Table of contents

Magnetic iron oxide nanoparticles (IONPs) have been widely used for various biomedical applications such as magnetic resonance imaging and drug delivery. However, their potential toxic effects, including genotoxicity, need to be thoroughly understood. In the present study, the genotoxicity of IONPs with different particle sizes (10, 30 nm) and surface coatings (PEG, PEI) were assessed using three standard genotoxicity assays, the Salmonella typhimurium reverse mutation assay (Ames test), the in vitro mammalian chromosome aberration test, and the in vivo micronucleus assay. In the Ames test, SMG-10 (PEG coating, 10 nm) showed a positive mutagenic response in all the five test bacterial strains with and without metabolic activation, whereas SEI-10 (PEI coating, 10 nm) showed no mutagenesis in all tester strains regardless of metabolic activation. SMG-30 (PEG coating, 30 nm) was not mutagenic in the absence of metabolic activation, and became mutagenic in the presence of metabolic activation. In the chromosomal aberration test, no increase in the incidence of chromosomal aberrations was observed for all three IONPs. In the in vivo micronucleus test, there was no evidence of increased micronuclei frequencies for all three IONPs, indicating that they were not clastogenic in vivo. Taken together, our results demonstrated that IONPs with PEG coating exhibited mutagenic activity without chromosomal and clastogenic abnormalities, and smaller IONPs (SMG-10) had stronger mutagenic potential than larger ones (SMG-30); whereas, IONPs with SEI coating (SEI-10) were not genotoxic in all three standard genotoxicity assays. This suggests that the mutagenicity of IONPs depends on their particle size and surface coating.

Specific expression patterns of microRNA (miRNA) molecules have been linked to cancer initiation, progression, and metastasis. The accumulating evidence for the role of oncogenic or tumor-suppressing miRNAs identified the need for nano-scaled platform that can help deliver nucleotides to modulate miRNAs. Here we report the synthesis of novel layered gadolinium hydroxychloride (LGdH) nanoparticles, a member of the layered double hydroxide (LDH) family, with physiochemical properties suitable for cell uptake and tracing via magnetic resonance (MR) imaging. As a proof of concept, we demonstrate the inhibition of mature miRNA-10b in metastatic breast cancer cell line using LGdH nanoparticle as a delivery platform. Through characterization analysis, we show that nanoparticles are easily and stably loaded with anti-miRNA oligonucleotides (AMO) and efficiently penetrate cell membranes. We demonstrate that AMOs delivered by LGdH nanoparticles remain functional by inducing changes in the expression of its downstream effector and by curbing the invasive properties. Furthermore, we demonstrate the traceability of LGdH nanoparticles via T1 weighted MR imaging. LGdH nanoparticles, which are biocompatible with cells in vitro, provide a promising multifunctional platform for microRNA therapeutics through their diagnostic, imaging, and therapeutic potentials.

Enhancing therapeutic efficacy is essential for successful treatment of chemoresistant cancers such as metastatic hormone-refractory prostate cancer (HRPC). To improve the efficacy of doxorubicin (DOX) for treating chemoresistant disease, the feasibility of using nanodiamond (ND) particles was investigated. Utilizing the pH responsive properties of ND, a novel protocol for complexing NDs and DOX was developed using a pH 8.5 coupling buffer. The DOX loading efficiency, loading on the NDs, and pH responsive release characteristics were determined utilizing UV-Visible spectroscopy. The effects of the ND-DOX on HRPC cell line PC3 were evaluated with MTS and live/dead cell viability assays. ND-DOX displayed exceptional loading efficiency (95.7%) and drug loading on NDs (23.9 wt%) with optimal release at pH 4 (80%). In comparison to treatment with DOX alone, cell death significantly increased when cells were treated with ND-DOX complexes demonstrating a 50% improvement in DOX efficacy. Of the tested treatments, ND-DOX with 2.4 μg mL⁻¹ DOX exhibited superior efficacy (60% cell death). ND-DOX with 1.2 μg mL⁻¹ DOX achieved 42% cell death, which was comparable to cell death in response to 2.4 μg mL⁻¹ of free DOX, suggesting that NDs aid in decreasing the DOX dose necessary to achieve a chemotherapeutic efficacy. Due to its enhanced efficacy, ND-DOX can be used to successfully treat HRPC and potentially decrease the clinical side effects of DOX.

Temperature dependent electronic properties of GaSb/InAsSb core/shell and GaSb nanowires have been studied. Results from two-probe and four-probe measurements are compared to distinguish between extrinsic (contact-related) and intrinsic (nanowire) properties. It is found that a thin (2–3 nm) InAsSb shell allows low barrier charge carrier injection to the GaSb core, and that the presence of the shell also improves intrinsic nanowire mobility and conductance in comparison to bare GaSb nanowires. Maximum intrinsic field effect mobilities of 200 and 42 cm² Vs⁻¹ were extracted for the GaSb/InAsSb core/shell and bare-GaSb NWs at room temperature, respectively. The temperature-dependence of the mobility suggests that ionized impurity scattering is the dominant scattering mechanism in bare GaSb while phonon scattering dominates in core/shell nanowires. Top-gated field effect transistors were fabricated based on radial GaSb/InAsSb heterostructure nanowires with shell thicknesses in the range 5–7 nm. The fabricated devices exhibited ambipolar conduction, where the output current was studied as a function of AC gate voltage and frequency. Frequency doubling was experimentally demonstrated up to 20 kHz. The maximum operating frequency was limited by parasitic capacitance associated with the measurement chip geometry.

Redox-based resistive memory cells exhibit changes of OFF or intermediate resistance values over time and even ON states can be completely lost in certain cases. The stability of these resistance states and the time until resistance loss strongly depends on the materials system. On the basis of electrical measurements and chemical analysis we found a viable explanation for these volatile resistance states (VRSs) in Ag-GeS_x-based electrochemical metallization memory cells and identified a technological application in the field of crossbar memories. Complementary resistive switches usually suffer from the necessity of a destructive read-out procedure increasing wear and reducing read-out speed. From our analysis we deduced a solution to use the VRS as an inherent selector mechanism without the need for additional selector devices.

We study quasi-ballistic electron transport in metallic $(6,0)$ carbon nanotubes (CNTs) of variable length in contact with Al, Cu, Pd, Pt, Ag, and Au electrodes by using the non-equilibrium Greenʼs function formalism in combination with either density functional theory or self-consistent extended Hückel theory. We find good agreement between both. Visualizing the local device density of states of the systems gives a descriptive link between electronic structure and transport properties. In comparison with bare finite and infinite tubes, we show that the electronic structure of short metallic CNTs is strongly modified by the presence of the metallic electrodes, which leads to pronounced size effects in the conductance. The mean conductances and linear response currents allow a ranking of the metals regarding their ability to form low-Ohmic contacts with the nanotube: ${\rm Ag}\lesssim {\rm Au}\lt {\rm Cu}\ll {\rm Pt}\approx {\rm Pd}\ll {\rm Al}$. These findings are contrasted with similar trends in contact distance, binding energy, calculated work function of the metal surfaces, and various results from literature.

Exploring the role of electrode metals on the resistive switching properties of metal electrode/oxide/metal electrode sandwiched structures provides not only essential information to understand the underlying switching mechanism of the devices, but also useful guidelines for the optimization of the switching performance. A systematic study has been performed to investigate the influence of electrodes on the resistive switching characteristics of zinc oxide (ZnO) films in this contribution, in terms of both the intrinsic and interfacial effects. It has been found that the low-resistance state resistances (Ω_LRS) of all the investigated devices are below 50 Ω, which can be attributed to the formation of highly conductive channels throughout the ZnO films. On the other hand, the high-resistance state resistances (Ω_HRS) depend on the electronegativity and ionic size of the employed electrode metals. Devices with electrode metals of high electronegativity and large ionic size possess high Ω_HRS values, while those with electrode metals of low electronegativity and small ionic size carry low Ω_HRS values. A similar trend of the set voltages has also been observed, while the reset voltages are all distributed in a narrow range close to ±0.5 V. Moreover, the forming voltages of the switching devices strongly depend on the roughness of the metal/ZnO and/or ZnO/metal interface. The present work provides essential information for better understanding the switching mechanism of zinc oxide based devices, and benefits the rational selection of proper electrode metals for the device performance optimization.

Magnetoresistance oscillations were observed on networks of superconducting ultrathin Nb nanowires presenting evidence of either thermal or quantum activated phase slips. The magnetic transport data, discussed in the framework of different scenarios, reveal that the system behaves coherently in the temperature range where the contribution of the fluctuations is important.

One-dimensional Sn-3.5Ag alloy nanosolders have been successfully fabricated by a dc electrodeposition technique into nanoporous templates, and their soldering quality has been demonstrated in nanoscale electrical welding for the first time, which indicates that they can easily form remarkably reliable conductive joints. The electrical measurement shows that individual 1D Sn-3.5Ag nanosolders have a resistivity of 28.9 μΩ·cm. The morphology, crystal structure and chemistry of these nanosolders have been characterized at the nanoscale. It is found that individual 1D Sn-3.5Ag alloy nanosolders have a continuous morphology and smooth surface. XPS confirms the presence of tin and silver with a mass ratio of 96.54:3.46, and EDX elemental mappings clearly reveal that the Sn and Ag elements have a uniform distribution. Coveragent beam electron diffractions verify that the crystal phases of individual 1D Sn-3.5Ag alloy nanosolders consist of matrix β-Sn and the intermetallic compound Ag₃Sn. The reflow experiments reveal that the eutectic composition of the 1D Sn-Ag alloy nanowire is shifted to the Sn rich corner. This work may contribute one of the most important tin-based alloy nanosolders for future nanoscale welding techniques, which are believed to have broad applications in nanotechnology and the future nano-industry.

We report on a nanoscaled thermocouple (ThC) as a temperature sensor of a highly sensitive bolometer for probing the dissipative damping of spin dynamics in nanosized Permalloy (Py) stripes. The Au-Pd ThC based device is fabricated by standard electron beam lithography on a 200 nm silicon nitride membrane to minimize heat dissipation through the substrate. We show that this thermal sensor allows not only measurements of the temperature change on the order of a few mK due to the uniform resonant microwave (MW) absorption by the Py stripe but also detection of standing spin waves of different mode numbers. Using a 3D finite element method, we estimate the absorbed MW power by the stripe in resonance and prove the necessity of using substrates with an extremely low heat dissipation like a silicon nitride membrane for successful thermal detection. The voltage responsivity and the noise equivalent power for the ThC-based bolometer are equal to 15 V W⁻¹ and 3 nW Hz^−1/2, respectively. The ThC device offers a magnetic resonance response of 1 nV/(μ_B W) corresponding to a sensitivity of 10⁹ spins and a temperature resolution of 300 μK under vacuum conditions.

Capacity degradation and ion insertion of a miniaturized electrochemical capacitor are studied using ionic liquid [EMI] [TFSI] as the electrolyte. This capacitor is featured with two comb-like electrodes of vertical carbon nanotubes, ∼70 μm in height and 20 μm in interelectrode gap. We quantify the levels of ion insertion damage with Raman spectroscopy after the electrode experiences 120 consecutive voltammetric cycles to various potential limits. Distinct structural damage emerges due to [EMI] when the negative potential reaches −1.7 V, and those due to [TFSI] arise when the positive potential reaches 1.7 V vs. RHE. Judging from the peak broadenings, [EMI] is more detrimental than [TFSI]. When the voltage window ΔU is set as less than or equal to 2.8 V, both electrode potentials are within the two intercalation limits, little or no decay is observed in 10⁴ charge/discharge cycles. When ΔU is 3.4 V, the positive potential exceeds the upper limit, but the negative potential stays within the lower limit, the cell capacitance decreases moderately. When ΔU increases to 3.8 V, both electrodes suffer from damages because of exceeding the intercalation limits. And the cell capacitance decreases substantially, even leading to a premature failure.

We report enhanced thermoelectric (TE) performance in CdO by using thermally insulating nano-particles to mimic nano pores in the composite. Through simply mechanical alloying, we fabricated CdO–SiO₂ composites with varying nano-SiO₂ concentration from 0.1 to 3 at%. Due to the very low thermal conductivity of nano-SiO₂ distributed in the CdO matrix, the thermal conductivity of the composite was substantially reduced by about 80%, which lead to the dimensionless figure of merit (ZT) value increment about 28% (from 0.32 to 0.41) at 1000 K. TEM shows the nano inclusions formed within the CdO matrix and grain boundaries as well, which is thought to contribute to the reduction of thermal conductivity of the composite by additional scattering mechanism for the mid- to long-wavelength phonons. This facile and low-cost approach might be widely adopted and synergized to other TE materials systems to further improve their performance.

Cantilevers play an important role as linear transducers in nanoscience, with nanomechanical detection of mass and stress as a clear example. We performed gas sensing experiments with a standard functionalized cantilever driven strongly into the regime of nonlinear oscillations. We compared the cantilever response to the selective adsorption of ethanol vapour in the nonlinear regime, to the ones obtained in the conventional linear static and dynamic sensing modes. In the nonlinearly driven cantilever, the adsorption and desorption-induced frequency shifts were enhanced by over a factor of three compared to resonant sensing with the same mode in the linear regime. This demonstrates a route towards gas detectors that exploit nonlinearity to enhance the responsivity, which can be implemented with standard cantilever devices.

This publication presents one of the first uses of silicon oxide nanoparticles to detect fingermarks. The study is not confined to showing successful detection of fingermarks, but is focused on understanding the mechanisms involved in the fingermark detection process. To gain such an understanding, various chemical groups are grafted onto the nanoparticle surface, and parameters such as the pH of the solutions or zeta potential are varied to study their influence on the detection. An electrostatic interaction has been the generally accepted hypothesis of interaction between nanoparticles and fingermarks, but the results of this research challenge that hypothesis, showing that the interaction is chemically driven. Carboxyl groups grafted onto the nanoparticle surfaces react with amine groups of the fingermark secretion. This formation of amide linkage between carboxyl and amine groups has further been favoured by catalyzing the reaction with a compound of diimide type. The research strategy adopted here ought to be applicable to all detection techniques using nanoparticles. For most of them the nature of the interaction remains poorly understood.

Carbon nanotube (CNT) film nanobolometers take advantages of high infrared absorption of CNTs, proving a promising alternative for low-cost, uncooled infrared detection. The performance of the CNT nanobolometers is determined by the optoelectronic process on CNTs at a microscopic scale, which links intimately to the diameter of the CNT—a critical parameter that intrinsically affects the band gap and hence infrared absorption, as well as extrinsically affects the surface oxygen adsorption effect and thermal-link of the CNT detector element to the environment. Both the intrinsic and extrinsic factors play important roles in the photoresponse, noise spectrum and the figure-of-merit detectivity D* of the CNT nanobolometers and their interplay determines the device's ultimate performance. In this work, we present a systematic study of the effect of CNT diameter in the range of 1–50 nm on the physical properties relevant to CNT nanobolometers. The optimal CNT diameter was found to be in the range of 2–12 nm with the D* up to 3.3 × 10⁷ cm(Hz)^1/2 W⁻¹, which represents an order of magnitude improvement over the best D* reported previously on CNT film nanobolometers.

When developing an electronic skin with touch sensation, an array of tactile pressure sensors with various ranges of pressure detection need to be integrated. This requires low noise, highly reliable sensors with tunable sensing characteristics. We demonstrate the operation of tactile pressure sensors that utilize the spatial distribution of contact electrodes to detect various ranges of tactile pressures. The device consists of a suspended elastomer diaphragm, with a carbon nanotube thin-film on the bottom, which makes contact with the electrodes on the substrate with applied pressure. The electrodes separated by set distances become connected in sequence with tactile pressure, enabling consecutive electrodes to produce a signal. Thus, the pressure is detected not by how much of a signal is produced but by which of the electrodes is registering an output. By modulating the diaphragm diameter, and suspension height, it was possible to tune the pressure sensitivity and sensing range. Also, adding a fingerprint ridge structure enabled the sensor to detect the periodicity of sub-millimeter grating patterns on a silicon wafer.

New magnetic hydroxyapatite-based nanomaterials as bone-specific systems for controlled drug delivery have been synthesized. The synthesized hydroxyapatite, HA, decorated with magnetite nanoparticles by a deposition method (HA/Fe₃O₄) and the nanocomposite system obtained using magnetic multi-walled carbon nanotubes (HA/MWCNT/Fe₃O₄) as a filler for HA have been characterized by chemical and morphological analyses, and their biological behavior was investigated. The systems have also been doped with clodronate in order to combine the effect of bone biomineralization induced by hydroxyapatite-based composites with the decrease of osteoclast formation induced by the drug. An analysis of the preosteoclastic RAW264.7 cell proliferation by MTT assay confirmed the high biocompatibility of the three systems. TRAP staining of RAW 264.7 conditioned with sRAKL to induce osteoclastogenesis, cultured in the presence of the systems doped and undoped with clodronate, showed the inhibitory effect of clodronate after we counted the MNC TRAP⁺cells but only in the osteoclast formation; in particular, the system HA/Fe₃O₄-Clo exerted a high inhibitory effect compared to the drug alone. These results demonstrate that the synthesized nanocomposites are a biocompatible magnetic drug delivery system and can represent a useful multimodal platform for applications in bone tissue engineering.

The gas injection line of the latest spherical aberration-corrected environmental transmission electron microscope has been modified for achieving real-time/atomic-scale observations in moisturised gas atmospheres for the first time. The newly developed Wet-TEM system is applied to platinum carbon electrode catalysts to investigate the effect of water molecules on the platinum/carbon interface during deactivation processes such as sintering and corrosion. Dynamic in situ movies obtained in dry and 24% moisturised nitrogen environments visualize the rapid rotation, migration and agglomeration of platinum nanoparticles due to the physical adsorption of water and the hydroxylation of the carbon surface. The origin of the long-interconnected aggregation of platinum nanoparticles was discovered to be a major deactivation process in addition to conventional carbon corrosion.

A multi-scale theoretical model is presented that is the first to offer quantitative agreement with experimental measurements of self-retraction and oscillation of bilayer graphene. The model integrates density-functional theory calculations of the energetics driving flake retraction and molecular-dynamics simulations capturing the dynamic response of laterally-offset rough surfaces. We demonstrate that nanoscale roughness explains self-retraction motion and propose a recipe for tuning that motion by controlling friction.

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile strength etc. The smaller the size of the particles, the larger is the interface where interactions between polymer molecules and fillers can generate new properties. Using temperature-modulated differential scanning calorimetry and dynamic mechanical analysis, we investigated the properties of pure styrene-butadiene rubber (SBR) and SBR/alumina nanoparticles. Beside a reinforcement effect seen in the complex elastic moduli, small amounts of nanoparticles of about 2 wt% interestingly lead to an acceleration of the relaxation modes responsible for the thermal glass transition. This leads to a minimum in the glass transition temperature as a function of nanoparticle content in the vicinity of this critical concentration. The frequency dependent elastic moduli are used to discuss the possible reduction of the entanglement of rubber molecules as one cause for this unexpected behavior.

We report on silver nanowires (AgNWs) coated with molecularly imprinted silica (MIP SiO₂) for recognition of tryptophan (Trp). The use of AgNWs as a template confers an imprinted material with adequate mechanical strength and with a capability of recognizing Trp due to its nanomorphology when compared to spherical microparticles with a similar surface-to-volume ratio. Studies on adsorption isotherms showed the MIP-SiO₂-AgNWs to exhibit homogeneous affinity sites with narrow affinity distribution. This suggests that the synthesized material behaves as a 1D nanomaterial with a large area and small thickness with very similar affinity sites. Trp release from MIP-SiO₂-AgNWs was demonstrated to be dominated by the diffusion rate of Trp as controlled by the specific interactions with the imprinted silica shell. Considering these results and the lack of toxicity of silica sol-gel materials, the material offers potential in the field of drug or pharmaceutical controlled delivery, but also in optoelectronic devices, electrodes and sensors.

We demonstrate here a method using a multi-probe UHV instrument to isolate and measure individual metal contacts controllably fabricated on the tips of free standing ZnO nanowires (NWs). The measurements show Au can form reliable Ohmic and rectifying contacts by exercising control over the surface properties. In the as-grown state the Au contacts display low-resistance characteristics which are determined by the adsorbed species and defects on the NW surface. Subjecting the NWs to an oxidising agent (H₂O₂) increases the surface potential barrier creating more rectifying contacts. These developments are crucial for controllable NW array devices.