Salen-like Chromium and Aluminum Complexes as Catalysts in the Copolymerization of Epoxides with Cyclic Anhydrides for the Synthesis of Polyesters.

Chromium and aluminum complexes bearing salalen ligands were explored as catalysts for the ring-opening copolymerization (ROCOP) of succinic (SA), maleic (MA), and phthalic (PA) anhydrides with several epoxides: cyclohexene oxide (CHO), propylene oxide (PO), and limonene oxide (LO). Their behavior was compared with that of traditional salen chromium complexes. A completely alternating enchainment of monomers to provide pure polyesters was achieved with all the catalysts when used in combination with 4-(dimethylamino)pyridine (DMAP) as the cocatalyst. Poly(propylene maleate-block-polyglycolide), a diblock polyester with a precise composition, was obtained by switch catalysis, in which the same catalyst was able to combine the ROCOP of propylene oxide and maleic anhydride with the ring-opening polymerization (ROP) of glycolide (GA) through a one-pot procedure, starting from an initial mixture of the three different monomers.

Degradable Elastomers: Is There a Future in Tyre Compound Formulation?

Problems related to non-biodegradable waste coming from vulcanized rubber represent one of the pre-eminent challenges for modern society. End-of-life tyres are an important source of this typology of waste and the increasingly high accumulation in the environment has contributed over the years to enhance land and water pollution. Moreover, the release into the environment of non-degradable micro-plastics and other chemicals as an effect of tyre abrasion is not negligible. Many solutions are currently applied to reuse end-of-life tyres as a raw material resource, such as pyrolysis, thermo-mechanical or chemical de-vulcanisation, and finally crumbing trough different technologies. An interesting approach to reduce the environmental impact of vulcanised rubber wastes is represented by the use of degradable thermoplastic elastomers (TPEs) in tyre compounds. In this thematic review, after a reviewing fossil fuel-based TPEs, an overview of the promising use of degradable TPEs in compound formulation for the tyre industry is presented. Specifically, after describing the properties of degradable elastomers that are favourable for tyres application in comparison to used ones, the real scenario and future perspectives related to the use of degradable polymers for new tyre compounds will be realized.

Biocompatibility of Resorbable Polymers: A Historical Perspective and Framework for the Future.

The history of resorbable polymers containing glycolide, lactide, ε-caprolactone and trimethylene carbonate, with a special emphasis being placed on the time frame of the 1960s-1990s is described. Reviewing the history is valuable when looking into the future perspectives regarding how and where these monomers should be used. This story includes scientific evaluations indicating that these polymers are safe to use in medical devices, while the design of the medical device is not considered in this report. In particular, we present the data regarding the tissue response to implanted polymers, as well as the toxicity and pharmacokinetics of their degradation products. In the translation of these polymers from "the bench to the bedside," various challenges have been faced by surgeons, medical doctors, biologists, material engineers and polymer chemists. This Perspective highlights the visionary role played by the pioneers, addressing the problems that occurred on a case by case basis in translational medicine.

Template-Assisted Enzymatic Synthesis of Oligopeptides from a Polylactide Chain.

Peptides are often attached to polymer materials, as bioactive components, for the control of interactions between the material and its surrounding proteins and cells. However, synthesizing peptides and attaching them to polymers can be challenging and laborious. Herein, we describe the grafting of oligopeptides to an aliphatic polyester, using a one-step chemo-enzymatic synthesis with papain as the biocatalyst. To enable enzyme-mediated functionalization of the polyester, ethyl hept-6-enoylalaninate (grafter) was synthesized and attached to polylactide chains using thiol-ene click reactions. The oligopeptides were grafted onto the polylactide chains using two different synthetic routes: the grafting from strategy, in which the grafter was attached to the polyester prior to oligopeptide synthesis, or the grafting to strategy, in which oligopeptides were synthesized on the grafter first, then attached to the polymer chain. The final products were analyzed and their structures were confirmed using nuclear magnetic resonance (NMR). The peptide attachment was evaluated using size exclusion chromatography (SEC), contact angle measurement and energy-dispersive X-ray spectroscopy-scanning electron microscopy (EDS-SEM). Furthermore, the mechanistic aspects of the synthesis of the oligopeptides on the grafter were studied using molecular dynamics (MD) simulations. The simulation revealed that hydrogen bonding (between the P1 amide nitrogen of the grafter backbone and the carbonyl oxygen of D158 in the papain) maintain the grafter in a productive conformation to stabilize the transition state of nitrogen inversion, a key step of the biocatalytic mechanism. Apart from being biologically relevant, both experimental and computational results suggest that the designed grafter is a good template for initiating chemo-enzymatic synthesis. The results also showed that the grafting to strategy was more successful compared to the grafting from strategy. Overall, a successful synthesis of predefined peptide functionalized polylactide was prepared, where the oligopeptides were grafted in an easy, time efficient, and environmentally friendly way.

A Route to Aliphatic Poly(ester)s with Thiol Pendant Groups: From Monomer Design to Editable Porous Scaffolds.

Biodegradable aliphatic polyesters such as poly(lactide) and poly(ε-caprolactone), largely used in tissue engineering applications, lack suitable functional groups and biological cues to enable interactions with cells. Because of the ubiquity of thiol groups in the biological environment and the pliability of thiol chemistry, we aimed to design and synthesize poly(ester) chains bearing pendant thiol-protected groups. To achieve this, 3-methyl-6-(tritylthiomethyl)-1,4-dioxane-2,5-dione, a lactide-type monomer possessing a pendant thiol-protected group, was synthesized. This molecule, when used as a monomer in controlled ring-opening polymerization in combination with lactide and ε-caprolactone, appeared to be a convenient "building block" for the preparation of functionalized aliphatic copolyesters, which were easily modified further. A polymeric sample bearing pyridyl disulfide groups, able to bind a cysteine-containing peptide, was efficiently obtained from a two-step modification reaction. Porous scaffolds were then prepared by blending this latter copolymer sample with poly(L-lactide-co-ε-caprolactone) followed by salt leaching. A further disulfide exchange reaction performed in aqueous medium formed porous scaffolds with covalently linked arginine-glycine-aspartic acid sequences. The scaffolds were characterized by thermal and mechanical tests, and scanning electron microscopy surface images revealed a highly porous morphology. Moreover, a cytotoxicity test indicated good cell viability.

Different insight into amphiphilic PEG-PLA copolymers: influence of macromolecular architecture on the micelle formation and cellular uptake.

One constrain in the use of micellar carriers as drug delivery systems (DDSs) is their low stability in aqueous solution. In this study "tree-shaped" copolymers of general formula mPEG-(PLA)n (n = 1, 2 or 4; mPEG = poly(ethylene glycol) monomethylether 2K or 5K Da; PLA = atactic or isotactic poly(lactide)) were synthesized to evaluate the architecture and chemical composition effect on the micelles formation and stability. Copolymers with mPEG/PLA ratio of about 1:1 wt/wt were obtained using a "core-first" synthetic route. Dynamic Light Scattering (DLS), Field Emission Scanning Electron Microscopy (FESEM), and Zeta Potential measurements showed that mPEG2K-(PD,LLA)2 copolymer, characterized by mPEG chain of 2000 Da and two blocks of atactic PLA, was able to form monodisperse and stable micelles. To analyze the interaction among micelles and tumor cells, FITC conjugated mPEG-(PLA)n were synthesized. The derived micelles were tested on two, histological different, tumor cell lines: HEK293t and HeLa cells. Fluorescence Activated Cells Sorter (FACS) analysis showed that the FITC conjugated mPEG2K-(PD,LLA)2 copolymer stain tumor cells with high efficiency. Our data demonstrate that both PEG size and PLA structure control the biological interaction between the micelles and biological systems. Moreover, using confocal microscopy analysis, the staining of tumor cells obtained after incubation with mPEG2K-(PD,LLA)2 was shown to be localized inside the tumor cells. Indeed, the mPEG2K-(PD,LLA)2 paclitaxel-loaded micelles mediate a potent antitumor cytotoxicity effect.

Interface interactions driven antioxidant properties in olive leaf extract/cellulose nanocrystals/poly(butylene adipate-co-terephthalate) biomaterials.

Functional packaging represents a new frontier for research on food packaging materials. In this context, adding antioxidant properties to packaging films is of interest. In this study, poly(butylene adipate-co-terephthalate) (PBAT) and olive leaf extract (OLE) have been melt-compounded to obtain novel biomaterials suitable for applications which would benefit from the antioxidant activity. The effect of cellulose nanocrystals (CNC) on the PBAT/OLE system was investigated, considering the interface interactions between PBAT/OLE and OLE/CNC. The biomaterials' physical and antioxidant properties were characterized. Morphological analysis corroborates the full miscibility between OLE and PBAT and that OLE favours CNC dispersion into the polymer matrix. Tensile tests show a stable plasticizer effect of OLE for a month in line with good interface PBAT/OLE interactions. Simulant food tests indicate a delay of OLE release from the 20 wt% OLE-based materials. Antioxidant activity tests prove the antioxidant effect of OLE depending on the released polyphenols, prolonged in the system at 20 wt% of OLE. Fluorescence spectroscopy demonstrates the nature of the non-covalent PBAT/OLE interphase interactions in π-π stacking bonds. The presence of CNC in the biomaterials leads to strong hydrogen bonding interactions between CNC and OLE, accelerating OLE released from the PBAT matrix.

Poly(ε-caprolactone)-poly(ethylene glycol) Tri-Block Copolymer as Quercetin Delivery System for Human Colorectal Carcinoma Cells: Synthesis, Characterization and In Vitro Study.

Quercetin is a hydrophobic molecule with short blood circulation times and instability. The development of a nano-delivery system formulation of quercetin may increase its bioavailability, resulting in greater tumor suppressing effects. Triblock ABA type polycaprolactone-polyethylenglycol- polycaprolactone (PCL-PEG-PCL) copolymers have been synthetized using ring-opening polymerization of caprolactone from PEG diol. The copolymers were characterized by nuclear magnetic resonance (NMR), diffusion-ordered NMR spectroscopy (DOSY), and gel permeation chromatography (GPC). The triblock copolymers self-assembled in water forming micelles consisting of a core of biodegradable polycaprolactone (PCL) and a corona of polyethylenglycol (PEG). The core-shell PCL-PEG-PCL nanoparticles were able to incorporate quercetin into the core. They were characterized by dynamic light scattering (DLS) and NMR. The cellular uptake efficiency of human colorectal carcinoma cells was quantitatively determined by flow cytometry using nanoparticles loaded with Nile Red as hydrophobic model drug. The cytotoxic effect of quercetin-loaded nanoparticles was evaluated on HCT 116 cells, showing promising results.

Simple magnesium alkoxides: synthesis, molecular structure, and catalytic behaviour in the ring-opening polymerization of lactide and macrolactones and in the copolymerization of maleic anhydride and propylene oxide.

The synthesis of two chiral bulky alkoxide pro-ligands, 1-adamantyl-tert-butylphenylmethanol HOCAdtBuPh and 1-adamantylmethylphenylmethanol HOCAdMePh, is reported and their coordination chemistry with magnesium(II) is described and compared with the coordination chemistry of the previously reported achiral bulky alkoxide pro-ligand HOCtBu2Ph. Treatment of n-butyl-sec-butylmagnesium with two equivalents of the racemic mixture of HOCAdtBuPh led selectively to the formation of the mononuclear bis(alkoxide) complex Mg(OCAdtBuPh)2(THF)2. 1H NMR spectroscopy and X-ray crystallography suggested the selective formation of the C2-symmetric homochiral diastereomer Mg(OCRAdtBuPh)2(THF)2/Mg(OCSAdtBuPh)2(THF)2. In contrast, the less sterically encumbered HOCAdMePh led to the formation of dinuclear products indicating only partial alkyl group substitution. The mononuclear Mg(OCAdtBuPh)2(THF)2 complex was tested as a catalyst in different reactions for the synthesis of polyesters. In the ROP of lactide, Mg(OCAdtBuPh)2(THF)2 demonstrated very high activity, higher than that shown by Mg(OCtBu2Ph)2(THF)2, although with moderate control degrees. Both Mg(OCAdtBuPh)2(THF)2 and Mg(OCtBu2Ph)2(THF)2 were found to be very effective in the polymerization of macrolactones such as ω-pentadecalactone (PDL) and ω-6-hexadecenlactone (HDL) also under mild reaction conditions that are generally prohibitive for these substrates. The same catalysts demonstrated efficient ring-opening copolymerization (ROCOP) of propylene oxide (PO) and maleic anhydride (MA) to produce poly(propylene maleate).

One-Pot Terpolymerization of Macrolactones with Limonene Oxide and Phtalic Anhydride to Produce di-Block Semi-Aromatic Polyesters.

The synthesis of novel block copolymers, namely poly(limonene-phthalate)-block-poly(pentadecalactone) and poly(limonene-phthalate)-block-poly(pentadecalactone) is here described. To achieve this synthesis, a bimetallic aluminum based complex (1) was used as catalyst in the combination of two distinct processes: the ring-opening polymerization (ROP) of macrolactones such as ω-pentadecalactone (PDL) and ω-6-hexadecenlactone (HDL) and the ring-opening copolymerization (ROCOP) of limonene oxide (LO) and phthalic anhydride (PA). The synthesis of di-block polyesters was performed in a one-pot procedure, where the semi-aromatic polyester block was firstly formed by ROCOP of LO and PA, followed by the polyethylene like portion produced by ROP of macrolactones (PDL or HDL). The obtained di-block semiaromatic polyesters were characterized by NMR and GPC. The structural organization was analyzed through XRD. Thermal properties were evaluated using differential thermal analysis (DSC) and thermogravimetric measurements (TGA) either in air or in nitrogen atmosphere.

Thermo-Rheological and Shape Memory Properties of Block and Random Copolymers of Lactide and ε-Caprolactone.

Biodegradable block and random copolymers have attracted numerous research interests in different areas, due to their capability to provide a broad range of properties. In this paper, an efficient strategy has been reported for preparing biodegradable PCL-PLA copolymers with improved thermal, mechanical and rheological properties. Two block-copolymers are synthesized by sequential addition of the cyclic esters lactide (L-LA or D,L-LA) and ε-caprolactone (CL) in presence of a dimethyl(salicylaldiminato)aluminium compound. The random copolymer of L-LA and CL was synthetized by using the same catalyst. Chain structure, molar mass, thermal, rheological and mechanical properties are characterized by NMR, SEC, TGA, DSC, Rheometry and DMTA. Experimental results show that by changing the stereochemistry and monomer distribution of the copolymers it is possible to obtain a variety of properties. Promising shape-memory properties are also observed in the di-block copolymers characterized by the co-crystallization of CL and L-LA segments. These materials show great potential to substitute oil-based polymers for packaging, electronics, and medicine applications.

The contribution of metalloporphyrin complexes in molecular sensing and in sustainable polymerization processes: a new and unique perspective.

This review highlights the recent developments in the field of metalloporphyrins as optical probes for biologically relevant molecules, such as nitric oxide (NO) and hydrogen sulfide (H2S), and as catalysts for the preparation of sustainable polymers such as polyesters, by the ring-opening polymerization (ROP) of cyclic esters and the ring-opening co-polymerization (ROCOP) of epoxides and anhydrides, and polycarbonates by the chemical fixation of carbon dioxide (CO2). The great potential of porphyrins is mainly due to the possibility of making various synthetic modifications to the porphyrin ring, such as modifying the coordinated metal, peripheral substituents, or even the molecular skeleton. Due to the strict structure-property relationships, one can use porphyrinoids in several different applications such as, for instance, activation of molecular oxygen or catalysis of photosynthetic processes. These possibilities broaden the application of porphyrins in several different fields of research, further mimicking what nature does. In this context, here, we want to provide evidence for the great flexibility of metalloporphyrins by presenting an overview of results obtained by us and others in the research fields we are currently involved in. More specifically, we report a survey of our most significant achievements regarding their use as optical probes in the context of the results reported in the literature from other research groups, and of the use of porphyrin metal(iii) complexes as catalysts for sustainable polymerization processes. As for the optical probe section, in addition to the metalloporphyrins synthesized ad hoc in the laboratory, the present work also covers the natural proteins containing a porphyrin core.

Salen-type aluminum and zinc complexes as two-faced Janus compounds: contribution to molecular sensing and polymerization catalysis.

The aim of the present review is to highlight the most recent achievements in different fields of application of salen-based zinc and aluminum complexes. More specifically this article focuses on the use of aluminum and zinc salen-type complexes as optical probes for biologically relevant molecules, as catalysts for the ring opening polymerization (ROP) of cyclic esters and co-polymerization of epoxides and anhydrides (ROCOP) and in the chemical fixation of carbon dioxide (CO2). The intention is to provide an overview of the most recent results from our group within the framework of the state-of-art-results in the literature.

Ring-opening homo- and co-polymerization of lactides and ε-caprolactone by salalen aluminum complexes.

Aluminum complexes of non-chiral-salalen ligands were investigated in the catalysis of ring-opening polymerization (ROP) of lactide and ε-caprolactone and in their copolymerization. The aluminum-salalen complexes were found to polymerize all varieties of lactide, namely: l-, d-, rac- and meso-lactide, and showed moderate productivities. rac-LA gave rise to isotactic polylactides (with Pm up to 72%), while meso-LA gave rise to heterotactic polylactides (with a Pm of 79%). An experiment was designed for distinguishing between chain-end control and enantiomorphic-site control combined with polymeryl exchange for the isotactic stereoblock microstructure observed for the PLA produced from rac-LA; it gave strong evidence for polymeryl exchange between propagating species. Finally, this class of catalysts promoted the copolymerization of ε-caprolactone and lactides. In particular, compound allowed controlled random copolymerization of ε-caprolactone and l-lactide.