Influence of polylactide coating stereochemistry on mechanical and in vitro degradation properties of porous bioactive glass scaffolds for bone regeneration.

The mechanical properties of polylactide stereocomplexes (PLA SC) have been primarily studied through tensile testing, with inconsistent results, and the compressive properties of PLA SC compared to homocrystalline or amorphous PLA remain poorly understood. In this study, we coated porous bioactive glass 13-93 scaffolds with amorphous, homocrystalline, or stereocomplex PLA to investigate their mechanical and degradation properties before and after immersion in simulated body fluid. The glass scaffolds had interconnected pores and an average porosity of 76%. The PLA coatings, which were 10-100 µm thick and approximately 3% of the glass scaffold mass, covered the glass to a large extent. The compressive strength and toughness of all PLA-coated scaffolds were significantly higher than those of uncoated scaffolds, with approximately a fourfold increase before immersion and a twofold increase after immersion. The compressive strength and toughness of PLA SC-coated scaffolds were similar to those of scaffolds with homocrystalline PLA coating, and significantly higher than for scaffolds with amorphous PLA coating. All PLA coatings moderated the initial pH increase caused by the glass, which could benefit surrounding cells and bone tissue in vivo after implantation.

Attenuation of celecoxib cardiac toxicity using Poly(δ-decalactone) based nanoemulsion via oral route.

Celecoxib (CLX), a poorly soluble anti-inflammatory drug, requires administration in higher concentrations to produce therapeutic effects, oftentimes resulting in cardiac toxicity. Therefore, in this study, we employed a nanoemulsion technology to improve the solubility of CLX using poly(δ-decalactone) (PDL) polymer as an oil and mPEG-b-PDL as a surfactant. The nanoemulsion (NE) was successfully prepared via the nanoprecipitation method. In vitro characterization was performed for size, drug release, and stability. In vivo studies were performed to establish anti-inflammatory activity, CLX induced cardiac toxicity, and pharmacokinetic profile of NE, post-oral administration. The globular size of less than 100 nm was obtained in NE with high CLX loading. The in vitro drug release studies suggested ∼90% of CLX release from NE within 96 h. A significant anti-inflammatory activity with lowered cardiac marker values was observed for CLX NE compared to a marketed drug formulation. The pharmacokinetic study revealed that the mean retention time of CLX was significantly increased with NE in contrast to the marketed formulation, suggesting the advantage of administering CLX in the form of NE owing to the higher solubility and sustained release pattern. The long-term storage stability study reveals that NE does not show significant changes in terms of size with only a slight decrement in CLX content was observed after 24 months. The obtained results indicate that CLX bioavailability has been considerably improved without being toxic to the heart with the aid of NE and advocate the use of PDL NE for developing oral formulations for poorly soluble drugs.

Functional block copolymer micelles based on poly (jasmine lactone) for improving the loading efficiency of weakly basic drugs.

Functionalization of polymers is an attractive approach to introduce specific molecular forces that can enhance drug-polymer interaction to achieve higher drug loading when used as drug delivery systems. The novel amphiphilic block copolymer of methoxy poly(ethylene glycol) and poly(jasmine lactone) i.e., mPEG-b-PJL, derived from renewable jasmine lactone provides free allyl groups on the backbone thus, allowing flexible and facile post-synthesis functionalization. In this study, mPEG-b-PJL and its carboxyl functionalized polymer mPEG-b-PJL-COOH were utilised to explore the effect of ionic interactions on the drug-polymer behaviour. Various drugs with different pK a values were employed to prepare drug-loaded polymeric micelles (PMs) of mPEG-b-PJL, mPEG-b-PJL-COOH and Soluplus® (polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer) via a nanoprecipitation method. Electrostatic interactions between the COOH pendant on mPEG-b-PJL-COOH and the basic drugs were shown to influence the entrapment efficiency. Additionally, molecular dynamics (MD) simulations were employed to understand the polymer-drug interactions at the molecular level and how polymer functionalization influenced these interactions. The release kinetics of the anti-cancer drug sunitinib from mPEG-b-PJL and mPEG-b-PJL-COOH was assessed, and it demonstrated a sustainable drug release pattern, which depended on both pH and temperature. Furthermore, the cytotoxicity of sunitinib-loaded micelles on cancer cells was evaluated. The drug-loaded micelles exhibited dose-dependent toxicity. Also, haemolysis capacity of these polymers was investigated. In summary, polymer functionalization seems a promising approach to overcome challenges that hinder the application of polymer-based drug delivery systems such as low drug loading degree.

Significance of Polymers with "Allyl" Functionality in Biomedicine: An Emerging Class of Functional Polymers.

In recent years, polymer-based advanced drug delivery and tissue engineering have grown and expanded steadily. At present, most of the polymeric research has focused on improving existing polymers or developing new biomaterials with tunable properties. Polymers with free functional groups offer the diverse characteristics needed for optimal tissue regeneration and controlled drug delivery. Allyl-terminated polymers, characterized by the presence of a double bond, are a unique class of polymers. These polymers allow the insertion of a broad diversity of architectures and functionalities via different chemical reactions. In this review article, we shed light on various synthesis methodologies utilized for generating allyl-terminated polymers, macromonomers, and polymer precursors, as well as their post-synthesis modifications. In addition, the biomedical applications of these polymers reported in the literature, such as targeted and controlled drug delivery, improvement i aqueous solubility and stability of drugs, tissue engineering, and antimicrobial coatings, are summarized.

The Synthesis of Low-Viscosity Organotin-Free Moisture-Curable Silane-Terminated Poly(Urethane-Urea)s.

This work explores the possibility of synthesizing moisture-curable silane-terminated poly(urethane-urea)s (SPURs) of low viscosity. First, NCO-terminated urethane prepolymers were prepared, followed by silane end-capping. The impact of polyol molecular weight and the ratio of isocyanate to polyol (NCO/OH) on viscosity and the properties of SPUR were examined. As alternatives to the organotin catalysts traditionally used for the polyurethane synthesis and curing processes, bismuth carboxylate catalysts were evaluated. In addition, the effect of organofunctional groups in the aminosilane structure (R1⁻NH⁻R2⁻Si(OR3)3), i.e., R1 (alkyl, aryl or trimethoxysilyl-propyl), the spacer R2 (α or γ) and alkyl group R3 (methyl or ethyl), was examined. The chemical and physical structures of the SPUR were investigated by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR) and the mechanical properties were evaluated by tensile tests. The results reveal that silane-terminated, moisture-curable polyurethanes can be successfully synthesized and cured with bismuth carboxylate catalysts. SPUR exhibiting low viscosity, with adequate tensile strength and elongation can be prepared using environmentally benign bismuth carboxylate catalyst having a high metal content of 19%⁻21%, by utilizing secondary aminosilane end-cappers and an optimal combination of the polyol molecular weight and NCO/OH ratio.

Investigation on the Influence of Chain Extenders on the Performance of One-Component Moisture-Curable Polyurethane Adhesives.

In this work, a number of chain extended moisture-curable urethane prepolymers were synthesized in order to develop isocyanate terminated urethane prepolymer formulations that would simultaneously display both high adhesive strength and low viscosity. Proton nuclear magnetic resonance spectroscopy (¹H-NMR), size exclusion chromatography (SEC), differential scanning calorimetry (DSC), and Brookfield viscometry were utilized for characterizing the prepared urethane prepolymers. In addition, the adhesion strength of the cured prepolymers was determined by tensile shear strength test according to the DIN EN (Deutsches Institut für Normung, the German Institute for Standardization) 1465 standard. Especially, the role of different types of linear (butanediol, pentanediol) and branched chain extenders (dipropyleneglycol (di-PPG), tripropyleneglycol (tri-PPG) and the influence of their dosage on the degree of microphase separation between hard segments (HS) and soft segments (SS) in urethane prepolymers were studied. Furthermore, the benefits of utilizing either a one-step versus a two-step polymerization process were investigated. The results revealed that the extent of phase separation of different urethane prepolymers was dependent on the extent of hydrogen bonding interactions which was extensively studied by attenuated total reflectance infrared spectroscopy (ATR-FTIR). The incorporation of branched chain extenders (di-PPG and tri-PPG) did not result in notable phase separation between hard segments and soft segments, while linear chain extenders (pentanediol and butanediol) readily promoted phase separation. The degree of phase separation was particularly pronounced for butanediol, and when the linear chain extender ratio was higher than or equal to 0.74. Compared with a two-stage process, one-stage process produced more randomly distributed polymer chains with highly dispersed hard segments. Thus, urethane prepolymers exhibiting strong adhesive strength with simultaneously low viscosity were successfully developed by systematic adjustment of structural parameters.

Structure⁻Property Studies on a New Family of Halogen Free Flame Retardants Based on Sulfenamide and Related Structures.

A wide variety of molecules containing S⁻N or S⁻N⁻S cores were synthesized, and their flame retardant properties in polypropylene (PP), low density polyethylene (LDPE) and polystyrene (PS) were investigated. In addition, polymers or oligomers bearing the sulfenamide functionality (SN) were also synthesized. It was shown that this radical generator family based on sulfenamides is very versatile in terms of structural modifications, and the thermal decomposition range can be easily adjusted by changing the R groups attached to the core. The thermal stabilities of the different sulfenamides were examined by thermogravimetric analysis (TGA). Radicals generated by the homolytic cleavage of the S⁻N or S⁻N⁻S bonds at an elevated temperature can effectively interact with the intermediate products of polymer thermolysis and provide excellent flame retardant properties. The choice of most suitable SN-structure varies depending on the polymer type. For polypropylene DIN 4102-1 B2 and UL94 VTM-2 classifications were achieved with only 0.5 to 1 wt % of sulfenamide, and, in some cases, no flaming dripping was observed. Also for LDPE thin films, sulfenamides offered the DIN 4102-1 B2 rating at low dosage. In the case of polystyrene, the very stringent UL94 V-0 classification was even achieved at a loading of 5 wt % of sulfenamide.

Environmentally friendly transistors and circuits on paper.

We created environmentally friendly low-voltage, ion-modulated transistors (IMTs) that can be fabricated successfully on a paper substrate. A range of ionic liquids (ILs) based on choline chloride (ChoCl) were used as the electrolytic layer in the IMTs. Different organic compounds were mixed with ChoCl to create solution-processable deep eutectic mixtures that are liquid or semiliquid at room temperature. In the final, solid version of the IMT, the ILs are also solidified by using a commercial binder to create printable transistor structures The semiconductor layer in the IMT is also substituted with a blend of the original semiconductor and a biodegradable polymer insulator. This reduces the amount of expensive and potentially harmful semiconductor used, and it also provides increased transistor performance, especially increasing the device switching speed. These environmentally friendly IMTs are then used to create ring oscillators, logic gates, and memories on paper.