Photophysical properties of thin films and solid phase of switchable supermolecular anthracene-based rotaxanes

Polycrystalline powders and thin films of a novel rotaxane, methyl-exopyridine-anthracene rotaxane (EPAR-Me), and of the related thread and stoppers 10-[3,5-di (ter butyl)phenoxy]decyl-2-({2-[(9-anthrylcarbonyl) amino] acetyl}amino) acetate (ANTPEP), have been characterised by photoluminescence, absorption and photoluminescence excitation spectroscopy. A rather unusual, i.e. unstructured and largely red-shifted, photoluminescence spectral behaviour of the rotaxane has been found. Preliminary time resolved measurements indicate a fast energy transfer from the anthracene unit to different species the nature of which is still not assigned.

In Situ Compatibilization of Biopolymer Ternary Blends by Reactive Extrusion with Low-Functionality Epoxy-Based Styrene Acrylic Oligomer

[EN] The present study reports on the use of low-functionality epoxy-based styrene¿acrylic oligomer (ESAO) to compatibilize immiscible ternary blends made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polylactide (PLA), and poly(butylene adipate-co-terephthalate) (PBAT). The addition during melt processing of low-functionality ESAO at two parts per hundred resin (phr) of biopolymer successfully changed the soften inclusion phase in the blend system to a thinner morphology, yielding biopolymer ternary blends with higher mechanical ductility and also improved oxygen barrier performance. The compatibilization achieved was ascribed to the in situ formation of a newly block terpolymer, i.e. PHBVb- PLA-b-PBAT, which was produced at the blend interface by the reaction of the multiple epoxy groups present in ESAO with the functional terminal groups of the biopolymers. This chemical reaction was mainly linear due to the inherently low functionality of ESAO and the more favorable reactivity of the epoxy groups with the carboxyl groups of the biopolymers, which avoided the formation of highly branched and/or cross-linked structures and thus facilitated the films processability. Therefore, the reactive blending of biopolymers at different mixing ratios with low-functionality ESAO represents a straightforward methodology to prepare sustainable plastics at industrial scale with different physical properties that can be of interest in, for instance, food packaging applications.This research was funded by the EU H2020 project YPACK (Reference number 773872) and by the Spanish Ministry of Science, Innovation, and Universities (MICIU) with project numbers MAT2017-84909-C2-2-R and AGL2015-63855-C2-1-R. L. Quiles-Carrillo wants to thank the Spanish Ministry of Education, Culture, and Sports (MECD) for financial support through his FPU Grant Number FPU15/03812. Torres-Giner also acknowledges the MICIU for his Juan de la Cierva contract (IJCI-2016-29675).Quiles-Carrillo, L.; Montanes, N.; Lagaron, J.; Balart, R.; Torres-Giner, S. (2019). In Situ Compatibilization of Biopolymer Ternary Blends by Reactive Extrusion with Low-Functionality Epoxy-Based Styrene Acrylic Oligomer. 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One-Pot Synthesis for Biocompatible Amphiphilic Hyperbranched Polyurea Micelles

<p>Here we report, for the first time to our knowledge, a method to synthesize AB(2) monomers, the corresponding hyperbranched and the corresponding amphiphilic hyperbranched polymers in a one-pot procedure, starting from two commercial available compounds. Since the B groups were blocked isocyanates (BIs), the end groups of the hyperbranched polyurea were BIs as well. Coupling of a range of monomethoxy-poly(ethylene glycol)s onto the BIs yielded a platform of arnphiphilic hyperbranched polymers, with controllable hydrophobic cores and hydrophilic shells. After the three consecutive reaction steps, without intermediate purification, the final polymers were purified by precipitation in a nonsolvent, in which the polymer precipitated and the excess PEG remained dissolved. Pyrene inclusion experiments showed the formation of micelles above a critical concentration. Both cryo-EM and DLS revealed the presence of two distinct particle populations, being the primary micelles and aggregates thereof All micelles showed a LCST behavior, with transitions close to body temperature. The low cytotoxicity of the micelles make them promising for drug delivery.</p>

Survival of Adhering Staphylococci during Exposure to a Quaternary Ammonium Compound Evaluated by Using Atomic Force Microscopy Imaging▿

Effects of a quaternary ammonium compound (QAC) on the survival of adhering staphylococci on a surface were investigated using atomic force microscopy (AFM). Four strains with different minimal inhibitory concentrations (MIC) and minimal bactericidal concentrations (MBC) for the QAC were exposed to three different concentrations of the QAC in potassium phosphate buffer (0.5×, 1×, and 2× MBC) while adhering to glass. Adhering staphylococci were repeatedly imaged with AFM in the contact mode, and the cell surface was found to wrinkle upon progressive exposure to the QAC until bacteria disappeared from the substratum. Higher concentrations of QAC yielded faster wrinkling and the disappearance of bacteria during imaging. Two slime-producing staphylococcal strains survived longer on the surface than two non-slime-producing strains despite similar MICs and MBCs. All staphylococci adhering in unscanned areas remained adhering during exposure to QAC. Since MICs and MBCs did not relate to bacterial cell surface hydrophobicities and zeta potentials, survival on the surface is probably not determined by the direct interaction of QAC molecules with the cell surface. Instead, it is suggested that the pressure of the AFM tip assists the incorporation of QAC molecules in the membrane and enhances their bactericidal efficacy. In addition, the prolonged survival under pressure from slime-producing strains on a surface may point to a new protective role of slime as a stress absorber, impeding the incorporation of QAC molecules. The addition of Ca2+ ions to a QAC solution yielded longer survival of intact, adhering staphylococci, suggesting that Ca2+ ions can impede the exchange of membrane Ca2+ ions required for QAC incorporation

Excimer-like electroluminescence from thin films of switchable supermolecular anthracene-based rotaxanes

Thin films of 10-[3,5-di(terbutyl)phenoxy]decyl-2-({2-[(9-anthrylcarbonyl)amino]acetyl}amino) acetate (ANTPEP), the thread of an anthracene-based rotaxane, have been processed by the spin coating technique in a polycarbonate (PC) matrix. A single layer organic light emitting diode (OLED) has been demonstrated with an external emission of 2 cd/m2. The light emission, both photo- and electrostimulated, originates from species formed in the excited state and not existing in the ground state. We assign the origin of photo- and electro-emission to molecular excimers.

A chlorhexidine-releasing epoxy-based coating on titanium implants prevents Staphylococcus aureus experimental biomaterial-associated infection

Prevention of biomaterial-associated infections (BAI) remains a challenging problem, in particular due to the increased risk of resistance development with the current antibiotic-based strategies. Metallic orthopaedic devices, such as non-cemented implants, are often inserted under high mechanical stress. These non-cemented implants cannot be protected by e.g. antibioticreleasing bone cement or other antimicrobial approaches, such as the use of bioactive glass. Therefore, in order to avoid abrasion during implantation procedures, we developed an antimicrobial coating with great mechanical stability for orthopaedic implants, to prevent Staphylococcus aureus BAI. We incorporated 5 and 10 wt % chlorhexidine in a novel mechanically stable epoxy-based coating, designated CHX5 and CHX10, respectively. The coatings displayed potent bactericidal activity in vitro against S. aureus, with over 80 % of the release (19 µg/cm2 for CHX5 and 41 µg/cm2 for CHX10) occurring within the first 24 h. In mice, the CHX10 coating significantly reduced the number of CFU (colony forming units), both on the implants and in the peri-implant tissues, 1 d after S. aureus challenge. The CHX10-coated implants were well-tolerated by the animals, with no signs of toxicity observed by histological analysis. Moreover, the coating significantly reduced the frequency of culture-positive tissues 1 d, and of culture-positive implants 1 and 4 d after challenge. In summary, the chlorhexidine-releasing mechanically stable epoxy-based CHX10 coating prevented implant colonisation and S. aureus BAI in mice and has good prospects for clinical developmen