Vacuum-deposited thin film porous ZnO-metal oxide hybrid systems for microsupercapacitor applications with Ir/IrO2in ZnO as a new, high-performance electrode.

We fabricate porous nanostructured 1µm thick ZnO-metal/metal oxide hybrid material thin films using a unique approach utilizing physical vapor deposition with postdeposition annealing. We study Pt, Pd, Ru, Ir and Sn as the metals and find they all form hybrid structures, however with differing physical and electrochemical properties. We investigate their applicability in microsupercapacitor electrodes in a LiCl aqueous electrolyte and find that the ZnO hybrid with Ir exhibits the highest capacitances. We follow with optimization and more detailed material studies of the ZnO-Ir hybrid showing that a significant amount of Ir is present in the material in the form of metallic Ir and indiffused Ir, while IrO2is also present in the nanoscale. We obtain electrodes with 5.25 mF · cm-2capacitance with 90% retention over 10 000 charge/discharge cycles in an aqueous LiCl electrolyte, which is better than the reported values for other Ir-based hybrids. Finally, we showed that the electrodes provide 2.64 mF · cm-2in a symmetric device with an operating voltage of 0.8 V. With this report, we discuss the influence of both Ir and IrO2on the capacitance, underlining the synergistic effect, and show them as promising inorganic matterials for integration with other supercapacitor electrodes.

The ROS-generating photosensitizer-free NaYF4:Yb,Tm@SiO2upconverting nanoparticles for photodynamic therapy application.

In this work we adapt rare-earth-ion-doped NaYF4nanoparticles coated with a silicon oxide shell (NaYF4:20%Yb,0.2%Tm@SiO2) for biological and medical applications (for example, imaging of cancer cells and therapy at the nano level). The wide upconversion emission range under 980 nm excitation allows one to use the nanoparticles for cancer cell (4T1) photodynamic therapy (PDT) without a photosensitizer. The reactive oxygen species (ROS) are generated by Tm/Yb ion upconversion emission (blue and UV light). Thein vitroPDT was tested on 4T1 cells incubated with NaYF4:20%Yb,0.2%Tm@SiO2nanoparticles and irradiated with NIR light. After 24 h, cell viability decreased to below 10%, demonstrating very good treatment efficiency. High modification susceptibility of the SiO2shell allows for attachment of biological molecules (specific antibodies). In this work we attached the anti-human IgG antibody to silane-PEG-NHS-modified NaYF4:20%Yb,0.2%Tm@SiO2nanoparticles and a specifically marked membrane model by bio-conjugation. Thus, it was possible to perform a selective search (a high-quality optical method with a very low-level organic background) and eventually damage the targeted cancer cells. The study focuses on therapeutic properties of NaYF4:20%Yb,0.2%Tm@SiO2nanoparticles and demonstrates, upon biological functionalization, their potential for targeted therapy.

A simple, low-cost and green method for controlling the cytotoxicity of MXenes.

MXene phases are a member of the intriguing 2D material family, beyond graphene. They are good candidates for many applications, however, their potential toxicity is of crucial importance for future development. Herein, we present a simple, low-cost and fully green approach for controlling the potential cytotoxicity of 2D MXenes after delamination by harnessing the interactions that occur between the surface of MXene phases and natural biomacromolecule - collagen. We also demonstrate that the step-by-step adsorption and desorption of collagen from the surface of 2D MXenes is easily controlled using in situ zeta potential measurements coupled with dynamic light scattering (DLS) method. The obtained results demonstrated that the electrostatically driven unprecedented susceptibility of the MXenes' surfaces to collagen. Surface-modification reduces toxicity of MXenes in vitro i.e. adjust cells' viabilities as well as reduce their oxidative stress. This indicates enhanced biocompatibility of 2D Ti3C2 and Ti2C MXenes surface-modified with collagen, which is involved in many bio-interactions as important building blocks in the human body. The presented study opens new avenues for designing MXenes with defined surface properties and paves the way for their future successful management in nano-medicinal applications.

Multilayered stable 2D nano-sheets of Ti2NTx MXene: synthesis, characterization, and anticancer activity.

BACKGROUND: The biological activity of MXenes has been studied for several years because of their potential biomedical applications; however, investigations have so far been limited to 2D titanium carbides. Although monolayered Ti2NTx MXene has been expected to have biological activity, experimental studies revealed significant difficulties due to obstacles to its synthesis, its low stability and its susceptibility to oxidation and decomposition. RESULTS: In this paper, we report our theoretical calculations showing the higher likelihood of forming multilayered Ti2NTx structures during the preparation process in comparison to single-layered structures. As a result of our experimental work, we successfully synthesized multilayered Ti2NTx MXene that was suitable for biological studies by the etching of the Ti2AlN MAX phase and further delamination. The biocompatibility of Ti2NTx MXene was evaluated in vitro towards human skin malignant melanoma cells, human immortalized keratinocytes, human breast cancer cells, and normal human mammary epithelial cells. Additionally, the potential mode of action of 2D Ti2NTx was investigated using reactive oxygen tests as well as SEM observations. Our results indicated that multilayered 2D sheets of Ti2NTx showed higher toxicity towards cancerous cell lines in comparison to normal ones. The decrease in cell viabilities was dose-dependent. The generation of reactive oxygen species as well as the internalization of the 2D sheets play a decisive role in the mechanisms of toxicity. CONCLUSIONS: We have shown that 2D Ti2NTx in the form of multilayered nanoflakes exhibits fair stability and can be used for in vitro studies. These results show promise for its future applications in biotechnology and nanomedicine.

Influence of modification of Ti3C2 MXene with ceramic oxide and noble metal nanoparticles on its antimicrobial properties and ecotoxicity towards selected algae and higher plants.

The number of investigations regarding the application of 2D nanosheets of MXenes in different technological areas is growing rapidly. Different surface modifications of MXenes have been introduced to date in order to tailor their properties. As a result, surface-modified MXenes could be released in the environment from filtration membranes, adsorbents, or photocatalysts. On the other hand, assessment of their environmental impact is practically unexplored. In the present study, we examined how modification of the antimicrobial Ti3C2 MXene with ceramic oxide and noble metal nanoparticles affects its toxic behavior. The expanded 2D sheets of the Ti3C2 MXene phase were modified with Al2O3/Ag, SiO2/Ag, and SiO2/Pd nanoparticles using the sol-gel method and extensively characterized. The obtained 2D nanocomposite structures were characterized by antibacterial properties. The ecotoxicological assays considered green algae (Desmodesmus quadricauda) as well as two higher plants: sorghum (Sorghum saccharatum) and charlock (Sinapis alba). Our results revealed that obtained nanomaterials can cause both stimulating and inhibiting effects towards algae, and the ecotoxicity depended on the concentration and the type of modification. The study reveals the intriguing property of pristine Ti3C2 which highly stimulated green algae growth at low concentrations. It also shows that modification of pristine Ti3C2 MXene with different nanoparticles changes the ecotoxicological effects of the resulting nanocomposite 2D structures. We have also indicated nanocomposite structures that does not revealed the toxic effect on tested organisms i.e. the Ti3C2 MXene surface-modified with Al2O3/Ag was not phyto- and eco-toxic. This work helps with better understanding of the reactivity of surface-modified MXenes towards chosen organisms, giving more information concerning the potential impact of tested nanocomposites on the ecosystems.

Mammalian cell defence mechanisms against the cytotoxicity of NaYF4:(Er,Yb,Gd) nanoparticles.

Water-soluble upconversion nanoparticles (UCNPs), based on polyvinylpyrrolidone (PVP)-coated NaYF4:Er3+,Yb3+,Gd3+, with various concentrations of Gd3+ ions and relatively high upconversion efficiencies, were synthesized. The internalization and cytotoxicity of the thus obtained UCNPs were evaluated in three cell lines (HeLa, HEK293 and astrocytes). No cytotoxicity was observed even at concentrations of UCNPs up to 50 µg ml-1. The fate of the UCNPs within the cells was studied by examining their upconversion emission spectra with confocal microscopy and confirming these observations with transmission electron microscopy. It was found that the cellular uptake of the UCNPs occurred primarily by clathrin-mediated endocytosis, whereas they were secreted from the cells via lysosomal exocytosis. The results of this study, focused on the mechanisms of the cellular uptake, localization and secretion of UCNPs, demonstrate, for the first time, the co-localization of UCNPs within discrete cell organelles.

In vitro studies on cytotoxicity of delaminated Ti3C2 MXene.

MXenes are a novel family of 2D materials, the biological activity of which has been largely unexplored. The present study, for the first time, shows some aspects of the in vitro toxicity of 2D sheets of Ti3C2 MXene. The Ti3AlC2 MAX phase was used in an expansion and delamination process to obtain Ti3C2 material in the form of 2D sheets. The obtained 2D material was characterized using SEM, TEM, DLS, XPS, and zeta potential. The biological activity of the MXene was determined on two normal (MRC-5 and HaCaT) and two cancerous (A549 and A375) cell lines. The cytotoxicity results indicated that the observed toxic effects were higher against cancerous cells compared to normal ones. The mechanisms of potential toxicity were also elucidated. It was shown that MXene may affect the occurrence of oxidative stress and, in consequence, the generation of reactive oxygen species (ROS). The results of the present study provide the principal knowledge to date regarding the biological activity of the MXenes; the lack of such knowledge is the major obstacle on the MXenes' road to further research and development on their applications in bioscience and biotechnology, e.g. as drug-delivery systems.

Highly transparent supercapacitors based on ZnO/MnO2 nanostructures.

The recent rapid development of transparent electronics, notably displays and control circuits, requires the development of highly transparent energy storage devices, such as supercapacitors. The devices reported to date utilize carbon-based electrodes for high performance, however at the cost of their low transparency around 50%, insufficient for real transparent devices. To overcome this obstacle, in this communication highly transparent supercapacitors were fabricated based on ZnO/MnO2 nanostructured electrodes. ZnO served as an intrinsically transparent skeleton for increasing the electrode surface, while MnO2 nanoparticles were applied for high capacitance. Two MnO2 synthesis routes were followed, based on the reaction of KMnO4 with Mn(Ac)2 and PAH, leading to the synthesis of ß-MnO2 with minority α-MnO2 nanoparticles and amorphous MnO2 with embedded ß-MnO2, respectively. The devices based on such electrodes showed high capacitances of 2.6 mF cm-2 and 1.6 mF cm-2, respectively, at a scan rate of 1 mV s-1 and capacitances of 104 µF cm-2 and 204 µF cm-2 at a very high rate of 1 V s-1, not studied for transparent supercapacitors previously. Additionally, the Mn(Ac)2 devices exhibited very high transparencies of 86% vs. air, far superior to other transparent energy storage devices reported with similar charge storage properties. This high device performance was achieved with a non-acidic LiCl gel electrolyte, reducing corrosion and handling risks associated with conventional highly concentrated acidic electrolytes, enabling applications in safe, wearable, transparent devices.

Room temperature sputter deposited catalyst-free nanowires with wurtzite/zinc blende ZnO superstructure and their application in electromechanical nanogenerators on polymer and paper substrates.

Catalyst-free growth of ZnO nanowires using reactive magnetron sputtering at room temperature is reported. We discuss the growth of the nanowires using reactive magnetron sputtering as a function of argon and oxygen flow values changing at a set ratio of 10:2. A transition from nanostructured Zn to nanowire ZnO growth is observed at 20 sccm Ar and 4 sccm O2. Densification and improved alignment of the nanowires is visible for increasing flow values up to 50 sccm Ar and 10 sccm O2. Nanowires exhibit stacking fault regions of zinc blende ZnO in wurtzite ZnO. The regions encompass the whole width of the nanowires and their quantum well behavior is manifested in the photoluminescence spectra. The nanowires were subsequently deposited on paper and PET substrates and electromechanical nanogenerators were fabricated. Manual pressing and depressing of the devices induced voltages of 50 µV and 2 µV for the devices on PET and paper substrates, respectively.

Wurtzite (Ga,Mn)As nanowire shells with ferromagnetic properties.

(Ga,Mn)As having a wurtzite crystal structure was coherently grown by molecular beam epitaxy on the {1100} side facets of wurtzite (Ga,In)As nanowires and further encapsulated by (Ga,Al)As and low temperature GaAs. For the first time, a truly long-range ferromagnetic magnetic order is observed in non-planar (Ga,Mn)As, which is attributed to a more effective hole confinement in the shell containing Mn by the proper selection/choice of both the core and outer shell materials.

Formation of Highly Ordered Spherical Aggregates from Drying Microdroplets of Colloidal Suspension.

The formation of highly ordered spherical aggregates of silica nanoparticles by the evaporation of single droplets of an aqueous colloidal suspension levitated (confined) in the electrodynamic quadrupole trap is reported. The transient and final structures formed during droplet evaporation have been deposited on a silicon substrate and then studied with SEM. Various successive stages of the evaporation-driven aggregation of nanoparticles have been identified: formation of the surface layer of nanoparticles, formation of the highly ordered spherical structure, collapse of the spherical surface layer leading to the formation of densely packed spherical aggregates, and rearrangement of the aggregate into the final structure of a stable 3D quasi-crystal. The evaporation-driven aggregation of submicrometer particles in spherical symmetry leads to sizes and morphologies of the transient and final structures significantly different than in the case of aggregation on a substrate. The numerical model presented in the article allows us to predict and visualize the observed aggregation stages and their dynamics and the final aggregates observed with SEM.

The utility and cost of routine follow-up procedures in the surveillance of ovarian and primary peritoneal carcinoma: a 16-year institutional review.

BACKGROUND: The purpose of this study was to evaluate the number of ovarian cancer and primary peritoneal cancer (PPC) progressive disease cases identified via routine follow-up procedures and the corresponding cost throughout a 16-year period at a single medical institution. METHODS: Previously undiagnosed epithelial ovarian (n=241), PPC (n=23), and concurrent ovarian and uterine (n=24) cancer patients were treated and then followed via CA-125, imaging (e.g., CT scan, chest X-ray), physical examination and vaginal cytology. RESULTS: In the group of 287 patients, there were 151 cases of disease progression. Serial imaging detected the highest number of progressive disease cases (66 initial and 45 confirmatory diagnoses), but the cost was rather high ($13,454 per patient recurrence), whereas CA-125 testing (74 initial and 20 corroborative diagnoses) was the least expensive ($3,924) per recurrent diagnosis. The total cost of surveillance during the 16-year period was nearly $2,400,000. CONCLUSION: Ultimately, serial imaging and the CA-125 assay detected the highest number of ovarian cancer and PCC progressive disease cases in comparison to physical examination and vaginal cytology, but nevertheless, all of the procedures were conducted at a considerable financial expense.

The effects of dwarfing genes on seedling root growth of wheat.

Most modern wheat cultivars contain major dwarfing genes, but their effects on root growth are unclear. Near-isogenic lines (NILs) containing Rht-B1b, Rht-D1b, Rht-B1c, Rht8c, Rht-D1c, and Rht12 were used to characterize the effects of semi-dwarfing and dwarfing alleles on root growth of 'Mercia' and 'Maris Widgeon' wheat cultivars. Wheat seedlings were grown in gel chambers, soil-filled columns, and in the field. Roots were extracted and length and dry mass measured. No significant differences in root length were found between semi-dwarfing lines and the control lines in any experiment, nor was there a significant difference between the root lengths of the two cultivars grown in the field. Total root length of the dwarf lines (Rht-B1c, Rht-D1c, and Rht12) was significantly different from that of the control although the effect was dependent on the experimental methodology; in gel chambers root length of dwarfing lines was increased by approximately 40% while in both soil media it was decreased (by 24-33%). Root dry mass was 22-30% of the total dry mass in the soil-filled column and field experiments. Root length increased proportionally with grain mass, which varied between NILs, so grain mass was a covariate for the analysis of variance. Although total root length was altered by dwarf lines, root architecture (average root diameter, lateral root:total root ratio) was not affected by reduced height alleles. A direct effect of dwarfing alleles on root growth during seedling establishment, rather than a secondary partitioning effect, was suggested by the present experiments.

Differentiated reactivity of whole blood neonatal platelets to various agonists.

Neonatal platelets have been occasionally reported to show a reduced response to various agonists. The molecular mechanism(s) of such a depressed reactivity remains unclear. To further address this problem we studied neonatal platelet activation with thrombin, TRAP (thrombin receptor activating peptide, Ser-Phe-Leu-Leu-Arg-Asn-Pro-Asn-Asp-Lys-Tyr-Glu-Pro-Phe) and ADP in 42 healthy 1-2 day old neonates using a whole peripheral blood flow cytometry. The neonates did not show an increased fraction of P-selectin-positive circulating platelets, whereas the expression of GPIb (glycoprotein Ib) in resting neonatal platelets was significantly lower compared to adults. Neonatal platelets were significantly less reactive than adult platelets to thrombin and TRAP, especially at lower agonist concentrations, but not to ADP or when incubated for 1 h at room temperature. Activation of neonatal platelets with agonists resulted in a marked alterations in the expression of P-selectin, whereas the internalization of GPIb was not affected. The reduced neonatal platelet sensitivity to thrombin and TRAP was accompanied by significantly reduced ATIII (antithrombin III) and increased prothrombin fragment F(1+2) in neonatal plasma. We conclude that various receptor systems potentially able to bind thrombin are relatively insensitive in neonatal platelets. The novelty of our work is that neonatal platelet hyposensitivity is not a generalized phenomenon, but concerns only selected agonists and selected receptor systems.

Differential metabolic effects of energy restriction in dogs using diets varying in fat and fiber content.

The role of dietary fat and fiber in energy restriction for the management of obesity was examined. Twelve male castrated dogs were energy restricted for 7 weeks by feeding 60% of their calculated maintenance energy requirements (MER = 1500 kcal/m2/d) for ideal body weight. Six dogs were restricted on a high-fat (35.4 kcal% from fat), low-fiber (2.9% dry matter basis [DMB]) diet while the other six dogs were restricted on a low-fat (24.5 kcal% from fat), high-fiber (27% DMB) diet. Compared with the high-fat, low-fiber diet, energy restriction on the low-fat, high-fiber diet resulted in significantly greater decreases in body fat (1472 +/- 166 vs. 853 +/- 176 g; p < 0.05) and total serum cholesterol concentrations (108.7 +/- 11.3 vs. 51.5 +/- 13.9 mg/dL; p < 0.005). Reductions in body weight (2.86 +/- 0.3 vs. 2.14 +/- 0.3 kg; p < 0.09), and mean arterial blood pressure (17.4 +/- 6.1 vs. 6.7 +/- 2.9 mmHg; p < 0.12) were also greater on the low-fat diet; however, these diet effects did not reach statistical significance. These data suggest that the fat and fiber content of the diet during energy restriction are important factors in the management of obesity.