Design, manufacturing and testing of a green non-isocyanate polyurethane prosthetic heart valve.

The sole effective treatment for most patients with heart valve disease is valve replacement by implantation of mechanical or biological prostheses. However, mechanical valves represent high risk of thromboembolism, and biological prostheses are prone to early degeneration. In this work, we aim to determine the potential of novel environmentally-friendly non-isocyanate polyurethanes (NIPUs) for manufacturing synthetic prosthetic heart valves. Polyhydroxyurethane (PHU) NIPUs are synthesized via an isocyanate-free route, tested in vitro, and used to produce aortic valves. PHU elastomers reinforced with a polyester mesh show mechanical properties similar to native valve leaflets. These NIPUs do not cause hemolysis. Interestingly, both platelet adhesion and contact activation-induced coagulation are strongly reduced on NIPU surfaces, indicating low thrombogenicity. Fibroblasts and endothelial cells maintain normal growth and shape after indirect contact with NIPUs. Fluid-structure interaction (FSI) allows modeling of the ideal valve design, with minimal shear stress on the leaflets. Injection-molded valves are tested in a pulse duplicator and show ISO-compliant hydrodynamic performance, comparable to clinically-used bioprostheses. Poly(tetrahydrofuran) (PTHF)-NIPU patches do not show any evidence of calcification over a period of 8 weeks. NIPUs are promising sustainable biomaterials for the manufacturing of improved prosthetic valves with low thrombogenicity.

Bioactive surface coating for preventing mechanical heart valve thrombosis.

BACKGROUND: Prosthetic heart valves are the only treatment for most patients with severe valvular heart disease. Mechanical valves, made of metallic components, are the most long-lasting type of replacement valves. However, they are prone to thrombosis and require permanent anticoagulation and monitoring, which leads to higher risk of bleeding and impacts the patient's quality of life. OBJECTIVES: To develop a bioactive coating for mechanical valves with the aim to prevent thrombosis and improve patient outcomes. METHODS: We used a catechol-based approach to produce a drug-releasing multilayer coating adherent to mechanical valves. The hemodynamic performance of coated Open Pivot valves was verified in a heart model tester, and coating durability in the long term was assessed in a durability tester producing accelerated cardiac cycles. Coating antithrombotic activity was evaluated in vitro with human plasma or whole blood under static and flow conditions and in vivo after surgical valve implantation in a pig's thoracic aorta. RESULTS: We developed an antithrombotic coating consisting of ticagrelor- and minocycline-releasing cross-linked nanogels covalently linked to polyethylene glycol. We demonstrated the hydrodynamic performance, durability, and hemocompatibility of coated valves. The coating did not increase the contact phase activation of coagulation, and it prevented plasma protein adsorption, platelet adhesion, and thrombus formation. Implantation of coated valves in nonanticoagulated pigs for 1 month efficiently reduced valve thrombosis compared with noncoated valves. CONCLUSION: Our coating efficiently inhibited mechanical valve thrombosis, which might solve the issues of anticoagulant use in patients and the number of revision surgeries due to valve thrombosis despite anticoagulation.

Thermal and UV Curable Formulations of Poly(propylene glycol)-Poly(hydroxyurethane) Elastomers toward Nozzle-Based 3D Photoprinting.

In this work, isocyanate-free formulations for poly(propylene glycol) polyurethane elastomers are studied. These formulations are based on poly(propylene glycol) end-capped by CO2-sourced cyclic carbonate (bisCC PPG) macromonomers able to react with amines leading to poly(hydroxyurethane)s. In order to obtain covalent networks, two curing approaches are studied. First, the direct thermally activated cross-linking of bisCC PPG with a mixture of various aliphatic or aromatic diamines and a triamine is investigated, and in particular the nature of the diamine on the mechanical properties. In the second approach, UV-activated formulations are developed by reacting bisCC PPG with allylamine followed by the addition of a trithiol by photoactivated thiol-ene reaction. The swelling tests show that both systems provide highly cross-linked polymer networks and complementary characterizations highlighted excellent mechanical properties. Thanks to the fast curing and adapted viscosity of the developed photoactive formulation, the latter was found suitable for use as a photoresin for 3D printing as demonstrated by printing a vaginal ring by a nozzle-based photoprinter.

Understanding the Influence of Surface Oxygen Groups on the Electrochemical Behavior of Porous Carbons as Anodes for Lithium-Ion Batteries.

The present study elucidates the role of surface oxygen functional groups on the electrochemical behavior of porous carbons when used as anodes for Li-ion batteries. To achieve this objective, a carbon xerogel (CX) obtained by pyrolysis of a resorcinol-formaldehyde gel, was modified by different postsynthesis treatments in order to modulate its surface chemistry while maintaining its external surface constant. Various surface modifications were obtained by oxidation in air, in situ polymerization of dopamine, and finally by grafting of a polyethylene oxide layer on the polydopamine coating. While oxidation in air did not affect the pore texture of the CX, modifications by coating techniques substantially decreased the micropore fraction. Detailed electrochemical characterizations of the materials processed as electrodes were performed by capacitance measurements and galvanostatic cycling. Surface chemistry results, from X-ray photoelectron spectroscopy, show that the accessibility and the capacity increase when carbonyl (R-C═O) groups are formed on the CX, but not with oxides and hydroxyls. The amount of surface carbonyls, and in particular, aldehyde (O═CH) groups, is found to be the key parameter because it is directly correlated with the modified CX electrochemical behavior. Overall, the explored surface coatings tend to reduce the micropore volume and add mainly hydroxyl functional groups but hardly change the Li+ insertion/deinsertion capacities, while oxidation in air adds carbonyl groups, increasing the Li+ ion storage capacity, thanks to an improved accessibility to the carbon network, which is not caused by any textural change.

Aldehyde-conjugated chitosan-graphene oxide glucodynamers: Ternary cooperative assembly and controlled chemical release.

Simultaneous condensation of aromatic aldehydes (ArxCHO; x = 1-4) on chitosan biopolymer (CS) affords, after water-evaporation, structurally-conjugated aryl-functionalized CS-Arx-f films. Similarly, cooperative assembly of two-dimensional nanometric graphene oxide (GO), aromatic aldehyde and chitosan provides transparent, flexible and crack-free aldehyde-functionalized, ternary-reinforced CS-Arx-GO-f nanocomposite films. Homogenous films were obtained using ortho-hydroxybenzaldehyde Ar1 while the para-hydroxybenzaldehyde Ar4 was prone to packing inside. Textural and mechanical properties were investigated and expectedly, significant improvement was found for CS-Ar1-GO-f because of the great dispersion of the aromatic and the presence of the filler. The sensitivity of unsaturated CN imine bond to hydrolysis was explored for triggering controlled release of aromatics from the as-prepared films. All of them were found to induce a time-dependent aromatic release. It has been moreover observed that the release was significantly delayed in CS-Arx-GO-f compared to CS-Arx-f, a fact attributed to the interplay of the ring with the basal and edges of graphene oxide, through π-π stacking and additional hydrogen bonding interactions. This finding shows that beyond the conventional wisdom using fillers for improving thermal and mechanical properties, the tiny carbon sheets can act as a regulator for aldehyde release, thereby providing a way for more controlled chemical delivery from confined nanocomposites.

Multicomponent Radziszewski Emulsion Polymerization toward Macroporous Poly(ionic liquid) Catalysts.

Interconnected macroporous imidazolium-based monoliths are produced via the modified Radziszewski multicomponent reaction (MCR) applied to triamines under high internal phase emulsion (HIPE) conditions. This straightforward one-pot synthesis combines the efficiency and versatility of MCRs with the ease of implementation of the emulsion templating polymerization process. The characterization of the chemical structure and morphology of the resulting materials confirms the formation of the expected macroporous poly(ionic liquid)s (PILs) networks. The promising catalytic activity and recyclability of these porous PIL monoliths are illustrated for the transesterification reaction and the decarboxylation of caffeic acid. In these cases, almost complete conversion is reached while benefiting from the advantages associated with a heterogeneous catalyst.

Poly(ionic liquid)-Derived N-Doped Carbons with Hierarchical Porosity for Lithium- and Sodium-Ion Batteries.

The performance of lithium- and sodium-ion batteries relies notably on the accessibility to carbon electrodes of controllable porous structure and chemical composition. This work reports a facile synthesis of well-defined N-doped porous carbons (NPCs) using a poly(ionic liquid) (PIL) as precursor, and graphene oxide (GO)-stabilized poly(methyl methacrylate) (PMMA) nanoparticles as sacrificial template. The GO-stabilized PMMA nanoparticles are first prepared and then decorated by a thin PIL coating before carbonization. The resulting NPCs reach a satisfactory specific surface area of up to 561 m2 g-1 and a hierarchically meso- and macroporous structure while keeping a nitrogen content of 2.6 wt%. Such NPCs deliver a high reversible charge/discharge capacity of 1013 mA h g-1 over 200 cycles at 0.4 A g-1 for lithium-ion batteries, and show a good capacity of 204 mA h g-1 over 100 cycles at 0.1 A g-1 for sodium-ion batteries.

Bioinspired Redox-Active Catechol-Bearing Polymers as Ultrarobust Organic Cathodes for Lithium Storage.

Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by higher discharge potentials than para-quinones, the latter being extensively used as organic cathode materials for lithium ion batteries (LIBs). Here, this study demonstrates that the rational molecular design of copolymers bearing catechol- and Li+ ion-conducting anionic pendants endow redox-active polymers (RAPs) with ultrarobust electrochemical energy storage features when combined to carbon nanotubes as a flexible, binder-, and metal current collector-free buckypaper electrode. The importance of the structure and functionality of the RAPs on the battery performances in LIBs is discussed. The structure-optimized RAPs can store high-capacities of 360 mA h g-1 at 5C and 320 mA h g-1 at 30C in LIBs. The high ion and electron mobilities within the buckypaper also enable to register 96 mA h g-1 (24% capacity retention) at an extreme C-rate of 600C (6 s for total discharge). Moreover, excellent cyclability is noted with a capacity retention of 98% over 3400 cycles at 30C. The high capacity, superior active-material utilization, ultralong cyclability, and excellent rate performances of RAPs-based electrode clearly rival most of the state-of-the-art Li+ ion organic cathodes, and opens up new horizons for large-scalable fabrication of electrode materials for ultrarobust Li storage.

Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry.

Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,…). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample's polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state. Graphical Abstract ᅟ.

Fluorinated Poly(ionic liquid) Diblock Copolymers Obtained by Cobalt-Mediated Radical Polymerization-Induced Self-Assembly.

Poly(ionic liquid)s (PILs) have attracted considerable attention as innovative single-ion solid polyelectrolytes (SPEs) in substitution to the more conventional electrolytes for a variety of electrochemical devices. Herein, we report the precise synthesis, characterization, and use as single-ion SPEs of a novel double PIL-based amphiphilic diblock copolymer (BCP), i.e., where all monomer units are of N-vinyl-imidazolium type, with triethylene glycol pendant groups in the first block and a statistical distribution of N-vinyl-3-ethyl- and N-vinyl-3-perfluorooctyl-imidazolium bromides in the second block. BCP synthesis is achieved directly in water by a one-pot process, by cobalt-mediated radical polymerization-induced self-assembly (CMR-PISA). A subsequent anion exchange reaction substituting bis(trifluoromethylsulfonyl)imide (Tf2N-) for bromide (Br-) counter-anions leads to PIL BCPs with two different lengths of the first block. They demonstrate ionic conductivity σDC = 1-3 × 10-7 S cm-1, as determined by broadband dielectric spectroscopy at 30 °C (under anhydrous conditions), and exhibit wide electrochemical stability (up to 4.8 V versus Li+/Li) and form free-standing films with mechanical properties suited for SPE applications (Young's modulus = 3.8 MPa, elongation at break of 250%) as determined by stress/strain experiments.

A new design of organic radical batteries (ORBs): carbon nanotube buckypaper electrode functionalized by electrografting.

A novel hybrid material displaying a fast and reversible charge storage capability is prepared by electrografting of an alkoxyamine-bearing acrylate onto a carbon nanotube buckypaper, followed by the quantitative generation of an electroactive polynitroxide.

Development of a procedure to simultaneously isolate RNA, DNA, and proteins for [corrected] characterizing cells invading or cultured on chitosan scaffolds.

For many years, chitosan and its derivatives have been considered to be promising biomaterials for tissue engineering and repair. However, information regarding their biological effect on cell phenotype is usually limited to evaluation of cell proliferation and survival, overlooking proteomic and transcriptomic analysis. This is largely related to the lack of efficient and quantitative procedures for protein and nucleic acid purification from cells cultured on, or inside, chitosan scaffold. Here we describe an ultracentrifugation procedure enabling the simultaneous and quantitative recovery of high quality RNA, DNA and proteins from cells growing in close contact of biomaterial matrices containing chitosan.

Temperature responsive complex coacervate core micelles with a PEO and PNIPAAm corona.

In aqueous solutions at room temperature, poly( N-methyl-2-vinyl pyridinium iodide)- block-poly(ethylene oxide), P2MVP 38- b-PEO 211 and poly(acrylic acid)- block-poly(isopropyl acrylamide), PAA 55- b-PNIPAAm 88 spontaneously coassemble into micelles, consisting of a mixed P2MVP/PAA polyelectrolyte core and a PEO/PNIPAAm corona. These so-called complex coacervate core micelles (C3Ms), also known as polyion complex (PIC) micelles, block ionomer complexes (BIC), and interpolyelectrolyte complexes (IPEC), respond to changes in solution pH and ionic strength as their micellization is electrostatically driven. Furthermore, the PNIPAAm segments ensure temperature responsiveness as they exhibit lower critical solution temperature (LCST) behavior. Light scattering, two-dimensional 1H NMR nuclear Overhauser effect spectrometry, and cryogenic transmission electron microscopy experiments were carried out to investigate micellar structure and solution behavior at 1 mM NaNO 3, T = 25, and 60 degrees C, that is, below and above the LCST of approximately 32 degrees C. At T = 25 degrees C, C3Ms were observed for 7 < pH < 12 and NaNO 3 concentrations below approximately 105 mM. The PEO and PNIPAAm chains appear to be (randomly) mixed within the micellar corona. At T = 60 degrees C, onion-like complexes are formed, consisting of a PNIPAAm inner core, a mixed P2MVP/PAA complex coacervate shell, and a PEO corona.

Surface modification of metallic cardiovascular stents by strongly adhering aliphatic polyester coatings.

This article reports on a novel two-step strategy for the coating of cardiovascular stents by strongly adhering biocompatible and biodegradable aliphatic polyesters. First, a precoating of poly(ethylacrylate) (PEA) was electrografted onto the metallic substrate by cathodic reduction of the parent monomer in dimethylformamide (DMF). The electrodeposition of PEA, in a good solvent of it, was confirmed by both Infra-red and Raman spectroscopies. The pendant ester groups of PEA were then chemically reduced into aluminum alkoxides, able to initiate the ring-opening polymerization (ROP) of either D,L-lactide (LA) or epsilon-caprolactone (CL). Growth of biodegradable PLA or PCL coatings from the adhering precoating was confirmed by both Infra-red and Raman spectroscopies, and directly observed by scanning electron microscopy (SEM). This type of coating can act as an anchoring layer for the subsequent casting of drug-loaded polyester films allowing the controlled release of antiproliferative agents for the treatment of in-stent restenosis.

An easy and economically viable route for the decoration of carbon nanotubes by magnetite nanoparticles, and their orientation in a magnetic field.

A simple, cheap and tunable approach for the decoration of carbon nanotubes by magnetite nanoparticles and their orientation in a magnetic field is reported.