The Response of Tomato Fruit Cuticle Membranes Against Heat and Light

Two important biophysical properties, the thermal and UV-Vis screening capacity, of isolated tomato fruit cuticle membranes (CM) have been studied by differential scanning calorimetry (DSC) and UV-Vis spectrometry, respectively. A first order melting, corresponding to waxes, and a second order glass transition (Tg) thermal events have been observed. The glass transition was less defined and displaced toward higher temperatures along the fruit ripening. In immature and mature green fruits, the CM was always in the viscous and more fluid state but, in ripe fruits, daily and seasonal temperature fluctuations may cause the transition between the glassy and viscous states altering the mass transfer between the epidermal plant cells and the environment. CM dewaxing reduced the Tg value, as derived from the role of waxes as fillers. Tg reduction was more intense after polysaccharide removal due to their highly interwoven distribution within the cutin matrix that restricts the chain mobility. Such effect was amplified by the presence of phenolic compounds in ripe cuticle membranes. The structural rigidity induced by phenolics in tomato CMs was directly reflected in their mechanical elastic modulus. The heat capacity (Cprev) of cuticle membranes was found to depend on the developmental stage of the fruits and was higher in immature and green stages. The average Cprev value was above the one of air, which confers heat regulation capacity to CM. Cuticle membranes screened the UV-B light by 99% irrespectively the developmental stage of the fruit. As intra and epicuticular waxes contributed very little to the UV screening, this protection capacity is attributed to the absorption by cinnamic acid derivatives. However, the blocking capacity toward UV-A is mainly due to the CM thickness increment during growth and to the absorption by flavone chalconaringenin accumulated during ripening. The build-up of phenolic compounds was found to be an efficient mechanism to regulate both the thermal and UV screening properties of cuticle membranes.

Ionic liquid-plasticised composites of chitosan and hybrid 1D and 2D nanofillers

The focus of this research was to study the effect of combining nanofillers with different geometry and surface chemistry on the structure and properties of biopolymers as an alternative to traditional plastics. How the inclusion of 2D graphene oxide (GO) or reduced GO (rGO) combined with 1D sepiolite (SPT) or cellulose nanocrystals (CNCs) affect the structure and properties of chitosan and chitosan/carboxymethyl cellulose (CMC) materials was investigated. A 3D interconnected microstructure formed, composed of GO and SPT due to the strong interactions between these hydrophilic nanofillers. The chitosan/CMC/GO/SPT composite had the highest tensile strength (77.5 ± 1.2 MPa) and Young’s modulus (1925.9 ± 120.7 MPa). For the un-plasticised matrices, hydrophobic rGO nanosheets generally hindered the interaction of SPT or CNCs with the polysaccharides (chitosan and CMC) and consequently, composite properties were mainly determined by the rGO. However, for the chitosan matrix plasticised by 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), rGO + CNCs or rGO + SPT disrupted polymer chain interactions more effectively than the nanofillers when added alone and resulted in the chitosan being more plasticised, as shown by increased chain mobility, ductility, and surface hydrophilicity. For the [C2mim][OAc]-plasticised chitosan/CMC matrix, the advantages of including hybrid fillers, rGO + CNCs or rGO + SPT, were also obtained, resulting in higher thermal stability and surface hydrophobicity. Graphical Abstract

High-Temperature-Induced Shape Memory Copolyimide

A series of polyimide (PI) films with a high-temperature-induced shape memory effect and tunable properties were prepared via the facile random copolymerization of 4,4′-oxydianiline (ODA) with 4,4′-(hexafluoroisopropyl)diphthalic anhydride (6FDA) and 4,4′-oxydiphthalic anhydride (ODPA). The trigger temperature can be controlled from 294 to 326 °C by adjusting the ratio of monomers. The effects of monomer rigidity on the chain mobility, physical properties, and shape memory performance of as-prepared copolyimide were systematically investigated. The introduction of ODPA could enhance the mobility of PI macromolecular chains, which made chain entanglement more likely to occur and increased the physical crosslinking density, thereby improving the PI’s shape recovery up to 97%. Meanwhile, the existence of 6FDA enabled PI films to set quickly at low temperatures with a shape fixation of 98%. The shape memory cycling characteristics of the polyimide films are also studied, and the relationship between the PI chemical structure and the film properties are further discussed.

Novel Poly(Vinylidene Fluoride)/Montmorillonite Polymer Inclusion Membrane: Application to Cr(VI) Extraction from Polluted Water

Novel hybrid polymer inclusion membranes (PIMs) based on poly(vinylidene fluoride) (PVDF) (polymer matrix) and Aliquat 336 (ion carrier) and containing native sodium (Cloisite Na+ (CNa)) and organo-modified (Cloisite 30B (C30B)) Montmorillonites were elaborated and tested for the removal of toxic Cr(VI) ions from the aqueous solution. The influence of the nanoclay incorporation on the physicochemical properties of PVDF-based PIMs was studied and the resulting membrane transport properties of the Cr(VI) ions were investigated in detail. The water contact angle measurements reveal that the incorporation of the CNa nanofiller affects the membrane wettability as less hydrophilic surface is obtained in this case—~47° in the presence of CNa as compared with ~15° for PIMs with C30B. The membrane rigidity is found to be dependent on the type and size of the used Montmorillonite. The increase of Young’s modulus is higher when CNa is incorporated in comparison with C30B. The stiffness of the PIM is strongly increased with CNa amount (four times higher with 30 wt %) which is not the case for C30B (only 1.5 times). Higher Cr(VI) permeation flux is obtained for PIMs containing CNa (~2.7 µmol/(m2·s)) owing to their porous structure as compared with membranes loaded with C30B and those without filler (~2 µmol/(m2·s) in both cases). The PIM with 20 wt % of native sodium Montmorillonite revealed satisfactory stability during five cycles of the Cr(VI) transport due to the high membrane rigidity and hydrophobicity. Much lower macromolecular chain mobility in this case allows limiting the carrier loss, thus increasing the membrane stability. On the contrary, a deterioration of the transport performance is recorded for the membrane filled with C30B and that without filler. The obtained results showed the possibility to extend the PIM lifetime through the incorporation of nanoparticles that diminish the carrier loss (Aliquat 336) from the membrane into the aqueous phase by limiting its mobility within the membrane by tortuosity effect and membrane stiffening without losing its permselective properties.

Influence of sterilization conditions on sulfate-functionalized polyGGE

Sulfated biomolecules are known to influence numerous biological processes in all living organisms. Particularly, they contribute to prevent and inhibit the hypercoagulation condition. The failure of polymeric implants and blood contacting devices is often related to hypercoagulation and microbial contamination. Here, bioactive sulfated biomacromolecules are mimicked by sulfation of poly(glycerol glycidyl ether) (polyGGE) films. Autoclaving, gamma-ray irradiation and ethylene oxide (EtO) gas sterilization techniques were applied to functionalized materials. The sulfate group density and hydrophilicity of sulfated polymers were decreased while chain mobility and thermal degradation were enhanced post autoclaving when compared to those after EtO sterilization. These results suggest that a quality control after sterilization is mandatory to ensure the amount and functionality of functionalized groups are retained.

Poly(Alkylene 2,5-Thiophenedicarboxylate) Polyesters: A New Class of Bio-Based High-Performance Polymers for Sustainable Packaging

In the present study, 100% bio-based polyesters of 2,5-thiophenedicarboxylic acid were synthesized via two-stage melt polycondensation using glycols containing 3 to 6 methylene groups. The so-prepared samples were characterised from the molecular point of view and processed into free-standing thin films. Afterward, both the purified powders and the films were subjected to structural and thermal characterisation. In the case of thin films, mechanical response and barrier properties to O2 and CO2 were also evaluated. From the results obtained, it emerged that the length of glycolic sub-units is an effective tool to modulate the chain mobility and, in turn, the kind and amount of ordered phases developed in the samples. In addition to the usual amorphous and 3D crystalline phases, in all the samples investigated it was possible to evidence a further phase characterised by a lower degree of order (mesophase) than the crystalline one, whose amount is strictly related to the glycol sub-unit length. The relative fraction of all these phases is responsible for the different mechanical and barrier performances. Last, but not least, a comparison between thiophene-based homopolymers and their furan-based homologues was carried out.

Influence of LiCl and AgNO3 Doping on the Electrical Conductivity of PVA Flexible Electrolyte Polymer Film

Recently, the electrical conductive electrolyte based on flexible polymeric films have been attracted much attentions, due to their applications in batteries, thermoelectrics, temperature sensors and others. In this regard, two polymeric electrolytes (PVA/LiCl) and (PVA/AgNO3) films have been engineered and the influence of the dopants and the annealing temperature on the structural, morphology and ac and dc conductivities is extensively studied. It was found that the films crystallinity has the order PVA/AgNO3 (49.44%) > PVA (38.64%) > PVA/LiCl (26.82%). Additionally, the dc conductivity of the films is increased with embedding the dopants into the PVA as the order PVA/AgNO3 (13.7 × 10−4 S/cm) > PVA/LiCl (1.63 × 10−5 S/cm) > PVA (1.71 × 10−6 S/cm) at 110 °C. It is also found that there is a sharp increase for σac as the frequency increases up to 107 Hz and also as the temperature increases to 110 °C. However, the order of increasing the σac is PVA/LiCl (155 × 10−3 S/cm) > PVA/AgNO3 (2.5 × 10−5 S/cm) > PVA (2 × 10−6 S/cm) at f = 107 Hz and 110 °C. The values of exponent are 0.870, 0.405 and 0.750 for PVA, PVA/AgNO3 and PVA/LiCl, respectively, and it is increased as the temperature increases for PVA and PVA/LiCl, but it is decreased for PVA/AgNO3. The activation energies Ea are 0.84, 0.51 and 0.62 eV for PVA, PVA/AgNO3 and PVA/LiCl, respectively. Moreover, the values of activation energy for charge carrier migration Em are 0.60, 0.34 and 0.4 eV for PVA, PVA/AgNO3 and PVA/LiCl, respectively. By using a simple approximation, the carrier concentration, carrier mobility and carrier diffusivity are calculated, and their values are increased as the temperature increases for all samples, but they are higher for PVA/LiCl than that of PVA/AgNO3. These results are discussed in terms of some obtained parameters such as hopping frequency, free volume and chain mobility. Interestingly, the conduction mechanism was found to be the electronic charge hopping for PVA and PVA/LiCl films, however it was found to be the ionic charge diffusion (n < 0.5) for PVA/AgNO3 film. It has been predicted that these electrolytic films have a prospective applications in batteries design, temperature sensors, electronic and wearable apparatuses at an affordable cost.

Enhancing Chain Mobility of Ultrahigh Molecular Weight Polyethylene by Regulating Residence Time under a Consecutive Elongational Flow for Improved Processability

Improving the processability of ultrahigh molecular weight polyethylene (UHMWPE) and understanding the effect of the polymeric chain mobility has long been a challenging task. Herein, we show that UHMWPE without any processing aids can be processed at a lower temperature of 180 °C compared to conventional processing temperatures (~250 °C) under a continuous elongational flow (CEF) by using an eccentric rotor extruder (ERE). By probing the effect of the residence time of UHMWPE samples under a CEF on the morphology, rheological behavior and molecular orientation, we find that the long polymer chains of UHMWPE are apt to orientate under a consecutive volume elongational deformation, thereby leading to a higher residual stress for the extruded sample. Meanwhile, the residence time of samples can regulate the polymeric chain mobility, giving rise to the simultaneous decrease of the melting defects and residual stress as well as Hermans orientation function with increasing residence time from 0 to 60 s. This also engenders the enhanced diffusion of UHMWPE segments, resulting in a defect-free morphology and higher entanglement with lower crystallinity but without causing obvious thermal oxidative degradation of UHMWPE. This interesting result could originate from the fast chain entanglement and particle welding enabled by a desirably short residence time, which could be explained by the empirical, entropy-driven melting explosion mechanism.