Nanoscale Modification Research Articles

Multi-layered domain morphology in relaxor single crystals with nano-patterned composite electrode

(1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT) single crystals, especially with compositions near its morphotropic phase boundary (MPB), have been employed for a broad range of applications such as ultrasound transducers, sensors, and actuators. To further enhance the properties of PMN-PT, electrode patterning, as a method of domain engineering, was proved to be an effective approach. In our previous report, a 200 nm grating pattern electrode (Ti/Au–MnOx) (nano-electrode) was prepared on one surface of PMN-PT crystal, exhibiting 30% d33 enhancement. In this work, the multi-layered domain morphology and the domain engineering from nano-electrode were characterized using piezoresponse force microscopy (PFM). A hypothetical domain engineering model for nano-electrodes is established to explain the experimental results as well as the property enhancement from the nano-electrode. The electrode patterning proves that the nano-scale modification can tune the macro-scale piezoelectric properties of the bulk material.

Nanoscale modification of silicon and germanium surfaces exposed to low-energy helium plasma

Complex surface nanostructures were observed in germanium and silicon samples exposed to low energy (24 or 36 eV ion kinetic energy) helium plasma. Pyramidal growth is observed in germanium across the temperature range studied (185 °C to 336 °C), while significant modification in silicon was only observed at 630 °C. Nano-wire growth was observed in both germanium and silicon, and appears to be linked to the strength of the electric field, which in turn determines the implantation energy of the helium ions. Nanostructure formation is proposed to be driven by surface adatom migration which is strongly influenced by an Ehrlich-Schwoebel-type surface instability. The role of helium in this model is to drive germanium interstitial formation by ejecting germanium atoms from lattice sites, leading to germanium interstitial diffusion towards the sample surface and subsequent adatom and surface nanostructure formation.

From nanoscale modification to separation - The role of substrate and modifiers in the transport properties of ceramic membranes in membrane distillation

The set of various ceramic substrates Al2O3-100nm, TiO2-75nm, ZrO2-3nm, and ZrO2-200nm were used in the hydrophobization process with different silane-based modifiers fluorinated and fluorine-free, possessing different reactive groups (ethoxy, methoxy, and chlorine) and different length of the alkyl-chain (C6 and C16). It was investigated how these variables can influence the features of the material and then transport and separation properties. A comprehensive material study including evaluation of morphological, wetting and structural properties was performed and referred to the membrane performance in membrane distillation. Transport features, particularly various driving forces (range 105–685 mbar) and their impact on the overall membrane performance were studied. The highest grafting effectiveness was observed for superhydrophobic Al2O3-100nm-C16Cl3 (contact angle 154°, hysteresis 10°) possessing critical surface tension of 12.4 mN m−1 and polar part of surface free energy 1.1 mN m−1. Improvement in mechanical properties determined by nanoindentation of all tested ceramics after hydrophobization was observed. Al2O3-100nm-C6OEt3 has the best transport properties. Such results were ensured by an appropriate substrate selection with the highest level of hydroxyl groups ready for modification on pristine material and lower reactivity of ethoxy groups in comparison to chlorine one. All membrane possessed a very high salt rejection coefficient ca.99%.

Can We Further Improve Titanium Implant Surfaces at Nanoscale to Enhance Osseointegration?

The main aim of this review study was to report the state of art on the technological improvements of titanium implant surfaces to accelerate the osseointegration process.Several methods of surface modification are chronologically described bridging ordinary methods (e.g. grit blasting and etching) and novel physicochemical approaches such as 3D-laser printing and biomimetic modification. Advanced functionalization procedures by using proteins, peptides, and bioactive ceramics have provided an enhancement of wettability and bioactivity of implant surfaces. Furthermore, recent findings have revealed a combined beneficial effect of micro- and nano-scale modification and biomimetic functionalization of titanium surfaces. However, some technological developments of implant surfaces are not commercially available yet due to costs and a lack of clinical validation of the novel surfaces. Further in vitro and in vivo studies are necessary to endorse of the use of enhanced biomimetic implant surfaces.

Annealing-assisted high-pressure torsion in Zr55Cu30Al10Ni5 metallic glass

For bulk metallic glasses (BMGs) structural anisotropy has been studied for many years, but usually for small creep strains, rather than for large strains associated with the viscoplastic flow. In this study, the structural modifications in the short-to-medium range order of Zr55Cu30Al10Ni5 BMG is deliberated for the first time upon simultaneous high-pressure torsion (HPT) and in-situ annealing around the glass transition temperature (Tg). The changes are evaluated in terms of hardness by microindentation, thermal properties by differential thermal calorimetry, chemistry by energy dispersive X-ray, and structural properties by synchrotron X-ray diffraction and transmission electron microscopy. A remarkable increase of the glass transition temperature and the absence of the shoulder of the crystallization peak along with remarkable softening and shear thinning reveals that even at Tg the material gains flow characteristics because of the extreme pressure applied. A clear shift towards smaller wave vector Q in the peak positions of the partial distribution function G(r), and reconfiguration of the bonding between Zr−Zr and Zr−Cu atomic pairs extracted from the deconvolution of the radial distribution function RDF(r) are observed with changing the processing temperature. The findings give insight into the atomic and nano-scale modifications in BMGs due to high-pressure torsion at different temperatures which would be essential to tune the intrinsic properties of BMGs to attain the desirable hardness and thermal stability for a specific application.

Inhibition of Wild Enterobacter cloacae Biofilm Formation by Nanostructured Graphene- and Hexagonal Boron Nitride-Coated Surfaces.

Although biofilm formation is a very effective mechanism to sustain bacterial life, it is detrimental in medical and industrial sectors. Current strategies to control biofilm proliferation are typically based on biocides, which exhibit a negative environmental impact. In the search for environmentally friendly solutions, nanotechnology opens the possibility to control the interaction between biological systems and colonized surfaces by introducing nanostructured coatings that have the potential to affect bacterial adhesion by modifying surface properties at the same scale. In this work, we present a study on the performance of graphene and hexagonal boron nitride coatings (h-BN) to reduce biofilm formation. In contraposition to planktonic state, we focused on evaluating the efficiency of graphene and h-BN at the irreversible stage of biofilm formation, where most of the biocide solutions have a poor performance. A wild Enterobacter cloacae strain was isolated, from fouling found in a natural environment, and used in these experiments. According to our results, graphene and h-BN coatings modify surface energy and electrostatic interactions with biological systems. This nanoscale modification determines a significant reduction in biofilm formation at its irreversible stage. No bactericidal effects were found, suggesting both coatings offer a biocompatible solution for biofilm and fouling control in a wide range of applications.

Parallel multiphase nanofluidics utilizing nanochannels with partial hydrophobic surface modification and application to femtoliter solvent extraction.

In the field of microfluidics, utilizing parallel multiphase flows with immiscible liquid/liquid or gas/liquid interfaces along a microchannel has achieved the integration of various chemical processes for analyses and syntheses. Recently, our group has developed nanofluidics that exploits 100 nm nanochannels to realize ultra-small (aL to fL scale) and highly efficient chemical operations. Novel applications such as single-molecule analyses and single-cell omics are anticipated. However, the formation of parallel multiphase flows in a nanochannel remains challenging. To this end, here we developed a novel method for nanoscale partial hydrophobic surface modification of a nanochannel utilizing a focused ion beam. Hydrophobic and hydrophilic areas could be patterned beside one another even in a 60 nm glass nanochannel. Because this patterning maintained the liquid/liquid interface in the nanochannel based on the difference in wettability, stable aqueous/organic parallel two-phase flow in a 40 fL nanochannel was realized for the first time. Utilizing this flow, nanoscale unit operations involving phase confluence, extraction and phase separation were integrated to demonstrate solvent extraction of a lipid according to the Bligh-Dyer method, which is a broadly used pretreatment process in lipidomics. We accomplished the separation of a lipid and an amino acid in a sample volume of 4 fL (250 times smaller than the pL volume of a single cell) with a processing time of 1 ms (10 000 times faster than that in a microchannel). This study therefore provides a technological breakthrough that advances the field of nanofluidics to allow multiphase chemical processing at fL volumes.

Nanoscale modification of magnetic properties for effective domain wall pinning

Abstract Magnetic domain wall memory technology, wherein the information is stored in magnetic domains of multiple magnetic nanowires, is a potential concept proposed to store the large amount of digital data in the near future, which is generated due to the widespread use of social media and computing devices. However, one of the technological challenges which remains to be solved in domain wall memory is the controllable pinning of the domain walls at the nanometer scale. Here, we demonstrate the possibility to stabilize domain walls with nanoscale modification of magnetic properties by using thermal diffusion of elements from crossbar configuration. We have inspected and evaluated the magnetic properties of the nanowires using Kerr microscopy. The pinning field induced by Cr diffusion of our Ni80Fe20 nanowire was estimated to be about 8 kA/m as determined from minor loop (magnetoresistance vs. magnetic field) measurements. The proposed concept can potentially be used in future domain wall memory applications.

Rapid nano-scale surface modification on micro-arc oxidation coated titanium by microwave-assisted hydrothermal process

Nano to submicron scaled surface possesses excellent biological affinity and several processes have been undertaken to develop titanium implant with specific surface chemical and phase composition and nano-scale features. A simple process was used to modify the nano topographies on a micro-arc-oxidation (MAO) surface which shortens the time for the conventional hydrothermal process (HT). Nano-scaled anatase precipitates on the MAO surface with different crystallinities and morphologies were regulated via microwave-assisted hydrothermal in pure water (MWDD) or in pH conditioned mediums containing calcium and phosphorus ions (MWCP, MWCP9, MWCP11). The surface morphologies and structures were investigated by SEM, XRD, FTIR, and TEM. Anatase crystals as nano-spikes along [001] direction were observed on the surface of the MWDD and MWCP groups. Increasing the pH of the conditioned medium leads the precipitate to lose its crystallinity; the surface of MWCP11 is covered with amorphous anatase which has a 3D nano-sheet architecture. The MW treated surfaces possess superior hydrophilicity can adsorb more proteins (fibronectin and bovine serum albumin), and the osteoblasts-like MG63 cells on these surfaces have higher spreading ratios than on the MAO and HT groups. The cell viabilities in the MW groups were significantly higher than in the MAO and HT groups on the 7th day (P < 0.05), although their cell viabilities were similar on the first day. MWCP and MWCP11 have higher alkaline phosphatase activity on days 7 and 14 compared to other groups (P < 0.05). The MW treatment produces different nanomorphologies on the MAO surface and retains the original micro/submicron pores and surface calcium and phosphorus contents, thus it is expected to promote osseointegration without compromising the bond strength.

Biocompatible Nanocomposite Implant with Silver Nanoparticles for Otology-In Vivo Evaluation.

The aim of this work was to investigate of biocompatibility of polymeric implants modified with silver nanoparticles (AgNPs). Middle ear prostheses (otoimplants) made of the (poly)acrylonitrile butadiene styrene (ABS) and ABS modified with silver nanoparticles were prepared through extrusion and injection moulding process. The obtained prostheses were characterized by SEM-EDX, micro-CT and mechanical tests, confirming their proper shape, good AgNPs homogenization and mechanical parameters stability. The biocompatibility of the implants was evaluated in vivo on rats, after 4, 12, 24 and 48 weeks of implantation. The tissue-healing process and cytotoxicity of the implants were evaluated on the basis of microscopic observations of the materials morphology after histochemical staining with cytochrome c oxidase (OCC) and acid phosphatase (AP), as well as via micro-tomography (ex vivo). The in vivo studies confirmed biocompatibility of the implants in the surrounding tissue environment. Both the pure ABS and nanosilver-modified ABS implants exhibited a distinct decrease in the area of granulation tissue which was replaced with the regenerating muscle tissue. Moreover, a slightly smaller area of granulation tissue was observed in the surroundings of the silver-doped prosthesis than in the case of pure ABS prosthesis. The kinetics of silver ions releasing from implants was investigated by ICP-MS spectrometry. The measurement confirmed that concentration of the silver ions increased within the implant’s immersion period. Our results showed that middle ear implant with the nanoscale modification is biocompatible and might be used in ossicular reconstruction.

Interfacial Electron Beam Lithography: Chemical Monolayer Nanopatterning via Electron-Beam-Induced Interfacial Solid-Phase Oxidation.

Chemical nanopatterning-the deliberate nanoscale modification of the chemical nature of a solid surface-is conveniently realized using organic monolayer coatings to impart well-defined chemical functionalities to selected surface regions of the coated solid. Most monolayer patterning methods, however, exploit destructive processes that introduce topographic as well as other undesired structural and chemical transformations along with the desired surface chemical modification. In particular in electron beam lithography (EBL), organic monolayers have been used mainly as ultrathin resists capable of improving the resolution of patterning via local deposition or removal of material. On the basis of the recent discovery of a class of radiation-induced interfacial chemical transformations confined to the contact surface between two solids, we have advanced a direct, nondestructive EBL approach to chemical nanopatterning-interfacial electron beam lithography (IEBL)-demonstrated here by the e-beam-induced local oxidation of the -CH3 surface moieties of a highly ordered self-assembled n-alkylsilane monolayer to -COOH while fully preserving the monolayer structural integrity and molecular organization. In this conceptually different EBL process, the traditional resist is replaced by a thin film coating that acts as a site-activated reagent/catalyst in the chemical modification of the coated surface, here the top surface of the to-be-patterned monolayer. Structural and chemical transformations induced in the thin film coating and the underlying monolayer upon exposure to the electron beam were elucidated using a semiquantitative surface characterization methodology that combines multimode AFM imaging with postpatterning surface chemical modifications and quantitative micro-FTIR measurements. IEBL offers attractive opportunities in chemical nanopatterning, for example, by enabling the application of the advanced EBL technology to the straightforward nanoscale functionalization of the simplest commonly used organosilane monolayers.

A first-principles study of 2D antimonene electrodes for Li ion storage

Antimony (Sb) has shown great potential as an anode material for rechargeable Lithium ion batteries (LIBs) because of its low price, high specific capacity and moderate working voltage. But it suffers from poor cycling performance due to the large volume expansion during the charge/discharge process. Nano-scale modification is an effective strategy to solve this problem. Herein, the electronic structure modulation, chemical stability, Li adsorption and diffusion properties as well as structural deformation of two-dimensional (2D) monolayer antimonene have been systematically investigated using first-principles calculations based on vdW corrected density functional theory. The calculated results reveal the adsorption energies of Li on antimonene are relatively strong (1.70–1.91 eV), and it exhibits a semiconductor to metal electronic phase transition with significant electrons transfer from Li metal to antimonene upon Li adsorbed. Meanwhile, Li atom shows fast diffusion on antimonene with the energy barrier of 0.20 eV, much lower than that in bulk antimony (1.73 eV). More importantly, antimonene shows relatively small structure deformation upon adsorption of high Li concentrations. The present results suggest that 2D antimonene can be a promising flexible anode material for LIBs with large specific capacity, excellent rate capability and long cycling performance. Our results highlight the nanostructure design of high-performance electrode materials for LIBs.

In vivo detection of nanometer-scale structural changes of the human tympanic membrane in otitis media

Otitis media (OM) is a common ear infection and a leading cause of conductive hearing loss in the pediatric population. Current technologies such as otoscopy, pneumatic otoscopy, tympanometry, and acoustic reflectometry are used to diagnose OM, which can reasonably diagnose the infection with a sensitivity and specificity of 50–90% and 60–90%, respectively. However, these techniques provide limited information about the physical architecture of the tympanic membrane (TM), or what may lie behind it. Here, we report the detection of nanometer-scale structural changes of the TM using nano-sensitive optical coherence tomography (nsOCT). In total, an image dataset from 65 pediatric subjects from three different groups (normal, acute OM, and chronic OM) and with longitudinal image-based analysis of ear infections were included in this study. The nsOCT data were correlated with physician diagnosis and with OCT thickness measurements and were found to be in good agreement with these results. We report that nsOCT detects in vivo structural deformations of the TM earlier than OCT alone, and enhances the detection sensitivity of OCT measurements. This unique technique for early detection of nano-scale structural modifications in the TM has the potential to aid in our understanding of microbiological effects, and possibly for early diagnosis and more effective treatment of OM.

Nanoscale Imaging of Light-Matter Coupling Inside Metal-Coated Cavities with a Pulsed Electron Beam.

Many applications in (quantum) nanophotonics rely on controlling light-matter interaction through strong, nanoscale modification of the local density of states (LDOS). All-optical techniques probing emission dynamics in active media are commonly used to measure the LDOS and benchmark experimental performance against theoretical predictions. However, metal coatings needed to obtain strong LDOS modifications in, for instance, nanocavities, are incompatible with all-optical characterization. So far, no reliable method exists to validate theoretical predictions. Here, we use subnanosecond pulses of focused electrons to penetrate the metal and excite a buried active medium at precisely defined locations inside subwavelength resonant nanocavities. We reveal the spatial layout of the spontaneous-emission decay dynamics inside the cavities with deep-subwavelength detail, directly mapping the LDOS. We show that emission enhancement converts to inhibition despite an increased number of modes, emphasizing the critical role of optimal emitter location. Our approach yields fundamental insight in dynamics at deep-subwavelength scales for a wide range of nano-optical systems.

(Invited) Nanoscale Design and Modification of Plasmonic Aerogels for Photocatalytic Hydrogen Generation

Composite catalytic aerogels comprise a highly-flexible design motif for the creation of solar fuels photocatalysts. We exploit the compositional and interfacial design flexibility of catalytic aerogels to couple surface plasmon resonant (SPR) guests to nanometric oxidation and reduction catalysts in one hierarchical photocatalytic composite architecture. In our composite aerogels, the nanoscale TiO2 aerogel acts as a 3D-interconnected network of nanowires that couples all of the functional elements required to photogenerate molecular hydrogen from visible light and water: visible light sensitization, electron and ion transport, and oxidation and reduction catalysis. We investigate the effects of synthetically modifying the TiO2 aerogel network and the nanoparticulate Au||TiO2 interfaces in plasmonic Au–TiO2 aerogels on light sensitization, carrier (electron–hole pair) generation, and photocatalytic H2 evolution under both broadband (i.e., UV + visible) and visible excitation. We also introduce oxidation and reduction co-catalyst nanoparticles into the plasmonic aerogels, creating composite aerogels that perform visible light SPR–driven photocatalytic reduction of water to generate H2. The nanostructured high surface–area network in the aerogel spatially and effectively separates charge while electrochemically connecting plasmonic nanoparticle sensitizers and metal nanoparticle all in one mesoscale architecture and at length scales compatible with the kinetics of each reaction. Reference: "Plasmonic aerogels as a 3D nanoscale platform for solar fuels photocatalysis.” P. A. DeSario, J. J. Pietron, A. Dunkelburger, T.H. Brintlinger, O. Baturina, R. M. Stroud, J. C. Owrutsky, and D. R. Rolison, Langmuir, 2017, 33, 9444–9454; doi: 10.1021/acs.langmuir.7b01117 This work is supported by the U.S. Office of Naval Research.

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO’s properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li2O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.

Advanced Functional Materials Solutions to Engineering the Neural Interface

Advanced Functional Materials Solutions to Engineering the Neural Interface

Nanoscale modification of chrysin for improved of therapeutic efficiency and cytotoxicity

Chrysin, as a flavone, is a promising drug candidate because of its multifaceted properties, such as anti-inflammatory, antioxidant and anticancer. However, its poor bioavailability is a bottleneck for pharmaceutical applications. To enhance the bioactive effects, chrysin-loaded poly (D,L-lactic-co-glycolic acid) and polyvinyl alcohol were successfully prepared to overcome problems associated with chrysin. The properties of modified nanochrysin were analysed by in vitro dissolution study, XRD, FTIR and SEM. Free radical scavenging potentials of the modified nanochrysin against DPPH were confirmed based on its stable antioxidant effects. A DNA instability enhancement was observed after H2O2 exposure, whereas chrysin decreased the H2O2 activity, and modified nanochrysin was more potent in this regard. Blood compatibility on red blood cells was confirmed by haemolytic and in vitro cytotoxicity assays. The in vitro anticancer activity of the modified nanochrysin towards MCF-7 and SKOV-3 cell lines using various parameters was investigated. The nanochrysin was found to exert cell growth arrest against both cancer cells in a dose-dependent manner. IC50 value was significantly decreased in nanochrysin in comparison with pure chrysin and induced apoptotic cell death pathway. The results of this study suggest that the nanochrysin might be used for medical applications and offer a beneficial formulation for chemotherapy.

An Efficient and Robust Surface-Modified Iron Electrode for Oxygen Evolution in Alkaline Water Electrolysis

Iron is unstable as an oxygen evolution electrode in alkaline media. Thus, relatively expensive nickel-based electrodes are used in industrial alkaline water electrolysis. We show that an iron substrate can be rendered stable and electrocatalytically active for the oxygen evolution reaction by nano-scale surface modification with nickel. The electrocatalytic activity of such a surface-modified iron electrode is comparable to the recently-reported nickel-based catalysts. The electrocatalytic activity is due to a 50-nanometer layer of a high-surface area α-nickel hydroxide on the iron electrode. The nickel modification renders the iron electrode electrically-conductive, prevents dielectric breakdown, and thus endows anodic stability. The electrocatalytic activity is unchanged even after 1000 hours of continuous operation. The temperature of preparation is critical, as excessive dehydration of the hydroxide layer results in nickel ferrite formation and a drastic reduction in electrocatalytic activity. We report significant insight into the surface chemical composition and structure of the catalyst layer by X-ray Absorption Spectroscopy, Photoelectron Spectroscopy, and Transmission Electron Microscopy. Electrochemical kinetics analysis suggests that surface hydroxo-intermediates react with the hydroxide ions from the solution to evolve oxygen. Thus, the surface-modified iron substrates present an opportunity for improving the performance and reducing the cost of alkaline water electrolysis systems.

Modeling of the interaction between osteoblasts and biocompatible substrates as a function of adhesion strength.

A goal of current implantology research is to design devices that induce controlled, guided, and rapid healing. Nanoscale structured substrates [e.g., titania nanotubes (TNTs) or carbon nanotubes (CNTs)] dramatically improve the functions of conventional biomaterials. The present investigation evaluated the behavior of osteoblasts cells cultured on smooth and nanostructured substrates, by measuring osteoblasts specific biomarkers [alkaline phosphatase (AP) and total protein] and cells adhesion strength to substrates, followed by semi-empirical modeling to predict the experimental results. Findings were in total agreement with the current state of the art. The proliferation, as well as the AP and total protein levels were higher on the nanostructure phases (TNTs, CNTs) comparing to the smooth ones (plastic and pure titanium). Cells adhesion strength measured was found higher on the nanostructured materials. This coincided with a higher value of proteins which are directly implicated in the process of adherence. Results were accurately predicted through the Viscoelastic Hybrid Interphase Model. A gradual adherence of bone cells to implants using multilayered biomaterials that involve biodegradable polymeric films and a nanoscale modification of titanium surface is suggested to improve performance through an interphase-mediated osteointegration of orthopedic implants. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 621-628, 2018.