of different acrylate-based polymers could be exploited. Herein butyl methacrylate (BUMA)-based lattices were obtained via free radical polymerization in water by adding (i) methacrylic acid (MA)/methyl methacrylate (MMA) and (ii) methacrylamide (MAC) respectively, as an aqueous phase in Pickering emulsions, thanks to both the excellent polymer shells’ stability and the high encapsulation efficiency. A series of BUMA_MA_MMA terpolymers with complex macromolecular structures and BUMA_MAC linear copolymers were synthesized and used as dispersing media of an active material. Rate and yield of encapsulation, active substance adsorption onto the polymer wall, capsule morphology, shelf-life and controlled release were investigated. The effectiveness of the prepared BUMA-based microcapsules was demonstr...
Pharmaceutics
The paper entitled “Mucoadhesive Budesonide Formulation for the Treatment of Eosinophilic Esophag... more The paper entitled “Mucoadhesive Budesonide Formulation for the Treatment of Eosinophilic Esophagitis Pharmaceutics 2020, 12, 211” discusses the physicochemical and technological characterization of a formulation to treat eosinophilic esophagitis [...]
Acta Crystallographica Section A Foundations and Advances
Polymers
The first example of solvent-free, organocatalyzed, polymerization of 1,3-dioxolan-4-ones, used a... more The first example of solvent-free, organocatalyzed, polymerization of 1,3-dioxolan-4-ones, used as easily accessible monomers for the synthesis of polylactic acid (PLA), is described here. An optimization of reaction conditions was carried out, with p-toluensulfonic acid emerging as the most efficient Brønsted acid catalyst. The reactivity of the monomers in the tested conditions was studied following the monomer conversion by 1H NMR and the molecular weight growth by SEC analysis. A double activation polymerization mechanism was proposed, pointing out the key role of the acid catalyst. The formation of acetal bridges was demonstrated, to different extents depending on the nature of the aldehyde or ketone employed for lactic acid protection. The polymer shows complete retention of stereochemistry, as well as good thermal properties and good polydispersity, albeit modest molecular weight.
Applied Sciences
In this work, three types of cellulose nanocrystals (CNCs) were used: CNCSO3H extracted from wood... more In this work, three types of cellulose nanocrystals (CNCs) were used: CNCSO3H extracted from wood pulp by sulfuric acid (H2SO4), CNCCOOH extracted from cotton linters by ammonium persulfate (APS) and CNCCOOR obtained by esterification of the previous two CNCCOOH and CNCSO3H. For a comparative assessment of gas barrier performance, plastic films such as PLA, PET, PE, PP, OPP and OPA were selected, coated with the three types of CNCs and finally laminated with a solvent-based polyurethanic adhesive. First, all dispersed CNCs were characterized by apparent hydrodynamic diameter and Z potential by means of dynamic light scattering (DLS) and electrophoretic light scattering (ELS) techniques, respectively, followed by the crystallinity index (XRD), thermogravimetric analysis (TGA) and evaluation of Fourier-transform infrared spectroscopy (FTIR), as well as the charges density. The surface chemistry of coated plastics (CNCs-P) was assessed by the Z potential through the electrokinetic tech...
Polymers
Polylactide (PLA)-based polymers, functionalized with biobased antioxidants, were synthesized, to... more Polylactide (PLA)-based polymers, functionalized with biobased antioxidants, were synthesized, to develop an intrinsically active, biobased and potentially biodegradable material for food packaging applications. To achieve this result, phenolic antioxidants were exploited as initiators in the ring opening polymerization of l-lactide. The molecular weight, thermal properties and in vitro radical scavenging activity of the polymers obtained were compared with the ones of a PLA Natureworks 4043D, commonly used for flexible food packaging applications. The most promising synthesized polymer, bearing vanillyl alcohol as initiator (PLA-VA), was evaluated for active food packaging applications. Packaging with PLA-VA films reduced color and fat oxidation of salami during its shelf life.
Pharmaceutics
Eosinophilic esophagitis (EE) is a chronic immune/antigen-mediated esophageal inflammatory diseas... more Eosinophilic esophagitis (EE) is a chronic immune/antigen-mediated esophageal inflammatory disease for which off-label topical corticosteroids (e.g., budesonide) are widely used in clinic. In general, thickening excipients are mixed with industrial products to improve the residence time of the drug on the esophageal mucosa. The compounding procedures are empirical and the composition is not supported by real physicochemical and technological characterization. The current study aimed to propose a standardized budesonide oral formulation intended to improve the resistance time of the drug on the esophageal mucosa for EE treatment. Different placebo and drug-loaded (0.025% w/w) formulations were prepared by changing the percentage of xanthan gum alone or in ratio 1:1 with guar gum. Both excipients were added in the composition for their mucoadhesive properties. The formulative space was rationalized based on the drug physicochemical stability and the main critical quality attributes of...
Journal of Toxicology and Environmental Health, Part A
Polymers
Polyamide 6 (PA6) suffers from fast degradation in humid conditions due to hydrolysis of amide bo... more Polyamide 6 (PA6) suffers from fast degradation in humid conditions due to hydrolysis of amide bonds, which limits its durability. The addition of nanotubular fillers represents a viable strategy for overcoming this issue, although the additive/polymer interface at high filler content can become privileged site for moisture accumulation. As a cost-effective and versatile material, halloysite nanotubes (HNT) were investigated to prepare PA6 nanocomposites with very low loadings (1–45% w/w). The roles of the physicochemical properties of two differently sourced HNT, of filler functionalization with (3-aminopropyl)triethoxysilane and of dispersion techniques (in situ polymerization vs. melt blending) were investigated. The aspect ratio (5 vs. 15) and surface charge (−31 vs. −59 mV) of the two HNT proved crucial in determining their distribution within the polymer matrix. In situ polymerization of functionalized HNT leads to enclosed and well-penetrated filler within the polymer matrix....
International Journal of Environmental Research and Public Health
Chlorine dioxide (ClO2) has been widely used as a disinfectant in drinking water in the past but ... more Chlorine dioxide (ClO2) has been widely used as a disinfectant in drinking water in the past but its effects on water pipes have not been investigated deeply, mainly due to the difficult experimental set-up required to simulate real-life water pipe conditions. In the present paper, four different kinds of water pipes, two based on plastics, namely random polypropylene (PPR) and polyethylene of raised temperature (PERT/aluminum multilayer), and two made of metals, i.e., copper and galvanized steel, were put in a semi-closed system where ClO2 was dosed continuously. The semi-closed system allowed for the simulation of real ClO2 concentrations in common water distribution systems and to simulate the presence of pipes made with different materials from the source of water to the tap. Results show that ClO2 has a deep effect on all the materials tested (plastics and metals) and that severe damage occurs due to its strong oxidizing power in terms of surface chemical modification of metals...
To overcome the well-known technical problems of Poly(3,4-Ethylenedioxythiophene) (PEDOT), i.e. d... more To overcome the well-known technical problems of Poly(3,4-Ethylenedioxythiophene) (PEDOT), i.e. difficult processability and patterning, due to its poor solubility in common organic and inorganic solvents, PEDOTs characterized by a full miscibility in the reaction solvents used, were successfully synthesized by a direct oxidative polycondensation reaction between Ethylenedioxythiophene (EDOT) and an oxidant species, i.e. ferric sulfate, in four organic reaction solvents: N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP). The oxidative polycondensation of EDOT in the presence of Sulfonated Polyarylethersulfone (SPAES) as doping agent characterized by three increasing degree of sulfonation (DS), i.e. 0.5, 0.75 and 1.0 (meq SO3-•g-1 of polymer), was performed for the first time, leading to a new conducting material: PEDOT_SPAES. PEDOT_SPAES can be easily processed and casted onto the surface of glassy carbon electrodes, reaching better electrochemical performances with respect to the precursors. PEDOT_SPAES chemical structure was investigated via wide-angle scattering (WAXS): comparing WAXS spectra of unmodified PEDOT and commercial PEDOT doped with 2-Naphthalenesulfonic acid, having crystalline structures, with the spectra of PEDOT_SPAESs, that are characterized by amorphous structures, it is possible to assess that for the first time PEDOT-based materials doped with SPAES were synthesized.
Polymers
In this work, new co- and ter-polymers of methyl methacrylate (MMA), ethyl methacrylate (EMA), an... more In this work, new co- and ter-polymers of methyl methacrylate (MMA), ethyl methacrylate (EMA), and N-butyl methacrylate (nBuMA), containing just 1% mol × mol−1 of a fluorinated co-monomer, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl methacrylate (POMA), were synthesized. After an UV accelerated aging test, the photo-chemical stability of the polymers prepared was determined by 1H NMR and FT-IR spectroscopy, size exclusion chromatography, differential scanning calorimetry and wettability measurements. The polymers were applied to Botticino tiles to achieve better performances in terms of water repellency and consequently deterioration resistance. One-year prolonged exposure to a real environment was conducted and the properties of the coated materials and their performances were studied using different surface techniques such as water contact angle (WCA) and colorimetric measurements (CIELaB), capillary absorption, permeability (RVP) tests and soluble salts determination. The effec...
RSC Advances, 2017
Oligoamides based on natural raw materials, l-lysine and l-tartaric acid, were synthesized using ... more Oligoamides based on natural raw materials, l-lysine and l-tartaric acid, were synthesized using one-pot processes. A l-lysine diketopiperazine structure was obtained with good selectivity without protection/deprotection steps.
Royal Society Open Science, 2018
Allyl saccharide/vinyl copolymers were synthesized using renewable feedstocks (α,α′-trehalose and... more Allyl saccharide/vinyl copolymers were synthesized using renewable feedstocks (α,α′-trehalose andd-glucose) to obtain ‘green monomers’. Properly designed synthetic procedures were used to obtain copolymers with high purity and without protection/deprotection steps in agreement with the principles of green chemistry and industrial sustainability. The use of saccharide derivatives as monomers allowed products to be obtained that showed high affinity and compatibility for the cellulosic substrates, like paper or wood, and that were suitable for applications like adhesion or consolidation in the field of cultural heritage. All reaction products were characterized by FT-IR and NMR spectroscopies and SEC analyses, while thermal properties were evaluated by DSC analyses.
Polymers, 2021
Poly(3,4-ethylenedioxythiophene) (PEDOT) plays a key role in the field of electrically conducting... more Poly(3,4-ethylenedioxythiophene) (PEDOT) plays a key role in the field of electrically conducting materials, despite its poor solubility and processability. Various molecules and polymers carrying sulfonic groups can be used to enhance PEDOT’s electrical conductivity. Among all, sulfonated polyarylether sulfone (SPAES), prepared via homogenous synthesis with controlled degree of sulfonation (DS), is a very promising PEDOT doping agent. In this work, PEDOT was synthesized via high-concentration solvent-based emulsion polymerization using 1% w/w of SPAES with different DS as dopant. It was found that the PEDOT:SPAESs obtained have improved solubility in the chosen reaction solvents, i.e., N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone and, for the first time, the role of doping agent, DS and polymerization solvents were investigated analyzing the electrical properties of SPAESs and PEDOT:SPAES samples and studying the different morphology of ...
Journal of Hazardous Materials
Polymers
Despite the poor photochemical stability of capsules walls, polyacrylate is one of the most succe... more Despite the poor photochemical stability of capsules walls, polyacrylate is one of the most successful polymers for microencapsulation. To improve polyacrylate performance, the combined use of different acrylate-based polymers could be exploited. Herein butyl methacrylate (BUMA)-based lattices were obtained via free radical polymerization in water by adding (i) methacrylic acid (MA)/methyl methacrylate (MMA) and (ii) methacrylamide (MAC) respectively, as an aqueous phase in Pickering emulsions, thanks to both the excellent polymer shells’ stability and the high encapsulation efficiency. A series of BUMA_MA_MMA terpolymers with complex macromolecular structures and BUMA_MAC linear copolymers were synthesized and used as dispersing media of an active material. Rate and yield of encapsulation, active substance adsorption onto the polymer wall, capsule morphology, shelf-life and controlled release were investigated. The effectiveness of the prepared BUMA-based microcapsules was demonstr...
Pharmaceutics
The paper entitled “Mucoadhesive Budesonide Formulation for the Treatment of Eosinophilic Esophag... more The paper entitled “Mucoadhesive Budesonide Formulation for the Treatment of Eosinophilic Esophagitis Pharmaceutics 2020, 12, 211” discusses the physicochemical and technological characterization of a formulation to treat eosinophilic esophagitis [...]
Acta Crystallographica Section A Foundations and Advances
Polymers
The first example of solvent-free, organocatalyzed, polymerization of 1,3-dioxolan-4-ones, used a... more The first example of solvent-free, organocatalyzed, polymerization of 1,3-dioxolan-4-ones, used as easily accessible monomers for the synthesis of polylactic acid (PLA), is described here. An optimization of reaction conditions was carried out, with p-toluensulfonic acid emerging as the most efficient Brønsted acid catalyst. The reactivity of the monomers in the tested conditions was studied following the monomer conversion by 1H NMR and the molecular weight growth by SEC analysis. A double activation polymerization mechanism was proposed, pointing out the key role of the acid catalyst. The formation of acetal bridges was demonstrated, to different extents depending on the nature of the aldehyde or ketone employed for lactic acid protection. The polymer shows complete retention of stereochemistry, as well as good thermal properties and good polydispersity, albeit modest molecular weight.
Applied Sciences
In this work, three types of cellulose nanocrystals (CNCs) were used: CNCSO3H extracted from wood... more In this work, three types of cellulose nanocrystals (CNCs) were used: CNCSO3H extracted from wood pulp by sulfuric acid (H2SO4), CNCCOOH extracted from cotton linters by ammonium persulfate (APS) and CNCCOOR obtained by esterification of the previous two CNCCOOH and CNCSO3H. For a comparative assessment of gas barrier performance, plastic films such as PLA, PET, PE, PP, OPP and OPA were selected, coated with the three types of CNCs and finally laminated with a solvent-based polyurethanic adhesive. First, all dispersed CNCs were characterized by apparent hydrodynamic diameter and Z potential by means of dynamic light scattering (DLS) and electrophoretic light scattering (ELS) techniques, respectively, followed by the crystallinity index (XRD), thermogravimetric analysis (TGA) and evaluation of Fourier-transform infrared spectroscopy (FTIR), as well as the charges density. The surface chemistry of coated plastics (CNCs-P) was assessed by the Z potential through the electrokinetic tech...
Polymers
Polylactide (PLA)-based polymers, functionalized with biobased antioxidants, were synthesized, to... more Polylactide (PLA)-based polymers, functionalized with biobased antioxidants, were synthesized, to develop an intrinsically active, biobased and potentially biodegradable material for food packaging applications. To achieve this result, phenolic antioxidants were exploited as initiators in the ring opening polymerization of l-lactide. The molecular weight, thermal properties and in vitro radical scavenging activity of the polymers obtained were compared with the ones of a PLA Natureworks 4043D, commonly used for flexible food packaging applications. The most promising synthesized polymer, bearing vanillyl alcohol as initiator (PLA-VA), was evaluated for active food packaging applications. Packaging with PLA-VA films reduced color and fat oxidation of salami during its shelf life.
Pharmaceutics
Eosinophilic esophagitis (EE) is a chronic immune/antigen-mediated esophageal inflammatory diseas... more Eosinophilic esophagitis (EE) is a chronic immune/antigen-mediated esophageal inflammatory disease for which off-label topical corticosteroids (e.g., budesonide) are widely used in clinic. In general, thickening excipients are mixed with industrial products to improve the residence time of the drug on the esophageal mucosa. The compounding procedures are empirical and the composition is not supported by real physicochemical and technological characterization. The current study aimed to propose a standardized budesonide oral formulation intended to improve the resistance time of the drug on the esophageal mucosa for EE treatment. Different placebo and drug-loaded (0.025% w/w) formulations were prepared by changing the percentage of xanthan gum alone or in ratio 1:1 with guar gum. Both excipients were added in the composition for their mucoadhesive properties. The formulative space was rationalized based on the drug physicochemical stability and the main critical quality attributes of...
Journal of Toxicology and Environmental Health, Part A
Polymers
Polyamide 6 (PA6) suffers from fast degradation in humid conditions due to hydrolysis of amide bo... more Polyamide 6 (PA6) suffers from fast degradation in humid conditions due to hydrolysis of amide bonds, which limits its durability. The addition of nanotubular fillers represents a viable strategy for overcoming this issue, although the additive/polymer interface at high filler content can become privileged site for moisture accumulation. As a cost-effective and versatile material, halloysite nanotubes (HNT) were investigated to prepare PA6 nanocomposites with very low loadings (1–45% w/w). The roles of the physicochemical properties of two differently sourced HNT, of filler functionalization with (3-aminopropyl)triethoxysilane and of dispersion techniques (in situ polymerization vs. melt blending) were investigated. The aspect ratio (5 vs. 15) and surface charge (−31 vs. −59 mV) of the two HNT proved crucial in determining their distribution within the polymer matrix. In situ polymerization of functionalized HNT leads to enclosed and well-penetrated filler within the polymer matrix....
International Journal of Environmental Research and Public Health
Chlorine dioxide (ClO2) has been widely used as a disinfectant in drinking water in the past but ... more Chlorine dioxide (ClO2) has been widely used as a disinfectant in drinking water in the past but its effects on water pipes have not been investigated deeply, mainly due to the difficult experimental set-up required to simulate real-life water pipe conditions. In the present paper, four different kinds of water pipes, two based on plastics, namely random polypropylene (PPR) and polyethylene of raised temperature (PERT/aluminum multilayer), and two made of metals, i.e., copper and galvanized steel, were put in a semi-closed system where ClO2 was dosed continuously. The semi-closed system allowed for the simulation of real ClO2 concentrations in common water distribution systems and to simulate the presence of pipes made with different materials from the source of water to the tap. Results show that ClO2 has a deep effect on all the materials tested (plastics and metals) and that severe damage occurs due to its strong oxidizing power in terms of surface chemical modification of metals...
To overcome the well-known technical problems of Poly(3,4-Ethylenedioxythiophene) (PEDOT), i.e. d... more To overcome the well-known technical problems of Poly(3,4-Ethylenedioxythiophene) (PEDOT), i.e. difficult processability and patterning, due to its poor solubility in common organic and inorganic solvents, PEDOTs characterized by a full miscibility in the reaction solvents used, were successfully synthesized by a direct oxidative polycondensation reaction between Ethylenedioxythiophene (EDOT) and an oxidant species, i.e. ferric sulfate, in four organic reaction solvents: N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP). The oxidative polycondensation of EDOT in the presence of Sulfonated Polyarylethersulfone (SPAES) as doping agent characterized by three increasing degree of sulfonation (DS), i.e. 0.5, 0.75 and 1.0 (meq SO3-•g-1 of polymer), was performed for the first time, leading to a new conducting material: PEDOT_SPAES. PEDOT_SPAES can be easily processed and casted onto the surface of glassy carbon electrodes, reaching better electrochemical performances with respect to the precursors. PEDOT_SPAES chemical structure was investigated via wide-angle scattering (WAXS): comparing WAXS spectra of unmodified PEDOT and commercial PEDOT doped with 2-Naphthalenesulfonic acid, having crystalline structures, with the spectra of PEDOT_SPAESs, that are characterized by amorphous structures, it is possible to assess that for the first time PEDOT-based materials doped with SPAES were synthesized.
Polymers
In this work, new co- and ter-polymers of methyl methacrylate (MMA), ethyl methacrylate (EMA), an... more In this work, new co- and ter-polymers of methyl methacrylate (MMA), ethyl methacrylate (EMA), and N-butyl methacrylate (nBuMA), containing just 1% mol × mol−1 of a fluorinated co-monomer, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl methacrylate (POMA), were synthesized. After an UV accelerated aging test, the photo-chemical stability of the polymers prepared was determined by 1H NMR and FT-IR spectroscopy, size exclusion chromatography, differential scanning calorimetry and wettability measurements. The polymers were applied to Botticino tiles to achieve better performances in terms of water repellency and consequently deterioration resistance. One-year prolonged exposure to a real environment was conducted and the properties of the coated materials and their performances were studied using different surface techniques such as water contact angle (WCA) and colorimetric measurements (CIELaB), capillary absorption, permeability (RVP) tests and soluble salts determination. The effec...