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International audience; Temperature-sensitive rod-like colloidal particles were synthesized by grafting a temperature-responsive polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMA), on the surface of high aspect ratio silica rods by surface-initiated atom transfer radical polymerization. The stability of the grafted polymer on the surface of the particles in aqueous solutions was found to deteriorate with time, leading to a gradual decrease of the polymer content of the hybrid colloids, which was attributed to the mechanically activated hydrolysis of the labile bonds at the polymer–silica interface. The polymer degrafting was significantly suppressed by first growing a hydrophobic poly(methyl methacrylate) block onto the particle surface to act as a barrier layer for the penetration of water molecules at the polymer–particle interface, followed by chain-extension with the hydrophilic PDMA chains. Dynamic light scattering, microscopy, and rheological measurements revealed that the PDMA block conferred a temperature-responsive behavior to the rod-like particles, which formed aggregates at temperatures above the lower critical solution temperature (LCST) of the polymer. However, in contrast to their spherical counterparts, the polymer-grafted rod-like particles did not exhibit complete thermo-reversibility upon lowering the solution temperature below the LCST of PDMA, which was reflected by different values of the diffusion coefficient for the heating and cooling cycles, indicating an irreversible rod particle aggregation upon increasing the temperature.

Hybrid, organic-inorganic, biocidal films exhibiting polishing properties were developed as effective long-lasting antimicrobial surface coatings. The films were prepared using cationically modified chitosan, synthesized by the reaction with 3-bromo-N,N,N-trimethylpropan-1-aminium bromide, to introduce permanent biocidal quaternary ammonium salt (QAS) groups along the polymer backbone and were cross-linked by a novel, pH-cleavable acetal cross-linker, which allowed polishing the hybrid coatings with the solution pH. TiO2 nanoparticles, modified with reduced graphene oxide (rGO) sheets, to narrow their band gap energy value and shift their photocatalytic activity in the visible light regime, were introduced within the polymer film to enhance its antibacterial activity. The hybrid coatings exhibited an effective biocidal activity in the dark (∼2 Log and ∼3 Log reduction for Gram-negative and Gram-positive bacteria, respectively), when only the QAS sites interacted with the bacteria membrane, and an excellent biocidal action upon visible-light irradiation (∼5 Log and ∼6 Log reduction for Gram-negative and Gram-positive bacteria, respectively) due to the synergistic antimicrobial effect of the QAS moieties and the rGO-modified TiO2 nanoparticles. The gradual decrease in the film thickness, upon immersion of the coatings in mildly basic (pH 8), neutral (pH 7), and acidic (pH 6) media, reaching 10, 20, and 70% reduction, respectively, after 60 days of immersion time, confirmed the polishing behavior of the films, whereas their effective antimicrobial action was retained. The biocompatibility of the hybrid films was verified in human cell culture studies. The proposed approach enables the facile development of highly functional coatings, combining biocompatibility and bactericidal action with a "kill and self-clean" mechanism that allows the regeneration of the outer surface of the coating leading to a strong and prolonged antimicrobial action.

Complex formation between a natural polysaccharide – gellan and an antimicrobial drug – ofloxacin was studied in aqueous solution. Conductimetric and potentiometric titration curves revealed that gellan and ofloxacin forms a water-soluble complex of composition 2:1 mol/mol stabilized by ionic and hydrogen bonds. The formation of the gellan-ofloxacin complex was confirmed by FTIR spectroscopy, dynamic light scattering, zeta-potential and thermogravimetric analysis. The average hydrodynamic size of the complex was found 307±5 nm and its zeta-potential was negative and equal to -15 mV. Thin films of the gellan-ofloxacin complex, gelled in 0.3 wt.% of CaCl2, were used to study the release kinetics of ofloxacin in distilled water and phosphate buffer. The drug release kinetics evaluated by UV-Vis spectroscopy at λmax = 289 nm and calculated by the Ritger-Peppas model correspond to non-Fickian diffusion in distilled water and Case II transport (zero-order kinetics) in phosphate buffer. The cumulative release of ofloxacin from the gellan-ofloxacin films was equal to 96±2% and 36±2% in phosphate buffer and distilled water, respectively. It is expected that the gellan-ofloxacin complex is able to form in situ gel on the surface of the eye and to prolong the drug residence time in the tear fluid.

A combination of rheology, optical microscopy and computer simulations was used to investigate the microstructural changes of a semi-dilute suspension of attractive rigid rods in an imposed shear flow. The aim is to understand the relation of the microstructure with the viscoelastic response, and the yielding and flow behaviour in different shear regimes of gels built from rodlike colloids. A semi-dilute suspension of micron sized, rodlike silica particles suspended in 11 M CsCl salt solution was used as a model system for attractive rods' gel. Upon application of steady shear the gel microstructure rearranges in different states and exhibits flow instabilities depending on shear rate, attraction strength, volume fraction and geometrical confinement. At low rod volume fractions, the suspension forms large, vorticity aligned, particle rich flocs that roll in the flow-vorticity plane, an effect that is due to an interplay between hydrodynamic interactions and geometrical confinement as suggested by computer simulations. Experimental data allow the creation of a state diagram, as a function of volume fraction and shear rates, identifying regimes of stable (or unstable) floc formation and of homogeneous gel or broken clusters. The transition is related to dimensionless Mason number, defined as the ratio of shear forces to interparticle attractive force.

Quaternized poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes bearing quaternary ammonium groups of different alkyl chain lengths (ACLs) were prepared and assessed as biocidal coatings. For the synthesis of the antimicrobial brushes, first well-defined PDMAEMA chains were grown by surface-initiated atom transfer radical polymerization on glass and silicon substrates. Next, the tertiary amine groups of the polymer brushes were modified via a quaternization reaction, using alkyl halides, to obtain the cationic polymers. The polymer films were characterized by Fourier-transform infrared spectroscopy, ellipsometry, atomic force microscopy, and water contact angle measurements. The effect of the ACL of the quaternary ammonium groups on the physicochemical properties of the films as well as the contact killing efficiency of the surfaces against representative Gram-positive and Gram-negative bacteria was investigated. A hydrophilic to hydrophobic transition of the surfaces and a significant decrease of the degree of quaternization of the DMAEMA moieties was found upon increasing the ACL of the quaternization agent above six carbon atoms, allowing the wettability, the thickness, and the pH-response of the brushes to be tuned via a facile postpolymerization, quaternization reaction. At the same time, antimicrobial tests revealed that the hydrophilic polymer brushes exhibited enhanced bactericidal activity against Escherichia coli and Bacillus cereus, whereas the hydrophobic surfaces showed a significant deterioration of the in vitro bactericidal performance. Our results elucidate the antimicrobial action of quaternized polymer brushes, dictating the appropriate choice of the ACL of the quaternization agent for the development of coatings that effectively inhibit biofilm formation on surfaces.

Acrylonitrile–butadiene–styrene (ABS) nanocomposite filaments for 3D-printing were produced by melt compounding and extrusion. Two types of nanoadditives were employed: (a) graphene nanoplatelets (GnP) at various concentrations and (b) carbon nanotubes (CNTs). Fused filament fabrication (FFF) 3D printer was used for the fabrication of specimens, according to international standards to be employed for the determination of the tension and flexural mechanical properties of the specimens and the correlation with their microstructure. Nanocomposite filaments were also tested in tension, to evaluate the effect of 3D printing on the material. Moreover, the electrical properties of the specimens were also determined. As found out, a decrease in the tensile strength, the tensile modulus of elasticity, the flexural strength, and the flexural modulus of elasticity can be observed with the increase in the GnP concentration, in every case. ABS specimens filled with CNTs exhibited higher tensile and flexural strength and a more brittle behavior when compared to pure ABS and ABS with GnP. Regarding the electrical properties of the composites, it was found that dielectric constant increases by increasing GnP content, the specimens remaining at the same time rather nonconductive, even at a concentration of 10 wt.% in GnP. In contrast, ABS filled with CNTs at a concentration of 10% illustrated a large conductivity.

There is a growing concern about wound care, since traditional dressings such as bandages and sutures can no longer meet existing needs. To address the demanding requirements, naturally occurring polymers have been extensively exploited for use in modern wound management. Polysaccharides, being the most abundant biopolymers, have some distinct characteristics, including biocompatibility and biodegradability, which render them ideal candidates for wound healing applications. Combining them with inorganic and organic moieties can produce effective multifunctional composites with the desired mechanical properties, high wound healing efficiencies and excellent antibacterial behavior. Recent research endeavors focus on the development of stimuli-responsive polysaccharide composites for biomedical applications. Polysaccharide composites, being sensitive to the local environment, such as changes of the solution temperature, pH, etc., can sense and react to the wound conditions, thus promoting an effective interaction with the wound. This review highlights the recent advances in stimuli-responsive polysaccharide hydrogels and their composites for use in wound healing applications. The synthetic approaches, physical, chemical, and biochemical properties as well as their function in wound healing will be discussed.

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.

Polymer microrods of aspect ratio ∼10, and tunable flexibility are attractive model systems to study density and index matched liquid crystalline phases. However, the synthesis of anisotropic polymer particles is arduous, due to the lack of directional polymer growth mechanisms. In this work, non-cross-linked, hollow polymer microrods are developed from a dense block copolymer brush grown from the surface of micron-sized silica rods. The copolymer brush, comprising a hydrophobic inner block and a hydrophilic outer layer, is synthesized by surface-initiated atom transfer radical polymerization, and is exploited in the preparation of robust polymer rod particles in water, following etching of the inorganic core. The solvent-incompatible inner block is crucial for the synthesis of the rod-like polymer particles, in the absence of chemical cross-links, and the block copolymer composition affects the colloidal stability and flexibility of the hollow anisotropic colloids. For shorter hydrophobic block lengths, well-defined, yet flexible, hollow rods are obtained, whereas increasing the hydrophobic content of the copolymer results in rigid, tube-like particles. The approach is generic and could be easily employed to obtain polymer rod particles in any solvent medium, upon the appropriate selection of the solvent-incompatible inner block and the solvent-compatible outer block.

One of the approaches used to eliminate tumor cells is directed destruction/modification of their RNA molecules. In this regard, ribonucleases (RNases) possess a therapeutic potential that remains largely unexplored. It is believed that the biological effects of secreted RNases, namely their antitumor and antiviral properties, derive from their catalytic activity. However, a number of recent studies have challenged the notion that the activity of RNases in the manifestation of selective cytotoxicity towards cancer cells is exclusively an enzymatic one. In this review, we have analyzed available data on the cytotoxic effects of secreted RNases, which are not associated with their catalytic activity, and we have provided evidence that the most important factor in the selective apoptosis-inducing action of RNases is the structural organization of these enzymes, which determines how they interact with cell components. The new idea on the preponderant role of non-catalytic interactions between RNases and cancer cells in the manifestation of selective cytotoxicity will contribute to the development of antitumor RNase-based drugs.

Multi-functional materials are of paramount importance in biomedical engineering. In this work, we present the synthesis of a hybrid, organic–inorganic material functionalized with covalently-attached natural antimicrobial moeties based on thymol, an essential oil found in thyme. The hybrid material is a double organic–inorganic network formed by sol–gel chemistry followed by photopolymerizaton of the organic moeities, and allows the fabrication of highly accurate 3D scaffolds by means of multi-photon polymerization. The cytocompatibility of the materials and scaffolds was proved by the excellent cell adhesion and proliferation of dental pulp stem cells, whereas their osteogenic potential was evidenced by the significant production of calcium in the matrix, following functionalization with bone morphogenetic protein-2. The antimicrobial activity of the thymol-functionalized 3D scaffolds against E. coli and B. cereus was demonstrated by the inhibition of bacterial growth after 1 and 4 days in culture. These dual-functional, hybrid materials, exhibiting simultaneously biocompatibility and osteogenic potential, as well as an effective antimicrobial activity are excellent candidates for bone tisue engineering.

Multiphoton lithography, based on multiphoton polymerization, is a powerful technique for the fabrication of complex three-dimensional (3D) structures. Herein, we report on the photostructuring of novel biopolymer-based hybrid hydrogels, comprising gelatin methacrylamide and a water-soluble chitosan derivative, via multiphoton polymerization. The nontoxic, Food and Drug Administration-approved, biocompatible photosensitizer eosin Y was exploited as the sole photoinitiator, without the coinitiators and/or comonomer that are commonly used, allowing for further expansion of the available wavelengths up to 800 nm. Importantly, the obtained hybrid material exhibits excellent biocompatibility, evidenced by the increased proliferation of dental pulp stem cells, compared with the individual components and the polystyrene control, after 7 days in culture. Additionally, the 3D hybrid scaffolds promote the matrix mineralization, following their functionalization with bone morphogenetic protein 2. These tailor-made synthetic, biocompatible materials pave the way for further opportunities in 3D scaffold fabrication, including in situ and in vivo biofabrication.

Surfaces for guided cell adhesion and growth are indispensable in several diagnostic and therapeutic applications. Towards this direction, four diblock copolymers comprising polyethylene glycol (PEG) and poly(2-tetrahydropyranyl methacrylate) (PTHPMA) are synthesized employing PEG macroinitiators of different chain lengths. The copolymer with a 5000 Da PEG block and a PEG-PTHPMA comonomers weight ratio of 43-57 provides a film with the highest stability in the culture medium and the strongest cell repellent properties. This copolymer is used to develop a positive photolithographic material and create stripe patterns onto silicon substrates. The highest selectivity regarding smooth muscle cell adhesion and growth and the highest fidelity of adhered cells for up to 3 days in culture is achieved for stripe patterns with widths between 25 and 27.5 µm. Smooth muscle cells cultured on such patterned substrates exhibit a decrease in their proliferation rate and nucleus area and an increase in their major axis length, compared to the cells cultured onto non-patterned substrates. These alterations are indicative of the adoption of a contractile rather than a synthetic phenotype of the smooth muscle cells grown onto the patterned substrates and demonstrate the potential of the novel photolithographic material and patterning method for guided cell adhesion and growth.

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.

In this work, we report a one-step sputtering method for direct preparation of Cu2O and CuO coatings on different substrates, i.e. glass, thin polymer films and titanium alloy. Interestingly, these coatings possessing micro- and nanostructures exhibiting controlled dual-scale roughness and the wettability investigation reveals that we can tune the wetting properties.

In tissue engineering, the use of biomaterials as templates or scaffolds to guide tissue development in vivo provokes the inevitable action of the immune system of the host. This induced immune response often determines the success of the scaffold, including angiogenesis and regeneration or failure causing inflammation and fibrosis. Therefore, it is crucial to predict or even better to promote the proper immune response following implantation. The aim of the present study was to evaluate the immunomodulatory potential of chitosan

Ultrafast laser 3D lithography based on non-linear light–matter interactions, widely known as multi-photon lithography (MPL), offers unrivaled precision rapid prototyping and flexible additive manufacturing options. 3D printing equipment based on MPL is already commercially available, yet there is still no comprehensive understanding of factors determining spatial resolution, accuracy, fabrication throughput, repeatability, and standardized metrology methods for the accurate characterization of the produced 3D objects and their functionalities. The photoexcitation mechanisms, spatial-control or photo-modified volumes, and the variety of processable materials are topics actively investigated. The complexity of the research field is underlined by a limited understanding and fragmented knowledge of light-excitation and material response. Research to date has only provided case-specific findings on photoexcitation, chemical modification, and material characterization of the experimental data. In this review, we aim to provide a consistent and comprehensive summary of the existing literature on photopolymerization mechanisms under highly confined spatial and temporal conditions, where, besides the excitation and cross-linking, parameters such as diffusion, temperature accumulation, and the finite amount of monomer molecules start to become of critical importance. Key parameters such as photoexcitation, polymerization kinetics, and the properties of the additively manufactured materials at the nanoscale in 3D are examined, whereas, the perspectives for future research and as well as emerging applications are outlined.

Ultrafast laser 3D lithography based on non-linear light-matter interactions, widely known as multi-photon lithography (MPL), offers unrivaled precision rapid prototyping and flexible additive manufacturing options. 3D printing equipment based on MPL are already commercially available, yet there is still no comprehensive understanding of factors determining spatial resolution, accuracy, fabrication throughput, repeatability, and standardized metrology methods for the accurate characterization of the produced 3D objects and their functionalities. The photoexcitation mechanisms, spatial-control or photo-modified volumes, and the variety of processable materials are topics actively investigated. The complexity of the research field is underlined by limited understanding and fragmented knowledge of light-excitation and material response. Research to date has only provided case-specific findings on photoexcitation, chemical modification, and material characterization of the experimental data. In this review, we aim to provide a consistent and comprehensive summary of the existing literature on photopolymerization mechanisms under highly confined spatial and temporal conditions, where, besides the excitation and cross-linking, parameters such as diffusion, temperature accumulation, and the finite amount of monomer molecules start to become of critical importance. Key parameters such as, photoexcitation, polymerization kinetics, and the properties of the additively manufactured materials at the nanoscale in 3D are examined, whereas, the perspectives for future research and as well as emerging applications are outlined.

Amphiphilic ionizable model co-networks based on near-monodisperse, linear ABA and BAB triblock and statistical copolymers of 2-(dimethylamino)ethyl methacrylate (DMAEMA, hydrophilic ionizable) and n-butyl methacrylate (BuMA, hydrophobic non-ionic) were synthesized using group-transfer polymerization in tetrahydrofuran (THF) with the use of the hydrophobic ethylene glycol dimethacrylate (EGDMA) as cross-linker. Seven model co-networks were prepared in which the architecture and copolymer composition were varied systematically. One randomly cross-linked copolymer co-network was also prepared. The co-networks were characterized in terms of their degree of swelling in water as a function of pH and in THF. An increase in the aqueous degree of swelling was observed below pH 6 because of the ionization of the DMAEMA residues. The aqueous degrees of swelling at low pH decreased with the co-network composition in hydrophobic BuMA units. The maximum aqueous degrees of swelling of the copolymer co-networks were architecture-dependent, with the co-networks comprising the statistical copolymer chains swelling about 4 times more than their triblock copolymer counterparts. This was attributed to microphase separation in the triblock copolymer co-networks, which reduced the effective chain length between cross-links due to the collapse of the hydrophobic blocks. The mechanical properties of the water-swollen co-networks at pH 3 and 9 were investigated by determining the co-network uniaxial compression modulus. This modulus was higher at pH 9 than 3, and increased linearly with the BuMA content.

The incorporation of graphene nanoplatelets (GnPs) within a polymer matrix can play an important role in the physical properties and the functionality of the composite material. Composites consisting of low-density polyethylene (LDPE) and GnPs of different concentrations were developed by mixing GnPs with a molten form of the polymeric matrix. The effect of the GnPs content on the morphological, structural, and electrical properties of the composites were investigated. As shown, graphene presence and its concentration significantly modified the polymer matrix properties, a behavior that can be employed for tailoring its applicability in electrical applications. It was found that the increase of the graphene platelets concentration seems to promote the formation of graphene agglomerates, air gaps, and inhomogeneities, while higher dielectric constant/lower dielectric losses can be achieved.

Arrays of hierarchical microstructures are considered nowadays as an effective method to create hydrophobic surfaces. Herein, we use femtosecond 3D printing to manufacture microstructures in different geometric patterns. Direct laser writing and, in particular, multiphoton polymerization lithography (MPL) with ultrafast laser pulses has taken additive manufacturing all the way down to the sub-micrometer scale. MPL is a 3D nanoscale manufacturing tool offering great potential for rapid prototyping and the manufacture of photonic devices, tissue scaffolds and biomechanical parts. In this study, we demonstrate the tuning of the wetting performance of surfaces via trichomes designs of 3D microstructures.

The design and synthesis of new biomaterials with adjustable physicochemical and biological properties for tissue engineering applications have attracted great interest. In this work, chitosan-graft-poly(l-lactide) (CS-g-PLLA) copolymers were prepared by chemically binding poly(l-lactide) (PLLA) chains along chitosan (CS) via the &ldquo, grafting to&rdquo, approach to obtain hybrid biomaterials that present enhanced mechanical stability, due to the presence of PLLA, and high bioactivity, conferred by CS. Two graft copolymers were prepared, CS-g-PLLA(80/20) and CS-g-PLLA(50/50), containing 82 wt % and 55 wt % CS, respectively. Degradation studies of compressed discs of the copolymers showed that the degradation rate increased with the CS content of the copolymer. Nanomechanical studies in the dry state indicated that the copolymer with the higher CS content had larger Young modulus, reduced modulus and hardness values, whereas the moduli and hardness decreased rapidly following immersion of the copolymer discs in alpha-MEM cell culture medium for 24 h. Finally, the bioactivity of the hybrid copolymers was evaluated in the adhesion and growth of MC3T3-E1 pre-osteoblastic cells. In vitro studies showed that MC3T3-E1 cells exhibited strong adhesion on both CS-g-PLLA graft copolymer films from the first day in cell culture, whereas the copolymer with the higher PLLA content, CS-g-PLLA(50/50), supported higher cell growth.

Multifunctional, stimuli-responsive block copolymers have been prepared via the sequential atom transfer radical polymerization (ATRP) of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and the in-house synthesized 1′-(2-methacryloxyethyl)-3′,3′-dimethyl-6-nitrospiro-(2H-1-benzopyran-2,2′-indoline) (SPMA) monomer. Two PDMAEMA-b-PSPMA diblock copolymers, containing 3 and 14 mol % SPMA, were synthesized. The amphiphilic nature of the PDMAEMA-b-PSPMA diblock copolymers led to the formation of well-defined spherical micelles, comprising a hydrophobic PSPMA core and a hydrophilic PDMAEMA shell, in water. The combination of the pH- and temperature-responsive character of PDMAEMA with the pH-, temperature-, and light-sensitive properties of the PSPMA block has resulted in a complex responsive behavior of the copolymer micelles in aqueous solution, when applying three different external stimuli (i.e., light irradiation, pH, and temperature). More importantly, the synergistic response of the block copolymer micelles ...

ZnO-TiO2 core–shell photocatalysts of a complex flower-like architecture were synthesized, using a well-controlled sol–gel coating reaction of presynthesized ZnO flower-like structures. The samples...

Polyampholytic hybrid Janus nanoparticles comprising an inorganic silica core and a shell consisting of compartmentalized poly(acrylic acid) and poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) grafted polymer chains have been prepared. The synthesis of the nanoparticles was accomplished via a multi-step process commenced by a styrene/methanol Pickering emulsion using amine-functionalized silica nanoparticles (D = 100 nm) as the stabilizer, followed by the free radical polymerization of the styrene droplets to obtain silica nanoparticle stabilized polystyrene colloidosomes. Two different polymers, poly(tert-butyl acrylate) poly(t-BA) and PDMAEMA, were grown from the opposite sides of initiator-modified Janus silica nanoparticles by a two-step surface-initiated atom transfer radical polymerization (ATRP). Following acid hydrolysis of the t-butyl ester groups, the polyampholytic bicomponent particles were obtained. The asymmetric polymer decoration of the silica nanoparticles was verified by scanning electron microscopy, whereas the aqueous solution properties of the hybrid nanoparticles were investigated by potentiometric titration, zeta-potential measurements and dynamic light scattering. Studies on the size of the polyampholytic nanoparticles as a function of the solution pH revealed the presence of individual Janus nanoparticles with a symmetric V-shape change in their size signifying the absence of interparticle aggregation upon ionization of the compartmentalized oppositely charged polyelectrolyte chains.

Αbstract The enhancement of the photocatalytic performance of anatase TiO2 nanoparticles is demonstrated by a facile route, involving their in-situ surface modification with preformed polymer chains. Random copolymers of poly(ethylene glycol) methyl ether acrylate-co-methacrylic acid (PEGA-co-MAA) or poly(ethylene glycol) methyl ether acrylate-co-dopamine methacrylamide (PEGA-co-DMA) were synthesized by reversible addition−fragmentation chain-transfer (RAFT) polymerization and were bound onto the surface of anatase titania nanoparticles via the “grafting to” method. The hybrid nanocatalysts were characterized by fourier transform infrared spectroscopy, zeta-potential measurements, X-ray powder diffraction, thermogravimetric analysis and transmission electron microscopy. Their photocatalytic performance was evaluated by the decoloration of methylene blue (MB) dye in aqueous media under UV–vis light irradiation. The enhanced photoactivity and reusability of the polymer modified photocatalysts compared to that of bare TiO2 nanoparticles was attributed to their improved dispersability and colloidal stability, the smaller particle size that leads to a larger surface area and the increased adsorption capacity of the dye onto the polymer modified nanoparticles.

The design and synthesis of new biomaterials with adjustable physicochemical and biological properties for tissue engineering applications have attracted great interest. In this work, chitosan-graft-poly(l-lactide) (CS-g-PLLA) copolymers were prepared by chemically binding poly(l-lactide) (PLLA) chains along chitosan (CS) via the “grafting to” approach to obtain hybrid biomaterials that present enhanced mechanical stability, due to the presence of PLLA, and high bioactivity, conferred by CS. Two graft copolymers were prepared, CS-g-PLLA(80/20) and CS-g-PLLA(50/50), containing 82 wt % and 55 wt % CS, respectively. Degradation studies of compressed discs of the copolymers showed that the degradation rate increased with the CS content of the copolymer. Nanomechanical studies in the dry state indicated that the copolymer with the higher CS content had larger Young modulus, reduced modulus and hardness values, whereas the moduli and hardness decreased rapidly following immersion of the copolymer discs in alpha-MEM cell culture medium for 24 h. Finally, the bioactivity of the hybrid copolymers was evaluated in the adhesion and growth of MC3T3-E1 pre-osteoblastic cells. In vitro studies showed that MC3T3-E1 cells exhibited strong adhesion on both CS-g-PLLA graft copolymer films from the first day in cell culture, whereas the copolymer with the higher PLLA content, CS-g-PLLA(50/50), supported higher cell growth.

Nanocomposites, consisting of Acrylonitrile Butadiene Styrene (ABS) and ZnO of various concentrations were developed by dry mixing the nano filler with the matrix in powder form, followed by melt mixing in an extrusion system, fabrication of filaments and 3D printing of specimens. The effect of the ZnO content on the dielectric properties of the nanocomposite specimens was investigated and as shown, ZnO induces a reduction of the dielectric constant, a behavior that can be employed for tailoring the applicability of ABS in electrical applications.

The development of dynamically responsive 3D photonic elements, which is crucial for the design of active integrated photonic circuits, requires the incorporation of material systems with fast and tunable response. To this end, semiconductor quantum dots have been widely used to perform as the active material system to be integrated; nonetheless, multiple-step processing is usually required for the active functions to be preserved, thereby restricting functionality of integrated 3D quantum photonic elements mostly to the infrared. Here, we report a simple scheme for the realization of visible light active 3D photonic devices by combining direct laser writing with two-photon absorption and in situ synthesis of cadmium sulfide (CdS) nanoparticles. The novel active 3D printable hybrid material is synthesized by crosslinking precursors of CdS quantum dots into a photo-structurable organic–inorganic zirconium–silicon hybrid composite integrating functional properties of both high spatial resolution and high third-order nonlinearity into the photonic matrix. As a proof-of-demonstration for 3D printed active photonic devices, woodpile photonic crystals with an inlayer periodicity down to 500 nm are successfully fabricated showing clear photonic stop bands in the visible spectral region, while for the first time, evidence of an ultrafast dynamic response in the visible is also demonstrated.

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.

Nanografting as a pathway to create functionalized two-dimensional inorganic surfaces capable of immobilizing fluorogenic substituted-fluorene dye is demonstrated. Of particular importance is that the self-assembled monolayer of 3-aminopropyltriethoxysilane is successfully modified with 9H-fluorene-9-carbonyl chloride carbonyl chloride via amide coupling reactions. Physico-chemical properties of self-assembled monolayer are studied by water contact angle (WCA) measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The optical properties were determined by photoluminescence spectroscopy. The WCA and AFM data suggest that employing the same functionalization protocol on two different surfaces, (SiO2/Si) and GaN/Al2O3 respectively, may lead to different but meaningful results. XPS results confirm fluorene dye covalently attached onto two-dimensional inorganic surfaces via self-assembled monolayer of aminopropyl silane.

Well-defined poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) has been modified at low degrees of quaternization of the tertiary amine groups using alkyl halides with long alkyl chains as the quaternization agents. The resulting PDMAEMA-co-PQDMAEMA copolymers were studied in aqueous solution using potentiometric titrations, turbidimetry, surface tensiometry, dynamic light scattering and zeta potential measurements. An increase of the hydrophilicity of the precursor polymer, leading to an increase or even elimination of the lower critical solution temperature (LCST) for the quaternized copolymers was found; this extended the temperature range of the stable polymer solution. At the same time, it was shown that the hydrophobic character of the polymer increases upon quaternization, leading to higher surface activity compared to the precursor PDMAEMA homopolymer, and, thus, to more effective polymeric surfactants. This contradiction in the copolymer behavior was attributed to the interplay between the polymer self-assembly in the aqueous medium and the polymer adsorption at the air/water interface, which dominate the cloud point and the surface properties, respectively.

Stimuli responsive materials have attracted a great deal of attention during the last few decades and are expected to lead to great advances in the areas of nano- and bio-technology. Chemical and biochemical stimuli that allow one to control the material properties and functions have been extensively investigated; however, recently physical stimuli have been of much interest because they can be applied remotely, they often allow spatiotemporal control and, depending on the required intensity, they can be biocompatible. Progress in this rapidly expanding field may result in advancements in dynamically controlled systems for use, among others, in drug delivery and tissue engineering, artificial muscles and robotics, (bio)sensors and actuators, space and ocean applications and self-healing materials. In this review we highlight recent progress in the emerging field of photo-, electro-, magnetic- and ultrasound-sensitive polymers. Novel synthetic routes to these polymers as well as their responsive properties and functions are presented. Future perspectives and challenges in the field towards the development of more complex systems are also discussed.

In tissue engineering, the use of biomaterials as templates or scaffolds to guide tissue development in vivo provokes the inevitable action of the immune system of the host. This induced immune response often determines the success of the scaffold, including angiogenesis and regeneration or failure causing inflammation and fibrosis. Therefore, it is crucial to predict or even better to promote the proper immune response following implantation. The aim of the present study was to evaluate the immunomodulatory potential of chitosan-graft-poly(e-caprolactone) copolymers (CS-g-PCL) by analyzing the differentiation of primary bone marrow derived macrophages (BMDM) cultured in vitro on copolymer thin films. In order to evaluate the role of the chitosan content of the copolymer on macrophage polarization, two different copolymers containing 50 and 78% w/w chitosan were studied. Our data from cytokines secretion detection by ELISA show that the CS-g-PCL copolymer significantly decreases the secretion of the induc...

Tissue regeneration necessitates the development of appropriate scaffolds that facilitate cell growth and tissue development by providing a suitable substrate for cell attachment, proliferation, and differentiation. The optimized scaffolds should be biocompatible, biodegradable, and exhibit proper mechanical behavior. In the present study, the nanomechanical behavior of a chitosan-graft-poly(ε-caprolactone) copolymer, in hydrated and dry state, was investigated and compared to those of the individual homopolymers, chitosan (CS) and poly(ε-caprolactone) (PCL). Hardness and elastic modulus values were calculated, and the time-dependent behavior of the samples was studied. Submersion of PCL and the graft copolymer in α-MEM suggested the deterioration of the measured mechanical properties as a result of the samples’ degradation. However, even after three days of degradation, the graft copolymer presented sufficient mechanical strength and elastic properties, which resemble those reported for soft tissues. The in vitro biological evaluation of the material clearly demonstrated that the CS-g-PCL copolymer supports the growth of Wharton’s jelly mesenchymal stem cells and tissue formation with a simultaneous material degradation. Both the mechanical and biological data render the CS-g-PCL copolymer appropriate as a scaffold in a cell-laden construct for soft tissue engineering.

A sensing system, based on tailor-made qPDMAEMA polymers, with the ability to discriminate between methanol and ethanol vapors in the presence or absence of humidity without the need of a separation column and at room temperature is designed and implemented. The miniaturized sensing system is comprised of four polymer coated planar capacitors along with the readout electronic module. The capacitors are fabricated with mainstream microelectronic/micromachining processes forming a planar InterDigitated Electrodes outline with 1 μm critical dimension. Tailor-made, hydrophilic homopolymers and a copolymer based on poly((2-dimethylamino)ethyl methacrylate), synthesized via GTP and quaternized with either methyl iodide or 1-(chloromethyl)naphthalene were used as the sensing layer and were compared to a hydrophobic, commercially available polymer. The sensing system was evaluated upon exposure to humidity, volatile organic compounds and binary mixtures of the latter. Data processing with Principal Component Analysis (PCA) highlights the ability of the proposed sensing system to discriminate between polar analytes, and more importantly between low molecular weight alcohol vapors, ethanol and methanol, in the presence of humidity.

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Controlling the cell behavior on biocompatible polymer surfaces is critical for the development of suitable medical implant coatings as well as in anti-adhesive applications. Synthetic glycopolymer brushes, based on sugar methacrylate monomers have been reported as robust surfaces to resist protein adsorption and cell adhesion. In this study, poly(D-gluconamidoethyl methacrylate) (PGAMA) brushes of various chain lengths were synthesized directly from initiator functionalized glass substrates using surface-initiated atom transfer radical polymerization. The glycopolymer film thicknesses were determined by ellipsometry, whereas the wettability and the morphology of the surfaces were characterized by static water contact angle measurements and atomic force microscopy, respectively. Stable, grafted films with thicknesses in the dry state between 4 and 20 nm and of low roughness (~1 nm) were obtained by varying the polymerization time. Cell experiments with MC3T3-E1 pre-osteoblasts cultured on the PGAMA brushes were performed to examine the effect of film thickness on the cell morphology, cytoskeleton organization and growth. The results revealed good cell spreading and proliferation on PGAMA layers of low film thickness, whereas cell adhesion was prevented on polymer films with thickness higher than ~10 nm, indicating their potential use in medical implants and anti-adhesive surfaces, respectively.

Highly cross-linked polystyrene–porphyrin nanoparticles were synthesized by a facile approach using emulsion free-radical copolymerization of styrene (St) with a tetra-functional cross-linker, 5,10,15,20-tetrakis(4-phenylmethacrylate)-21H,23H-porphine (PO), and a bifunctional cross-linker, divinylbenzene (DVB), in aqueous solution. Two samples were prepared, PO-St-DVB(1) and PO-St-DVB(2), with 0.7 and 2.6 mol% PO, respectively. The cross-link density of the particles increased with the increase of the PO content at a constant St/cross-linkers mol feed ratio. The morphology and the size of the polymer particles were studied by scanning and transmission electron microscopies. Gas adsorption measurements showed that the polystyrene–porphyrin nanoparticles possessed an inherently large surface area when dried by supercritical CO2 from their dispersions in EtOH or DMF. In particular, the sample with the highest PO content (PO-St-DVB(2)) exhibited a Brunauer–Emmett–Teller (BET) surface area up to 334 m2 g−1 (282 m2 g−1 calculated from CO2 adsorption) with a total pore volume of 0.37 cm3 g−1 when dried from EtOH. Analysis of the CO2 and CH4 adsorption data using the ideal adsorption solution theory revealed that the PO-St-DVB(2) nanoparticles exhibited an adsorption selectivity for CO2 over CH4 of 25 at 263 K and 12 at 273 K, rendering them attractive candidates for use in CO2/CH4 separation and carbon dioxide sequestration processes.

In this work, Ag nanoparticles were loaded by chemical reduction onto TiO 2 P25 under different loadings ranging from 1 up to 4 wt% and hydrothermally deposited on reduced graphene oxide sheets. Chemical reduction was determined to be an effective preparation approach for Ag attachment to titania, leading to the formation of small silver nanoparticles with an average diameter of 4.2 nm. The photocatalytic performance of the hybrid nanocomposite materials was evaluated via methylene blue (MB) dye removal under visible-light irradiation. The rate of dye decolorization was found to depend on the metal loading, showing an increase till a threshold value of 3 wt%, above which the rate drops. Next, the as prepared sample of TiO 2 /Ag of better photocatalytic response, i.e., at a 3 wt% loading value, was hydrothermally deposited on a platform of reduced graphene oxide (rGO) of tunable content (mass ratio). TiO 2 /Ag/rGO coupled nanocomposite presented significantly enhanced photocatalytic activity compared to the TiO 2 /Ag, TiO 2 /rGO composites and bare P25 titania semiconductor photocatalysts. In particular, after 45 min of irradiation almost complete decolorization of the dye was observed for the TiO 2 /Ag/rGO nanocatalyst, while the respective removal efficiency was 92% for TiO 2 /Ag, 93% for TiO 2 /rGO and only 80% for the bare TiO 2 nanoparticles. This simple step by step preparation strategy allows for optimum exploitation of the advanced properties of metal plasmonic effect and reduced graphene oxide as the critical host for boosting the overall photocatalytic activity towards visible-light.