Novel Biobased Copolymers Based on Poly(butylene succinate) and Cutin: In Situ Synthesis and Structure Properties Investigations.

The present work describes the synthesis of poly(butylene succinate) (PBSu)-cutin copolymers by the two-stage melt polycondensation method, esterification and polycondensation. Cutin was added in four different concentrations, 2.5, 5, 10, and 20 wt%, in respect to succinic acid. The obtained copolymers were studied using a variety of techniques such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarized light microscopy (PLM), as well as diffuse reflectance spectroscopy (DRS). A series of results, in agreement between different techniques, revealed the formation of PBSu-cutin interactions, confirming indirectly the successful in situ synthetic route of copolymers. DSC and XRD combined with PLM results provided indications that the crystallization temperature increases with the addition of small amounts of cutin and gradually decreases with increasing concentration. The crystallization process was easier and faster at 2.5%, 5%, and 10% concentrations, whereas at 20%, it was comparable to neat PBSu. The presence of cutin, in general, leads to the facilitated crystallizability of PBSu (direct effect), whereas a moderate drop in the glass transition temperature is recorded, the latter being an indirect effect of cutin via crystallization. The thermal stability improved in the copolymers compared to neat PBSu. Water contact angle measurements confirmed that the addition of cutin decreased the hydrophilicity. The local and segmental relaxation mapping is demonstrated for PBSu/cutin here for the first time. Enzymatic hydrolysis and soil degradation tests showed that, overall, cutin accelerated the decomposition of the polymers. The copolymers may be proven useful in several applications.

Water slowing down drives the occurrence of the low temperature dynamical transition in microgels.

The protein dynamical transition marks an increase in atomic mobility and the onset of anharmonic motions at a critical temperature (T d), which is considered relevant for protein functionality. This phenomenon is ubiquitous, regardless of protein composition, structure and biological function and typically occurs at large protein content, to avoid water crystallization. Recently, a dynamical transition has also been reported in non-biological macromolecules, such as poly(N-isopropyl acrylamide) (PNIPAM) microgels, bearing many similarities to proteins. While the generality of this phenomenon is well-established, the role of water in the transition remains a subject of debate. In this study, we use atomistic molecular dynamics (MD) simulations and elastic incoherent neutron scattering (EINS) experiments with selective deuteration to investigate the microscopic origin of the dynamical transition and distinguish water and PNIPAM roles. While a standard analysis of EINS experiments would suggest that the dynamical transition occurs in PNIPAM and water at a similar temperature, simulations reveal a different perspective, also qualitatively supported by experiments. From room temperature down to about 180 K, PNIPAM exhibits only modest changes of dynamics, while water, being mainly hydration water under the probed extreme confinement, significantly slows down and undergoes a mode-coupling transition from diffusive to activated. Our findings therefore challenge the traditional view of the dynamical transition, demonstrating that it occurs in proximity of the water mode-coupling transition, shedding light on the intricate interplay between polymer and water dynamics.

Keratin-PNIPAM Hybrid Microgels: Preparation, Morphology and Swelling Properties.

Combinations of synthetic polymers, such as poly(N-isopropylacrylamide) (PNIPAM), with natural biomolecules, such as keratin, show potential in the field of biomedicine, since these hybrids merge the thermoresponsive properties of PNIPAM with the bioactive characteristics of keratin. This synergy aims to produce hybrids that can respond to environmental stimuli while maintaining biocompatibility and functionality, making them suitable for various medical and biotechnological uses. In this study, we exploit keratin derived from wool waste in the textile industry, extracted via sulfitolysis, to synthesize hybrids with PNIPAM microgel. Utilizing two distinct methods-polymerization of NIPAM with keratin (HYB-P) and mixing preformed PNIPAM microgels with keratin (HYB-M)-resulted in hybrids with 20% and 25% keratin content, respectively. Dynamic light scattering (DLS) and transmission electron microscopic (TEM) analyses indicated the formation of colloidal systems with particle sizes of around 110 nm for HYB-P and 518 nm for HYB-M. The presence of keratin in both systems, 20% and 25%, respectively, was confirmed by spectroscopic (FTIR and NMR) and elemental analyses. Distinct structural differences were observed between HYB-P and HYB-M, suggesting a graft copolymer configuration for the former hybrid and a complexation for the latter one. Furthermore, these hybrids demonstrated temperature responsiveness akin to PNIPAM microgels and pH responsiveness, underscoring their potential for diverse biomedical applications.

Oxidative NHC Catalysis: An Unconventional Tool for Macrocyclic Oligoesters Synthesis.

The application of N-heterocyclic carbene (NHC) catalysis under highly diluted oxidative condition to the polycondensation of dialdehydes and diols is herein presented as an alternative, atom-economical synthetic route to macrocyclic oligoesters (MCOs). The disclosed protocol paves the way to the straightforward access to MCOs, starting from commercial dialdehydes, avoiding the use of toxic diacyl chlorides, commonly employed in traditional MCOs synthetic processes. The method is totally metal-free, takes place in the green Me-THF solvent and requires the use of a fully recyclable quinone oxidant. The protocol versatility is confirmed by the employment of fossil-based and bio-based monomers such as 2,5-diformylfuran (DFF), 2,5-bis(hydroxymethyl)furan (BHMF), and isomannide, synthesizing a series of novel and known synthetically relevant macrocyclic oligoesters, fully characterized by NMR and MALDI-TOF MS analysis, with product yields (51-86 %) comparable to those obtained by traditional synthetic routes. Finally, to emphasize the synthetic relevance of the target macrocycles, an entropically-driven ring opening polymerization (ED-ROP) key study has been performed, optimizing the organocatalyzed synthesis of poly(2,5-furan-dimethylene 2,5 furandicarboxylate) (PBHMF) with number-average molecular weight up to 8200 g mol-1 and 66 % isolated yield.

Glycolysis of semi-interpenetrated polymer network foam based on poly(vinyl chloride) for recovery and reuse of the individual components.

Rigid semi-Interpenetrated Polymer Network (semi-IPN) foam based on poly(vinyl chloride) (PVC) and crosslinked polyurea/isocyanurate are complex materials that at present are not recyclable. They are used in many fields, including wind blade cores. In this work we studied the depolymerization of the crosslinked portion of the foam under glycolysis conditions for the separation and reuse of the individual components. Reaction products were characterized by FT-IR, NMR, solvent solubility, DSC, elemental analysis, titration of amine and hydroxyl groups and rheology measurements. Triisocyanurates and urea moieties were synthesized and used as model compounds. Glycolysis conditions were optimized to maximize depolymerization while minimizing PVC degradation. The parameters studied were reaction time (8 min to 3 h), temperature (155 to 200 °C), catalyst (potassium acetate or dibutyl tin dilaurate (DBTL)), glycol (ethylene glycol, 1,4 butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol), as well as the effect of PVC thermal stabilizers such as hindered phenols and organo-phosphites. The results showed that the optimal reaction condition for foam glycolysis is 165-175 °C for 20-30 min, using DBTL as catalyst and including thermal stabilizers. No drastic difference was noticed by the kind of glycol used, except for PEG that led to greater PVC degradation. The greatest part of the crosslinked portion (≥90 %) was depolymerized and the result were mainly hydroxyl- and in minor amount amine- terminated oligomers. The recovered PVC (purity roughly 90 %) had a low degree of degradation and a viscosity suitable for its processing as thermoplastic material, i.e. by injection moulding.

Electrical conduction and noise spectroscopy of sodium-alginate gold-covered ultrathin films for flexible green electronics.

Green electronics is an emerging topic that requires the exploration of new methodologies for the integration of green components into electronic devices. Therefore, the development of alternative and eco-friendly raw materials, biocompatible and biodegradable, is of great importance. Among these, sodium-alginate is a natural biopolymer extracted from marine algae having a great potential in terms of transparency, flexibility, and conductivity, when functionalized with a thin gold (Au) layer. The electrical transport of these flexible and conducting substrates has been studied, by DC measurements, from 300 to 10 K, to understand the interplay between the organic substrate and the metallic layer. The results were compared to reference bilayers based on polymethyl-methacrylate, a well-known polymer used in electronics. In addition, a detailed investigation of the electric noise properties was also performed. This analysis allows to study the effect of charge carriers fluctuations, providing important information to quantify the minimum metallic thickness required for electronic applications. In particular, the typical noise behavior of metallic compounds was observed in samples covered with 5 nm of Au, while noise levels related to a non-metallic conduction were found for a thickness of 4.5 nm, despite of the relatively good DC conductance of the bilayer.

Keratin/Polylactic acid/graphene oxide composite nanofibers for drug delivery.

In this work keratin/poly(lactic acid) (PLA) 50/50 wt blend nanofibers with different loadings of graphene-oxide (GO) were prepared by electrospinning and tested as delivery systems of Rhodamine Blue (RhB), selected as a model of a drug. The effect of GO on the electrospinnability and drug release mechanism and kinetics was investigated. Rheological measurements carried out on the blend solutions revealed unsatisfactory compatibility between keratin and PLA under quiet condition. Accordingly, poor interfacial adhesion between the two phases was observed by SEM analysis of a film prepared by solution casting. On the contrary, keratin chains seem to rearrange under the flux conditions of the electrospinning process thus promoting better interfacial interactions between the two polymers, thereby enhancing their miscibility, which resulted in homogeneous and defect-free nanofibers. The loading of GO into the keratin/PLA solution contributes to increase its viscosity, its shear thinning behavior, and its conductivity. Accordingly, thinner and more homogeneous nanofibers resulted from solutions with a relatively high conductivity coupled with a pronounced shear thinning behavior. FTIR and DSC analyses have underlined, that while the PLA/GO interfacial interactions significantly compete with the PLA/keratin ones, there are no significant effects of GO on the structural organization of keratin in blend with the PLA. However, GO offers several advantages from the application point of view by slightly improving the mechanical properties of the electrospun mats and by slowing down the release of the model drug through the reduction of the matrix swelling.

Rheological Response of Polylactic Acid Dispersions in Water with Xanthan Gum.

In this work, the rheological behavior of stable poly(lactic acid) (PLA) dispersions in water, intended for coating applications, was investigated. The newly prepared dispersion consists of PLA particles with an average diameter of 222 ± 2 nm based on dynamic light scattering (DLS) and scanning electron microscopy (SEM) analyses, at concentrations varying in the 5-22 wt % range. Xanthan gum (XG), a bacterial polysaccharide, was used as a thickening agent to modulate the viscosity of the formulations. The rheological properties of the PLA dispersions with different XG and PLA contents were studied in steady shear, amplitude sweep, and frequency sweep experiments. Under steady shear conditions, the viscosity of all the formulations showed a shear-thinning behavior similar to XG solutions in the whole investigated 1-1000 s-1 range, with values dependent on both PLA particles and XG concentrations. Amplitude and frequency sweep data revealed a weak-gel behavior except in the case of the most diluted sample, with moduli dependent on both PLA and XG contents. A unified scaling parameter was identified in the volume fraction (ϕ) of the PLA particles, calculated by considering the dependence of the continuous phase density on the XG concentration. Accordingly, a master curve at different volume fractions was built using the time-concentration-superposition approach. The master curve describes the rheological response of the system over a wider frequency window than the experimentally accessible one and reveals the presence of a superimposed ß relaxation process in the high-frequency region.

Selective Capture of Anti-N-glucosylated NTHi Adhesin Peptide Antibodies by a Multivalent Dextran Conjugate.

Tentacle-like polymers decorated with several copies of peptide antigens can be interesting tools for increasing the ability to capture circulating antibodies in patient sera, using cooperative effects for stronger avidity. We previously showed that antibodies from multiple sclerosis (MS) patient sera preferentially recognize hyperglucosylated adhesin protein HMW1ct of non-typeable Haemophilus influenzae (NTHi). We selected the C-terminal HMW1ct(1347-1354) minimal epitope and prepared the diglucosylated analogue Ac-KAN(Glc)VTLN(Glc)TTG-K(N3 )-NH2 to graft a 40 kDa dextran scaffold modified with glycidyl-propargyl moieties to perform a copper catalyzed alkyne-azide coupling reaction (CuAAC). Quantitative NMR measurements allowed the characterization of the peptide loading (19.5 %) on the multivalent dextran conjugate. This novel polymeric structure displayed optimal capturing properties of both IgG and, more interestingly, IgM antibodies in MS sera. Specific antibodies from a representative MS serum, were successfully depleted using a Sepharose resin bearing the new glucosylated multivalent conjugate, as confirmed by ELISA. These results may offer a promising proof-of-concept for the selective purification of high affinity autoantibodies from sera of autoimmune patients, in general, and of specific high affinity antibodies against a minimally glcosylated epitope Asn(Glc) from sera of multiple sclerosis (MS) patients, in particular.

Synthesis and Exon-Skipping Properties of a 3'-Ursodeoxycholic Acid-Conjugated Oligonucleotide Targeting DMD Pre-mRNA: Pre-Synthetic versus Post-Synthetic Approach.

Steric blocking antisense oligonucleotides (ASO) are promising tools for splice modulation such as exon-skipping, although their therapeutic effect may be compromised by insufficient delivery. To address this issue, we investigated the synthesis of a 20-mer 2'-OMe PS oligonucleotide conjugated at 3'-end with ursodeoxycholic acid (UDCA) involved in the targeting of human DMD exon 51, by exploiting both a pre-synthetic and a solution phase approach. The two approaches have been compared. Both strategies successfully provided the desired ASO 51 3'-UDC in good yield and purity. It should be pointed out that the pre-synthetic approach insured better yields and proved to be more cost-effective. The exon skipping efficiency of the conjugated oligonucleotide was evaluated in myogenic cell lines and compared to that of unconjugated one: a better performance was determined for ASO 51 3'-UDC with an average 9.5-fold increase with respect to ASO 51.

Preparations of Poly(lactic acid) Dispersions in Water for Coating Applications.

A green, effective methodology for the preparation of water-based dispersions of poly(lactic acid) (PLA) for coating purposes is herein presented. The procedure consists of two steps: in the first one, an oil-in-water emulsion is obtained by mixing a solution of PLA in ethyl acetate with a water phase containing surfactant and stabilizer. Different homogenization methods as well as oil/water phase ratio, surfactant and stabilizer combinations were screened. In the second step, the quantitative evaporation of the organic provides water dispersions of PLA that are stable, at least, over several weeks at room temperature or at 4 °C. Particle size was in the 200-500 nm range, depending on the preparation conditions, as confirmed by scanning electron microscope (SEM) analysis. PLA was found not to suffer significant molecular weight degradation by gel permeation chromatography (GPC) analysis. Furthermore, two selected formulations with glass transition temperature (Tg) of 51 °C and 34 °C were tested for the preparation of PLA films by drying in PTFE capsules. In both cases, continuous films that are homogeneous by Fourier-transform infrared spectroscopy (FT-IR) and SEM observation were obtained only when drying was performed above 60 °C. The formulation with lower Tg results in films which are more flexible and transparent.

Thermoresponsivity of poly(N-isopropylacrylamide) microgels in water-trehalose solution and its relation to protein behavior.

HYPOTHESES: Additives are commonly used to tune macromolecular conformational transitions. Among additives, trehalose is an excellent bioprotectant and among responsive polymers, PNIPAM is the most studied material. Nevertheless, their interaction mechanism so far has only been hinted without direct investigation, and, crucially, never elucidated in comparison to proteins. Detailed insights would help understand to what extent PNIPAM microgels can effectively be used as synthetic biomimetic materials, to reproduce and study, at the colloidal scale, isolated protein behavior and its sensitivity to interactions with specific cosolvents or cosolutes. EXPERIMENTS: The effect of trehalose on the swelling behavior of PNIPAM microgels was monitored by dynamic light scattering; Raman spectroscopy and molecular dynamics simulations were used to explore changes of solvation and dynamics across the swelling-deswelling transition at the molecular scale. FINDINGS: Strongly hydrated trehalose molecules develop water-mediated interactions with PNIPAM microgels, thereby preserving polymer hydration below and above the transition while drastically inhibiting local motions of the polymer and of its hydration shell. Our study, for the first time, demonstrates that slowdown of dynamics and preferential exclusion are the principal mechanisms governing trehalose effect on PNIPAM microgels, at odds with preferential adsorption of alcohols, but in full analogy with the behavior observed in trehalose-protein systems.

Polymer Identification and Specific Analysis (PISA) of Microplastic Total Mass in Sediments of the Protected Marine Area of the Meloria Shoals.

Microplastics (MPs) quantification in benthic marine sediments is typically performed by time-consuming and moderately accurate mechanical separation and microscopy detection. In this paper, we describe the results of our innovative Polymer Identification and Specific Analysis (PISA) of microplastic total mass, previously tested on either less complex sandy beach sediment or less demanding (because of the high MPs content) wastewater treatment plant sludges, applied to the analysis of benthic sediments from a sublittoral area north-west of Leghorn (Tuscany, Italy). Samples were collected from two shallow sites characterized by coarse debris in a mixed seabed of Posidonia oceanica, and by a very fine silty-organogenic sediment, respectively. After sieving at <2 mm the sediment was sequentially extracted with selective organic solvents and the two polymer classes polystyrene (PS) and polyolefins (PE and PP) were quantified by pyrolysis-gas chromatography-mass spectrometry (Pyr-GC/MS). A contamination in the 8-65 ppm range by PS could be accurately detected. Acid hydrolysis on the extracted residue to achieve total depolymerization of all natural and synthetic polyamides, tagging of all aminated species in the hydrolysate with a fluorophore, and reversed-phase high performance liquid chromatography (HPLC) (RP-HPLC) analysis, allowed the quantification within the 137-1523 ppm range of the individual mass of contaminating nylon 6 and nylon 6,6, based on the detected amounts of the respective monomeric amines 6-aminohexanoic acid (AHA) and hexamethylenediamine (HMDA). Finally, alkaline hydrolysis of the residue from acid hydrolysis followed by RP-HPLC analysis of the purified hydrolysate showed contamination by polyethylene terephthalate (PET) in the 12.1-2.7 ppm range, based on the content of its comonomer, terephthalic acid.

Chemical-Physical Behaviour of Microgels Made of Interpenetrating Polymer Networks of PNIPAM and Poly(acrylic Acid).

Microgels composed of stimuli responsive polymers have attracted worthwhile interest as model colloids for theorethical and experimental studies and for nanotechnological applications. A deep knowledge of their behaviour is fundamental for the design of new materials. Here we report the current understanding of a dual responsive microgel composed of poly(N-isopropylacrylamide) (PNIPAM), a temperature sensitive polymer, and poly(acrylic acid) (PAAc), a pH sensitive polymer, at different temperatures, PAAc contents, concentrations, solvents and pH. The combination of multiple techniques as Dynamic Light Scattering (DLS), Raman spectroscopy, Small Angle Neutron Scattering (SANS), rheology and electrophoretic measurements allow to investigate the hydrodynamic radius behaviour across the typical Volume Phase Transition (VPT), the involved molecular mechanism and the internal particle structure together with the viscoelastic properties and the role of ionic charge in the aggregation phenomena.

Electric Transport in Gold-Covered Sodium-Alginate Free-Standing Foils.

The electric transport properties of flexible and transparent conducting bilayers, realized by sputtering ultrathin gold nanometric layers on sodium-alginate free-standing films, were studied. The reported results cover a range of temperatures from 3 to 300 K. In the case of gold layer thicknesses larger than 5 nm, a typical metallic behavior was observed. Conversely, for a gold thickness of 4.5 nm, an unusual resistance temperature dependence was found. The dominant transport mechanism below 70 K was identified as a fluctuation-induced tunneling process. This indicates that the conductive region is not continuous but is formed by gold clusters embedded in the polymeric matrix. Above 70 K, instead, the data can be interpreted using a phenomenological model, which assumes an anomalous expansion of the conductive region upon decreasing the temperature, in the range from 300 to 200 K. The approach herein adopted, complemented with other characterizations, can provide useful information for the development of innovative and green optoelectronics.

Exploring Oxidative NHC-Catalysis as Organocatalytic Polymerization Strategy towards Polyamide Oligomers.

The polycondensation of diamines and dialdehydes promoted by an N-heterocyclic carbene (NHC) catalyst in the presence of a quinone oxidant and hexafluoro-2-propanol (HFIP) is herein presented for the synthesis of oligomeric polyamides (PAs), which are obtained with a number-average molecular weight (Mn ) in the range of 1.7-3.6 kg mol-1 as determined by NMR analysis. In particular, the utilization of furanic dialdehyde monomers (2,5-diformylfuran, DFF; 5,5'-[oxybis(methylene)]bis[2-furaldehyde], OBFA) to access known and previously unreported biobased PAs is illustrated. The synthesis of higher molecular weight PAs (poly(decamethylene terephthalamide, PA10T, Mn = 62.8 kg mol-1 ; poly(decamethylene 2,5-furandicarboxylamide, PA10F, Mn = 6.5 kg mol-1 ) by a two-step polycondensation approach is also described. The thermal properties (TGA and DSC analyses) of the synthesized PAs are reported.

Thermal Behaviour of Microgels Composed of Interpenetrating Polymer Networks of Poly(N-isopropylacrylamide) and Poly(acrylic acid): A Calorimetric Study.

Stimuli-responsive microgels have recently attracted great attention in fundamental research as their soft particles can be deformed and compressed at high packing fractions resulting in singular phase behaviours. Moreover, they are also well suited for a wide variety of applications such as drug delivery, tissue engineering, organ-on-chip devices, microlenses fabrication and cultural heritage. Here, thermoresponsive and pH-sensitive cross-linked microgels, composed of interpenetrating polymer networks of poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAAc), are synthesized by a precipitation polymerization method in water and investigated through differential scanning calorimetry in a temperature range across the volume phase transition temperature of PNIPAM microgels. The phase behaviour is studied as a function of heating/cooling rate, concentration, pH and PAAc content. At low concentrations and PAAc contents, the network interpenetration does not affect the transition temperature typical of PNIPAM microgel in agreement with previous studies; on the contrary, we show that it induces a marked decrease at higher concentrations. DSC analysis also reveals an increase of the overall calorimetric enthalpy with increasing concentration and a decrease with increasing PAAc content. These findings are discussed and explained as related to emerging aggregation processes that can be finely controlled by properly changing concentration, PAAc content an pH. A deep analysis of the thermodynamic parameters allows to draw a temperature-concentration state diagram in the investigated concentration range.

Formation and Stability of Smooth Thin Films with Soft Microgels Made of Poly(N-Isopropylacrylamide) and Poly(Acrylic Acid).

In this work, soft microgels of Poly(N-Isopropylacrylamide) (PNIPAm) at two different sizes and of interpenetrated polymer network (IPN) composed of PNIPAm and Poly(Acrylic Acid) (PAAc) were synthesized. Then, solutions of these different types of microgels have been spin-coated on glass substrates with different degrees of hydrophobicity. PNIPAm particles with a larger diameter form either patches or a continuous layer, where individual particles are still distinct, depending on the dispersion concentration and spin speed. On the other, PNIPAm particles with a smaller diameter and IPN particles form a continuous and smooth film, with a thickness depending on the dispersion concentration and spin-speed. The difference in morphology observed can be explained if one considers that the microgels may behave as colloidal particles or macromolecules, depending on their size and composition. Additionally, the microgel size and composition can also affect the stability of the depositions when rinsed in water. In particular, we find that the smooth and continuous films show a stimuli-dependent stability on parameters such as temperature and pH, while large particle layers are stable under any condition except on hydrophilic glass by washing at 50 °C.

Poly(N-isopropylacrylamide) based thin microgel films for use in cell culture applications.

Poly(N-isopropylacrylamide) (PNIPAm) is widely used to fabricate cell sheet surfaces for cell culturing, however copolymer and interpenetrated polymer networks based on PNIPAm have been rarely explored in the context of tissue engineering. Many complex and expensive techniques have been employed to produce PNIPAm-based films for cell culturing. Among them, spin coating has demonstrated to be a rapid fabrication process of thin layers with high reproducibility and uniformity. In this study, we introduce an innovative approach to produce anchored smart thin films both thermo- and electro-responsive, with the aim to integrate them in electronic devices and better control or mimic different environments for cells in vitro. Thin films were obtained by spin coating of colloidal solutions made by PNIPAm and PAAc nanogels. Anchoring the films to the substrates was obtained through heat treatment in the presence of dithiol molecules. From analyses carried out with AFM and XPS, the final samples exhibited a flat morphology and high stability to water washing. Viability tests with cells were finally carried out to demonstrate that this approach may represent a promising route to integrate those hydrogels films in electronic platforms for cell culture applications.

Oxidative NHC-Catalysis as Organocatalytic Platform for the Synthesis of Polyester Oligomers by Step-Growth Polymerization.

The application of N-heterocyclic carbene (NHC) catalysis to the polycondensation of diols and dialdehydes under oxidative conditions is herein presented for the synthesis of polyesters using fossil-based (ethylene glycol, phthalaldehydes) and bio-based (furan derivatives, glycerol, isosorbide) monomers. The catalytic dimethyl triazolium/1,8-diazabicyclo[5.4.0]undec-7-ene couple and stoichiometric quinone oxidant afforded polyester oligomers with a number-average molecular weight (Mn ) in the range of 1.5-7.8 kg mol-1 as determined by NMR analysis. The synthesis of a higher molecular weight polyester (polyethylene terephthalate, PET) by an NHC-promoted two-step procedure via oligoester intermediates is also illustrated together with the catalyst-controlled preparation of cross-linked or linear polyesters derived from the trifunctional glycerol. The thermal properties (TGA and DSC analyses) of the synthesized oligoesters are also reported.