Multifunctional Hybrid MoS2-PEGylated/Au Nanostructures with Potential Theranostic Applications in Biomedicine.

In this work, flower-like molybdenum disulfide (MoS2) microspheres were produced with polyethylene glycol (PEG) to form MoS2-PEG. Likewise, gold nanoparticles (AuNPs) were added to form MoS2-PEG/Au to investigate its potential application as a theranostic nanomaterial. These nanomaterials were fully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), photoelectron X-ray spectroscopy (XPS), Fourier-transformed infrared spectroscopy (FTIR), cyclic voltammetry and impedance spectroscopy. The produced hierarchical MoS2-PEG/Au microstructures showed an average diameter of 400 nm containing distributed gold nanoparticles, with great cellular viability on tumoral and non-tumoral cells. This aspect makes them with multifunctional characteristics with potential application for cancer diagnosis and therapy. Through the complete morphological and physicochemical characterization, it was possible to observe that both MoS2-PEG and MoS2-PEG/Au showed good chemical stability and demonstrated noninterference in the pattern of the cell nucleus, as well. Thus, our results suggest the possible application of these hybrid nanomaterials can be immensely explored for theranostic proposals in biomedicine.

Structure, Properties and Applications of Two-Dimensional Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) has emerged as a strong candidate for two-dimensional (2D) material owing to its exciting optoelectrical properties combined with mechanical robustness, thermal stability, and chemical inertness. Super-thin h-BN layers have gained significant attention from the scientific community for many applications, including nanoelectronics, photonics, biomedical, anti-corrosion, and catalysis, among others. This review provides a systematic elaboration of the structural, electrical, mechanical, optical, and thermal properties of h-BN followed by a comprehensive account of state-of-the-art synthesis strategies for 2D h-BN, including chemical exfoliation, chemical, and physical vapor deposition, and other methods that have been successfully developed in recent years. It further elaborates a wide variety of processing routes developed for doping, substitution, functionalization, and combination with other materials to form heterostructures. Based on the extraordinary properties and thermal-mechanical-chemical stability of 2D h-BN, various potential applications of these structures are described.

Micro Scalable Graphene Oxide Productions Using Controlled Parameters in Bench Reactor.

The detailed study of graphene oxide (GO) synthesis by changing the graphite/oxidizing reagents mass ratios (mG/mROxi), provided GO nanosheets production with good yield, structural quality, and process savings. Three initial samples containing different amounts of graphite (3.0 g, 4.5 g, and 6.0 g) were produced using a bench reactor under strictly controlled conditions to guarantee the process reproducibility. The produced samples were analyzed by Raman spectroscopy, atomic force microscopy (AFM), x-ray diffraction (XDR), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR) and thermogravimetry (TGA) techniques. The results showed that the major GO product comprised of nanosheets containing between 1-5 layers, with lateral size up to 1.8 µm. Therefore, it was possible to produce different batches of graphene oxide with desirable physicochemical characteristics, keeping the amount of oxidizing reagent unchanged. The use of different proportions (mG/mROxi) is an important strategy that provides to produce GO nanostructures with high structural quality and scale-up, which can be well adapted in medium-sized bench reactor.

Study of Friction and Wear Effects in Aluminum Parts Manufactured via Single Point Incremental Forming Process Using Petroleum and Vegetable Oil-Based Lubricants.

This paper focuses on studying how mineral oil, sunflower, soybean, and corn lubricants influence friction and wear effects during the manufacturing of aluminum parts via the single point incremental forming (SPIF) process. To identify how friction, surface roughness, and wear change during the SPIF of aluminum parts, Stribeck curves were plotted as a function of the SPIF process parameters such as vertical step size, wall angle, and tool tip semi-spherical diameter. Furthermore, lubricant effects on the surface of the formed parts are examined by energy dispersive spectroscopy (EDS) and scanning electron microscope (SEM) images, the Alicona optical 3D measurement system, and Fourier-transform infrared spectroscopy (FTIR). Results show that during the SPIF process of the metallic specimens, soybean and corn oils attained the highest friction, along forces, roughness, and wear values. Based on the surface roughness measurements, it can be observed that soybean oil produces the worst surface roughness finish in the direction perpendicular to the tool passes (Ra =1.45 µm) considering a vertical step size of 0.25 mm with a 5 mm tool tip diameter. These findings are confirmed through plotting SPIFed Stribeck curves for the soybean and corn oils that show small hydrodynamic span regime changes for an increasing sample step-size forming process. This article elucidates the effects caused by mineral and vegetable oils on the surface of aluminum parts produced as a function of Single Point Incremental Sheet Forming process parameters.

Carbon Nanotori Structures for Thermal Transport Applications on Lubricants.

Carbon nanostructures have been recently applied to improve industrial manufacturing processes and other materials; such is the case for lubricants used in the metal-mechanic industry. Nanotori are toroidal carbon nanostructures, obtained from chemical treatment of multi-wall carbon nanotubes (MWCNTs). This material has been shown to have superb anti-wear and friction reduction performance, having the ability to homogeneously disperse within water in concentrations between 1-2 wt.%. Obtained results of these novel nanostructures under water mixtures and novel additives were a set point to our studies in different industrial lubricants. In the present work, nanotori structures have been applied in various filler fractions as reinforcement to evaluate the behavior in thermal transport of water-based (WB) and oil-based (OB) lubricants. Temperature-dependent experiments to evaluate the thermal conductivity were performed using a thermal water bath ranging from room temperature up to 323 K. The obtained results showed a highly effective and favorable improvement in the heat transport of both lubricants; oil-based results were better than water-based results, with nanotori structures increasing the lubricants' thermal transport properties by 70%, compared to pure lubricant.

Thermal Conductivity Performance of 2D hBN/MoS2/Hybrid Nanostructures Used on Natural and Synthetic Esters.

In this paper, the thermal conductivity behavior of synthetic and natural esters reinforced with 2D nanostructures-single hexagonal boron nitride (h-BN), single molybdenum disulfide (MoS2), and hybrid h-BN/MOS2-were studied and compared to each other. As a basis for the synthesis of nanofluids, three biodegradable insulating lubricants were used: FR3TM and VG-100 were used as natural esters and MIDEL 7131 as a synthetic ester. Two-dimensional nanosheets of h-BN, MoS2, and their hybrid nanofillers (50/50 ratio percent) were incorporated into matrix lubricants without surfactants or additives. Nanofluids were prepared at 0.01, 0.05, 0.10, 0.15, and 0.25 weight percent of filler fraction. The experimental results revealed improvements in thermal conductivity in the range of 20-32% at 323 K with the addition of 2D nanostructures, and a synergistic behavior was observed for the hybrid h-BN/MoS2 nanostructures.

Chemical Makeup and Hydrophilic Behavior of Graphene Oxide Nanoribbons after Low-Temperature Fluorination.

Here we investigated the fluorination of graphene oxide nanoribbons (GONRs) using H2 and F2 gases at low temperature, below 200 °C, with the purpose of elucidating their structure and predicting a fluorination mechanism. The importance of this study is the understanding of how fluorine functional groups are incorporated in complex structures, such as GONRs, as a function of temperature. The insight provided herein can potentially help engineer application-oriented materials for several research and industrial sectors. Direct (13)C pulse magic angle spinning (MAS) nuclear magnetic resonance (NMR) confirmed the presence of epoxy, hydroxyl, ester and ketone carbonyl, tertiary alkyl fluorides, as well as graphitic sp(2)-hybridized carbon. Moreover, (19)F-(13)C cross-polarization MAS NMR with (1)H and (19)F decoupling confirmed the presence of secondary alkyl fluoride (CF2) groups in the fluorinated graphene oxide nanoribbon (FGONR) structures fluorinated above 50 °C. First-principles density functional theory calculations gained insight into the atomic arrangement of the most dominant chemical groups. The fluorinated GONRs present atomic fluorine percentages in the range of 6-35. Interestingly, the FGONRs synthesized up to 100 °C, with 6-19% of atomic fluorine, exhibit colloidal similar stability in aqueous environments when compared to GONRs. This colloidal stability is important because it is not common for materials with up to 19% fluorine to have a high degree of hydrophilicity.

Low-density three-dimensional foam using self-reinforced hybrid two-dimensional atomic layers.

Low-density nanostructured foams are often limited in applications due to their low mechanical and thermal stabilities. Here we report an approach of building the structural units of three-dimensional (3D) foams using hybrid two-dimensional (2D) atomic layers made of stacked graphene oxide layers reinforced with conformal hexagonal boron nitride (h-BN) platelets. The ultra-low density (1/400 times density of graphite) 3D porous structures are scalably synthesized using solution processing method. A layered 3D foam structure forms due to presence of h-BN and significant improvements in the mechanical properties are observed for the hybrid foam structures, over a range of temperatures, compared with pristine graphene oxide or reduced graphene oxide foams. It is found that domains of h-BN layers on the graphene oxide framework help to reinforce the 2D structural units, providing the observed improvement in mechanical integrity of the 3D foam structure.

Binary and ternary atomic layers built from carbon, boron, and nitrogen.

Two-dimensional (2D) atomic layers derived from bulk layered materials are very interesting from both scientific and application viewpoints, as evidenced from the story of graphene. Atomic layers of several such materials such as hexagonal boron nitride (h-BN) and dichalcogenides are examples that complement graphene. The observed unconventional properties of graphene has triggered interest in doping the hexagonal honeycomb lattice of graphene with atoms such as boron (B) and nitrogen (N) to obtain new layered structures. Individual atomic layers containing B, C, and N of various compositions conform to several stable phases in the three-component phase diagram of B-C-N. Additionally, stacking layers built from C and BN allows for the engineering of new van-der-Waals stacked materials with novel properties. In this paper, the synthesis, characterization, and properties of atomically thin layers, containing B, C, and N, as well as vertically assembled graphene/h-BN stacks are reviewed. The electrical, mechanical, and optical properties of graphene, h-BN, and their hybrid structure are also discussed along with the applications of such materials.

Artificially stacked atomic layers: toward new van der Waals solids.

Strong in-plane bonding and weak van der Waals interplanar interactions characterize a large number of layered materials, as epitomized by graphite. The advent of graphene (G), individual layers from graphite, and atomic layers isolated from a few other van der Waals bonded layered compounds has enabled the ability to pick, place, and stack atomic layers of arbitrary compositions and build unique layered materials, which would be otherwise impossible to synthesize via other known techniques. Here we demonstrate this concept for solids consisting of randomly stacked layers of graphene and hexagonal boron nitride (h-BN). Dispersions of exfoliated h-BN layers and graphene have been prepared by liquid phase exfoliation methods and mixed, in various concentrations, to create artificially stacked h-BN/G solids. These van der Waals stacked hybrid solid materials show interesting electrical, mechanical, and optical properties distinctly different from their starting parent layers. From extensive first principle calculations we identify (i) a novel approach to control the dipole at the h-BN/G interface by properly sandwiching or sliding layers of h-BN and graphene, and (ii) a way to inject carriers in graphene upon UV excitations of the Frenkell-like excitons of the h-BN layer(s). Our combined approach could be used to create artificial materials, made predominantly from inter planar van der Waals stacking of robust bond saturated atomic layers of different solids with vastly different properties.

Electrically insulating thermal nano-oils using 2D fillers.

Different nanoscale fillers have been used to create composite fluids for applications such as thermal management. The ever increasing thermal loads in applications now require advanced operational fluids, for example, high thermal conductivity dielectric oils in transformers. These oils require excellent filler dispersion, high thermal conduction, but also electrical insulation. Such thermal oils that conform to this thermal/electrical requirement, and yet remain in highly suspended stable state, have not yet been synthesized. We report here the synthesis and characterization of stable high thermal conductivity Newtonian nanofluids using exfoliated layers of hexagonal boron nitride in oil without compromising its electrically insulating property. Two-dimensional nanosheets of hexagonal boron nitride are liquid exfoliated in isopropyl alcohol and redispersed in mineral oil, used as standard transformer oil, forming stable nanosuspensions with high shelf life. A high electrical resistivity, even higher than that of the base oil, is maintained for the nano-oil containing small weight fraction of the filler (0.01 wt %), whereas the thermal conductivity was enhanced. The low dissipation factor and high pour point for this nano-oil suggests several applications in thermal management.