Table of contents

Glucagon is a 29-residue amphiphatic hormone involved in the regulation of blood glucose levels in conjunction with insulin. In concentrated aqueous solutions, glucagon spontaneously aggregates to form amyloid fibrils, destroying its biological activity. In this study we utilize the atomic force microscope (AFM) to elucidate the fibrillation mechanism of glucagon at the nanoscale under acidic conditions (pH 2.0) by visualizing the nanostructures of fibrils formed at different stages of the incubation. Hollow disc-shaped oligomers form at an early stage in the process and subsequently rearrange to more solid oligomers. These oligomers co-exist with, and most likely act as precursors for, protofibrils, which subsequently associate to form at least three different classes of higher-order fibrils of different heights. A repeat unit of around 50 nm along the main fibril axis suggests a helical arrangement of interwoven protofibrils. The diversity of oligomeric and fibrillar arrangements formed at pH 2.0 complements previous spectroscopic analyses that revealed that fibrils formed under different conditions can differ substantially in stability and secondary structure.

The interface chemical composition of heterostructured GaP–GaAs nanowire segments was studied by the use of energy-dispersive x-ray analysis. An arsenic-rich tail in the GaP segments following GaAs could be minimized by reducing the AsH₃ molar fraction and the growth rate. For the temperature regime used for vapour–liquid–solid growth, we observe the opposite trend on interface sharpness compared to high-temperature layer-by-layer growth, that is, the sharpness of the interface improves with reducing temperature.

We have tested a range of imaging and spectroscopic techniques to address their ability to locally explore the interplay between surface reactivity and transport properties of the metal oxide nanostructure wired as a chemiresistor and chemi-FET. In particular, we used scanning surface potential microscopy (SSPM) to monitor the spatial and temporal particularities of the dc potential distributions in an operating device. We also successfully implemented synchrotron radiation-based photoelectron emission microscopy (PEEM) to explore submicron lateral compositional and electronic (work function) inhomogeneity on the surface of an individual nanowire sensor. These results open new avenues to visualize and spectroscopically address the chemical phenomena on an individual quasi-1D nanostructure both in real time and at nano- and mesoscopic level.

Spherical silver nanoparticles with various sizes and standard deviations were synthesized by the polyol process. Two different synthesis methods were compared in order to investigate the influence of reaction parameters on the resulting particle size and its distribution. In the precursor heating method, wherein a solution containing silver nitrate was heated to the reaction temperature, the ramping rate was determined to be a critical parameter affecting the particle size. In contrast, in the precursor injection method, in which a silver nitrate aqueous solution was injected into hot ethylene glycol, because of rapid nucleation, the injection rate and the reaction temperature were important factors in terms of reducing the particle size and attaining monodispersity. Silver nanoparticles with a size of 17 ± 2 nm were obtained at an injection rate of 2.5 ml s⁻¹ and a reaction temperature of 100 °C.

Molecular beam epitaxial growth of GaAs nanowires using Au particles as a catalyst was investigated. Prior to the growth during annealing, Au alloyed with Ga coming from the GaAs substrate, and melted. Phase transitions of the resulting particles were observed in situ by reflection high-energy electron diffraction (RHEED). The temperature domain in which GaAs nanowire growth is possible was determined. The lower limit of this domain (320 °C) is close to the observed catalyst solidification temperature. Below this temperature, the catalyst is buried by GaAs growth. Above the higher limit (620 °C), the catalyst segregates on the surface with no significant nanowire formation. Inside this domain, the influence of growth temperature on the nanowire morphology and crystalline structure was investigated in detail by scanning electron microscopy and transmission electron microscopy. The correlation of the nanowire morphology with the RHEED patterns observed during the growth was established. Wurtzite GaAs was found to be the dominant crystal structure of the wires.

We investigate the effects of erbium doping on SnO₂ nanoclustering in Sn-doped silica. Vibrational spectroscopy data from Raman and infrared absorption measurements show nanostructuring effects on the SnO₂ nanophase. Ultraviolet absorption spectra evidence a gap shift ascribable to size-dependent quantum confinement, also suggesting a role of erbium doping in determining cluster sizes and the amount of localized states on the nanophase boundary. Transmission electron microscopy confirms and details the spectroscopic data. As a result of these measurements, we find that the nanocrystal size distribution becomes narrower, increasing the erbium concentration, while the density of localized states at the nanocrystal surface decreases. The distribution of erbium ions among the possible environments is then examined through simultaneous spectroscopy of luminescence excited by nanocrystal-to-erbium energy transfer and the absorption of nanocrystal luminescence by erbium ions. This analysis shows that erbium behaves as an extrinsic nucleation centre of the SnO₂ nanophase at low doping levels, whereas at high concentrations it modifies the matrix, hindering the growth of SnO₂ crystals and passivating the interface.

Using (100) GaAs substrates as a reference, we present a study of the formation of Ga droplets on (311)A and (511)A GaAs substrates in which the effect of both the substrate temperature and the amount of Ga supplied on the droplet density and height for the three different surfaces have been investigated. Droplets on (100) substrates show a round shape; however, they appear as elongated balls with tails along the direction of the (311)A substrate and the direction of the (511)A substrate. It has been found that the Ga droplets on (511)A surfaces have lower densities and higher heights than those on (100) substrates. In contrast, Ga droplets on (311)A surfaces have lower heights and much higher densities compared to those for both (100) and (511)A. We observed that the decrease in the droplet density with increasing growth temperature for both (311)A and (511)A is more than twice that for the (100)GaAs surface due to the larger drop in the nucleation rate. Based on these observations, we offer a physical explanation based on the thermodynamics and the anisotropy of the high-index surfaces.

A series of ternary tetrapodal nanocrystals of CdSe_xTe_1−x with x = 0 (CdTe), 0.23, 0.53, 0.78, 1 (CdSe) were synthesized and used to fabricate hybrid nanocrystal/polymer solar cells. Herein, the nanocrystals acted as electron acceptors, and poly(2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) was used as an electron donor. It was found that the open circuit voltage (V_oc), short-circuit current (J_sc) and power conversion efficiency (η) of the devices all increased with increasing Se content in the CdSe_xTe_1−x nanocrystals under identical experimental conditions. The solar cell based on the blend of tetrapodal CdSe nanocrystals and MEH-PPV (9:1 w/w) showed the highest power conversion efficiency of 1.13% under AM 1.5, 80 mW cm⁻², and the maximum incident photon to converted current efficiency (IPCE) of the device reached 47% at 510 nm. The influence of nanocrystal composition on the photovoltaic properties of the hybrid solar cells was explained by the difference of the band level positions between MEH-PPV and the nanocrystals.

Gd₂O₃:Eu³⁺ nano-wire phosphors embedded in SBA-15 silica templates were synthesized using a combination of the sol–gel method and hydrothermal reactions followed by a sintering process at 1000 °C. The crystal structure of Gd₂O₃:Eu³⁺ was confirmed using x-ray diffraction. Observation using transmission electron microscopy shows that the nano-wire diameters were very uniform in the 7–9 nm range. In comparison with bulk Gd₂O₃:Eu³⁺ materials, we found that the photo-luminescent property of the nano-wire was different. The analysis shows that the main nano-wire emission peaks were at 585, 597, 613 and 620 nm. The CIE value (x = 0.62, y = 0.38) indicates that the nano-wire emitted a pink colour and not red as for the bulk material. The field emission experimental results agreed well with the photo-luminescent analysis results.

A nanogroove-striped pattern was formed on a NiO film surface. The periodic nanopattern was successfully obtained over the entire surface via high-temperature annealing of the epitaxial NiO thin film, which was grown on an atomically stepped sapphire substrate at low temperature. The depth, width and interval of straight nanogrooves were about 3 nm, 35 nm and about 100 nm, respectively. The periodicity of the stripe agrees well with that of the atomic steps of the substrate.

Nanocomposites consisting of magnetite and FAU zeolite with a high surface area and adsorption capacity have been prepared by mechanical activation using high-energy milling at room temperature. FTIR results, as well as HRTEM, EFTEM, and XPS measurements, show that the resulting magnetic nanoparticles are covered by a thin aluminosilicate coating. A saturation magnetization as high as 16 emu g⁻¹ and 94.2 Oe of coercivity were observed for the obtained composites. The main advantages of this synthesis procedure are (i) simplicity of the preparation procedure, (ii) prevention of agglomeration of the magnetite nanoparticles to a large extent, and (iii) absence of free magnetite outside the zeolitic matrix. In addition, in vitro experiments revealed that the nanoparticles prepared were able to store and release substantial amounts of doxorubicin. In view of these advantages, these magnetic nanoparticles can be considered as potential candidates for drug-delivery applications.

The laser generation of size-controlled semiconductor nanoparticle formation under gas phase conditions is investigated. It is shown that the size distribution can be changed if picosecond pulse sequences of tailored ultra short laser pulses (<200 fs) are employed. By delivering the laser energy in small packages, a temporal energy flux control at the target surface is achieved, which results in the control of the thermodynamic pathway the material takes. The concept is tested with silicon and germanium, both materials with a predictable response to double pulse sequences, which allows deduction of the materials' response to complicated pulse sequences. An automatic, adaptive learning algorithm was employed to demonstrate a future strategy that enables the definition of more complex optimization targets such as particle size on materials less predictable than semiconductors.

The growth of perfectly hexagonal-shaped ZnO nanorods, with Zn-terminated (0001) facets bounded with surfaces, has been performed on nickel-coated Si(100) substrate via thermal evaporation using metallic zinc powder and oxygen. Detailed structural investigations confirmed that the synthesized nanorods are single crystalline with the wurtzite hexagonal phase and preferentially grow along the c-axis direction. Raman spectra of the as-grown ZnO nanorods showed an optical-phonon E₂ mode at 438 cm⁻¹, indicating that as-grown nanostructures are in good crystallinity with the wurtzite hexagonal phase. The ZnO nanorods were found to show strong band edge emission with very weak or no deep-level emission, as shown by photoluminescence measurements. The clear observation of free excitons at low temperatures (13–50 K) indicates that the as-grown ZnO nanorods are of high quality.

In this work, we report on the fabrication of tetraethylorthosilicate (TEOS) thin dielectric film containing silicon nanocrystals (Si nc), synthesized by solid-state reaction, in a capacitor structure. A metal–insulator–semi-conductor (MIS) capacitor, with 28 nm thick Si nc in a TEOS thin film, has been fabricated. For this MIS, both electron and hole trapping in the Si nc are possible, depending on the polarity of the bias voltage. A V_FB shift greater than 1 V can be experienced by a bias voltage of 16 V applied to the metal electrode for 1 s. Though there is no top control oxide, the discharge time for 10% of charges can be up to 4480 s when it is biased at 16 V for 1 s. It is further demonstrated that charging and discharging mechanisms are due to the Si nc rather than the TEOS oxide defects. This form of Si nc in a TEOS thin film capacitor provides the possibility of memory applications at low cost.

Sub-100 nm patterns can be duplicated by nanoimprint lithography with high reproducibility, even on 200 mm wafers. Nevertheless, several problems have to be solved before this technique reaches a mature state for industrial applications. Several kinds of defect appear frequently in printed polymers. Some of them are induced by capillary effects and are related to mould deformation. Capillary bridges are observed on the flat surfaces around the pattern areas, or inside the printed structures. In this paper, the influence of the polymer molecular weight (M_w) on the capillary bridge distribution is presented. It will be shown that for smaller M_w, they appear first around the pattern areas and move towards the structures more rapidly. It is also demonstrated that this evolution depends directly on the printing temperature and pattern filling related to the feature density and the film thickness. Finally, it is shown that the influence of these parameters is related to the polymer viscosity, which is the dominant property of the capillary effects, and a trade-off has to be made between the limitation due to the capillary bridges, the decrease of the temperature, which is important to reduce the cycle time, and the sticking defects.

The electronic and structural properties of an (8, 0) single-walled carbon nanotube (SWNT) with a single vacancy and interacting with a Si atom are studied using first principles calculations based on the density-functional theory. Initially, the Si atom is positioned in the site above the vacancy, with its position fixed until the nanotube geometry is fully relaxed. After that, the Si atom approaches the tube and it is shown that one C atom is displaced outwards forming a bump. The final configuration, as well as each step of the process, is studied in detail and the resulting band structures and the total charge densities are systematically analysed.

Titanosilicates ETS-4 and ETS-10 contain octahedrally coordinated monatomic semiconductor –O–Ti–O– (titania) chains in their frameworks. Titania chains are isolated from one another by a siliceous matrix. Thus, these chains can be regarded as one-dimensional nanostructures, i.e., 'quantum wires'. Diffuse reflectance UV–vis (DR-UV–vis) spectroscopy analysis demonstrated a significant blue-shift of the optical absorption edge (>60 nm) for both ETS-4 and ETS-10 compared to bulk titania. This blue-shift is consistent with the hypothesis that the titania chains in ETS-4 and ETS-10 are acting as quantum wires. A broad range of ETS-4 and ETS-10 samples with diverse crystallo-chemical characteristics was prepared. The DR-UV–vis and Raman spectra of various ETS-4 and ETS-10 samples exhibited different characteristics, which were hypothesized to be related to the titania chain 'quality'. Detailed investigation of the spectroscopic bands associated with the titania chains in ETS-4 was performed for the first time. The 'quality' of these titania chains/quantum wires in ETS-4 and ETS-10 was correlated with the crystal growth mechanisms of these materials. Comparison of the growth mechanisms and the spectroscopic behaviour for ETS-4 and ETS-10 suggests that the control of 'quantum wire quality' via hydrothermal synthesis is possible in ETS-4 but would be difficult in ETS-10.

The excitation energies of small ZnS nanoclusters characterized in previous studies have been calculated using TDDFT. The relativistic pseudopotentials of Stevens et al have been used, including Zn 4s² electrons and S 3s² and 3p⁴ electrons as valence electrons. Results obtained with these pseudopotentials are compared to those obtained considering also Zn 3s²3p⁶3d¹⁰ electrons in the valence part, and demonstrated to be consistent. The results show that spheroid-like bubble structures have absorption energies in the range of 5–5.3 eV for small sizes, which decreases to 5 eV with increasing particle size.

Thin films consisting of Ag and Au nanoparticles embedded in amorphous ZrO₂ matrix were grown by pulsed laser deposition in a wide range of metal volume concentrations in the dielectric regime (0.08<x_Ag<0.28 and 0.08<x_Au<0.52). High resolution transmission electron microscopy (TEM) showed regular distribution of spherical Au and Ag nanoparticles having very sharp interfaces with the amorphous matrix. Mean particle size determined from x-ray diffraction agreed with direct TEM observation. The silver mean diameter increases more abruptly with metal volume content than that corresponding to gold particles prepared under the same conditions. Two mechanisms of particle growth are observed: nucleation and particle coalescence, their relative significance being different in both granular systems, which yields very different values of the percolation threshold (x_c(Ag)∼0.28 and x_c(Au)∼0.52).

Density functional theory (DFT) total-energy calculations have been used to investigate the effect of potassium on the adsorption geometry of gold on a TiO₂(110)- 1 × 1 surface. The gold prefers to sit between the two bridge oxygen atoms above the sixfold titanium atom. The addition of potassium significantly affects the bonding geometry of the gold. Potassium displaces gold from the bridge site and causes its migration to the top of the fivefold titanium atom. Our calculations suggest that potassium is bonded to the bridging oxygen atoms, and to the sixfold titanium atom as well as to gold. This excludes the formation of a K₂O-like compound at the surface.

We present steady state and time-resolved photoluminescence (PL) characteristics of differently charged CdTe quantum dots (QDs) adsorbed onto a polyelectrolyte (PE) multilayer. The PE multilayer is built up using a layer-by-layer assembly technique. We find that the diffusion of the QDs into the PE multilayer is an important factor in the case of 3-mercapto-1, 2-propanediol stabilized QDs (neutral surface charge), resulting in a ∼31-fold enhancement in PL intensity accompanied by a blue shift in the PL spectra and an increase in decay lifetime from 3.74 ns to a maximum of 11.65 ns. These modified emission properties are attributed to the enhanced surface related emission resulting from the interaction of the QD's surface with the PE. We find that diffusion does not occur for thioglycolic acid (TGA) stabilized QDs (negative surface charge) or 2-mercaptoethylamine stabilized QDs (positive surface charge), indicating localization of the QDs on top of the PE multilayer. However, the PL lifetime of the TGA stabilized QDs decreases from 9.58 to 5.78 ns with increasing PE multilayer thickness. This provides evidence for increased intrinsic exciton recombination relative to surface related emission, which results in an overall reduction in the average lifetime. Our studies indicate the importance of the QD surface charge in determining the interaction with the PE multilayers and the subsequent modification of the QD emission properties.

Chemiresistor-based vapour sensors made from network films of single-walled carbon nanotube (SWNT) bundles on flexible plastic substrates (polyethylene terephthalate, PET) can be used to detect chemical warfare agent simulants for the nerve agents Sarin (diisopropyl methylphosphonate, DIMP) and Soman (dimethyl methylphosphonate, DMMP). Large, reproducible resistance changes (75–150%), are observed upon exposure to DIMP or DMMP vapours, and concentrations as low as 25 ppm can be detected. Robust sensor response to simulant vapours is observed even in the presence of large equilibrium concentrations of interferent vapours commonly found in battle-space environments, such as hexane, xylene and water (10 000 ppm each), suggesting that both DIMP and DMMP vapours are capable of selectively displacing other vapours from the walls of the SWNTs. Response to these interferent vapours can be effectively filtered out by using a 2 µm thick barrier film of the chemoselective polymer polyisobutylene (PIB) on the SWNT surface. These network films are composed of a 1–2 µm thick non-woven mesh of SWNT bundles (15–30 nm diameter), whose sensor response is qualitatively and quantitatively different from previous studies on individual SWNTs, or a network of individual SWNTs, suggesting that vapour sorption at interbundle sites could be playing an important role. This study also shows that the line patterning method used in device fabrication to obtain any desired pattern of films of SWNTs on flexible substrates can be used to rapidly screen simulants at high concentrations before developing more complicated sensor systems.

Gold–polymethylmethacrylate (PMMA) nanocomposites were fabricated by mixing gold nanoparticles capped with oleylamine in polymethylmethacrylate. The samples were analysed using UV–vis absorption spectroscopy, transmission electron microscopy, small angle x-ray scattering, Fourier transform infrared spectrometry (FTIR) and x-ray photoelectron spectroscopy (XPS). Electrical resistivity of nanocomposite samples was measured by a four-probe technique in the 70–300 K range. The nanocomposites showed a transition with an onset at ∼160–165 K. They exhibited a semiconductor-like conductivity at higher temperatures and nearly temperature independent conductivity at lower temperatures. The interfacial interaction of Au nanoparticles and PMMA polymer is investigated using FTIR and XPS. A ligand-exchange process occurs when capped gold nanoparticles are incorporated in PMMA polymer.

Experimental data and theoretical modelling of the I–V characteristics of a gas sensor constructed from a mat of Au nanoparticle-coated GaN nanowires are presented. The principal mechanism for the response of the gas sensor to methane is explained in terms of the formation of a depletion layer within the nanowires due to the presence of the gold nanoparticles. The depth of the depletion layer is modulated by the potential induced by the physisorption of gas molecules onto the Au nanoparticles. A statistical model of the temperature-dependent I–V characteristics of bare and Au nanoparticle-decorated mats of GaN nanowires based on Poisson's equation has been used to determine the depth of the depletion layers of the nanowires. The room-temperature carrier concentration for the GaN nanowires was determined to be approximately 2.2 × 10¹⁷ cm⁻³. The induced potential due to methane physisorption onto the Au nanoparticles that decorate the GaN nanowires was determined to be approximately −37 mV.

Double-walled carbon nanotubes (DWNTs) are filled with ferrocene molecules by a vapour diffusion method for the first time. The as-synthesized ferrocene-filled DWNTs are characterized by transmission electron microscopy (TEM), energy-dispersive x-ray spectrometry (EDX) and Raman spectroscopy. Electronic properties of double-walled carbon nanotubes (DWNTs) filled with ferrocene molecules are studied by fabricating them as the channels of field-effect transistor (FET) devices. Our results reveal that electronic properties of ferrocene-filled DWNTs are greatly modified due to the charge transfer between ferrocene molecules and DWNTs. In addition, after ferrocene molecules are decomposed inside DWNTs, electronic properties of DWNTs exhibit a further change due to Fe encapsulation, and unipolar n-type semiconducting DWNTs are consequently obtained.

The purpose of this work was to determine the stability of pDNA/poly(L-lysine) complex (DNA/PLL) during microencapsulation, prepare transferrin (TF) conjugated PEGylated nanoparticles (TF-PEG-NP) loading DNA/PLL, and assess its physicochemical characteristics and in vitro transfection efficiency. The DNA/PLL was prepared by mixing plasmid DNA (pDNA) in deionized water with various amounts of PLL. PEGylated nanoparticles (PEG-NP) loading DNA/PLL were prepared by a water–oil–water double emulsion solvent evaporation technique. TF-PEG-NP was prepared by coupling TF with PEG-NP. The physicochemical characteristics of TF-PEG-NP and in vitro transfection efficiency on K562 cells were measured. The results showed that free pDNA reserved its double supercoiled form (dsDNA) for only on average 25.7% after sonification, but over 70% of dsDNA was reserved after pDNA was contracted with PLL. The particle size range of TF-PEG-NP loading DNA/PLL was 150–450 nm with entrapment efficiency over 70%. TF-PEG-NP exhibited the low burst effect (<10%) within 1 day. After the first phase, DNA/PLL displayed a sustained release. The amount of cumulated DNA/PLL release from TF-PEG-NP with 2% polymer over 7 days was 85.4% for DNA/PLL (1:0.3 mass ratio), 59.8% and 43.1% for DNA/PLL (1:0.6) and DNA/PLL (1:1.0), respectively. To TF-PEG-NP loading DNA/PLL without chloroquine, the percentage of EGFP expressing cells was 28.9% for complexes consisting of DNA/PLL (1:0.3), 38.5% and 39.7% for DNA/PLL (1:0.6) and DNA/PLL (1:1.0), respectively. In TF-PEG-NP loading DNA/PLL with chloroquine, more cells were transfected, the percentage of positive cells was 37.6% (DNA/PLL, 1:0.3), 47.1% (DNA/PLL, 1:0.6) and 45.8% (DNA/PLL, 1:1.0), which meant that the transfection efficiency of pDNA was increased by over 50 times when PLL and TF-PEG-NP were jointly used as a plasmid DNA carrier, in particular, the maximal percentage of positive cells (47.1%) from TF-PEG-NP loading DNA/PLL (1:0.6) was about 70 times the transfection efficiency of free plasmid DNA. The average cell viability of TF-PEG-NP loading DNA/PLL was about 90%, which meant that TF-PEG-NP appeared to be safer than PLL alone. As a result, TF-PEG-NP loading DNA/PLL could be a more effective non-viral vector for the delivery of pDNA.

A water-soluble cationic chitosan derivative, N,N,N-trimethyl chitosan chloride (TMC), was synthesized and used as a stabilizing reagent for the synthesis of highly stable Au, Ag and Pt nanoparticles in a single-phase of neutral aqueous solution. The morphology and stability of metallic nanoparticles were evaluated by transmission electron microscopy and UV–vis spectroscopy. The results showed that well-dispersed metallic nanoparticles have a spherical morphology with diameters of about 3 ± 0.5 nm. The prepared gold nanoparticles are stable in the aqueous solution (no significant changes in their morphology and size within 10 months) due to repulsion between the charged polymer shell coatings around the metallic nanoparticles. The relatively low affinity of TMC on gold nanoparticles was confirmed by using a ligand exchange experiment. The mechanism stabilizing the chitosan derivative and the neighbouring gold nanoparticles was identified by FTIR, ¹H NMR and ¹³C NMR measurements.

Uniform and square single-crystal InP nanopore arrays have been successfully fabricated on a (100) n-InP surface by a two-step etching method. The characteristic of slow etching rates in four equivalent crystalline (011) facets of (100) n-InP in a mixture of pure HCl and pure H₃PO₄ has been found, which is the main reason for the formation of square single-crystal InP nanopores. The distribution of nanopores can be closely associated with the distribution of carriers in the semiconductor during the electrochemical etching process. An oscillating behaviour of current has been observed, which can probably be attributed to the oscillations in concentration of the electrolyte at the pore tips caused by diffusion of the electrolyte in the nanopore channels.

We propose an approach for silica encapsulation of YV_(0.7)P_(0.3)O₄:Eu³⁺, Bi³⁺ nanophosphors through a microemulsion process. The resulting YV_(0.7)P_(0.3)O₄:Eu³⁺, Bi³⁺@SiO₂ core–shell nanophosphors were characterized by transmission electron microscopy, UV/vis absorption and photoluminescence spectroscopy, energy-dispersive x-ray analysis (EDAX), selected area electron diffraction and zeta-potential measurements. The obtained nanocomposites have quite a uniform spherical shape and diameters of about 15 nm. Zeta-potential measurements show that coated particles are stable at high volume fractions and can endure large variations in pH and electrolyte concentration without coalescence. These core–shell nanophosphors could also be used as ultrasensitive biological labels, because they are obtained in nanoscale and well dispersible in water.

A comprehensive totally aqueous phase synthesis of nickel-nitrilotriacetate (Ni-NTA) modified superparamagnetic Fe₃O₄ nanoparticles is presented. The Fe₃O₄-NTA–Ni nanoparticles are able to perform efficient and specific purification of 6-His tagged proteins from crude cell lysates, as evidenced by sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) and Western blot analysis. The average binding capacity, as demonstrated by streptopain (M_W 42 kDa), is 0.23 mg/mg (protein/Fe₃O₄-NTA–Ni). Considering the high affinity and specificity of the binding between hexahistidine motif and Ni-NTA, Ni-NTA modified nanoparticles could act as a module to carry 6-His tagged proteins on the particle surface with molecular orientation control, since only the 6-His domain could be attached. These modularly designed functional nanoparticles enhance cancer cell targeting, as supported by the in vitro receptor mediated targeting assay using RGD-4C-6-His fusion peptide. The nanoparticles show no significant hemolysis for human blood and could be investigated further for their in vivo functional imaging applications.

The purpose of this study was to demonstrate the magneto-motive ultrasonic detection of superparamagnetic iron oxide (SPIO) nanoparticles as a marker of macrophage recruitment in tissue. The capability of ultrasound to detect SPIO nanoparticles (core diameter ∼20 nm) taken up by murine liver macrophages was investigated. Eight mice were sacrificed two days after the intravenous administration of four SPIO doses (1.5, 1.0, 0.5, and 0.1 mmol Fe/kg body weight). In the iron-laden livers, ultrasound Doppler measurements showed a frequency shift in response to an applied time-varying magnetic field. M-mode scan and colour power Doppler images of the iron-laden livers also demonstrated nanoparticle movement under focused magnetic field excitation. In the livers of two saline injected control mice, no movement was observed using any ultrasound imaging modes. The results of our experiments indicate that ultrasound imaging of magneto-motive excitation is a candidate imaging modality to identify tissue-based macrophages containing SPIO nanoparticles.

This paper presents a novel method for fabricating an ordered array of metallic nanoshells with a controllable shape by a combination of a porous polymer template and a nanocrystal-seeded electroless plating technique. The morphology of hollow particles has a strong dependence on the seed-deposition time onto the surfaces of the original colloidal template. Using this method, ordered Pt nanobowls (bowl-shaped shells) and, alternatively, nanocups (cup-shaped shells) are prepared. These materials show some intriguing properties: (i) reduced symmetry of the building blocks; (ii) a well-ordered structure; and (iii) a high ratio of surface area to volume, all of which are useful in many areas such as catalysts, sensors, and photonic crystals.

We have used an electrochemical selective phase dissolution method to extract nanoprecipitates of the Ni₃Si-type intermetallic phase from two-phase Ni–Si and Ni–Si–Al alloys by dissolving the matrix phase. The extracted nanoparticles are characterized by transmission electron microscopy, energy-dispersive x-ray spectrometry, x-ray powder diffraction, and electron powder diffraction. It is found that the Ni₃Si-type nanoparticles have a core–shell structure. The core maintains the size, the shape, and the crystal structure of the precipitates that existed in the bulk alloys, while the shell is an amorphous phase, containing only Si and O (SiO_x). The shell forms around the precipitates during the extraction process. After annealing the nanoparticles in nitrogen at 700 °C, the tridymite phase recrystallizes within the shell, which remains partially amorphous. In contrast, on annealing in air at 1000 °C, no changes in the composition or the structure of the nanoparticles occur. It is suggested that the shell forms after dealloying of the matrix phase, where Si atoms, the main constituents of the shell, migrate to the surface of the precipitates.

Nanometre-size gold clusters supported on MoS₂(0001) are investigated by means of ultrahigh-vacuum frequency modulation dynamic force microscopy. Topography and frequency shift images are simultaneously obtained using the average tunnelling current to regulate the tip–substrate distance. Two families of clusters are observed, giving different frequency shift images. While the topographic and frequency shift profiles have similar shapes on small clusters (size  nm), they are quite different near the top of large clusters (size  nm): the topographic profile is rounded, but the frequency shift profile exhibits rather steep edges and a depression near the centre of the island. It is demonstrated that these differences result from the finite range of van der Waals forces. On small islands, the frequency shift is dominated by the interaction of the tip with the substrate. On large islands, it is dominated by the interaction with the island. The particular observed shape results from the geometry of the island. These interpretations are comforted by analytical and numerical calculations. In particular, the characteristic shape of the frequency shift profiles on large islands can be reproduced by introducing realistic parameters and considering only the contribution of van der Waals forces.

A simple method is described for the electrostatic assembly of CdS nanoparticles onto oxidized aligned multiwalled carbon nanotubes (MWCNTs) in aqueous solution. The method is convenient to control and allows the formation of a stable, water-soluble suspension of CdS/aligned-MWCNT heterostructures. The prepared CdS/aligned-MWCNT heterostructures are characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), energy dispersive x-ray spectroscopy (EDS), x-ray diffraction (XRD) and Fourier transform infrared spectrometry (FT-IR). The fluorescence and UV absorption spectral properties of the hybrid material demonstrate electron transfer from CdS nanoparticles to aligned-MWCNTs, which implies its potential applications in photovoltaic cells, photocatalysis, and solar energy conversion.

A simple, efficient and quick method has been established for the synthesis of CePO₄:Tb nanorods and CePO₄:Tb/LaPO₄ core/shell nanorods via ultrasound irradiation of inorganic salt aqueous solution under ambient conditions for 2 h. The as-prepared products were characterized by means of powder x-ray diffraction (PXRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectra and lifetimes. TEM micrographs show that all of the as-prepared cerium phosphate products have rod-like shape, and have a relatively high degree of crystallinity and uniformity. HRTEM micrographs and SAED results prove that these nanorods are single crystalline in nature. The emission intensity and lifetime of the CePO₄:Tb/LaPO₄ core/shell nanorods increased significantly with respect to those of CePO₄:Tb core nanorods under the same conditions. A substantial reduction in reaction time as well as reaction temperature is observed compared with the hydrothermal process.

A thermodynamically driven self-organization of microclusters of semiconductor nanocrystals with a narrow size distribution into periodic two-dimensional (2D) arrays is an attractive low-cost technique for the fabrication of 2D photonic crystals. We have found that CdSe/ZnS core/shell quantum dots or quantum rods, transferred in aqueous phase after capping with the bifunctional surface-active agent DL-cysteine, form on a poly-L-lysine coated surface homogeneously sized micro-particles, droplet-like spheroid clusters and hexagon-like colloidal crystals self-organized into millimetre-sized 2D hexagonal assemblies. The presence of an organic molecular layer around the micro-particles prevents immediate contact between them, forming an interstitial space which may be varied in thickness by changing the origin of the molecular layer capping nanocrystals. Due to the high refractive index of CdSe and the low refractive index of the interstitial spaces, these structures are expected to have deep gaps in their photonic band, forming hierarchically ordered 2D arrays of potentially photonic materials.

We have observed nanopattern formation with robust and controllable spatial ordering by laser-induced dewetting in nanoscopic metal films. Pattern evolution in Co film of thickness 1≤h≤8 nm on SiO₂ was achieved under multiple pulse irradiation using a 9 ns pulse laser. Dewetting leads to the formation of cellular patterns which evolve into polygons that eventually break up into nanoparticles with unimodal size distribution and short range ordering in nearest neighbour spacing R. Spatial ordering was attributed to a hydrodynamic thin film instability and resulted in a predictable variation of R and particle diameter D with h. The length scales R and D were found to be independent of the laser energy. These results suggest that spatially ordered metal nanoparticles can be robustly assembled by laser-induced dewetting.

The Sn/Si(111)-() surface is observed by using non-contact atomic force microscopy (NC-AFM) at room temperature. The images at relatively far tip–surface distances show four protrusions in each () unit cell, which are similar to previously reported scanning tunnelling microscopy (STM) images. On the other hand, it is found that, at closer tip–surface distances, eight protrusions are clearly resolved, which indicates that the spatial resolution of NC-AFM is higher than that of STM as far as imaging this surface is concerned. Our high-resolution NC-AFM images are in good agreement with a recently proposed model based on 13 Sn atoms per unit cell.

We examine power dissipation in different clocking schemes for molecular quantum-dot cellular automata (QCA) circuits. 'Landauer clocking' involves the adiabatic transition of a molecular cell from the null state to an active state carrying data. Cell layout creates devices which allow data in cells to interact and thereby perform useful computation. We perform direct solutions of the equation of motion for the system in contact with the thermal environment and see that Landauer's Principle applies: one must dissipate an energy of at least k_BT per bit only when the information is erased. The ideas of Bennett can be applied to keep copies of the bit information by echoing inputs to outputs, thus embedding any logically irreversible circuit in a logically reversible circuit, at the cost of added circuit complexity. A promising alternative which we term 'Bennett clocking' requires only altering the timing of the clocking signals so that bit information is simply held in place by the clock until a computational block is complete, then erased in the reverse order of computation. This approach results in ultralow power dissipation without additional circuit complexity. These results offer a concrete example in which to consider recent claims regarding the fundamental limits of binary logic scaling.

In order to explore the fundamental properties of one-dimensional nanostructured high-temperature superconductors and enhance their promising applications, a universal and general method for the synthesis of high-quality YBa₂Cu₃O_7−δ (YBCO) nanowire arrays is developed, which involves the combination of a novel sol–gel process to lower the crystallization temperature of YBCO, and porous anodic alumina (PAA) as an effective morphology-directing hard template. Field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) results indicate that the as-prepared YBCO nanowires have average diameters of about 50 nm and lengths up to several microns. The structures of the samples were analysed by x-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), energy-dispersive x-ray spectroscopy (EDX) and inductively coupled plasma (ICP) analysis, which indicate that the nanowires are well crystallized with orthorhombic YBCO-123 structure. The magnetization measurement under zero-field-cooled (ZFC) mode indicates that the superconducting transition temperature (T_c) of the nanowires is about 92 K, which is in agreement with that of a bulk YBCO sample.

In order to gain a better thermodynamic understanding of the phase diagram of alloying nanoparticles, we establish a size-dependent solid solubility model of binary metallic systems to elucidate the anomalous solid solubility in nanometre-sized alloying particles. It is found that a diameter of 20 nm seems a threshold value of the size of alloying nanoparticles for the unusual solid solubility, i.e. the solubility is greatly promoted with decreasing grain size when the size of alloying nanoparticles is less than 20 nm. Taking the Pb–Sn system as an example, we show that the theoretical predictions are consistent with experimental data.

We show that aqueous dispersions of single-walled carbon nanotubes (SWNTs), prepared with the aid of nucleic acids (NAs) such as RNA or DNA, can be separated into fractions using agarose gel electrophoresis. In a DC electric field, SWNT/NA complexes migrate in the gel in the direction of positive potential to form well-defined bands. Raman spectroscopy as a function of band position shows that nanotubes having different spectroscopic properties possess different electrophoretic mobilities. The migration patterns for SWNT/RNA and SWNT/DNA complexes differ. Parallel elution of the SWNT/NA complexes from the gel during electrophoresis and subsequent characterization by AFM reveals differences in nanotube diameter, length and curvature. The results suggest that fractionation of nanotubes can be achieved by this procedure. We discuss factors affecting the mobility of the nanotube complexes and propose analytical applications of this technique.

FePtMn nanoparticles with a narrow size distribution and an average diameter of 3 nm were synthesized by the chemical reduction of Fe(acac)₃ and Pt(acac)₂ by NaBH₄ and the thermal decomposition of Mn₂(CO)₁₀ in phenyl ether. The as-made nanoparticles have a disordered face-centred cubic (fcc) structure, which transformed after thermal treatment at 650 °C to an ordered face-centred tetragonal (fct) structure, possessing coercivity values up to 13.7 kOe at room temperature. The coercivity of the annealed samples depends on the amount of Mn added to the reaction mixture, with the coercive field increasing significantly with the partial substitution of Pt by Mn, while the partial substitution of Fe by Mn does not affect the magnetic properties strongly.

Linear and nonlinear optical properties of periodic triangular Au nanoparticle arrays were investigated. We compared the optical nonlinearity of periodic Au nanoparticle arrays with that of the ultra-thin gold film consisting of randomly distributed spheroidal clusters. A pronounced enhancement of the third-order nonlinear optical susceptibility χ⁽³⁾ in Au arrays was observed, and the figure of merit, χ⁽³⁾/α, of the periodic nanoparticle arrays is one order of magnitude larger than that of the ultra-thin film. Such an enhancement of the optical nonlinearity could be due to the strong local field near the triangular nanoparticles.

We report the synthesis of sphere-like α-Ni(OH)₂ nanoarchitecture by self-assembly with the aid of hexamethylenetetramine (HMT). The α-Ni(OH)₂ nanoarchitectures, with a diameter of several micrometres, are composed of many nanoflakelets about 10 nm in thickness. The influences of the reaction temperature, time, reagent, nickel salt and pH value on the morphology and structure of the α-Ni(OH)₂ were studied, the chemical and thermal stability are discussed, and the formation mechanism is proposed. The α-Ni(OH)₂ nanoarchitectures display a good electrochemical capacity.