The development of antibiotic resistance among pathogenic bacteria combined with increased implant-associated infections have determined a great interest towards new bactericidal materials containing various organic and inorganic substances. Among them, zinc oxide (ZnO) derived materials have received considerable attention due to their unique antibacterial, antifungal, and UV filtering properties as well as high catalytic and photochemical activities. In the present work, we investigate the antimicrobial properties against two Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) of ZnO microrods (MRs) and nanorods (NRs), produced in bulk quantities through simple and inexpensive methods. We demonstrate that the antimicrobial effect is strongly dependent on the rod size and dose. Scanning electron microscopy analysis revealed that the two investigated microbial types interact differently with the ZnO-MRs and NRs due to their different morphology. This resulted in different outcomes as reported by their respective Colony Forming Unit (CFU) capabilities. Moreover, Fourier Transform Infrared (FT-IR) spectroscopy revealed that changes in cell outer structures, i.e. membrane and exopolysaccharides (EPS), produced by the interaction with the ZnO structures, are responsible for the antimicrobial mechanism without the accumulation of reactive oxygen species. This was further strengthened by the increased survival observed in the case of bacterial cells treated in the presence of an osmotic support, like glycerol. In addition, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analysis showed that reduced cell viability is not strictly correlated to increased zinc ion release in the suspension. We then concluded that ZnO-NRs have a superior antimicrobial effect against both S. aureus and B. subtilis at much lower doses when compared to ZnO-MRs. This is mainly due to the smaller diameter of the NRs, which promotes surface damaging and protein alteration of the cell wall. Finally, the lack of toxicity and the antimicrobial properties of ZnO-NRs versus S. aureus, validated in vivo using the nematode Caenorhabditis elegans as host infection model, confirm the promising exploitation of ZnO-NRs in biomedical applications.
Nanomaterials are revolutionizing the field of medicine to improve the quality of life due to the myriad of applications stemming from their unique properties, including the antimicrobial activity against pathogens. In this study, the antimicrobial and antibiofilm properties of a novel nanomaterial composed by zinc oxide nanorods-decorated graphene nanoplatelets (ZNGs) are investigated. ZNGs were produced by hydrothermal method and characterized through field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) techniques. The antimicrobial activity of ZNGs was evaluated against Streptococcus mutans, the main bacteriological agent in the etiology of dental caries. Cell viability assay demonstrated that ZNGs exerted a strikingly high killing effect on S. mutans cells in a dose-dependent manner. Moreover, FE-SEM analysis revealed relevant mechanical damages exerted by ZNGs at the cell surface of this dental pathogen rather than reactive oxygen species (ROS) generation. In addition, inductively coupled plasma mass spectrometry (ICP-MS) measurements showed negligible zinc dissolution, demonstrating that zinc ion release in the suspension is not associated with the high cell mortality rate. Finally, our data indicated that also S. mutans biofilm formation was affected by the presence of graphene-zinc oxide (ZnO) based material, as witnessed by the safranin staining and growth curve analysis. Therefore, ZNGs can be a remarkable nanobactericide against one of the main dental pathogens. The potential applications in dental care and therapy are very promising.
Novel polymer-based piezoelectric nanocomposites with enhanced electromechanical properties open new opportunities for the development of wearable energy harvesters and sensors. This paper investigates how the dissolution of different types of hexahydrate metal salts affects β-phase content and piezoelectric response (d33) at nano- and macroscales of polyvinylidene fluoride (PVDF) nanocomposite films. The strongest enhancement of the piezoresponse is observed in PVDF nanocomposites processed with Mg(NO3)2⋅6H2O. The increased piezoresponse is attributed to the synergistic effect of the dipole moment associated with the nucleation of the electroactive phase and with the electrostatic interaction between the CF2 group of PVDF and the dissolved salt through hydrogen bonding. The combination of nanofillers like graphene nanoplatelets or zinc oxide nanorods with the hexahydrate salt dissolution in PVDF results in a dramatic reduction of d33, because the nanofiller assumes a competitive role with respect to H-bond formation between PVDF and the dissolved metal salt. The measured peak value of d33 reaches the local value of 13.49 pm/V, with an average of 8.88 pm/V over an area of 1 cm2. The proposed selection of metal salt enables low-cost production of piezoelectric PVDF nanocomposite films, without electrical poling or mechanical stretching, offering new opportunities for the development of devices for energy harvesting and wearable sensors.
Nanotechnologies are currently revolutionizing the world around us, improving the quality of our lives thanks to a multitude of applications in several areas including the environmental preservation, with the biodeterioration phenomenon representing one of the major concerns. In this study, an innovative nanomaterial consisting of graphene nanoplatelets decorated by zinc oxide nanorods (ZNGs) was tested for the ability to inhibit two different pathogens belonging to bacterial genera frequently associated with nosocomial infections as well as biodeterioration phenomenon: the Gram-positive Staphylococcus aureus and the Gram-negative Pseudomonas aeruginosa. A time- and dose-dependent bactericidal effect in cell viability was highlighted against both bacteria, demonstrating a strong antimicrobial potential of ZNGs. Furthermore, the analysis of bacterial surfaces through Field emission scanning electron microscopy (FESEM) revealed ZNGs mechanical interaction at cell wall level. ZNGs induced in those bacteria deep physical damages not compatible with life as a result of nanoneedle-like action of this nanomaterial together with its nanoblade effect. Cell injuries were confirmed by Fourier transform infrared spectroscopy, revealing that ZNGs antimicrobial effect was related to protein and phospholipid changes as well as a decrease in extracellular polymeric substances; this was also supported by a reduction in biofilm formation of both bacteria. The antibacterial properties of ZNGs applied on building-related materials make them a promising tool for the conservation of indoor/outdoor surfaces. Finally, ZNGs nanotoxicity was assessed in vivo by exploiting the soil free living nematode Caenorhabditis elegans. Notably, no harmful effects of ZNGs on larval development, lifespan, fertility as well as neuromuscular functionality were highlighted in this excellent model for environmental nanotoxicology. Overall, ZNGs represent a promising candidate for developing biocompatible materials that can be exploitable in antimicrobial applications without releasing toxic compounds, harmful to the environment.
Doping graphene with electron donating or accepting molecules is an interesting approach to introduce carriers into it, analogous to electrochemical doping accomplished in graphene when used in a field-effect transistor. Here, we use first-principles density-functional theory to determine changes in the electronic-structure and vibrational properties of graphene that arise from the adsorption of aromatic molecules such as aniline and nitrobenzene. Identifying the roles of various mechanisms of chemical interaction between graphene and a molecule, we bring out the contrast between electrochemical and molecular doping of graphene. Our estimates of various contributions to shifts in the Raman-active modes of graphene with molecular doping are fundamental to the possible use of Raman spectroscopy in (a) characterization of the nature and concentration of carriers in graphene with molecular doping, and (b) graphene-based chemical sensors.