Toxicity assessment of core-shell and superabsorbent polymers in cell-based systems.

The identification of health risks arising from occupational exposure to submicron/nanoscale materials is of particular interest and toxicological investigations designed to assess their hazardous properties can provide valuable insights. The core-shell polymers poly (methyl methacrylate)@poly (methacrylic acid-co-ethylene glycol dimethacrylate) [PMMA@P (MAA-co-EGDMA)] and poly (n-butyl methacrylate-co-ethylene glycol dimethacrylate)@poly (methyl methacrylate) [P (nBMA-co-EGDMA)@PMMA] could be utilized for the debonding of coatings and for the encapsulation and targeted delivery of various compounds. The hybrid superabsorbent core-shell polymers poly (methacrylic acid-co-ethylene glycol dimethacrylate)@silicon dioxide [P (MAA-co-EGDMA)@SiO2] could be utilized as internal curing agents in cementitious materials. Therefore, the characterization of their toxicological profile is essential to ensure their safety throughout manufacturing and the life cycle of the final products. Based on the above, the purpose of the present study was to assess the acute toxic effects of the above mentioned polymers on cell viability and on cellular redox state in EA. hy926 human endothelial cells and in RAW264.7 mouse macrophages. According to our results, the examined polymers did not cause any acute toxic effects on cell viability after any administration. However, the thorough evaluation of a panel of redox biomarkers revealed that they affected cellular redox state in a cell-specific manner. As regards EA. hy926 cells, the polymers disrupted redox homeostasis and promoted protein carbonylation. Concerning RAW264.7 cells, P (nBMA-co-EGDMA)@PMMA caused disturbances in redox equilibrium and special emphasis was placed on the triphasic dose-response effect detected in lipid peroxidation. Finally, P (MAA-co-EGDMA)@SiO2 activated cellular adaptive mechanisms in order to prevent from oxidative damage.

Pristine, carboxylated, and hybrid multi-walled carbon nanotubes exert potent antioxidant activities in in vitro-cell free systems.

Multi-walled carbon nanotubes (MWCNTs) are tubular-shaped carbon allotropes, composed of multiple concentric graphene cylinders. The extended systems of conjugated double bonds, that MWCNTs are constituted by, provide them with high electron affinities, enabling them to act as electron donors or acceptors. Consequently, their potential biomedical applications, as synthetic antioxidant agents, are of particular interest. Based on the above, the purpose of the present study was to evaluate the intrinsic antioxidant properties of pristine and carboxylated MWCNTs, as well as of novel hybrid nanocomposites of MWCNTs and inorganic nanoparticles. To this end, after the synthesis and characterization of MWCNTs, their antiradical, reducing, and antigenotoxic properties were assessed in cell-free assays, using a methodological approach that has been recently proposed by our research group. According to our results, most of the tested MWCNTs exhibited strong antioxidant activities. More elaborately, the hybrid material of MWCNTs and ferrous oxide nanoparticles, i.e., CNTs@Fe3O4, showed robust scavenging capacities in all free-radical scavenging assays examined. As regards reducing properties, the pristine MWCNTs, i.e., CNTs-Ref, exhibited the greater electron donating capacity. Finally, in terms of antigenotoxic properties, the hybrid material of MWCNTs and silicon carbide nanoparticles, i.e., CNTs@SiC, exhibited potent ability to inhibit the formation of peroxyl radicals, thus preventing from the oxidative DNA damage. Conclusively, our findings suggest that the MWCNTs of the study could be considered as promising broad-spectrum antioxidants, however, further investigations are required to evaluate their toxicological profile in cell-based and in vivo systems.

An integrated approach for assessing the in vitro and in vivo redox-related effects of nanomaterials.

Over the last few decades, nanotechnology has risen to the forefront of both the research and industrial interest, resulting in the manufacture and utilization of various nanomaterials, as well as in their integration into a wide range of fields. However, the consequent elevated exposure to such materials raises serious concerns regarding their effects on human health and safety. Existing scientific data indicate that the induction of oxidative stress, through the excessive generation of Reactive Oxygen Species (ROS), might be the principal mechanism of exerting their toxicity. Meanwhile, a number of nanomaterials exhibit antioxidant properties, either intrinsic or resulting from their functionalization with conventional antioxidants. Considering that their redox properties are implicated in the manifestation of their biological effects, we propose an integrated approach for the assessment of the redox-related activities of nanomaterials at three biological levels (in vitro-cell free systems, cell cultures, in vivo). Towards this direction, a battery of translational biomarkers is recommended, and a series of reliable protocols are presented in detail. The aim of the present approach is to acquire a better understanding with respect to the biological actions of nanomaterials in the interrelated fields of Redox Biology and Toxicology.

Carbon Nanofibers Functionalized with Active Screen Plasma-Deposited Metal Nanoparticles for Electrical Energy Storage Devices.

Supercapacitors are energy storage devices with higher energy densities than conventional capacitors but lower than batteries or fuel cells. There is a strong interest in increasing the volumetric and gravimetric capacitance of these devices to meet the growing demands of the electrical and electronic sectors. The capacitance depends largely on the electrode material, and carbon nanofibers (CNFs) have attracted much attention because of their relatively low cost, large surface area, and good electrical conductivity as well as chemical and thermal stability. The deposition of metal nanoparticles on CNFs is a promising way to increase their surface properties and, ultimately, the capacitance of the devices. In this study, nickel and silver nanoparticles were deposited on CNFs using the active screen plasma technology. The CNFs were characterized, and their electrochemical performance was assessed in a three-electrode cell. The results show significant improvements over the untreated CNFs, particularly after functionalization with silver nanoparticles.

Toxicity determinants of multi-walled carbon nanotubes: The relationship between functionalization and agglomeration.

The elucidation of toxicity determinants of multi-walled carbon nanotubes (MWCNT) is still incomplete. Functionalization with carboxyl groups is, however, commonly used to mitigate MWCNT toxicity, although the rationale for the mitigating effect has not been fully clarified yet. In this work, two optimized chemical vapor deposition methods were employed to obtain MWCNT of comparable length but different diameter, which were subsequently functionalized. For MWCNT of diameter larger than 40 nm, no detrimental effects on cell viability of macrophages were observed, while mild cytotoxicity was recorded for diameters between 15 and 40 nm, with a mitigating effect of functionalization. To investigate the factors responsible for the mitigation, we used the thinnest MWCNT preparation on different cell models, evaluating several endpoints, such as viability, production of nitric oxide (NO), expression of pro-inflammatory markers, the Trans-Epithelial Electrical Resistance (TEER), and clonogenic activity. Substantial mitigation of the changes caused by pristine MWCNT was observed not only with carboxyl- but also with amino-functionalized MWCNT, suggesting that negative or positive surface charge was not the main factor responsible for the effect. Instead, either functionalized preparation exhibited a stronger tendency to agglomerate that was strictly dependent on the presence of proteins. Moreover, we found that either carboxyl- or amino-functionalized MWCNT adsorbed a larger amount of serum proteins than pristine counterparts, with a distinctive pattern for each type of MWCNT. We propose, therefore, that the formation of larger agglomerates, dependent upon different protein coronae, contributes to mitigate the biological effects of functionalized MWCNT in protein-rich biological media.

Plasma micro-nanotextured, scratch, water and hexadecane resistant, superhydrophobic, and superamphiphobic polymeric surfaces with perfluorinated monolayers.

Superhydrophobic and superamphiphobic toward superoleophobic polymeric surfaces of polymethyl methacrylate (PMMA), polyether ether ketone (PEEK), and polydimethyl siloxane (PDMS) are fabricated in a two-step process: (1) plasma texturing (i.e., ion-enhanced plasma etching with simultaneous roughening), with varying plasma chemistry depending on the polymer, and subsequently (2) grafting of self-assembled perfluorododecyltrichlorosilane monolayers (SAMs). Depending on the absence or not of an etch mask (i.e., colloidal microparticle self-assembly on it), random or ordered hierarchical micro-nanotexturing can be obtained. We demonstrate that stable organic monolayers can be grafted onto all these textured polymeric surfaces. After the monolayer deposition, the initially hydrophilic polymeric surfaces become superamphiphobic with static contact angles for water and oils>153°, for hexadecane>142°, and hysteresis<10° for all surfaces. This approach thus provides a simple and generic method to obtain superamphiphobicity on polymers toward superoleophobicity. Hydrolytic and hexadecane immersion tests prove that superamphiphobicity is stable for more than 14 days. We also perform nanoscratch and post nanoscratch tests to prove the scratch resistance of both the texture and the SAM and demonstrate lower coefficient of friction of the SAM compared to the uncoated surface. Scanning electron microscope observation after the nanoscratch tests confirms the scratch resistance of the surfaces.

Tensile and microindentation properties of maxillofacial elastomers after different disinfecting procedures.

STATEMENT OF PROBLEM: Daily disinfection of maxillofacial prosthesis may reduce their service-life and lead to replacement. PURPOSE: The purpose of this study was to evaluate possible alterations in the mechanical behavior of two maxillofacial elastomers after application of four different disinfection procedures. MATERIAL AND METHODS: The materials tested were two maxillofacial elastomers, a commercially available polydimethylsiloxane (PDMS) and an experimental chlorinated polyethylene (CPE). Different disinfection procedures such as microwave exposure, hypochlorite solution, neutral soap and a commercially antimicrobial solution, were applied for a period which simulates one year of a real service life. Mechanical behavior was investigated through tensile and microindentation tests in various depths. Mathematical models were fitted to tensile curves. Alterations in tensile parameters (maximum stress, maximum strain, elasticity and viscoelasticity parameter) were subjected to two way ANOVA and Tukey's post hoc tests (α=.05). RESULTS: Most of the tensile parameters presented significant alterations among different disinfection procedures and maxillofacial materials which became also harder. Microwave exposure caused greater changes in PDMS and CPE elastomer whereas commercial antimicrobial solution and neutral soap did not significantly affect them. Microindentation and tensile tests revealed similar changes in materials' elastic modulus and hardness whereas the observed changes were greater into smaller depths. CONCLUSIONS: Tensile and microindentation properties of PDMS and CPE elastomers presented changes after disinfected with four different procedures. Changes in the surface of both materials were more intense than in the bulk of the materials. Microwave exposure affected most the two elastomers, so concerning the findings of this study is not recommended for the disinfection of the examined PDMS and CPE elastomers. Moreover, microwave exposure and hypochlorite solution caused greater changes in the surface (3µm) of CPE samples as indicated by microindentation results. PDMS affected less from the commercial antimicrobial agent and CPE from neutral soap, which seems to be the most suitable disinfection techniques.