Table of contents

Nanocarrier mediated therapy of gliomas has shown promise. The success of systemic nanocarrier-based chemotherapy is critically dependent on the so-called leaky vasculature to permit drug extravasation across the blood–brain barrier. Yet, the extent of vascular permeability in individual tumors varies widely, resulting in a correspondingly wide range of responses to the therapy. However, there exist no tools currently for rationally determining whether tumor blood vessels are amenable to nanocarrier mediated therapy in an individualized, patient specific manner today. To address this need for brain tumor therapy, we have developed a multifunctional 100 nm scale liposomal agent encapsulating a gadolinium-based contrast agent for contrast-enhanced magnetic resonance imaging with prolonged blood circulation. Using a 9.4 T MRI system, we were able to track the intratumoral distribution of the gadolinium-loaded nanocarrier in a rat glioma model for a period of three days due to improved magnetic properties of the contrast agent being packaged in a nanocarrier. Such a nanocarrier provides a tool for non-invasively assessing the suitability of tumors for nanocarrier mediated therapy and then optimizing the treatment protocol for each individual tumor. Additionally, the ability to image the tumor in high resolution can potentially constitute a surgical planning tool for tumor resection.

We demonstrate the capability of using immunotargeted gold nanoshells as contrast agents for in vitro two-photon microscopy. The two-photon luminescence properties of different-sized gold nanoshells are first validated using near-infrared excitation at 780 nm. The utility of two-photon microscopy as a tool for imaging live HER2-overexpressing breast cancer cells labeled with anti-HER2-conjugated nanoshells is then explored and imaging results are compared to normal breast cells. Five different imaging channels are simultaneously examined within the emission wavelength range of 451–644 nm. Our results indicate that under near-infrared excitation, superior contrast of SK-BR-3 cancer cells labeled with immunotargeted nanoshells occurs at an emission wavelength ranging from 590 to 644 nm. Luminescence from labeled normal breast cells and autofluorescence from unlabeled cancer and normal cells remain imperceptible under the same conditions.

We have developed the technique of growing amorphous a-SiO_x(Er) films and a-SiO_x(Er)/a-Si:H multilayer structures based on spatially separating the processes of the decomposition of an oxygen–silane gas mixture in an rf glow discharge plasma and remote magnetron sputtering of an Er target. This approach allows us to control independently the film deposition rate, the Er-ion concentration and its depth distribution in the film. Time-resolved photoluminescence measurements have shown that films and planar microcavities with an Er-doped active layer exhibit internal quantum efficiency for Er ion emission of ∼75%. The method that we suggest is a way of producing effectively emitting microcavity structures, in which the distribution profile of emission centers coincides with that of the electromagnetic field in individual layers of the structure.

The electron emission of position-controlled grown ZnO nanoflowers was investigated for application in cold cathode electron emission devices. ZnO nanoflower arrays, composed of several nanoneedles with sharp tips, were grown selectively on a conducting glass substrate using a chemical solution deposition method. The morphology and position of the ZnO nanoflowers were controlled by preparing polymethylmethacrylate submicron patterns using electron-beam lithography. Without the patterns, in contrast, vertical ZnO nanoneedles were randomly grown on the substrates with high density. Several samples prepared at the same conditions exhibited almost the same nanoflower morphology and field emission characteristics. Comparison of the field emission characteristics of the ZnO nanoflower arrays and ZnO nanoneedles showed that the arrays had excellent electron emission characteristics, with a low turn-on electric field of 0.13 V µm⁻¹ at 0.1 µA cm⁻² and a high emission current density of 0.8 mA cm⁻² in an applied electric field of 9.0 V µm⁻¹. Furthermore, light-emitting devices made using ZnO nanoflower arrays demonstrated strong light emission, and micropixels for display application were clearly displayed.

A method termed 'nanoglassblowing' is presented for fabricating integrated microfluidic and nanofluidic devices with gradual depth changes and wide, shallow nanochannels. This method was used to construct fused silica channels with out-of-plane curvature of channel covers from over ten micrometers to a few nanometers, nanochannel aspect ratios smaller than 2 × 10⁻⁵:1 (depth:width), and nanochannel depths as shallow as 7 nm. These low aspect ratios and shallow channel depths would be difficult to form otherwise without collapse of the channel cover, and the gradual changes in channel depth eliminate abrupt free energy barriers at the transition from microfluidic to nanofluidic regions. Devices were characterized with atomic force microscopy (AFM), white light interferometry, scanned height measurements, fluorescence intensity traces, and single molecule analysis of double-stranded deoxyribonucleic acid (DNA) velocity and conformation. Nanochannel depths and aspect ratios formed by nanoglassblowing allowed measurements of the radius of gyration, R_g, of single λ DNA molecules confined to slit-like nanochannels with depths, d, ranging from 11 nm to 507 nm. Measurements of R_g as a function of d agreed qualitatively with the scaling law R_g∝d^-0.25 predicted by Brochard for nanochannel depths from 36 nm to 156 nm, while measurements of R_g in 11 nm and 507 nm deep nanochannels deviated from this prediction.

We demonstrate the fabrication of large scale nano- and micropatterned copper periodic structures on a silicon substrate without imposed templates. In the electrodeposition process, we employ a periodic variation voltage in an ultrathin layer of concentrated CuSO₄ electrolyte. The pattern can be controlled by varying the frequency of the applied potential. We suggest that the observed periodic micro-/nanostructures are caused by the lag of the migrating ion concentration profile versus the applied voltage profile near the tip of the growth.

A self-assembled monolayer of polystyrene (PS) beads is formed on a silicon wafer by spin-coating. After drying at 80 °C, a thin film of metal/oxide is deposited. During the deposition, the PS beads are detached due to forces such as the inner stress induced by plasma sputtering deposition, mechanical vibration, and centrifugal shearing induced by substrate rotation, resulting in nanoring/nanohole formation. Further experiments demonstrate that the PS detachment can be controlled by scanning probe microscopy (SPM) tip manipulation. We believe this is a promising set of processes for fabricating nanodevice structures such as those of vertical nanotransistors, which provides high flexibility for nanocrystal characterizations and application for single-electron devices.

We have fabricated high-T_c nanoscale superconducting quantum interference devices (nanoSQUIDs) with a hole size of 250 nm × 250 nm based on a 100 nm bridge at 77 K by focused ion beam milling and ion implantation. At 78 K, the curve of the voltage branch became roughly linear and agreed with the Josephson-like behavior. The sample exhibited strong flux flow behavior at temperatures under 76 K. The voltage flux characteristic curves, V–I_mod, of the nanoSQUID at different bias currents at 78 K were observed. Typically, critical currents of 15 µA and peak-to-peak values of the voltage flux transfer function of 3.7 µV were measured. The measured data strongly suggest that the weak link structure could be a superconducting metal with a critical temperature T_c' smaller than that (T_c) of other YBa₂Cu₃O_7−x (YBCO) films. This fabrication method of combining a nanobridge and ion implantation can improve the yield of nanojunctions and nanoSQUIDs.

The behavior of soft magnetic films in spring magnets, as a function of the intensity and orientation of an external magnetic field, is described in the framework of spin-polarized non-collinear electronic structure calculations. As experimentally observed, the critical intensity of the external field required for the onset of the non-collinear spiral formation depends on both the thickness of the soft magnetic phase and the orientation of the field. The spin spiral structure undergoes a change of chirality in rotating fields. Our theoretical approach opens new prospects for investigating the response of other nanostructures to external magnetic fields beyond usual phenomenological models.

This paper introduces a novel nano-positioning actuator with large displacement and driving force, termed a flexure-based electromagnetic linear actuator (FELA). It mainly comprises an electromagnetic driving scheme and flexure-supporting bearings that provide infinite positioning resolution and highly repeatable motion. In this work, analytical modeling of the proposed electromagnetic scheme and flexure mechanism is presented. Solutions obtained from each model are evaluated by the experimental studies conducted on a FELA prototype. This prototype achieves a stroke of 4 mm with a positioning accuracy of ± 10 nm. With direct force control, it generates various force profiles with a force–current ratio of 60 N A⁻¹ and an accuracy of ± 0.3 N. Such capabilities make FELA a promising solution for realizing ultra-high precision layer-over-layer fabrication in the nano-imprinting process.

Synthesis of hematite (α-Fe₂O₃) nanostructures on a titania (TiO₂) nanotubular template is carried out using a pulsed electrodeposition technique. The TiO₂ nanotubes are prepared by the sonoelectrochemical anodization method and are filled with iron (Fe) by pulsed electrodeposition. The Fe/TiO₂ composite is then annealed in an O₂ atmosphere to convert it to Fe₂O₃/TiO₂ nanorod–nanotube arrays. The length of the Fe₂O₃ inside the TiO₂ nanotubes can be tuned from 50 to 550 nm by changing the deposition time. The composite material is characterized by scanning electron microscopy, transmission electron microscopy and diffuse reflectance ultraviolet–visible studies to confirm the formation of one-dimensional Fe₂O₃/TiO₂ nanorod–nanotube arrays. The present approach can be used for designing variable one-dimensional metal oxide heterostructures.

Three chiral cationic gelators were synthesized. They can form translucent hydrogels in pure water. These hydrogels become highly viscous liquids under strong stirring. Mesoporous silica nanotubes with coiled pore channels in the walls were prepared using the self-assemblies of these gelators as templates. The mechanism of the formation of this hierarchical nanostructure was studied using transmission electron microscopy at different reaction times. The results indicated that there are some interactions between the silica source and the gelator. The morphologies of the self-assemblies of gelators changed gradually during the sol–gel transcription process. It seems that the silica source directed the organic self-assemblies into helical nanostructures.

A simple microfluidic reactor system is described for the effective synthesis of enzyme functionalized nanoparticles which offers many advantages over batch reactions, including excellent enzyme efficiencies. Better control of the process parameters in the microfluidic reactor system over batch based methodology enables the production of silica nanoparticles with the optimum size for efficient enzyme immobilization with long-term stability. The synthetic approach is demonstrated with glucose oxidase (GOD) and two different nucleation catalysts of similar molecular mass: the natural R5 peptide, and polyethylenimine (PEI) polymer. Near-quantitative immobilization of GOD in the nanoparticles is obtained using PEI; the immobilization is attributed to electrostatic interaction between PEI and GOD. This interaction, however, limits the mobility of the immobilized enzyme, producing orientation hindrance of the enzyme's active sites as compared to free GOD in solution. In contrast, when the GOD is immobilized inside the silica nanoparticles using R5, lower enzyme immobilization efficiencies are obtained compared to using PEI polymers; however, similar Michaelis–Menten kinetic parameters (i.e. Michaelis constant and turnover number) to those of free GOD are observed. Reactions were monitored in situ using simple, rapid, separation-free amperometric detection.

A novel approach has been developed to synthesize magnetic nanoparticle and carbon nanotube (CNT) core–shell nanostructures, such as CoO/CNTs and Mn₃O₄/CNTs, by the nonaqueous solvothermal treatment of metal carbonyl on CNT templates using hexane as the solvent. The morphological and structural characterizations indicate that numerous cubic CoO or tetragonal Mn₃O₄ nanoparticles are deposited on the surfaces of the CNTs to form CNT-based core–shell nanostructures. It is revealed that the hydrophobic interaction between nanoparticles and CNTs in hexane plays the critical role for the formation of CNT-based core–shell nanostructures. A physical property measurement system (PPMS-9, Quantum Design) analysis indicates that the CoO/CNT core–shell nanostructures show weak ferromagnetic performance at 300 K due to the ferromagnetic Co clusters and the uncompensated surface spin states, while the Mn₃O₄/CNT core–shell nanostructures display ferromagnetic behavior at low temperature (34.5 K), which transforms into paramagnetic behavior with increasing temperature.

In this paper, we present a facile and robust approach to synthesize multifunctional organic/inorganic composite microspheres with chitosan-poly(methacrylic acid) (CS-PMAA) shells and cadmium tellurium/iron oxide nanoparticle cores. Due to the strong electrostatic interaction between the negatively charged nanoparticles and the protonated CS polymers, the CS/nanoparticle complexes were utilized as templates for the subsequent polymerization of methacrylic acid. The resulting composite microspheres with luminescence and magnetic properties have regular morphologies and narrow size distributions. In contrast to previous reports, this route was based on a one-pot strategy without the aid of surfactants, organic solvent, or polymerizable ligands in aqueous solution. The encapsulated CdTe semiconductor nanocrystals inside the microspheres exhibited strong and stable photoluminescence properties in the pH range 5.0–11.0. When the pH was adjusted below 4, the photoluminescence decreased sharply and even quenched completely. However, the weakened fluorescence emission could be recovered to some degree upon an increase of pH above 5. Additionally, when both Fe₃O₄ and CdTe nanoparticles were encapsulated within CS-PMAA microspheres, the magnetic content of the microspheres could be efficiently controlled by tuning the feeding molar ratio of MAA monomers and glucosamine units of CS. From the preliminary attempts, it was found that the multifunctional microspheres as imaging agents could improve the rate and extent of cellular uptake under short-term exposure to an applied magnetic field, and so exhibit a great potential as bioactive molecule carriers.

In this investigation, nanofluids of carbon nanotubes are prepared and the thermal conductivity and volumetric heat capacity of these fluids are measured using a thin layer technique as a function of time of ultrasonication, temperature, and volume fraction. It has been observed that after using the ultrasonic disrupter, the size of agglomerated particles and number of primary particles in a particle cluster was significantly decreased and that the thermal conductivity increased with elapsed ultrasonication time. The clustering of carbon nanotubes was also confirmed microscopically.

The strong dependence of the effective thermal conductivity on temperature and volume fraction of nanofluids was attributed to Brownian motion and the interparticle potential, which influences the particle motion.

The effect of temperature will become much more evident with an increase in the volume fraction and the agglomeration of the nanoparticles, as observed experimentally.

The data obtained from this work have been compared with those of other studies and also with mathematical models at present proven for suspensions. Using a 2.5% volumetric concentration of carbon nanotubes resulted in a 20% increase in the thermal conductivity of the base fluid (ethylene glycol).The volumetric heat capacity also showed a pronounced increase with respect to that of the pure base fluid.

The atomic scale structural stability of freestanding wavy gold (Au) nanofilms was investigated using molecular dynamics simulations. The waviness in the Au film was formed by cleaving sinusoidal surfaces from a bulk crystal. The degree of waviness was varied by changing the wavelength of the sinusoidal surface profile. Films were then equilibrated at different temperatures (between 10 and 1080 K) and their structural stability was monitored. The MD simulation results revealed that the stability of films depends on temperature as well as the waviness of the film surface. It was shown that the size-dependent melting point depression of Au plays the dominant role in causing the structural instability of wavy films.

In this study, the well-ordered alkanethiolate self-assembled monolayers (SAMs) of varied chain lengths and tail groups were employed as examples for nano-characterization on their mechanical properties. A novel nano-indentation technique with a constant harmonic frequency was applied on SAMs chemically adsorbed on Au to explore their contact mechanics, and furthermore to interpret how SAM molecules respond to an infinitesimal oscillation force without pressing them. Experimental results demonstrated that the harmonic contact stiffness along with the measured displacement of SAMs/Au was distinguishable using a dynamic contact modulus with the distinct feature of phase angles. Phase angles resulted from the relaxing continuation of an applied harmonic frequency and mostly influenced by the outermost tail group of SAM molecules. The harmonic contact stiffness of SAM molecules obviously increased with the densely packed alkyl chains and relatively intense agglomeration of the head group at the anchoring site. As a consequence, the result of this work is relevant to contact mechanics at the surface contact level for the distinction of molecular substances attached on a solid surface. Furthermore it is particularly anticipated to identify biological molecules of variable qualities under a fluid-like micro-environment.

The electronic transport properties of ordered networks using carbon nanotubes as building blocks (ON-CNTs) are investigated within the framework of a multiterminal Landauer–Buttiker formalism using an s,p_x,p_y,p_z parameterization of the tight-binding Hamiltonian for carbon. The networks exhibit electron pathway selectiveness, which is shown to depend on the atomic structure of the network nodes imposed by the specific architecture of the network and the distribution of its defects (non-hexagonal rings). This work represents the first understandings towards leading current through well-defined trajectories along an organic nanocircuit.

Continuous wave photoluminescence (cw PL) spectroscopy has been used to study the optical properties of a set of InGaNAs epilayers and single quantum wells with nitrogen concentration less than a few per cent at different temperatures and different excitation powers. We found that nitrogen has a critical role on the emission light of InGaNAs nanostructures and the recombination mechanism. The incorporation of a few per cent of nitrogen leads to shrinkage of the InGaNAs band gap. The physical origin of such band gap reduction has been investigated both experimentally and theoretically by using a band anticrossing model. We have found that localization of excitons that have been caused by incorporation of a few per cent of nitrogen in these structures is the main explanation of such anomalous behavior observed in the low-temperature photoluminescence spectra of these nanostructures. The localization energies of carriers have been evaluated by studying the variation of the quantum well (QW) emission versus temperature, and it was found that the localization energy increases with increasing nitrogen composition. Our data also show that, with increasing excitation intensity, the PL peak position moves to higher energies (blue shift) due to the filling of localized states and capture centers for excitons by photo-generated carriers.

The mechanical actuation of a (5, 5) single-walled carbon nanotube as a result of added charge is simulated using first-principles calculations. It is observed that while both positive and negative charging tend to expand the nanotube in the axial direction for most levels of charge, radial actuation is less even and symmetric with respect to charge. The spin distribution of the additional charges is investigated, and it is predicted that in some cases unpaired spin configurations are energetically favourable, significantly affecting actuation strains.

We present a complete theoretical study of the relationship between the structure (tip shape and dimensions) and function (selectivity and rectification) of asymmetric nanopores on the basis of previous experimental studies. The theoretical model uses a continuum approach based on the Nernst–Planck equations. According to our results, the nanopore transport properties, such as current–voltage (I–V) characteristics, conductance, rectification ratio, and selectivity, are dictated mainly by the shape of the pore tip (we have distinguished bullet-like, conical, trumpet-like, and hybrid shapes) and the concentration of pore surface charges. As a consequence, the nanopore performance in practical applications will depend not only on the base and tip openings but also on the pore shape. In particular, we show that the pore opening dimensions estimated from the pore conductance can be very different, depending on the pore shape assumed. The results obtained can also be of practical relevance for the design of nanopores, nanopipettes, and nanoelectrodes, where the electrical interactions between the charges attached to the nanostructure and the mobile charges confined in the reduced volume of the inside solution dictate the device performance in practical applications. Because single tracks are the elementary building blocks for nanoporous membranes, the understanding and control of their individual properties should also be crucial in protein separation, water desalination, and bio-molecule detection using arrays of identical nanopores.

Engineering ceramics have high stiffness, excellent thermostability, and relatively low density, but their brittleness impedes their use as structural materials. Incorporating carbon nanotubes (CNTs) into a brittle ceramic might be expected to provide CNT/ceramic composites with both high toughness and high temperature stability. Until now, however, materials fabrication difficulties have limited research on CNT/ceramic composites. The mechanical failure of CNT/ceramic composites reported previously is primarily attributed to poor CNT–matrix connectivity and severe phase segregation. Here we show that a novel processing approach based on the precursor method can diminish the phase segregation of multi-walled carbon nanotubes (MWCNTs), and render MWCNT/alumina composites highly homogeneous. The MWCNTs used in this study are modified with an acid treatment. Combined with a mechanical interlock induced by the chemically modified MWCNTs, this approach leads to improved mechanical properties. Mechanical measurements reveal that only 0.9 vol% acid-treated MWCNT addition results in 27% and 25% simultaneous increases in bending strength (689.6 ± 29.1 MPa) and fracture toughness (5.90 ± 0.27 MPa m^1/2), respectively.

Gas adsorption and capillary condensation of organic vapors are studied by optical interferometry, using anodized nanoporous alumina films with controlled geometry (cylindrical pores with diameters in the range of 10–60 nm). The optical response of the film is optimized with respect to the geometric parameters of the pores, for potential performance as a gas sensor device. The average thickness of the adsorbed film at low relative pressures is not affected by the pore size. Capillary evaporation of the liquid from the nanopores occurs at the liquid–vapor equilibrium described by the classical Kelvin equation with a hemispherical meniscus. Due to the almost complete wetting, we can quantitatively describe the condensation for isopropanol using the Cohan model with a cylindrical meniscus in the Kelvin equation. This model describes the observed hysteresis and allows us to use the adsorption branch of the isotherm to calculate the pore size distribution of the sample in good agreement with independent structural measurements. The condensation for toluene lacks reproducibility due to incomplete surface wetting. This exemplifies the relevant role of the fluid–solid (van der Waals) interactions in the hysteretic behavior of capillary condensation.

Future micro/nanodevices will contain very small features such that liquid lubrication is not practical and inherent lubricity is needed. In this study, a nanoscale friction investigation was carried out during the manipulation of Au and SiO₂ nanoparticles on silicon using atomic force microscopy (AFM). Nanoparticle sliding was characterized by quantifying the lateral force associated with the AFM tip twisting as it hits the particle edge. The friction force varies with particle area and humidity, illustrating how meniscus forces on nanoparticles affect friction. A large tip slid on the nanoparticle-coated surface exhibited friction reduction due to nanoparticle sliding and contact area reduction.

Nanocrystalline titanium oxide (TiO₂) is a promising material as a photocatalyst for photodecomposition of hazardous organic pollutants under illumination, because it is cheap, safe, environmentally benign, and chemically stable. However, the control of particle size and monodispersity of TiO₂ is a challenging task. The use of MCM-41, an inorganic template of uniform pore size (2–10 nm), can overcome this difficulty and produce stable nanoparticles of uniform size and shape. In an attempt to extend light absorption of the TiO₂-based photocatalyst towards the visible light range and eliminate the rapid recombination of excited electrons/holes during photoreaction, a new photocatalyst (25%TiO₂-loaded W-MCM-41) powder was prepared. W-MCM-41, with different ratios of Si to W (Si/W = 25, 50, 75), was synthesized by a hydrothermal method and loaded with 25 wt% TiO₂ utilizing a sol–gel method. In order to compare the photocatalytic activity of our sample, titania-loaded plain MCM-41 was also prepared. These materials were characterized by various physiochemical techniques such as UV–visible absorption spectroscopy, x-ray diffraction, nitrogen adsorption–desorption isotherm measurement, Fourier transform infrared (FT-IR) spectroscopy, and transmission electron microscopy. The photocatalytic activity of the prepared samples was evaluated using methyl orange as a model organic compound. It was found that the photodegradation ability of 25% TiO₂-loaded W-MCM-41 was highly related to the amount of W atoms present in the sample; the optimum atomic ratio of Si to W was 25. It has been confirmed that the recombination rate of electrons/holes in 25%TiO₂/W-MCM-41 declined due to the existence of W atoms in the sample.

Experimental data for antiferromagnetic nanoparticles are often analyzed as if the particles were ferromagnetic. However, due to the volume dependence of the magnetization resulting from uncompensated spins, such analysis will yield erroneous results. This is demonstrated as we analyze ac and dc magnetization data as well as Mössbauer spectra obtained for ferritin. The values of the median energy barrier obtained from the different data are in very close agreement when a distribution of volumes and a volume dependence of the magnetization are taken into account. However, when the volume dependence of the magnetization is neglected, erroneous values of the anisotropy energy barrier and the attempt time τ₀ are obtained.