Table of contents

A multifunctional 'all-in-one' nanocomposite is fabricated using a colloid, template and surface-modification method. This material encompasses magnetic induced target delivery, cell uptake promotion and controlled drug release in one system. The nanocomposite is characterized by scanning electron microscopy, transmission electron microscopy, x-ray diffraction, N₂ adsorption and vibrating sample magnetometry. The prepared material has a diameter of 350–400 nm, a high surface area of 420.29 m² g ^{− 1}, a pore size of 1.91 nm and a saturation magnetization of 32 emu g ^{− 1}. Doxorubicin (DOX) is loaded in mesopores and acid-sensitive blockers are introduced onto the orifices of the mesopores by a Schiff base linker to implement pH-dependent self-release. Folate was also introduced to improve DOX targeted delivery and endocytosis. The linkers remained intact to block pores with ferrocene valves and inhibit the diffusion of DOX at neutral pH. However, in lysosomes of cancer cells, which have a weak acidic pH, hydrolysis of the Schiff base group removes the nanovalves and allows the trapped DOX to be released. These processes are demonstrated by UV–visible absorption spectra, confocal fluorescence microscopy images and methyl thiazolyl tetrazolium assays in vitro, which suggest that the smart nanocomposite successfully integrates targeted drug delivery with internal stimulus induced self-release and is a potentially useful material for nanobiomedicine.

Effective formulations of hydrophobic drugs for cancer therapies are challenging. To address this issue, we have sought to nanoscale artificial oil bodies (NOBs) as an alternative. NOBs are lipid-based particles which consist of a central oil space surrounded by a monolayer of oleosin (Ole)-embedded phospholipids (PLs). Ole was first fused with the anti-HER2/neu affibody (Ole–ZH2), and the resulting hybrid protein was overproduced in Escherichia coli. ZH2-displayed NOBs were then assembled by sonicating the mixture containing plant oil, PLs, and isolated Ole–ZH2 in one step. To illustrate their usefulness, functionalized NOBs were employed to encapsulate a hydrophobic anticancer drug, Camptothecin (CPT). As a result, these CPT-loaded NOBs remained stable in serum and the release of CPT at the non-permissive condition exhibited a sustained and prolonged profile. Moreover, plain NOBs were biocompatible whereas CPT-loaded NOBs exerted a strong cytotoxic effect on HER2/neu-positive cells in vitro. Administration of xenograft nude mice with CPT-loaded NOBs also led to the regression of solid tumors in an effective way. Overall, the result indicates the potential of NOBs for targeted delivery of hydrophobic drugs.

Lymphatic metastasis can be greatly promoted by metastases growth and lymphangiogenesis in lymph nodes (LNs). LyP-1, a cyclic peptide, is able to specifically bind with tumor cells and tumor lymphatics in metastatic LNs. This work aimed to use LyP-1-conjugated liposomes (L-LS) loaded with doxorubicin (DOX) (L-LS/DOX) to suppress lymphatic metastasis by inhibiting both metastases and tumor lymphatics in LNs. L-LS were prepared and exhibited sizes around 90 nm and spherical morphology as characterized by transmission electron microscopy. The in vitro cellular studies showed that LyP-1 modification obviously increased liposome uptake by MDA-MB-435 tumor cells and enhanced the cytotoxicity of liposomal DOX. A popliteal and iliac LN metastases model was successfully established by subcutaneous inoculation of tumor cells to nude mice. The immunofluorescence staining analysis indicated that LyP-1 modification enabled specific binding of liposome with tumor lymphatics and enhanced the destroying effect of liposomal DOX on tumor lymphatics. The in vivo fluorescence imaging and pharmacodynamic studies showed that LyP-1 modification increased liposome uptake by metastatic LNs and that L-LS/DOX significantly decreased metastatic LN growth and LN metastasis rate. These results suggested that L-LS/DOX were an effective delivery system for suppressing lymphatic metastasis by simultaneously inhibiting LN metastases and tumor lymphatics.

The extensive use of silver nanoparticles needs a synthesis process that is greener without compromising their properties. The present study describes a novel green synthesis of silver nanoparticles using Guava (Psidium guajava) leaf extract. In order to compare with the conventionally synthesized ones, we also prepared Ag-NPs by chemical reduction. Their optical and morphological characteristics were thoroughly investigated and tested for their antibacterial properties on Escherichia coli. The green synthesized silver nanoparticles showed better antibacterial properties than their chemical counterparts even though there was not much difference between their morphologies. Fourier transform infrared (FTIR) spectroscopic analysis of the used extract and as-synthesized silver nanoparticles suggests the possible reduction of Ag ⁺ by the water-soluble ingredients of the guava leaf like tannins, eugenol and flavonoids. The possible reaction mechanism for the reduction of Ag ⁺ has been proposed and discussed. The time-dependent electron micrographs and the simulation studies indicated that a physical interaction between the silver nanoparticles and the bacterial cell membrane may be responsible for this effect. Based on the findings, it seems very reasonable to believe that this greener way of synthesizing silver nanoparticles is not just an environmentally viable technique but it also opens up scope to improve their antibacterial properties.

As applications of nanoparticles in medical imaging and biomedicine rapidly expand, the interactions of nanoparticles with living cells have become an area of active interest. For example, intracellular accumulation of nanoparticles—an important part of cell–nanoparticle interaction—has been well studied using plasmonic nanoparticles and optical or optics-based techniques due to the change in optical properties of the nanoparticle aggregates. However, magnetic nanoparticles, despite their wide range of clinical applications, do not exhibit plasmonic-resonant properties and therefore their intracellular aggregation cannot be detected by optics-based imaging techniques. In this study, we investigated the feasibility of a novel imaging technique—pulsed magneto-motive ultrasound (pMMUS)—to identify intracellular accumulation of endocytosed magnetic nanoparticles. In pMMUS imaging a focused, high intensity, pulsed magnetic field is used to excite the cells labeled with magnetic nanoparticles, and ultrasound imaging is then used to monitor the mechanical response of the tissue. We demonstrated previously that clusters of magnetic nanoparticles amplify the pMMUS signal in comparison to the signal from individual nanoparticles. Here we further demonstrate that pMMUS imaging can identify interaction between magnetic nanoparticles and living cells, i.e. intracellular accumulation of nanoparticles within the cells. The results of our study suggest that pMMUS imaging can not only detect the presence of magnetic nanoparticles but also provides information about their intracellular accumulation non-invasively and in real-time.

We report the fabrication and electron transport investigation of individual local-gated single-walled carbon nanotube field effect transistors (SWNT-FET) with high yield using a semiconducting-rich carbon nanotube solution. The individual semiconducting nanotubes were assembled at the selected position of the circuit via dielectrophoresis. Detailed electron transport investigations on 70 devices show that 99% display good FET behavior, with an average threshold voltage of 1 V, subthreshold swing as low as 140 mV/dec, and on/off current ratio as high as 8 × 10⁵. The high yield directed assembly of local-gated SWNT-FET will facilitate large scale fabrication of CMOS (complementary metal–oxide–semiconductor) compatible nanoelectronic devices.

We propose an experimental-based tool for dealing with fluorescence modulation close to nanoparticles for application in studies of fluorophores in the vicinity of gold nanoparticles (AuNPs), typically addressed via theoretical models. We performed a photophysical characterization of fluorophores in the vicinity of AuNPs, showing that correct Φ_F determination suffers from a local pH effect, and address the observed radiative enhancement. Our approach is based on the experimental assurance that the reference fluorophores are in the same optical conditions as those of the AuNP–fluorophore conjugates. We demonstrate the relevance for introducing corrections for the inner filter effect and the reabsorption of the emitted light caused by AuNPs. The proposed approach could circumvent the need for theoretical based corrections and allow for more accurate determination of fluorescence emission in the vicinity of gold nanoparticles.

We fabricated graphene pnp devices, by embedding pre-defined local gates in an oxidized surface layer of a silicon substrate. With neither deposition of dielectric material on the graphene nor electron-beam irradiation, we obtained high-quality graphene pnp devices without degradation of the carrier mobility even in the local-gate region. The corresponding increased mean free path leads to the observation of ballistic and phase-coherent transport across a local gate 130 nm wide, which is about an order of magnitude wider than reported previously. Furthermore, in our scheme, we demonstrated independent control of the carrier density in the local-gate region, with a conductance map very much distinct from those of top-gated devices. This was caused by the electric field arising from the global back gate being strongly screened by the embedded local gate. Our scheme allows the realization of ideal multipolar graphene junctions with ballistic carrier transport.

We construct a flexible pn heterostructured photodiode using a CdTe nanoparticle thin film and a single ZnO nanowire (NW) on a plastic substrate. The photocurrent characteristics of the flexible photodiode are examined under illumination with 325 nm wavelength light and the photocurrent efficiencies at bias voltages of ± 2.5 V are estimated to be 8.0 and 2.1 µA W ^{− 1} under forward and reverse bias conditions, respectively. The photocurrent generation of the pn heterostructured photodiode is dominantly associated with the transport of the photogenerated charge carriers in the single ZnO NW. Furthermore, the operations of our flexible photodiode are investigated in the upwardly and downwardly bent states, as well as in the flat state.

Highly ordered ZnO nanoboxes and nanowire structures with a width of ∼ 20 nm have been successfully fabricated by the combination of nanoimprint lithography and pulsed laser deposition utilizing a glancing angle deposition (GLAD) technique. The periodicity, size, and shape of the ZnO nanoboxes and nanobelts can be easily controlled over a large area by changing the molds and deposition conditions. At the initial stage of growth by GLAD, nanonucleation led to nanopillar structures, which agglomerated to form nanobox and nanobelt structures at room temperature (RT). The ZnO nanostructures have a c-axis orientation along the nanopillar direction after postannealing and exhibit an intense cathodoluminescence peak around 380 nm at RT.

This paper describes the preparation of nanoparticles composed of a magnetic core surrounded by two successive silica shells embedding two fluorophores, showing uniform nanoparticle size (50–60 nm in diameter) and shape, which allow ratiometric pH measurements in the pH range 5–8. Uncoated iron oxide magnetic nanoparticles (∼10 nm in diameter) were formed by the coprecipitation reaction of ferrous and ferric salts. Then, they were added to a water-in-oil microemulsion where the hydrophilic silica shells were obtained through hydrolysis and condensation of tetraethoxyorthosilicate together with the corresponding silylated dye derivatives—a sulforhodamine was embedded in the inner silica shell and used as the reference dye while a pH-sensitive fluorescein was incorporated in the outer shell as the pH indicator. The magnetic nanoparticles were characterized using vibrating sample magnetometry, dynamic light scattering, transmission electron microscopy, x-ray diffraction and Fourier transform infrared spectroscopy. The relationship between the analytical parameter, that is, the ratio of fluorescence between the sensing and reference dyes versus the pH was adjusted to a sigmoidal fit using a Boltzmann type equation giving an apparent pK_a value of 6.8. The fluorescence intensity of the reference dye did not change significantly (∼3.0%) on modifying the pH of the nanoparticle dispersion. Finally, the proposed method was statistically validated against a reference procedure using samples of water and physiological buffer with 2% of horse serum, indicating that there are no significant statistical differences at a 95% confidence level.

Nanoporous alumina (PA) arrays produced by self-ordering growth, using electrochemical anodization, have been extensively explored for potential applications based upon the unique thermal, mechanical and structural properties, and high surface-to-volume ratio of these materials. However, the potential applications and functionality of these materials may be further extended by molecular-level engineering of the surface of the pore rims. In this paper we present a method for the generation of chemical gradients on the surface of PA arrays based upon plasma co-polymerization of two monomers. We further extend these chemical gradients, which are also gradients of surface charge, to those of bound ligands and number density gradients of nanoparticles. The latter represent a highly exotic new class of materials, comprising aligned PA, capped by gold nanoparticles around the rim of the pores. Gradients of chemistry, ligands and nanoparticles generated by our method retain the porous structure of the substrate, which is important in applications that take advantage of the inherent properties of these materials. This method can be readily extended to other porous materials.

A facile electroless plating procedure for the controlled synthesis of nanoscale silver thin films and derived structures such as silver nanotubes was developed and the products were characterized by SEM, TEM and EDS. The highly stable plating baths consist of AgNO₃ as the metal source, a suitable ligand and tartrate as an environmentally benign reducing agent. Next to the variation of the coordinative environment of the oxidizing component, the influence of the pH value was evaluated. These two governing factors strongly affect the plating rate and the morphology of the developing silver nanoparticle films and can be used to adapt the reaction to synthetic demands. The refined electroless deposition allows the fabrication of homogeneous high aspect-ratio nanotubes in ion track etched polycarbonate. Template-embedded metal nanotubes can be interpreted as parallelled microreactors. Following this concept, both the silver nanotubes and spongy gold nanotubes obtained by the use of the silver structures as sacrificial templates were applied in the reduction of 4-nitrophenol by sodium borohydride, proving to be extraordinarily effective catalysts.

ZnO/SiO₂ core/shell particles were fabricated by successive coating of multilayer polyelectrolytes and then a SiO₂ shell onto ZnO particles. The as-prepared ZnO/SiO₂ core/shell particles were coated on poly(ethylene terephthalate) (PET) textiles, followed by hydrophobization with hexadecyltrimethoxysilane, to fabricate superhydrophobic surfaces with UV-shielding properties. Transmission electron microscopy and ζ potential analysis were employed to evidence the fabrication of ZnO/SiO₂ core/shell particles. Scanning electron microscopy and thermal gravimetric analysis were conducted to investigate the surface morphologies of the textile and the coating of the fibers. Ultraviolet–visible spectrophotometry and contact angle measurement indicated that the incorporation of ZnO onto fibers imparted UV-blocking properties to the textile surface, while the coating of SiO₂ shell on ZnO prohibited the photocatalytic degradation of hexadecyltrimethoxysilane by ZnO, making the as-treated PET textile surface show stable superhydrophobicity with good UV-shielding properties.

We report on the growth of AlGaInP quantum dots (QDs) with Al contents between 0% and 10% on GaP substrate by gas-source molecular beam epitaxy and the investigation of their morphological and low temperature photoluminescence properties. These high areal density QDs show short wavelength emission between 575 and 612 nm depending on their composition. The authors interpret the QD emission as originating from indirect type-II transitions. This interpretation is supported by a single-band effective-mass model, which allows us to describe the role of differing barrier composition in the QD emission. Time-resolved photoluminescence measurements are performed and discussed with respect to the calculations.

Channeling-enhanced electron energy-loss spectroscopy is applied to determine the polarity of ultra-small nitride semiconductor nanocolumns in transmission electron microscopy. The technique demonstrates some practical advantages in the nanostructure analysis, especially for feature sizes of less than 50 nm. We have studied GaN and (Al, Ga)N nanocolumns grown in a self-assembled way by molecular beam epitaxy directly on bare Si(111) substrates and on AlN buffer layers, respectively. The GaN nanocolumns on Si show an N polarity, while the (Al, Ga)N nanocolumns on an AlN buffer exhibit a Ga polarity. The different polarities of nanocolumns grown in a similar procedure are interpreted in terms of the specific interface bonding configurations. Our investigation contributes to the understanding of polarity control in III-nitride nanocolumn growth.

Achieving red emission from ZnO-based materials has long been a goal for researchers in order to realize, for instance, full-color display panels and solid-state light-emitting devices. However, the current technique using Eu^{3 +} doped ZnO for red emission generation has a significant drawback in that the energy transfer from ZnO to Eu^{3 +} is inefficient, resulting in a low intensity red emission. In this paper, we report an efficient energy transfer scheme for enhanced red emission from Eu^{3 +} doped ZnO nanocrystals by fabricating polymer nanofibers embedded with Eu^{3 +} doped ZnO nanocrystals to facilitate the energy transfer. In the fabrication, ZnO nanocrystals are uniformly dispersed in polymer nanofibers prepared by the high electrical field electrospinning technique. Enhanced red emission without defect radiation from the ZnO matrix is observed. Three physical mechanisms for this observation are provided and explained, namely a small ZnO crystal size, uniformity distribution of ZnO nanocrystals in polymers (PVA in this case), and strong bonding between ZnO and polymer through the –OH group bonding. These explanations are supported by high resolution transmission emission microscopy measurements, resonant Raman scattering characterizations, photoluminescence spectra and photoluminescence excitation spectra measurements. In addition, two models exploring the 'accumulation layer' and 'depletion layer' are developed to explain the reasons for the more efficient energy transfer in our ZnO nanocrystal system compared to that in the previous reports. This study provides an important approach to achieve enhanced energy transfer from nanocrystals to ions which could be widely adopted in rare earth ion doped materials. These discoveries also provide more insights into other energy transfer problems in, for example, dye-sensitized solar cells and quantum dot solar cells.

A simple, reliable and potentially cost-effective composite film casting procedure is presented using the evaporation of solvent (water) from a dilute mixture of multiwalled carbon nanotubes (MWCNTs) and polyethylene oxide (PEO) polymer. It is found that the fabrication method develops excellent dispersion of MWCNTs in PEO confirmed by morphology observations, final crystallinity of polymer (amorphous) and a lower percolation threshold (closer to theoretical value) as well as higher electrical conductivity. A film thickness prediction model is derived based upon the fact that final film thickness is mainly dependent upon the dimensions of the casting mold and the loading of the MWCNTs and polymer. This simple model provides important insight that the material loss and the actual density of the base polymer are critical factors making the current casting method truly cost effective and controlling final thickness.

The properties of Cu-doped TiO₂ nanoparticles (NPs) were independently controlled in a flame aerosol reactor by varying the molar feed ratios of the precursors, and by optimizing temperature and time history in the flame. The effect of the physico-chemical properties (dopant concentration, crystal phase and particle size) of Cu-doped TiO₂ nanoparticles on inactivation of Mycobacterium smegmatis (a model pathogenic bacterium) was investigated under three light conditions (complete dark, fluorescent light and UV light). The survival rate of M. smegmatis (in a minimal salt medium for 2 h) exposed to the NPs varied depending on the light irradiation conditions as well as the dopant concentrations.

In dark conditions, pristine TiO₂ showed insignificant microbial inactivation, but inactivation increased with increasing dopant concentration. Under fluorescent light illumination, no significant effect was observed for TiO₂. However, when TiO₂ was doped with copper, inactivation increased with dopant concentration, reaching more than 90% (>3 wt% dopant). Enhanced microbial inactivation by TiO₂ NPs was observed only under UV light. When TiO₂ NPs were doped with copper, their inactivation potential was promoted and the UV-resistant cells were reduced by over 99%. In addition, the microbial inactivation potential of NPs was also crystal-phase-and size-dependent under all three light conditions. A lower ratio of anatase phase and smaller sizes of Cu-doped TiO₂ NPs resulted in decreased bacterial survival. The increased inactivation potential of doped TiO₂ NPs is possibly due to both enhanced photocatalytic reactions and leached copper ions.

We show that hydrogen titanate (H₂Ti₃O₇) nanotubes form strongly associated reversible nano-bio-conjugates with the vital respiratory protein, cytochrome c. Resonance Raman spectroscopy along with direct electrochemical studies indicate that in this nano-bio-conjugate, cytochrome c exists in an equilibrium of two conformational states with distinctly different formal redox potentials and coordination geometries of the heme center. The nanotube-conjugated cytochrome c also showed enhanced peroxidase activity similar to the membrane-bound protein that is believed to be an apoptosis initiator. This suggests that such a nanotube–cytochrome c conjugate may be a good candidate for cancer therapy applications.

Single-walled carbon nanotubes (SWCNTs) have been incorporated into a (Pb, Zn)—phosphate glass host by a melt-quenching technique. Studies of the optical and electronic properties show that the nanotubes in the composite have suffered conformational deformations and attained a band structure of quasimetallic type, making the composite a good electrical conductor. Possible strains in the nanotubes of the composite such as radial compression, torsion and bending have been considered and their role in modulating the band structures has been analyzed by judging the change in band gap energies (ΔE) of the deformed SWCNTs using an equation which is based on the π-electron tight binding model. The effect of σ^*–π^* hybridization due to the radial compression in generating the metallicity is also discussed. The carrier transport in the composite above room temperature has been shown to be dominated by fluctuation induced tunneling.