Our work concerns the study of four candidate drug compounds of the terpenoid family, found as essential oil ingredients in species of the Greek endemic flora, namely carvacrol, p-cymene, γ-terpinene, and thymol, via the simulation method of molecular dynamics. Aquatic solutions of each compound, as well as a solution of all four together in realistic (experimental) proportions, are simulated at atmospheric pressure and 37 °C using an OPLS force field combined with TIP3P water. As verified, all four compounds exhibit a strong tendency to phase-separate, thereby calling for the use of carrier molecules as aids for the drug to circulate in the blood and enter the cells. Systems of two such carrier molecules, the hyperbranched poly(ethylene imine) (HBPEI) polyelectrolyte and hyperbranched polyglycerol (HPG), are examined in mixtures with carvacrol, the most abundant among the four compounds, at a range of concentrations, as well as with all four compounds present in natural proportions. Although a tendency of the terpenoids to cluster separately persists at high concentrations, promising association effects are observed for all drug–polymer ratios. HBPEI systems tend to form diffuse structures comprising small mixed clusters as well as freely floating polymer and essential oil molecules, a finding attributed to the polymer–polymer electrostatic repulsions, which here are only partially screened by the counterions. On the other hand, the electrically neutral HPG molecules cluster together with essential oil species to form a single nanodroplet. Currently, terpenoid–polymer clusters near lipid bilayer membranes are being studied to determine the propensity of the formed complexes to enter cell membranes. Full article

Isotactic polypropylene (PP) composite drawn fibers were prepared using melt extrusion and high-temperature solid-state drawing at a draw ratio of 7. Five different fillers were used as reinforcement agents (microtalc, ultrafine talc, wollastonite, attapulgite and single-wall carbon nanotubes). In all the prepared samples, antioxidant was added, while all samples were prepared with and without using PP grafted with maleic anhydride as compatibilizer. Material characterization was performed by tensile tests, differential scanning calorimetry, thermogravimetric analysis and Fourier transform infrared spectroscopy. Attapulgite composite fibers exhibited poor results in terms of tensile strength and thermal stability. The use of ultrafine talc particles yields better results, in terms of thermal stability and tensile strength, compared to microtalc. Better results were observed using needle-like fillers, such as wollastonite and single-wall carbon nanotubes, since, as was previously observed, high aspect ratio particles tend to align during the drawing process and, thus, contribute to a more symmetrical distribution of stresses. Competitive and synergistic effects were recognized to occur among the additives and fillers, such as the antioxidant effect being enhanced by the addition of the compatibilizer, while the antioxidant itself acts as a compatibilizing agent. Full article

In this work, the antimicrobial action of partially quaternized poly(2-(dimethylamino)ethyl methacrylate) (PQDMAEMA) copolymers using different alkyl halides is presented. The poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) homopolymer was synthesized by group transfer polymerization, followed by the modification of its tertiary amine groups, using bromoethane, iodoethane, bromohexane and bromoethanol, to introduce permanent cationic, quaternary ammonium salt moieties, randomly distributed along the polymer chains. In all cases, the degree of quaternization was low, at ~10 mol%, as verified by proton nuclear magnetic resonance spectroscopy to preserve the thermo-responsive character of the PDMAEMA precursor polymer. The biocidal activity of the lightly quaternized PQDMAEMA copolymers against Escherichia coli and Staphylococcus aureus was evaluated by calculating the minimum inhibitory concentration (MIC) as well as the minimum bactericidal concentration (MBC) of the polymers and by comparing them to the respective values of the precursor non-quaternized PDMAEMA homopolymer. The antibacterial mechanism of action in the solution was studied by zeta potential measurements, scanning electron microscopy and protein leakage tests signifying the disruption of the outer membrane of the bacterial cells to release their periplasmic proteins. Full article

In this study, the effect of the addition of multi-walled carbon nanotubes (MWCNTs), at three percentages, into the urea-formaldehyde (UF) shell-wall of microcapsules on the healing efficiency is reported. The modified shell-wall created a conductive network in semi-conductive epoxies, which led to an improvement of the electromagnetic interference shielding effectiveness (EMI SE); utilizing the excellent electrical properties of the CNTs. The microcapsule’s mean diameter and shell wall were examined via scanning electron microscopy (SEM). Thermal stability was evaluated via thermogravimetric analysis (TGA). The healing efficiency was assessed in terms of fracture toughness, while the electrical properties were measured using impedance spectroscopy. The measurements of the EMI SE were carried out in the frequency range of 7–9 GHz. The derived results indicated that the incorporation of the CNTs resulted in a decrease in the mean size of the microcapsules, while the thermal stability remained unchanged. In particular, the introduction of 0.5% w/v CNTs did not affect the healing efficiency, while it increased the initial mechanical properties of the epoxy after the incorporation of the self-healing system by 27%. At the same time, it led to the formation of a conductive network, providing electrical conductivity to the epoxies. The experimental results showed that the SE increased on average 5 dB or more after introducing conductive microcapsules. Full article

Light-mediated polymer degradation has attracted considerable attention in various applications, including photo-patterning, tissue engineering and photo-triggered drug delivery. In this study, we report the synthesis and characterization of a new, linear, main-chain photo- and acid-degradable copolymer based on acylhydrazone linkages. The polymer was synthesized via a step-growth copolymerization of adipic acid dihydrazide with a bifunctional poly(ethylene glycol) bearing benzaldehyde end-groups, under mild acidic conditions, to afford a hydrophilic PEG-alt-adipic acid (PEG-alt-AA) alternating copolymer. The synthesized polymer was characterized by size exclusion chromatography, proton nuclear magnetic resonance and attenuated total reflection-Fourier transform infrared spectroscopies. The main-chain photo- and acid-induced degradation of the copolymer in dimethylsulfoxide and water, respectively, was verified by UV-vis spectroscopy at light intensities as low as 0.1 mW cm⁻² at λ = 254 nm. Next, a model anticancer drug, doxorubicin (DOX), was chemically linked to the polymer chain end(s) via acylhydrazone bond(s), resulting in amphiphilic PEG-alt-adipic acid-DOX (PEG-alt-AA-DOX) polymer–drug conjugates. The conjugates were self-assembled in water to form spherical nanoparticles, as evidenced by scanning and transmission electron microscopies. The irradiation of the self-assembled PEG-alt-AA-DOX conjugates with UV light and the decrease of the solution pH resulted in the disruption of the assemblies due to the photolysis and acidolysis of the acylhydrazone bonds, and the release of the therapeutic cargo. Full article

Main chain polyesters have been extensively used in the biomedical field. Despite their many advantages, including biocompatibility, biodegradability, and others, these materials are rather inert and lack specific functionalities which will endow them with additional biological and responsive properties. In this work, novel pH-responsive main chain polyesters have been prepared by a conventional condensation polymerization of a vinyl functionalized diol with a diacid chloride, followed by a photo-induced thiol-ene click reaction to attach functional carboxylic acid side-groups along the polymer chains. Two different mercaptocarboxylic acids were employed, allowing to vary the alkyl chain length of the polymer pendant groups. Moreover, the degree of modification, and as a result, the carboxylic acid content of the polymers, was easily tuned by varying the irradiation time during the click reaction. Both these parameters, were shown to strongly influence the responsive behavior of the polyesters, which presented adjustable pKα values and water solubilities. Finally, the difunctional polyesters bearing the alkene and carboxylic acid functionalities enabled the preparation of cross-linked polyester films by chemically linking the pendant vinyl bonds on the polymer side groups. The biocompatibility of the cross-linked polymers films was assessed in L929 fibroblast cultures and showed that the cell viability, proliferation, and attachment were greatly promoted on the polyester surface, bearing the shorter alkyl chain length side groups and the higher fraction of carboxylic acid functionalities. Full article

This study aims to examine how core–shell super absorbent polymers (SAPs) can be effective in relation to recycling processes by using them as triggerable materials in coating binders. Super absorbent polymers are partially cross-linked, three-dimensional polymer networks that can absorb and retain water. Coatings based on an acrylic binder, including SAPs, were applied onto plastic substrates of acrylonitrile–butadiene–styrene/polycarbonate. The incorporation of 1 wt.% and 5 wt.% SAPs into the coatings resulted in the debonding of the coatings from the substrates under a steam treatment. The trigger mechanism for the core–shell hydrophilic SAPs relies on the different abilities of the core and shell materials to be swollen. Therefore, under the influence of steam, SAPs can enhance their shape due to water absorption and the breaking of the inorganic shell. This results in the reduction of the attachment between the primer layer and both the top coating and the substrate, thus enabling the detachment of the top coating from the corresponding substrate. The obtained results from this study can be considered as potential formulations for plastic recycling applications in industries. Full article

We report the preparation of mesoporous silica nanoparticles covered by layer by layer (LbL) oppositely charged weak polyelectrolytes, comprising poly(allylamine hydrochloride) (PAH) and a sodium alginate, highly grafted by N-isopropylacrylamide/N-tert-butylacrylamide random copolymers, NaALG-g-P(NIPAM₉₀-co-NtBAM₁₀) (NaALG-g). Thanks to the pH dependence of the degree of ionization of the polyelectrolytes and the LCST-type thermosensitivity of the grafting chains of the NaALG-g, the as-prepared hybrid nanoparticles (hNP) exhibit pH/thermo-responsive drug delivery capabilities. The release kinetics of rhodamine B (RB, model drug) can be controlled by the number of PAH/NaALG-g bilayers and more importantly by the environmental conditions, namely, pH and temperature. As observed, the increase of pH and/or temperature accelerates the RB release under sink conditions. The same NaALG-g was used as gelator to fabricate a hNP@NaALG-g hydrogel composite. This formulation forms a viscous solution at room temperature, and it is transformed to a self-assembling hydrogel (sol-gel transition) upon heating at physiological temperature provided that its T_gel was regulated at 30.7 °C, by the NtBAM hydrophobic monomer incorporation in the side chains. It exhibits excellent injectability thanks to its combined thermo- and shear-responsiveness. The hNP@NaALG-g hydrogel composite, encapsulating hNP covered with one bilayer, exhibited pH-responsive sustainable drug delivery. The presented highly tunable drug delivery system (DDS) (hNP and/or composite hydrogel) might be useful for biomedical potential applications. Full article

A facile, single-step, [4+2] Diels–Alder cycloaddition reaction for the surface functionalization of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (~230 °C) without any catalyst between the sp² network of carbon nanotubes, which acted as dienophile, and the diphenylethylene cyclobutene (DPE-CB) terminal group of the polystyrene chain. Anionic polymerization was employed for the synthesis of the polystyrene macromolecule, and successful and quantitative end-capping reaction with the DPE-CB molecule was confirmed by matrix-assisted laser desorption/ionization time of flight mass spectroscopy. Thermogravimetric analysis revealed the wt % of the grafted macromolecule on the CNT surface as well as the grafting density of the polymer chains on the SWNTs (0.027 chains nm⁻²). Direct evidence for the surface functionalization and the presence of thin polystyrene film was obtained by transmission electron microscopy (TEM) and by atomic force microscopy (AFM). Full article

The synthesis of statistical copolymers of N-vinylpyrrolidone (NVP) with isobornyl methacrylate (IBMA) was conducted by free radical and reversible addition-fragmentation chain transfer (RAFT) polymerization. The reactivity ratios were estimated using the Finemann-Ross, inverted Fineman-Ross, Kelen-Tüdos, extended Kelen-Tüdos and Barson-Fenn graphical methods, along with the computer program COPOINT, modified to both the terminal and the penultimate models. According to COPOINT the reactivity ratios were found to be equal to 0.292 for NVP and 2.673 for IBMA for conventional radical polymerization, whereas for RAFT polymerization and for the penultimate model the following reactivity ratios were obtained: r₁₁ = 4.466, r₂₂ = 0, r₂₁ = 14.830, and r₁₂ = 0 (1 stands for NVP and 2 for IBMA). In all cases, the NVP reactivity ratio was significantly lower than that of IBMA. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length. The thermal properties of the copolymers were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and differential thermogravimetry (DTG). The results were compared with those of the respective homopolymers. Full article

Composite materials that consisted of a polymer resin as matrix (PMCs), filled using construction and demolition (C&D) wastes powder of different grain sizing in micro-scale were manufactured and studied. Three different kinds of resins were used as the matrix for the purposes of this study. More specifically, composites made of epoxy and unsaturated polyester resins purchased from the market and phenolic resin (novolac) laboratory synthesized, were produced. The morphological and elemental analysis of these materials was performed through scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD). Additionally, mechanical performance and thermal insulating efficiency of these materials were examined through bending and shear strength tests according to the three-point method and via determination of the thermal conductivity coefficient λ. C&D wastes have undergone the appropriate processing in order to prepare filling products of the required granular size in pulverized form. In this research study, construction and demolition waste-based thermosetting polymer composites were produced with flexural strength in the range 20–60 MPa, shear strength in between 1–8 MPa, and thermal conductivity coefficients in the range of 0.27–1.20 W/mK. The developed materials embedded 30–50% w/w C&D wastes, depending on the resin used as the matrix. Full article

In this work, the synthesis and the aqueous solution self-assembly behavior of novel partially hydrophobically modified poly(2-(dimethylamino) ethyl methacrylate)-b-poly(oligo(ethylelene glycol) methyl ether methacrylatetabel) pH and temperature responsive random diblock copolymers (P(DMAEMA-co-Q_6/12DMAEMA)-b-POEGMA), are reported. The chemical modifications were accomplished via quaternization with 1-iodohexane (Q₆) and 1-iodododecane (Q₁₂) and confirmed by ¹H-NMR spectroscopy. The successful synthesis of PDMAEMA-b-POEGMA precursor block copolymers was conducted by RAFT polymerization. The partial chemical modification of the diblocks resulted in the permanent attachment of long alkyl chains on the amine groups of the PDMAEMA block and the presence of tertiary and quaternary amines randomly distributed within the PDMAEMA block. Light scattering techniques confirmed that the increased hydrophobic character results in the formation of nanoaggregates of high mass and tunable pH and temperature response. The characteristics of the aggregates are also affected by the aqueous solution preparation protocol, the nature of the quaternizing agent and the quaternization degree. The incorporation of long alkyl chains allowed the encapsulation of indomethacin within the amphiphilic diblock copolymer aggregates. Nanostructures of increased size were detected due to the encapsulation of indomethacin into the interior of the hydrophobic domains. Drug release studies demonstrated that almost 50% of the encapsulated drug can be released on demand by aid of ultrasonication. Full article

The synthesis of well-defined polypeptides exhibiting complex macromolecular architectures requires the use of monomers that can be orthogonally deprotected, containing primary amines that will be used as the initiator for the Ring Opening Polymerization (ROP) of N-carboxy anhydrides. The synthesis and characterization of the novel monomer N^ε-9-Fluorenylmethoxycarbonyl-l-Lysine N-carboxy anhydride (N^ε-Fmoc-l-Lysine NCA), as well as the novel linear Poly(N^ε-Fmoc-l-Lys)_n homopolypeptide and Poly(l-Lysine)₇₈–block–[Poly(l-Lysine)₁₀–graft–Poly(l-Histidine)₁₅] block-graft copolypeptide, are presented. The synthesis of the graft copolypeptide was conducted via ROP of the N^ε-Boc-l-Lysine NCA while using n-hexylamine as the initiator, followed by the polymerization of N^ε-Fmoc-l-Lysine NCA. The last block was selectively deprotected under basic conditions, and the resulting ε-amines were used as the initiating species for the ROP of N^im-Trityl-l-Histidine NCA. Finally, the Boc- and Trt- groups were deprotected by TFA. High Vacuum Techniques were applied to achieve the conditions that are required for the synthesis of well-defined polypeptides. The molecular characterization indicated that the polypeptides exhibited high degree of molecular and compositional homogeneity. Finally, Dynamic Light Scattering, ζ-potential, and Circular Dichroism measurements were used in order to investigate the ability of the polypeptide to self-assemble in different conditions. This monomer opens avenues for the synthesis of polypeptides with complex macromolecular architectures that can define the aggregation behavior, and, therefore, can lead to the synthesis of “smart” stimuli-responsive nanocarriers for controlled drug delivery applications. Full article

Polysaccharides are natural polymers with hydrophilic, biocompatible and biodegradable characteristics and have many opportunities in the food and pharmaceutical sectors. This review focuses on the field of nano and microstructures whose internal structure is based on networked polysaccharide chains in 3D i.e., polysaccharide nanogels (NGs) and microgels (MGs). As it is observed the number of articles on NGs and MGs in peer reviewed scientific journals has been increasing over the last two decades. At the same time, the relative contribution of polysaccharides in this field is gaining place. This review focuses on the different applied methods for the fabrication of a variety of polysaccharide-based NGs and MGs and aims to highlight the recent advances on the subject and present their potentials and properties with regards to their integration in aspects of medicinal and food sciences. The presentation of the recent advances in the application of polysaccharide NGs and MGs is divided in materials with potential as emulsion stabilizers and materials with potential as carriers of bioactives. For applications in the medical sector the division is based on the fabrication processes and includes self-assembled, electrostatically complexed/ionically crosslinked and chemically crosslinked NGs and MGs. It is concluded that many advances are expected in the application of these polysaccharide-based materials and in particular as nutrient-loaded emulsion stabilizers, viscosity modifiers and co-assembled structures in combination with proteins. Full article