Well aligned TiO2 nanotubes were successfully synthesized by anodization of Ti foil at 60 V in a fluorinated bath comprised of ethylene glycol with 5 wt% of NH4F and 5 wt% of H2O2. In order to enhance the visible light absorption and photoelectrochemical response of pure TiO2 nanotube arrays, a mixed oxide system (W-TiO2) was investigated. W-TiO2 nanotube arrays were prepared using radio-frequency (RF) sputtering to incorporate the W into the lattice of TiO2 nanotube arrays. The W atoms occupy the substitutional position within the vacancies of TiO2 nanotube arrays. The as-anodized TiO2 is amorphous in nature while the annealed TiO2 is anatase phase. The mixed oxide (W-TiO2) system in suitable TiO2 phase plays important roles in efficient electron transfers due to the reduction in electron-hole recombination. In this article, the effect of the sputtered W into the as-anodized/annealed TiO2 nanotube arrays on the photoelectrochemical response was presented.
Uniformly sized TiO2 nanotubes with high aspect ratios were synthesised on a large substrate (100 mm x 100 mm) via the bubbling system through anodisation of Ti in ethylene glycol containing 5 wt% NH4F and 5 wt% H2O2. The benefits of bubbling system in producing uniformly sized TiO2 nanotubes throughout the Ti foil are illustrated. Moreover, the effects of applied voltage and fluoride content on the resulting nanotubes were also considered. Such uniform sized TiO2 nanotubes are a key to produce hydrogen efficiently using PEC cell. The results show higher photocurrent responses for the high aspect ratio, uniform TiO2 nanotubes because of excellent interfacial electron transfer.
In this work, 18.5 microm titanium oxide (TiO(2)) nanotube arrays were formed by the anodization of titanium (Ti) foil in ethylene glycol containing 1 wt% water and 5 wt% fluoride for 60 min at 60 V. The fast growth rate of the nanotube arrays at 308 nm min(-1) was achieved due to the excess fluoride content and the limited amount of water in ethylene glycol used for anodization. Limited water content and excess fluoride in ethylene glycol inhibited the formation of a thick barrier layer by increasing the dissolution rate at the bottom of the nanotubes. This eased the transport of titanium, fluorine and oxygen ions, and allowed the nanotubes to grow deep into the titanium foil. At the same time, the neutral condition offered a protective environment along the tube wall and pore mouth, which minimized lateral and top dissolution. Results from x-ray photoelectron spectra revealed that the TiO(2) nanotubes prepared in ethylene glycol contained Ti, oxygen (O) and carbon (C) after annealing. The photocatalytic activity of the nanotube arrays produced was evaluated by monitoring the degradation of methyl orange. Results indicate that a nanotube with an average diameter of 140 nm and an optimal tube length of 18.5 microm with a thin tube wall (20 nm) is the optimum structure required to achieve high photocatalytic reaction. In addition, the existence of carbon, high degree of anatase crystallinity, smooth wall and absence of fluorine enhanced the photocatalytic activity of the sample.
The length of titania nanotubes formed by anodization of 0.1 mm thick titanium foil was found to be a strong function of the pH of the electrolyte. The longest nanotubes were formed by using an electrolyte consisting of 1 M Na(2)SO(4) plus 5 wt% NH(4)F with pH 7. At this pH, after 30 min of anodization, 3 microm length nanotubular titania arrays with top diameters of approximately 50 nm and bottom diameters of 100 nm were produced. No acid was added to this electrolyte. The formation of titania nanotubes in neutral pH systems was therefore successful due to the excess NH(4)F in the electrolyte which increases the chemical dissolution process at the metal/oxide interface. Since the pH of the electrolyte at the top part of the nanotubes is kept very high, the dissolution of the nanotubes at the surface is minimal. However, the amount is adequate to remove the initial barrier layer, forming a rather well-defined nanoporous structure. All anodized foils were weakly crystalline and the transformation to anatase phase was achieved by heat treatment at temperatures from 200 to 500 degrees C for 1 h in air. Annealing at temperatures above 500 degrees C induce rutile phase formation and annealing at higher temperatures accelerates the diffusion of Ti(4+) leading to excessive growth and the nanotubular structure diminishes.
A sustainable super-hydrophobic coating composed of silica from palm oil fuel ash (POFA) and polydimethylsiloxane (PDMS) was synthesised using isopropanol as a solvent and coated on a glass substrate. FESEM and AFM analyses were conducted to study the surface morphology of the coating. The super-hydrophobicity of the material was validated through goniometry, which showed a water contact angle of 151°. Cytotoxicity studies were conducted by assessing the cell viability and cell morphology of mouse fibroblast cell line (L929) and hamster lung fibroblast cell line (V79) via tetrazolium salt 3-(4-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and microscopic methods, respectively. The clonogenic assay was performed on cell line V79 and the cell proliferation assay was performed on cell line L929. Both results validate that the toxicity of PDMS: SS coatings is dependent on the concentration of the super-hydrophobic coating. The results also indicate that concentrations above 12.5 mg/mL invariably leads to cell toxicity. These results conclusively support the possible utilisation of the synthesised super-hydrophobic coating for biomedical applications.
Calotropis gigantea (C. gigantea) extract with an ecofriendly nanotechnology approach could provide promising antimicrobial activity against skin pathogens. This study investigates the antimicrobial capability of green synthesized binary ZnO-CuO nanocomposites from C. gigantea against non-MDR (Staphylococcus aureus and Escherichia coli) and MDR (Klebsiella pneumoniae, Pseudomonas aeruginosa and methicillin-resistant S. aureus) skin pathogens. Scanning electron microscopy and transmission electron microscopy revealed the size and shape of B3Z1C sample. Results of X-ray powder diffraction, energy-dispersive spectroscopy, FTIR and UV-Vis spectroscopy analyses confirmed the presence of mixed nanoparticles (i.e., zinc oxide, copper oxide, carbon and calcium) and the stabilising phytochemical agents of plant (i.e., phenol and carbonyl). Antimicrobial results showed that carbon and calcium decorated binary ZnO-CuO nanocomposites with compositions of 75 wt% of ZnO and 25 wt% CuO (B3Z1C) was a strong bactericidal agent with the MBC/MIC ratio of ≤ 4 and ≤ 2 for non-MDR and MDR pathogens, respectively. A significant non-MDR zone of inhibitions were observed for BZC by Kirby-Bauer disc-diffusion test. Further time-kill observation revealed significant fourfold reduction in non-MDR pathogen viable count after 12 h study period. Further molecular studies are needed to explain the biocidal mechanism underlying B3Z1C potential.
The emerging polymer nanocomposites have received industrial interests in diverse fields because of their added value in metal oxide-based nanocomposites, such as titanium (TiO2) and zinc oxide (ZnO). Linear low-density polyethylene (LLDPE)-based polymer has recently generated a huge market in the healthcare industry. TiO2 and ZnO are well known for their instant photocatalytic killing of hospital-acquired infections, especially multidrug-resistant (MDR) pathogens. This study investigated the actions of LLDPE/TiO2/ZnO (1:3) nanocomposites in different weight% against two representative MDR pathogens, namely, methicillin-resistant Staphylococcus aureus (MRSA) and Klebsiella pneumonia (K.pneumoniae). Antibacterial activities were quantified according to international standard guidelines of CLSI MO2-A11 (static condition) and ASTM E-2149 (dynamic condition). Preliminary observation via a scanning electron microscope revealed that LLDPE matrix with TiO2/ZnO nanocomposites changed the bacterial morphology and reduced the bacterial adherence and biofilm formation. Furthermore, a high ZnO weight ratio killed both types of pathogens. The bactericidal potential of the nanocomposite is highlighted by the enhancements in photocatalytic activity, zinc ion release and reactive species, and bacteriostatic/bactericidal activity against bacterial growth. This study provides new insights into the MDR-bactericidal potential of LLDPE with TiO2/ZnO nanocomposites for targeted healthcare applications.
Natural rubber is one of the most important renewable biopolymers used in many applications due to its special properties that cannot be easily mimicked by synthetic polymers. To sustain the existence of natural rubber in industries, modifications have been made to its chemical structure from time to time in order to obtain new properties and to enable it to be employed in new applications. The chemical structure of natural rubber can be modified by exposure to ultraviolet light to reduce its molecular weight. Under controlled conditions, the natural rubber chains will be broken by photodegradation to yield low-molecular-weight natural rubber. The aim of this work was to obtain what is known as liquid natural rubber via photodegradation, with titanium dioxide nanocrystals as the catalyst. Titanium dioxide, which was firstly synthesized using the sol⁻gel method, was confirmed to be in the form of an anatase, with a size of about 10 nm. In this work, the photodegradation was carried out in latex state and yielded low-molecular-weight natural rubber latex of less than 10,000 g/mol. The presence of hydroxyl and carbonyl groups on the liquid natural rubber (LNR) chains was observed, resulting from the breaking of the chains. Scanning electron microscopy of the NR latex particles showed that titanium dioxide nanocrystals were embedded on the latex surface, but then detached during the degradation reaction.
Effluent discharges from industry and domestic waste containing unknown inorganic pollutants. In this work, different mechanisms of heavy metal ions removal using ZnO particles were studied. ZnO particles were synthesized using solid precipitation technique. The morphology of ZnO particles was rod-like shape. The average length and diameter of ZnO particle were 497.34 ± 15.55 and 75.78 ± 10.39nm, respectively. These particles removed effectively heavy metal ions such as Cu(II), Ag(I) and Pb(II) ions with efficiency >85% under exposure of 1 hour of UV light. However, poor removal efficiency, i.e. <15% was observed for Cr(VI), Mn(II), Cd(II) and Ni(II) ions. The removal of these heavy metal ions was in the forms of metals or metal oxide via reduction/oxidation or adsorption mechanism.
In this work, mesoporous TiO2-modified ZnO quantum dots (QDs) were immobilised on a linear low-density polyethylene (LLDPE) polymer using a solution casting method for the photodegradation of tetracycline (TC) antibiotics under fluorescent light irradiation. Various spectroscopic and microscopic techniques were used to investigate the physicochemical properties of the floating hybrid polymer film catalyst (8%-ZT@LLDPE). The highest removal (89.5%) of TC (40 mg/L) was achieved within 90 min at pH 9 due to enhanced water uptake by the LDDPE film and the surface roughness of the hybrid film. The formation of heterojunctions increased the separation of photogenerated electron-hole pairs. The QDs size-dependent quantum confinement effect leads to the displacement of the conduction band potential of ZnO QDs to more negative energy values than TiO2. The displacement generates more reactive species with higher oxidation ability. The highly stable film photocatalyst can be separated easily and can be repeatedly used up to 8 cycles without significant loss in the photocatalytic ability. The scavenging test indicates that the main species responsible for the photodegradation was O2●-. The proposed photodegradation mechanism of TC was demonstrated in further detail based on the intermediates detected by LC-time-of-flight/mass spectrometry (LC/TOF-MS).
Cell growth and proliferative activities on titania nanotube arrays (TNA) have raised alerts on genotoxicity risk. Present toxicogenomic approach focused on epithelial HT29 cells with TNA surface. Fledgling cell-TNA interaction has triggered G0/G1 cell cycle arrests and initiates DNA damage surveillance checkpoint, which possibly indicated the cellular stress stimuli. A profound gene regulation was observed to be involved in cellular growth and survival signals such as p53 and AKT expressions. Interestingly, the activation of redox regulator pathways (antioxidant defense) was observed through the cascade interactions of GADD45, MYC, CHECK1, and ATR genes. These mechanisms furnish to protect DNA during cellular division from an oxidative challenge, set in motion with XRRC5 and RAD50 genes for DNA damage and repair activities. The cell fate decision on TNA-nanoenvironment has been reported to possibly regulate proliferative activities via expression of p27 and BCL2 tumor suppressor proteins, cogent with SKP2 and BCL2 oncogenic proteins suppression. Findings suggested that epithelial HT29 cells on the surface of TNA may have a positive regulation via cell-homeostasis mechanisms: a careful circadian orchestration between cell proliferation, survival, and death. This nanomolecular knowledge could be beneficial for advanced medical applications such as in nanomedicine and nanotherapeutics.
The polyvinyl alcohol (PVA) and neem extract were grafted onto coupled oxides (3ZT-CO) via reflux process to stabilize the particles to form 3ZT-CO/PVA and 3ZT-CO/Neem. These were then incorporated into LLDPE by melt blending process to give LLDPE/3ZT-CO/PVA and LLDPE/3ZT-CO/Neem composites. The Neem and PVA stabilized particles showed high zeta potential and dispersed homogeneously in water. The stabilization process altered the shape of the particles due to plane growth along the (002) polar direction. The stabilizers acted as capping agents and initiated the one-dimensional growth. The alkyl chain groups from PVA increased the polarity of the LLDPE/3ZT-CO/PVA and played a dominant role in the water adsorption process to activate the photocatalytic activity. This was further enhanced by the homogeneous distribution of the particles and low degree of crystallinity (20.87%) of the LLDPE composites. LLDPE/3ZT-CO/PVA exhibited the highest photodegradation (93.95%), which was better than the non-stabilized particles. Therefore, the photocatalytic activity of a polymer composite can be enhanced by grafting PVA and neem onto couple oxides. The LLDPE/3ZT-CO/PVA composite was further used to treat textile effluent. The results showed the composite was able to remove dye color by 93.95% and to reduce biochemical oxygen demand (BOD) and chemical oxygen demand (COD) by 99.99%.
An innovative nano-base polymer that scavenges radicals and reactive oxygen species exhibits potential antibacterial properties, which are crucial in the biomedical field, particularly in reducing nosocomial infections. However, the safety of this nano-based polymer, which has direct contact with the human system, has not been fully understood. The present study investigated the cytocompatibility and hemocompatibility responses of linear low-density polyethylene polymer (LLDPE) embedded with difference ratios of heterogeneous TiO2/ZnO nanocomposites. Exposure of the blood and fibroblast cells to LLDPE/100Z and LLDPE/25T75Z/10% nanocomposite films for 48 and 72 h decreased their viability by less than 40%, compared with LLDPE, LLDPE/100T and LLDPE/25T75Z/5% nanocomposite films. It also presented possible cellular damage and cytotoxicity, which was supported by the findings from the significant release of extracellular lactate dehydrogenase profiles and cell survival assay Further observation using an electron microscope revealed that LLDPE films with heterogeneous 25T75Z/5% promoted cell adhesion. Moreover, no hemolysis was detected in all ratios of heterogeneous TiO2/ZnO nanocomposite in LLDPE film as it was less than 0.2%, suggesting that these materials were hemocompatible. This study on LLDPE film with heterogeneous TiO2/ZnO nanocomposites demonstrated favorable biocompatible properties that were significant for advanced biomedical polymer application in a hospital setting.
Pupose: Cisplatin (CDDP), while amongst the recognised chemotherapeutic drugs currently available, is known to have limitations; the lack of a single treatment approach and non-specific targeted therapies. Therefore, the development of an innovative strategy that could achieve localised CDDP treatment is an urgent undertaking. Recent advances in titania nanotube arrays (TNAs) technology have demonstrated promising applications for localised chemotherapeutic drug treatment. The present work investigated the efficiency of a TNA nanosystem for the localised CDDP treatment of nasopharyngeal carcinoma (NPC). Methods: Two models of the TNA nanosystem were prepared: CDDP loaded onto the TNA nanosystem surface (CDDP-TNA) and the other consisted of chitosan-coated CDDP-TNA. CDDP release from these two nanosystems was comprehensively tested on the NPC cells NPC/HK-1 and C666-1. The NPC cytotoxicity profile of the two CDDP-TNA nanosystems was evaluated after incubation for 24, 48 and 72 hours. Intracellular damage profiles were studied using fluorescence microscopy analysis with Hoechst 33342, acridine orange and propidium iodide. Results: The half-maximal inhibitory concentrations (IC50) of CDDP at 24 hours were 0.50 mM for NPC/HK-1 and 0.05 mM for C666-1. CDDP in the CDDP-TNA and chitosan-coated CDDPTNA models presented a significant degree of NPC inhibition (P<0.05) after 24, 48 and 72 hours of exposure. The outcome revealed cellular damage and shrinkage of the cell membranes after 48 hours of exposure to CDDP-TNA. Conclusion: This in vitro work demonstrated the effectiveness of TNA nanosystems for the localised CDDP treatment of NPC cells. Further in vivo studies are needed to support the findings.
The most common material used for blood bags is PVC, which requires the addition of DEHP to increase its flexibility. DEHP is known to cross the polymer barrier and move into the stored blood and, ultimately, the patient's bloodstream. In this work, an alternative prototype composed of SEBS/PP was fabricated through blow-moulding and compared with the commercially available PVC-based blood bag which was designated as the control. The blow-moulded sample layers were welded together using CO2 lasers and optimized to obtain complete sealing of the sides. The samples' performance characteristics were analyzed using water permeability, oxygen permeability, shelf-life, and bioburden tests. The SEBS/PP sample exhibited the highest oxygen permeability rate of 1486.6 cc/m2/24 h after 40 days of ageing, indicating that the sample is conducive for red blood cell (RBC) respiration. On the other hand, the SEBS/PP sample showcased a lower water permeability rate of 0.098 g/h m2 after 40 days of aging, indicating a high-water barrier property and thus preventing water loss during storage. In comparison, the oxygen and water permeability rates of PVC-DEHP were found to be distinctly lower in performance (662.7 cc/m2/24 h and 0.221 g/h m2, respectively). In addition, shelf-life analyses revealed that after 40 days of ageing, polymer samples exhibited no visual damage or degradation. The optimal parameters to obtain adequate welding of the SEBS/PP were determined to be power of 60% (18 W), speed of 70 in/sec and 500 Pulse Per Inch (PPI). Furthermore, the bioburden estimates of SEBS/PP of 115 CFU are markedly lower compared to the bioburden estimate of PVC-DEHP of 213 CFU. The SEBS/PP prototype can potentially be an effective alternative to PVC-based blood bags, particularly for high-risk patients in order to reduce the likelihood of medical issues.
The present study deals with surface modification of Ti6Al4V alloy via anodization technique. The morphology, structure, adhesion and bioactivity of Ti6Al4V alloy after anodization process were investigated in detail. The influence of fluoride content and direct circuit (DC) applied voltage during anodization of Ti6Al4V alloy in a bath with electrolytes composed of ethylene glycol (EG) and ammonium fluoride (NH4F) were considered. It was found that the average pore sizes and length of nanoporous or nanotubes were increasing with the fluoride content and applied voltage. A minimum of 3 wt% of NH4F is required to grow a self-organized nanotube arrays. As the fluoride content was increased to 5 wt%, TiO2 nanotubes with average diameter of 110 nm and 3.4 microm lengths were successfully synthesized. It is noteworthy to point out that the rate of the nanotube formation was increasing up to 9 microm thick bioactive TiO2 nanotubes layer as anodization time was increased to 3 h. Based on the results obtained, the PA6 cells cultured on anodic Ti6Al4V alloy showed highest level of cell viability and greater cell adhesion compared to the flat Ti6Al4V foil substrate. In fact, highly ordered nanotubes structure on Ti6Al4V alloy can provide beneficial effects for PA6 cells in attachment and proliferation.
Metal oxide-polymer nanocomposite has been proven to have selective bactericidal effects against the main and common pathogens (Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli)) that can cause harmful infectious diseases. As such, this study looked into the prospect of using TiO₂/ZnO with linear low-density polyethylene (LLDPE) to inactivate S. aureus and E. coli. The physical, structural, chemical, mechanical, and antibacterial properties of the nanocomposite were investigated in detail in this paper. The production of reactive species, such as hydroxyl radicals (•OH), holes (h⁺), superoxide anion radicals (O₂•¯), and zinc ion (Zn2+), released from the nanocomposite were quantified to elucidate the underlying antibacterial mechanisms. LLDPE/25T75Z with TiO₂/ZnO (1:3) nanocomposite displayed the best performance that inactivated S. aureus and E. coli by 95% and 100%, respectively. The dominant reactive active species and the zinc ion release toward the superior antibacterial effect of nanocomposite are discussed. This work does not only offer depiction of the effective element required for antimicrobial biomedical appliances, but also the essential structural characteristics to enhance water uptake to expedite photocatalytic activity of LLDPE/metal oxide nanocomposite for long term application.
In biomedical implant technology, nanosurface such as titania nanotube arrays (TNA) could provide better cellular adaptation, especially for long-term tissue acceptance response. Mechanotransduction activities of TNA nanosurface could involve the cytoskeleton remodeling mechanism. However, there is no clear insight into TNA mechano-cytoskeleton remodeling activities, especially computational approaches. Epithelial cells have played critical interface between biomedical implant surface and tissue acceptance, particularly for long-term interaction. Therefore, this study investigates genomic responses that are responsible for cell-TNA mechano-stimulus using epithelial cells model. Findings suggested that cell-TNA interaction may improve structural and extracellular matrix (ECM) support on the cells as an adaptive response toward the nanosurface topography. More specifically, the surface topography of the TNA might improve the cell polarity and adhesion properties via the interaction of the plasma membrane and intracellular matrix responses. TNA nanosurface might engross the cytoskeleton remodeling activities for multidirectional cell movement and cellular protrusions on TNA nanosurface. These observations are supported by the molecular docking profiles that determine proteins' in silico binding mechanism on TNA. This active cell-surface revamping would allow cells to adapt to develop a protective barrier toward TNA nanosurface, thus enhancing biocompatibility properties distinctly for long-term interaction. The findings from this study will be beneficial toward nano-molecular knowledge of designing functional nanosurface technology for advanced medical implant applications.
The surge of medical devices associated with nosocomial infection (NI) cases, especially by multidrug-resistant (MDR) bacterial strains, is one of the pressing issues of present health care systems. Metal oxide nanoparticles (MNPs) have become promising antibacterial agents against a wide range of bacterial strains. This work study is on the bactericidal capacity of heterogeneous TiO2/ZnO nanocomposites with different weight percentages and concentrations against common MDR and non-MDR bacterial strains. The profiles on disk diffusion, minimum inhibitory concentration, minimum bactericidal concentration, tolerance determination, time-kill, and biofilm inhibition assay were determined after 24 h of direct contact with the nanocomposite samples. Findings from this work revealed that the heterogeneous TiO2/ZnO nanocomposite with a 25T75Z weight ratio showed an optimal tolerance ratio against Gram-positive and -negative bacteria, indicating their bactericidal capacity. Further observation suggests that higher molar ratio of Zn2+ may possibly involve generation of active ion species that enhance bactericidal effect against Gram-positive bacterial strains, especially for the MDR strains. Nano-based technology using MNPs may provide a promising solution for the prevention and control of NIs. Further work on biocompatibility and cytotoxicity profiles of this nanocomposite are needed.