Nanoscale Modification Research Articles

Size Controllable and Surface Tunable Zeolitic Imidazolate Framework-8-Poly(acrylic acid sodium salt) Nanocomposites for pH Responsive Drug Release and Enhanced in Vivo Cancer Treatment.

Nanoscale size controllable and surface modifiable zeolitic imidazolate framework-8-poly(acrylic acid sodium salt) (ZIF-8-PAAS) nanocomposites are fabricated by employing PAAS nanospheres as a soft template. These ZIF-8-PAAS nanocomposites have different sizes ranging from 30 to 200 nm and exhibit different crystallinity, and pH sensitivity. These nanocomposites can be employed as vectors to deliver doxorubicin for anticancer therapy, leading to greatly enhanced drug therapeutic efficacy when tested in cell lines and mice model. Systematic toxicity investigation including hematoxylin and eosin staining analysis of tumor and major organs, hematology analysis, and blood chemistry analysis indicates that the nanocomposites possess high biocompatibility. This work provides a strategy to make metal-organic frameworks (MOFs) nanocomposites with size tunability in nanoscale and flexible surface modification for various applications.

Plasmonic nano-printing: large-area nanoscale energy deposition for efficient surface texturing

The lossy nature of plasmonic wave due to absorption is shown to become an advantage for scaling-up a large area surface nanotexturing of transparent dielectrics and semiconductors by a self-organized sub-wavelength energy deposition leading to an ablation pattern—ripples—using this plasmonic nano-printing. Irreversible nanoscale modifications are delivered by surface plasmon polariton (SPP) using: (i) fast scan and (ii) cylindrical focusing of femtosecond laser pulses for a high patterning throughput. The mechanism of ripple formation on ZnS dielectric is experimentally proven to occur via surface wave at the substrate–plasma interface. The line focusing increase the ordering quality of ripples and facilitates fabrication over wafer-sized areas within a practical time span. Nanoprinting using SPP is expected to open new applications in photo-catalysis, tribology, and solar light harvesting via localized energy deposition rather scattering used in photonic and sensing applications based on re-scattering of SPP modes into far-field modes.

Non-metallic dopant modulation of conductivity in substoichiometric tantalum pentoxide: A first-principles study

We apply density-functional theory calculations to predict dopant modulation of electrical conductivity (σo) for seven dopants (C, Si, Ge, H, F, N, and B) sampled at 18 quantum molecular dynamics configurations of five independent insertion sites into two (high/low) baseline references of σo in amorphous Ta2O5, where each reference contains a single, neutral O vacancy center (VO0). From this statistical population (n = 1260), we analyze defect levels, physical structure, and valence charge distributions to characterize nanoscale modification of the atomistic structure in local dopant neighborhoods. C is the most effective dopant at lowering Ta2Ox σo, while also exhibiting an amphoteric doping behavior by either donating or accepting charge depending on the host oxide matrix. Both B and F robustly increase Ta2Ox σo, although F does so through elimination of Ta high charge outliers, while B insertion conversely creates high charge O outliers through favorable BO3 group formation, especially in the low σo reference. While N applications to dope and passivate oxides are prevalent, we found that N exacerbates the stochasticity of σo we sought to mitigate; sensitivity to the N insertion site and some propensity to form N-O bond chemistries appear responsible. We use direct first-principles predictions of σo to explore feasible Ta2O5 dopants to engineer improved oxides with lower variance and greater repeatability to advance the manufacturability of resistive memory technologies.

Nanoscale modifications in the early heating stages of bone are heterogeneous at the microstructural scale.

Nanoscale studies of bone provide key indicators to evidence subtle structural changes that may occur in the biomedical, forensic and archaeological contexts. One specific problem encountered in all those disciplines, for which the identification of nanostructural cues could prove useful, is to properly monitor the effect of heating on bone tissue. In particular, the mechanisms at work at the onset of heating are still relatively unclear. Using a multiscale approach combining Raman microspectroscopy, transmission electron microscopy (TEM), synchrotron quantitative scanning small-angle X-ray scattering imaging (qsSAXSI) and polarized light (PL) microscopy, we investigate the ultrastructure of cortical bovine bone heated at temperatures < 300°C, from the molecular to the macroscopic scale. We show that, despite limited changes in crystal structure, the mineral nanoparticles increase in thickness and become strongly disorganized upon heating. Furthermore, while the nanostructure in distinct anatomical quadrants appears to be statistically different, our results demonstrate this stems from the tissue histology, i.e. from the high degree of heterogeneity of the microstructure induced by the complex cellular processes involved in bone tissue formation. From this study, we conclude that the analysis of bone samples based on the structure and organization of the mineral nanocrystals requires performing measurements at the histological level, which is an advantageous feature of qsSAXSI. This is a critical aspect that extends to a much broader range of questions relating to nanoscale investigations of bone, which could also be extended to other classes of nanostructured heterogeneous materials.

Advances in Nanotechnology as They Pertain to Food and Agriculture: Benefits and Risks.

Nanotechnology is an emerging and rapidly developing toolbox that has novel and unique applications to food science and agriculture. Fast and impressive developments in nanotechnology for food and agriculture have led to new experimental prototype technologies and products. Developing various types of nanodelivery systems, detection tools, nanoscale modifications of bulk or surface properties, fabrication of wide-range bionanosensors, and biodegradable nanoplatforms can potentially improve consumer health and safety, product shelf life and stability, bioavailability, environmental sustainability, efficiency of processing and packaging, and real-time monitoring. Some recently developed nanotechnology techniques and potential product applications of nanotechnology are summarized in this review. Exposure to nanomaterials may be harmful to the consumer and the environment and might increase the potential of risk. For this reason, evaluation of the potential risks resulting from the interaction of nanomaterials with biological systems, humans, and the environment is also reviewed.

Micro-/nano-characterization of the surface structures on the divertor tiles from JET ITER-like wall

Micro-/nano-characterization of the surface structures on the divertor tiles used in the first campaign (2011–2012) of the JET tokamak with the ITER-like wall (JET ILW) were studied. The analyzed tiles were a single poloidal section of the tile numbers of 1, 3 and 4, i.e., upper, vertical and horizontal targets, respectively. A sample from the apron of Tile 1 was deposition-dominated. Stratified mixed-material layers composed of Be, W, Ni, O and C were deposited on the original W-coating. Their total thickness was ∼1.5μm. By means of transmission electron microscopy, nano-size bubble-like structures with a size of more than 100nm were identified in that layer. They could be related to deuterium retention in the layer dominated by Be. The surface microstructure of the sample from Tile 4 also showed deposition: a stratified mixed-material layer with the total thickness of 200–300nm. The electron diffraction pattern obtained with transmission electron microscope indicated Be was included in the layer. No bubble-like structures have been identified. The surface of Tile 3, originally coated by Mo, was identified as the erosion zone. This is consistent with the fact that the strike point was often located on that tile during the plasma operation. The study revealed the micro- and nano-scale modification of the inner tile surface of the JET ILW. In particular, a complex mixed-material deposition layer could affect hydrogen isotope retention and dust formation.

Focused Ion Beam Fabrication of SU-8 Waveguide Structures on Oxidized Silicon

ABSTRACTThis work deals with SU-8 waveguides and waveguide structures fabricated on an oxidized silicon substrate using ‘Focused ion beam (FIB) lithography’. From our experimentation it seems that FIB method is practically not suitable for fabricating long SU-8 waveguide structures, rather it is more suitable for nanoscale modification of already fabricated waveguides, such as, to fabricate photonic crystal structures.

Hybrid 3D–2D printing for bone scaffolds fabrication

It is a well-known fact that bone scaffold topography on micro- and nanometer scale influences the cellular behavior. Nano-scale surface modification of scaffolds allows the modulation of biological activity for enhanced cell differentiation. To date, there has been only a limited success in printing scaffolds with micro- and nano-scale features exposed on the surface. To improve on the currently available imperfect technologies, in our paper we introduce new hybrid technologies based on a combination of 2D (nano imprint) and 3D printing methods. The first method is based on using light projection 3D printing and simultaneous 2D nanostructuring of each of the layers during the formation of the 3D structure. The second method is based on the sequential integration of preliminarily created 2D nanostructured films into a 3D printed structure. The capabilities of the developed hybrid technologies are demonstrated with the example of forming 3D bone scaffolds. The proposed technologies can be used to fabricate complex 3D micro- and nanostructured products for various fields.

Dissecting charge relaxation pathways in CdSe/CdS nanocrystals using femtosecond two-dimensional electronic spectroscopy.

Exciton relaxation dynamics of CdSe and quasi-type-II CdSe/CdS core/shell nanocrystals were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The use of 2DES allowed for determination of structure-specific and state-resolved carrier dynamics for CdSe nanocrystals formed with five, or fewer, CdS passivation monolayers (ML). For CdSe and CdSe/CdS nanocrystals formed with one through three MLs of CdS, excitation using broad bandwidth femtosecond visible laser pulses generated electron-hole pairs among the |X1〉 = 2.14 eV and |X2〉 = 2.27 eV exciton states. For both excitations, the electron is promoted to the lowest energy excited (1Se) conduction-band state and the hole is in the 1S3/2 (X1) or 2S3/2 (X2) valence-band state. Therefore, the relaxation dynamics of the hot hole were isolated by monitoring the-time-dependent amplitude of 2DES cross peaks. The time constant for hot hole relaxation within the CdSe valence band was 150 ± 45 fs. Upon passivation by CdS, this hole relaxation time constant increased to 170 ± 30 fs (CdSe/CdS-3ML). This small increase was attributed to the formation of a graded, or alloyed, interfacial region that precedes the growth of a uniform CdS capping layer. The small increase in hole relaxation time reflects the larger nanocrystal volume of the CdSe/CdS system with respect to the CdSe nanocrystal core. In contrast, the dynamics of larger core/shell nanocrystals (≥4ML CdS) exhibited a picosecond buildup in 2DES cross-peak amplitude. This time-dependent response was attributed to interfacial hole transfer from CdS to CdSe valence-band states. Importantly, the 2DES data distinguish CdSe exciton relaxation from interfacial carrier transfer dynamics. In combination, isolation of structurally well-defined nanocrystals and state-resolved 2DES can be used to examine directly the influence of nanoscale structural modifications on electronic carrier dynamics, which are critical for developing nanocluster-based photonic devices.

Nanofeatured Titanium Surfaces for Dental Implantology: Biological Effects, Biocompatibility, and Safety

Nanotechnology enables the control and modification of the chemical and topographical characteristics of materials of size less than 100 nm, down to 10 nm. The goal of this review is to discuss the role of titanium substrates as nanoscale surface modification tools for improving various aspects of implantology, including osseointegration and antibacterial properties. Techniques that can impart nanoscale topographical features to endosseous implants are described. Since the advent of nanotechnology, cellular specific functions, such as adhesion, proliferation, and differentiation, have been better understood. By applying these technologies, it is possible to direct cellular responses and improve osseointegration. Conversely, modulating surface features by nanotechnology could have the effect of decreased bacterial colonization.

Nanoscale Surface Modifications of Medical Implants for Cartilage Tissue Repair and Regeneration.

Background: Natural cartilage regeneration is limited after trauma or degenerative processes. Due to the clinical challenge of reconstruction of articular cartilage, research into developing biomaterials to support cartilage regeneration have evolved. The structural architecture of composition of the cartilage extracellular matrix (ECM) is vital in guiding cell adhesion, migration and formation of cartilage. Current technologies have tried to mimic the cell’s nanoscale microenvironment to improve implants to improve cartilage tissue repair.Methods: This review evaluates nanoscale techniques used to modify the implant surface for cartilage regeneration.Results: The surface of biomaterial is a vital parameter to guide cell adhesion and consequently allow for the formation of ECM and allow for tissue repair. By providing nanosized cues on the surface in the form of a nanotopography or nanosized molecules, allows for better control of cell behaviour and regeneration of cartilage. Chemical, physical and lithography techniques have all been explored for modifying the nanoscale surface of implants to promote chondrocyte adhesion and ECM formation.Conclusion: Future studies are needed to further establish the optimal nanoscale modification of implants for cartilage tissue regeneration.

Nanoscale-Barrier Formation Induced by Low-Dose Electron-Beam Exposure in Ultrathin MoS2 Transistors

Utilizing an innovative combination of scanning-probe and spectroscopic techniques, supported by first-principles calculations, we demonstrate how electron-beam exposure of field-effect transistors, implemented from ultrathin molybdenum disulfide (MoS2), may cause nanoscale structural modifications that in turn significantly modify the electrical operation of these devices. Quite surprisingly, these modifications are induced by even the relatively low electron doses used in conventional electron-beam lithography, which are found to induce compressive strain in the atomically thin MoS2. Likely arising from sulfur-vacancy formation in the exposed regions, the strain gives rise to a local widening of the MoS2 bandgap, an idea that is supported both by our experiment and by the results of first-principles calculations. A nanoscale potential barrier develops at the boundary between exposed and unexposed regions and may cause extrinsic variations in the resulting electrical characteristics exhibited by the transistor. The widespread use of electron-beam lithography in nanofabrication implies that the presence of such strain must be carefully considered when seeking to harness the potential of atomically thin transistors. At the same time, this work also promises the possibility of exploiting the strain as a means to achieve "bandstructure engineering" in such devices.

Experimental study of heat transfer characteristics of high-velocity small slot jet impingement boiling on nanoscale modification surfaces

Jet impingement boiling is one of the most efficient methods to increase the critical heat flux. Through controlling surface chemical properties and topography, plain nickel foil surface, three kinds of plain nickel-based chemical treatment surfaces and four kinds of nickel-based electrochemical treatment surfaces with nanocone array structure were used in the jet impingement boiling experiments to investigate the quantitative effects and the effect mechanism of the surface characteristic parameters, including nanoscale roughness (Ra): solid–liquid contact angle (CA) and effective heat transfer area ratio (r: the ratio of the actual heat transfer area to its projected area) on the heat transfer coefficient (HTC) and the critical heat flux (CHF). It is revealed that: similar to the heat transfer in pool boiling, changing nanoscale Ra has little effect on the heat transfer characteristics; decreasing solid–liquid CA can enhance the HTC while worsen the CHF obviously; increasing r can intensify both the HTC and the CHF. Predictive correlations of the HTC and the CHF of jet impingement boiling which include the effects of surface characteristics are presented. The predictive correlations presented can be widely used in various conditions with different working fluids and heating surfaces.

Nanoscale modification of magnesium with highly textural lamellar nanosheets towards increasing the corrosion resistance and bioactivity

Abstract The present study aims to modify the surface of microarc oxidation (MAO) coated Mg using an alkaline fluoride solution so as to impart a nanoscale surface feature, which would be beneficial to improve the corrosion resistance and to promote a better bioactivity. The MAO coated Mg is modified with the formation of a highly textural lamellar nanosheet-like morphology after immersion in 0.1 M NaF (pH: 8.40) at 25 °C for 120 min, which completely covered the porous structure with the formation of nanosheets along with some agglomerated crystals. Thin film X-ray diffraction measurement, chemical composition analysis and Fourier transform infrared spectroscopy studies confirmed that the nanosheets are primarily Mg(OH)2 − xFx while the agglomerates are NaMgF3. The complete coverage of the porous structure by the modified layer along with the formation of Mg(OH)2 − xFx and NaMgF3 has enabled a better corrosion resistance for MAO coated Mg modified by NaF. The higher surface area of the nanosheets favoured nucleation of monocalcium phosphate anhydrous and newberyite, both of which are biologically relevant. The unique morphological feature of the modified surface helped to achieve an improved cell adhesion and proliferation of MC3T3-E1 osteoblast-like cells. The relative growth rate of both uncoated and coated Mg are > 75% on all the three days, fulfilled Grade 1 specification in terms of cytocompatibility as per ISO 10993-5 standard. The formation of nanoscale surface feature, improvement in corrosion resistance, better bioactivity and acceptable cytocompatibility point out that this methodology could be of immense help to modify the surface of Mg based absorbable implants.

Nanoscale surface modification of AISI 316L stainless steel by severe shot peening

Surface nanocrystallization is gaining increased attention due to its high potential of enhancing mechanical functionality and modulating material's interaction with the surrounding environment. Among mechanical approaches, severe shot peening has recently shown to be a very promising technique for surface grain refinement, considering its efficiency, eco-friendliness, relative low cost and minimum geometrical restrictions. This study evaluates the effect of severe shot peening on microstructural and mechanical properties of 316L stainless steel, which is widely used in biomedical, food preparation, structural and marine applications. 316L samples, shot peened with different peening parameters, were studied in terms of morphological and structural features, defect density, grain size, phase transformation, surface topography, surface wettability, residual stresses and microhardness. The results indicated that severe shot peening induced near surface grain refinement to nano and sub-micron range and transformed the austenite phase into strain-induced α’- martensite in a layered deformation band structure. Severe shot peening also induced compressive residual stresses and work hardening in the top surface layer. Surface roughness and surface wettability, both of which favorably contribute to modulating the interaction of material with biological environment, were also notably enhanced by severe shot peening.

Novel Osteogenic Ti-6Al-4V Device For Restoration Of Dental Function In Patients With Large Bone Deficiencies: Design, Development And Implementation.

Custom devices supporting bone regeneration and implant placement are needed for edentulous patients with large mandibular deficiencies where endosteal implantation is not possible. We developed a novel subperiosteal titanium-aluminum-vanadium bone onlay device produced by additive manufacturing (AM) and post-fabrication osteogenic micro-/nano-scale surface texture modification. Human osteoblasts produced osteogenic and angiogenic factors when grown on laser-sintered nano-/micro-textured surfaces compared to smooth surfaces. Surface-processed constructs caused higher bone-to-implant contact, vertical bone growth into disk pores (microCT and histomorphometry), and mechanical pull-out force at 5 and 10 w on rat calvaria compared to non surface-modified constructs, even when pre-treating the bone to stimulate osteogenesis. Surface-modified wrap-implants placed around rabbit tibias osseointegrated by 6 w. Finally, patient-specific constructs designed to support dental implants produced via AM and surface-processing were implanted on edentulous mandibular bone. 3 and 8 month post-operative images showed new bone formation and osseointegration of the device and indicated stability of the dental implants.

Superatom State-Resolved Dynamics of the Au25(SC8H9)18(-) Cluster from Two-Dimensional Electronic Spectroscopy.

Superatom state-resolved dynamics of the Au25(SC8H9)18(-) monolayer-protected cluster (MPC) were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The electronic ground state of the Au25(SC8H9)18(-) MPC is described by an eight-electron P-like superatom orbital. Hot electron relaxation (200 ± 15 fs) within the superatom D manifold of lowest-unoccupied molecular orbitals was resolved from hot hole relaxation (290 ± 20 fs) in the superatom P states by using 2DES in a partially collinear pump-probe geometry. Electronic relaxation dynamics mediated by specific superatom states were distinguished by examining the time-dependent cross-peak amplitudes for specific excitation and detection photon energy combinations. Quantification of the time-dependent amplitudes and energy positions of cross peaks in the 2.21/1.85 eV (excitation/detection) region confirmed that an apparent energetic blue shift observed for transient bleach signals results from rapid hot electron relaxation in the superatom D states. The combination of structurally precise MPCs and state-resolved 2DES can be used to examine directly the influence of nanoscale structural modifications on electronic carrier dynamics, which are critical for developing nanocluster-based photonic devices.

Biological Behavior of Osteoblast Cell and Apatite Forming Ability of the Surface Modified Ti Alloys.

Titanium as one kind of biomaterials comes in direct contact with the body, making evaluation of biocompatibility an important aspect to biomaterials development. Surface chemistry of titanium plays an important role in osseointegration. Different surface modification alters the surface chemistry and result in different biological response. In this study, three kinds of mixed acid solutions were used to treat Ti specimens to induce Ca-P formation. Following a strong mixed acid activation process, Ca-P coating successfully formed on the Ti surfaces in simulated body fluid. Strong mixed acid increased the roughness of the metal surface, because the porous and rough surface allows better adhesion between Ca-P coatings and substrates. After modification of titanium surface by mixed acidic solution and subsequently H2O2/HCL treatment evaluation of biocompatibility was conducted from hydroxyapatite formation by biomimetic process and cell viability on modified titanium surface. Nano-scale modification of titanium surfaces can alter cellular and tissue responses, which may benefit osseointegration and dental implant therapy. Results from this study indicated that surface treatment methods affect the surface morphology, type of TiO2 layer formed and subsequent apatite deposition and biological responses. The thermo scientific alamarblue cell viability assay reagent is used to quantitatively measure the viability of mammalian cell lines, bacteria and fungi by incorporating a rapid, sensitive and reliable fluorometric/colorimetric growth indicator, without any toxic and side effect to cell line. In addition, mixed acid treatment uses a lower temperature and shorter time period than widely used alkali treatment.

Characterization of a compact ECR plasma source and its applications to studies of helium ion damage to tungsten

Exposure of tungsten to low energy (<100 eV) helium plasmas at temperatures between 900–1900 K in both laboratory experiments and tokamaks has been shown to cause severe nanoscale modification of the near surface resulting in the growth of tungsten tendrils. Tendril formation can lead to non-sputtered erosion and dust formation. Here we report on characterization of a compact electron cyclotron resonance (ECR) He plasma source with an ion flux of ∼2.5 × 1019 ions m−2 s−1, average fluence of 3 × 1024 ions m−2, and the surface morphology changes seen on the exposed tungsten surfaces. Exposures of polished tungsten disks at temperatures up to 1270 K have been performed and characterized using scanning electron microscopy and atomic force microscopy (AFM) scans. Bubbles and craters have been seen on the exposed tungsten surface growing to up to 150 nm in diameter. The ECR source has been tested for eventual use on a scanning tunneling microscopy experiment intended to study the early stages of surface morphology change due to He ion exposure.

Nanopit-induced osteoprogenitor cell differentiation: The effect of nanopit depth

We aimed to assess osteogenesis in osteoprogenitor cells by nanopits and to assess optimal feature depth. Topographies of depth 80, 220 and 333 nm were embossed onto polycaprolactone discs. Bone marrow–derived mesenchymal stromal cells were seeded onto polycaprolactone discs, suspended in media and incubated. Samples were fixed after 3 and 28 days. Cells were stained for the adhesion molecule vinculin and the osteogenic transcription factor RUNX2 after 3 days. Adhesion was lowest on planar controls and it was the shallowest, and 80-nm-deep pits supported optimal adhesion formation. Deep pits (80 and 220 nm) induced most RUNX2 accumulation. After 28 days, osteocalcin and osteopontin expression were used as markers of osteoblastic differentiation. Deep pits (220 nm) produced cells with the highest concentrations of osteopontin and osteocalcin. All topographies induced higher expression levels than controls. We demonstrated stimulation of osteogenesis in a heterogeneous population of mesenchymal stromal cells. All nanopit depths gave promising results with an optimum depth of 220 nm after 28 days. Nanoscale modification of implant surfaces could optimise fracture union or osteointegration.