Differentiation of petro-sourced plastic microfilaments from organic microfilaments by SEM-EDX in environmental samples.

Quantifying microplastics (MPs) in marine environments is challenging due to the complexities of differentiation from other materials. This study aims to distinguish petro-sourced plastic microfilaments from organic ones in environmental samples using scanning electron microscope coupled with energy dispersive X-ray (SEM-EDX) analysis. Therefore, 38 particles resembling MPs (PRMPs) from sediments and organisms in Madagascar were analyzed. MPs identification thresholds were determined from SEM-EDX analysis of macroplastics and seaweed, the primary sources of microfilaments. SEM-EDX results of the 38 PRMPs were compared with identification/misidentification made by five MPs observation experts. Results indicated that a carbon/oxygen (C/O) ratio >1 distinguished macroplastics and MPs from other sources (seaweed and organic microfilaments). SEM-EDX analysis identified 81.58% of PRMPs as MPs. The average error made by one observer was 36.32%. These findings highlight the need for a method to assess identification error in MPs quantification and recommend SEM-EDX analysis of microfilaments to gauge observer error.

Recent Advances in Solid-State Modification for Thermoplastic Polymers: A Comprehensive Review.

This review introduces groundbreaking insights in polymer science, specifically spotlighting a novel review of the solid-state modification (SSM) approach of thermoplastic polymers, a method not extensively explored. Unlike traditional melt polymer modification, SSM stands out by incorporating monomers or oligomers into the amorphous phase of polymers through innovative exchange reactions. The background of the study places thermoplastics within the context of their increased use over the past century, highlighting their versatility in various applications and the associated environmental and health concerns due to certain additives. The results section outlines the unique aspects of SSM and its increasing recognition for its potential to enhance material performance in areas such as catalysts and composites. It also discusses the application of SSM in modifying different thermoplastic polymers, highlighting various studies demonstrating the method's effectiveness in altering polymer properties. Finally, this work emphasizes SSM's importance in environmental sustainability and its potential in the recycling and upcycling of plastic materials. It acknowledges the challenges and future perspectives in the field, particularly regarding the scalability of SSM techniques for industrial applications and their role in advancing a circular economy in the polymer industry.

Covalent Adaptable Networks through Dynamic N,S-Acetal Chemistry: Toward Recyclable CO2-Based Thermosets.

Finding new chemistry platforms for easily recyclable polymers has become a key challenge to face environmental concerns and the growing plastics demand. Here, we report a dynamic chemistry between CO2-sourced alkylidene oxazolidones and thiols, delivering circular non-isocyanate polyurethane networks embedding N,S-acetal bonds. The production of oxazolidone monomers from CO2 is facile and scalable starting from cheap reagents. Their copolymerization with a polythiol occurs under mild conditions in the presence of a catalytic amount of acid to furnish polymer networks. The polymer structure is easily tuned by virtue of monomer design, translating into a wide panel of mechanical properties similar to commodity plastics, ranging from PDMS-like elastomers [with Young's modulus (E) of 2.9 MPa and elongation at break (εbreak) of 159%] to polystyrene-like rigid plastics (with E = 2400 MPa, εbreak = 3%). The highly dissociative nature of the N,S-acetal bonds is demonstrated and exploited to offer three different recycling scenarios to the thermosets: (1) mechanical recycling by compression molding, extrusion, or injection molding─with multiple recycling (at least 10 times) without any material property deterioration, (2) chemical recycling through depolymerization, followed by repolymerization, also applicable to composites, and (3) upcycling of two different oxazolidone-based thermosets into a single one with distinct properties. This work highlights a new facile and scalable chemical platform for designing highly dynamic polymer networks containing elusive oxazolidone motifs. The versatility of this chemistry shows great potential for the preparation of materials (including composites) of tuneable structures and properties, with multiple end-of-life scenarios.

Protecting public health and the environment: towards a general ban on cellulose acetate cigarette filters in the European Union.

After the establishment of a causal relationship between tobacco use and cancer in the 1950s, cellulose acetate filters were introduced with the claim to reduce the adverse health impact of unfiltered cigarettes. Often perceived to be more pleasant and healthy, filters encouraged smoking. However, filtered cigarettes are more deeply inhaled to obtain the same nicotine demand while altered combustion releases more tobacco-specific nitrosamines. The increasing use of cigarette filter ventilation is associated with a sharp rise in lung adenocarcinomas in recent decades. While not preventing adverse health effects, a global environmental problem has been created due to the non-biodegradable filter litter, causing ecotoxicological effects and the spread of microplastics. Recently, the Belgian Superior Health Council advised policymakers to ban cigarette filters as single-use plastics at both national and European levels. This article outlines the arguments used to justify this plea (human health and environment), the expected effects of a filter ban, as well as the public reception and reactions of the tobacco industry. The specific context of the European Union is discussed including the revision of the Single-Use Plastics Directive, affording a new opportunity to ban plastic filters. This perspective article aims to fuel the momentum and cooperation among member states for this purpose.

Balancing the Strength-Impact Relationship and Other Key Properties in Polypropylene Copolymer-Natural CaSO4 (Anhydrite)-Filled Composites.

To develop novel mineral-filled composites and assess their enhanced properties (stiffness, a good balance between mechanical strength and impact resistance, greater temperature stability), a high-impact polypropylene copolymer (PPc) matrix containing an elastomeric discrete phase was melt mixed with natural CaSO4 ß-anhydrite II (AII) produced from gypsum rocks. First, in a prior investigation, the PPc composites filled with AII (without any modification) displayed enhanced stiffness, which is correlated with the relative content of the filler. The tensile and impact strengths dramatically decreased, especially at high filling (40 wt.%). Therefore, two key methods were considered to tune up their properties: (a) the ionomeric modification of PPc composites by reactive extrusion (REx) with zinc diacrylate (ZA), and (b) the melt mixing of PPc with AII surface modified with ethylenebis(stearamide) (EBS), which is a multifunctional processing/dispersant additive. The properties of composites produced with twin-screw extruders (TSEs) were deeply assessed in terms of morphology, mechanical, and thermal performance, including characterizations under dynamic mechanical solicitations at low and high temperatures. Two categories of products with distinct properties are obtained. The ionomeric modification by Rex (evaluated by FTIR) led to composites characterized by remarkable thermal stability, a higher temperature of crystallization, stronger interfacial interactions, and therefore noticeable mechanical properties (high tensile strength (i.e., 28 MPa), increased stiffness, moderate (3.3 kJ/m2) to good (5.0 kJ/m2) impact resistance) as well as advanced heat deflection temperature (HDT). On the other hand, the surface modification of AII with EBS facilitated the dispersion and debonding of microparticles, leading to composites revealing improved ductility (strain at break from 50% to 260%) and enhanced impact properties (4.3-5.3 kJ/m2), even at high filling. Characterized by notable mechanical and thermal performances, high whiteness, and a good processing ability, these new PPc-AII composites may be tailored to meet the requirements of end-use applications, ranging from packaging to automotive components.

Balancing Acute and Chronic Occupational Risks: The Use of Nitrile Butadiene Rubber Undergloves by Firefighters to Reduce Exposure to Toxic Contaminants.

Firefighters are exposed via multi-route exposure to a multitude of chemicals (PAHs, VOCs, flame retardants, dioxins, etc.) that may cause acute and long-term health effects. The dermal absorption of contaminants is a major contributor to the overall exposure and can be reduced by wearing appropriate personal protective equipment. As leather firefighters' gloves cannot be decontaminated regularly by wet cleaning, many Belgian firefighters wear supplementary undergloves made of nitrile butadiene rubber (NBR) to protect against the accumulation of toxicants. However, the safety of this practice has been questioned. In this commentary, the current practice and risks are outlined for the first time, assessed by an interdisciplinary working group of the Belgian Superior Health Council. As NBR sticks to the skin more at high temperatures, the contact time on removal will be prolonged, posing an additional risk for deeper burns. However, based on the physicochemical properties of NBR and the existing experience of firefighters and burn centers, it is estimated that such incidents occur relatively rarely in practice. On the other hand, the risk of repeated exposure to contaminated gloves if no undergloves are worn is unacceptable. Despite the slightly increased risk for deeper burns, it is concluded that wearing disposable NBR gloves under regular firefighters' gloves is an appropriate and effective preventive measure against toxic contamination. The nitrile butadiene rubber must always be fully covered to avoid any contact with the heat.

Ionically Modified Gelatin Hydrogels Maintain Murine Myogenic Cell Viability and Fusion Capacity.

For tissue engineering of skeletal muscles, there is a need for biomaterials which do not only allow cell attachment, proliferation, and differentiation, but also support the physiological conditions of the tissue. Next to the chemical nature and structure of the biomaterial, its response to the application of biophysical stimuli, such as mechanical deformation or application of electrical pulses, can impact in vitro tissue culture. In this study, gelatin methacryloyl (GelMA) is modified with hydrophilic 2-acryloxyethyltrimethylammonium chloride (AETA) and 3-sulfopropyl acrylate potassium (SPA) ionic comonomers to obtain a piezoionic hydrogel. Rheology, mass swelling, gel fraction, and mechanical characteristics are determined. The piezoionic properties of the SPA and AETA-modified GelMA are confirmed by a significant increase in ionic conductivity and an electrical response as a function of mechanical stress. Murine myoblasts display a viability of >95% after 1 week on the piezoionic hydrogels, confirming their biocompatibility. The GelMA modifications do not influence the fusion capacity of the seeded myoblasts or myotube width after myotube formation. These results describe a novel functionalization providing new possibilities to exploit piezo-effects in the tissue engineering field.

Long-term immersion of compostable plastics in marine aquarium: Microbial biofilm evolution and polymer degradation.

The best-selling compostable plastics, polylactic acid (PLA) and polybutylene adipate-co-terephthalate (PBAT), can accidentally end up in the marine environment due to plastic waste mismanagement. Their degradation and colonization by microbial communities are poorly documented in marine conditions. To better understand their degradation, as well as the dynamics of bacterial colonization after a long immersion time (99, 160, and 260 days), PBAT, semicrystalline, and amorphous PLA films were immersed in a marine aquarium. Sequencing and chemical analyses were used in parallel to characterize these samples. Despite the variation in the chemical intrinsic parameters of these plastics, their degradation remains very slow. Microbial community structure varied according to the immersion time with a high proportion of Archaea. Moreover, the plastisphere structure of PBAT was specific. A better understanding of compostable plastic degradability is crucial to evaluate their impact on ecosystems and to eco-design new recyclable plastics with optimal degradation properties.

Design of Thermoplastic Polyurethanes with Conferred Antibacterial, Mechanical, and Cytotoxic Properties for Catheter Application.

Thermoplastic polyurethanes (TPUs) are proposed as suitable solution for the fabrication of biocompatible catheters with appropriate mechanical parameters and confirmed antibacterial and cytocompatible properties. For this purpose, a series of quaternary ammonium salts (QASs) and quaternary phosphonium salts (QPSs) based monomers were prepared followed by the determination of their minimal inhibitory concentrations (MICs) against Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Pseudomonas aeruginosa (P. aeruginosa). A combination of the most active ammonium (QAS-C14) and phosphonium (QPS-TOP) salts led to a MIC down to 2.4 µg/mL against S. aureus and 9 µg/mL against P. aeruginosa, corroborating the existence of a synergistic effect. These quaternary onium salt (QOS) units were successfully incorporated along the polymer chain, as part of a two-step synthesis approach. The resulting TPU-QOS materials were subsequently characterized through thermal, mechanical, and surface analyses. TPU-Mix (combining the most active QAS-C14 and QPS-TOP units) showed the highest antibacterial efficiency, confirming the synergistic effect between both QOS groups. Finally, an MTT assay on the SiHa cell line revealed the low cytotoxicity level of these polymeric films, making these materials suitable for biomedical application. To go one step further in the preindustrialization approach, proof of concept regarding the catheter prototype fabrication based on TPU-QAS/QPS was validated by extrusion.

Pegylated Curcumin Derivative: Water-Soluble Conjugates with Antitumor and Antibacterial Activity.

During the past years, the synthesis of polymer prodrug structures, based on natural phytochemical compounds with a great range of valuable biological properties, has become a promising solution in cancer prevention, imaging, and detection. Curcumin (Curc) remains one of the most studied natural products, due to the impressive palette of biological properties and the possibility to be easily loaded in various micro- and nanostructures and chemically modified. In this study, pegylated curcumin derivatives were prepared by a direct esterification reaction between poly(ethylene glycol)diacid (PEG of 600 g/mol molar mass, PEG600) and Curc in the presence of N,N'-dicyclohexylcarbodiimide (PEG600-Curc). The successful reaction resulted in a water-soluble stable product that was characterized by infrared spectroscopy (Fourier transform infrared (FT-IR)) and proton (1H) and carbon (13C) NMR. The effect of the pH values of buffer solutions on PEG600-Curc spectral properties (absorption and photoluminescence) was investigated by UV-vis and fluorescence spectrophotometry. Based on the biological tests, it was confirmed that PEG600-Curc exhibits cytotoxic activity against Graffi cell lines, as a function of the Curc concentration in the conjugate and the incubation time. PEG600-Curc antibacterial activity was validated in microbiological tests against pathogenic microorganisms such as Staphylococcus aureus. Most importantly, despite the covalent attachment of Curc to PEG and the slight reduction in the therapeutic index of the conjugate, both the anticancer and antimicrobial activities remain the highest reported, thus opening the gate for further, more clinically oriented studies.

Pellet-Based Fused Filament Fabrication (FFF)-Derived Process for the Development of Polylactic Acid/Hydroxyapatite Scaffolds Dedicated to Bone Regeneration.

Scaffolds can be defined as 3D architectures with specific features (surface properties, porosity, rigidity, biodegradability, etc.) that help cells to attach, proliferate, and to differentiate into specific lineage. For bone regeneration, rather high mechanical properties are required. That is why polylactic acid (PLA) and PLA/hydroxyapatite (HA) scaffolds (10 wt.%) were produced by a peculiar fused filament fabrication (FFF)-derived process. The effect of the addition of HA particles in the scaffolds was investigated in terms of morphology, biological properties, and biodegradation behavior. It was found that the scaffolds were biocompatible and that cells managed to attach and proliferate. Biodegradability was assessed over a 5-month period (according to the ISO 13781-Biodegradability norm) through gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and compression tests. The results revealed that the presence of HA in the scaffolds induced a faster and more complete polymer biodegradation, with a gradual decrease in the molar mass (Mn) and compressive mechanical properties over time. In contrast, the Mn of PLA only decreased during the processing steps to obtain scaffolds (extrusion + 3D-printing) but PLA scaffolds did not degrade during conditioning, which was highlighted by a high retention of the mechanical properties of the scaffolds after conditioning.

Green Topochemical Esterification Effects on the Supramolecular Structure of Chitin Nanocrystals: Implications for Highly Stable Pickering Emulsions.

In nature, chitin is organized in hierarchical structures composed of nanoscale building blocks that show outstanding mechanical and optical properties attractive for nanomaterial design. For applications that benefit from a maximized interface such as nanocomposites and Pickering emulsions, individualized chitin nanocrystals (ChNCs) are of interest. However, when extracted in water suspension, their individualization is affected by ChNC self-assembly, requiring a large amount of water (above 90%) for ChNC transport and stock, which limits their widespread use. To master their individualization upon drying and after regeneration, we herein report a waterborne topochemical one-pot acid hydrolysis/Fischer esterification to extract ChNCs from chitin and simultaneously decorate their surface with lactate or butyrate moieties. Controlled reaction conditions were designed to obtain nanocrystals of a comparable aspect ratio of about 30 and a degree of modification of about 30% of the ChNC surface, under the rationale to assess the only effect of the topochemistry on ChNC supramolecular organization. The rheological analysis coupled with polarized light imaging shows how the nematic structuring is hindered by both surface ester moieties. The increased viscosity and elasticity of the modified ChNC colloids indicate a gel-like phase, where typical ChNC clusters of liquid crystalline phases are disrupted. Pickering emulsions have been prepared from lyophilized nanocrystals as a proof of concept. Our results demonstrate that only the emulsions stabilized by the modified ChNCs have excellent stability over time, highlighting that their individualization can be regenerated from the dry state.

Nanocluster-Based Drug Delivery and Theranostic Systems: Towards Cancer Therapy.

Over the last decades, the global life expectancy of the population has increased, and so, consequently, has the risk of cancer development. Despite the improvement in cancer therapies (e.g., drug delivery systems (DDS) and theranostics), in many cases recurrence continues to be a challenging issue. In this matter, the development of nanotechnology has led to an array of possibilities for cancer treatment. One of the most promising therapies focuses on the assembly of hierarchical structures in the form of nanoclusters, as this approach involves preparing individual building blocks while avoiding handling toxic chemicals in the presence of biomolecules. This review aims at presenting an overview of the major advances made in developing nanoclusters based on polymeric nanoparticles (PNPs) and/or inorganic NPs. The preparation methods and the features of the NPs used in the construction of the nanoclusters were described. Afterwards, the design, fabrication and properties of the two main classes of nanoclusters, namely noble-metal nanoclusters and hybrid (i.e., hetero) nanoclusters and their mode of action in cancer therapy, were summarized.

Proof of concept of a predictive model of drug release from long-acting implants obtained by fused-deposition modeling.

In the pharmaceutical field, there is a growing interest in manufacturing of drug delivery dosage forms adapted to the needs of a large variety of patients. 3D printing has proven to be a powerful tool allowing the adaptation of immediate drug delivery dosage forms. However, there are still few studies focusing on the adaptation of long-acting dosage forms for patient suffering of neurological diseases. In this study, paliperidone palmitate (PP) was chosen as a model drug in combination with different polymers adapted for fused-deposition modeling (FDM). The impact of different printing parameters on the release of PP were investigated. The layer thickness and the infill percentage were studied using a quality by design approach. Indeed, by defining the critical quality attributes (CQA), a proof of concept of a prediction system, and a quality control system were studied through designs of experiments (DoE). The first part of this study was dedicated to the release of PP from a fix geometry. In the second part, the prediction system was developed to require only surface and surface to volume ratio. From that point, it was possible to get rid of a fix geometry and predict the amount of PP released from complex architectures.

Paliperidone palmitate as model of heat-sensitive drug for long-acting 3D printing application.

In this work, two technologies were used to prepare long-acting implantable dosage forms in the treatment of schizophrenia. Hot-melt extrusion (HME) as well as fused deposition modelling (FDM) were used concomitantly to create personalized 3D printed implants. Different formulations were prepared using an amorphous PLA as matrix polymer and different solid-state plasticizers. Paliperidone palmitate (PP), a heat sensitive drug prescribed in the treatment of schizophrenia was chosen as model drug. After extrusion, different formulations were characterized using DSC and XRD. Then, an in vitro dissolution test was carried out to discriminate the formulation allowing a sustained drug release of PP. The formulation showing a sustained drug release of the drug was 3D printed as an implantable dosage form. By modulating the infill, the release profile was related to the proper design of tailored dosage form and not solely to the solubility of the drug. Indeed, different release profiles were achieved over 90 days using only one formulation. In addition, a stability test was performed on the 3D printed implants for 3 months. The results showed the stability of the amorphous state of PP, independently of the temperature as well as the integrity of the matrix and the drug.

A dynamic passive thermoregulation fabric using metallic microparticles.

Maintaining comfort using photonic thermal management textiles has a large potential to decrease the energy cost for heating and cooling in residential and office buildings. We propose a thermoregulating fabric using metallic microparticles, which provides a dynamic and passive control of the infrared transmission, by adapting to the ambient temperature and humidity. The fabric is composed of tailored metal microparticles and a stimuli-responsive polymer actuator matrix, in order to benefit from strong scattering effects to control the wideband transmission of thermal radiation and to provide a sharp, dynamic response. The detailed numerical design demonstrates a wide dynamic ambient setpoint temperature window of ∼8 °C, with the wearer staying comfortable in the range between 18 and 26 °C. Its compatibility for large-scale manufacturing, with a safe and strong thermoregulating performance indicates a vital energy-saving potential and paves the way to a more sustainable society.

Solvent-Free Design of Biobased Non-isocyanate Polyurethanes with Ferroelectric Properties.

Increasing energy autonomy and lowering dependence on lithium-based batteries are more and more appealing to meet our current and future needs of energy-demanding applications such as data acquisition, storage, and communication. In this respect, energy harvesting solutions from ambient sources represent a relevant solution by unravelling these challenges and giving access to an unlimited source of portable/renewable energy. Despite more than five decades of intensive study, most of these energy harvesting solutions are exclusively designed from ferroelectric ceramics such as Pb(Zr,Ti)O3 and/or ferroelectric polymers such as polyvinylidene fluoride and its related copolymers, but the large implementation of these piezoelectric materials into these technologies is environmentally problematic, related with elevated toxicity and poor recyclability. In this work, we reveal that fully biobased non-isocyanate polyurethane-based materials could afford a sustainable platform to produce piezoelectric materials of high interest. Interestingly, these non-isocyanate polyurethanes (NIPUs) with ferroelectric properties could be successfully synthesized using a solvent-free reactive extrusion process on the basis of an aminolysis reaction between resorcinol bis-carbonate and different diamine extension agents. Structure-property relationships were established, indicating that the ferroelectric behavior of these NIPUs depends on the nanophase separation inside these materials. These promising results indicate a significant potential for fulfilling the requirements of basic connected sensors equipped with low-power communication technologies.

Interfacial Compatibilization into PLA/Mg Composites for Improved In Vitro Bioactivity and Stem Cell Adhesion.

The present work highlights the crucial role of the interfacial compatibilization on the design of polylactic acid (PLA)/Magnesium (Mg) composites for bone regeneration applications. In this regard, an amphiphilic poly(ethylene oxide-b-L,L-lactide) diblock copolymer with predefined composition was synthesised and used as a new interface to provide physical interactions between the metallic filler and the biopolymer matrix. This strategy allowed (i) overcoming the PLA/Mg interfacial adhesion weakness and (ii) modulating the composite hydrophilicity, bioactivity and biological behaviour. First, a full study of the influence of the copolymer incorporation on the morphological, wettability, thermal, thermo-mechanical and mechanical properties of PLA/Mg was investigated. Subsequently, the bioactivity was assessed during an in vitro degradation in simulated body fluid (SBF). Finally, biological studies with stem cells were carried out. The results showed an increase of the interfacial adhesion by the formation of a new interphase between the hydrophobic PLA matrix and the hydrophilic Mg filler. This interface stabilization was confirmed by a decrease in the damping factor (tanδ) following the copolymer addition. The latter also proves the beneficial effect of the composite hydrophilicity by selective surface localization of the hydrophilic PEO leading to a significant increase in the protein adsorption. Furthermore, hydroxyapatite was formed in bulk after 8 weeks of immersion in the SBF, suggesting that the bioactivity will be noticeably improved by the addition of the diblock copolymer. This ceramic could react as a natural bonding junction between the designed implant and the fractured bone during osteoregeneration. On the other hand, a slight decrease of the composite mechanical performances was noted.

Pathways to Green Perspectives: Production and Characterization of Polylactide (PLA) Nanocomposites Filled with Superparamagnetic Magnetite Nanoparticles.

In the category of biopolymers, polylactide or polylactic acid (PLA) is one of the most promising candidates considered for future developments, as it is not only biodegradable under industrial composting conditions, but it is produced from renewable natural resources. The modification of PLA through the addition of nanofillers is considered as a modern approach to improve its main characteristic features (mechanical, thermal, barrier, etc.) and to obtain specific end-use properties. Iron oxide nanoparticles (NPs) of low dimension (10-20 nm) such as magnetite (Fe3O4), exhibit strong magnetization in magnetic field, are biocompatible and show low toxicity, and can be considered in the production of polymer nanocomposites requiring superparamagnetic properties. Accordingly, PLA was mixed by melt-compounding with 4-16 wt.% magnetite NPs. Surface treatment of NPs with a reactive polymethylhydrogensiloxane (MHX) was investigated to render the nanofiller water repellent, less sensitive to moisture and to reduce the catalytic effects at high temperature of iron (from magnetite) on PLA macromolecular chains. The characterization of nanocomposites was focused on the differences of the rheology and morphology, modification, and improvements in the thermal properties using surface treated NPs, while the superparamagnetic behavior was confirmed by VSM (vibrating sample magnetometer) measurements. The PLA-magnetite nanocomposites had strong magnetization properties at low magnetic field (values close to 70% of Mmax at H = 0.2 T), while the maximum magnetic signal (Mmax) was mainly determined by the loading of the nanofiller, without any significant differences linked to the surface treatment of MNPs. These bionanocomposites showing superparamagnetic properties, close to zero magnetic remanence, and coercivity, can be further produced at a larger scale by melt-compounding and can be designed for special end-use applications, going from biomedical to technical areas.

Potential of poly(alkylene terephthalate)s to control endothelial cell adhesion and viability.

Poly(ethylene terephthalate) (PET) is known for its various useful characteristics, including its applicability in cardiovascular applications, more precisely as synthetic bypass grafts for large diameter (≥ 6 mm) blood vessels. Although it is widely used, PET is not an optimal material as it is not interactive with endothelial cells, which is required for bypasses to form a complete endothelium. Therefore, in this study, poly(alkylene terephthalate)s (PATs) have been studied. They were synthesized via a single-step solution polycondensation reaction, which requires mild reaction conditions and avoids the use of a catalyst or additives like heat stabilizers. A homologous series was realized in which the alkyl chain length varied from 5 to 12 methylene groups (n = 5-12). Molar masses up to 28,000 g/mol were obtained, while various odd-even trends were observed with modulated differential scanning calorimetry (mDSC) and rapid heat-cool calorimetry (RHC) to access the thermal properties within the homologous series. The synthesized PATs have been subjected to in vitro cell viability assays using Human Umbilical Vein Endothelial Cells (HUVECs) and Human Dermal Microvascular Endothelial Cells (HDMECs). The results showed that HUVECs adhere and proliferate most pronounced onto PAT(n=9) surfaces, which could be attributed to the surface roughness and morphology as determined by atomic force microscopy (AFM) (i.e. Rq = 204.7 nm). HDMECs were investigated in the context of small diameter vessels and showed superior adhesion and proliferation after seeding onto PAT(n=6) substrates. These preliminary results already pave the way towards the use of PAT materials as substrates to support endothelial cell adhesion and growth. Indeed, as superior endothelial cell interactivity compared to PET was observed, time-consuming and costly surface modifications of PET grafts could be avoided by exploiting this novel material class.