Table of contents

This special issue of Nanotechnology contains research papers contributed by the participants of the Fourth Topical Conference on Nanoscale Science and Engineering at the Annual Meeting of the American Institute of Chemical Engineers (AIChE), which was held in Austin, Texas, USA, 7–12 November, 2004. This conference saw 284 oral presentations from institutions around the world, which is the highest number for this topical conference series to date. These presentations were organized into 64 sessions, covering the range of nanotechnology subject areas in which chemical engineers are currently engaged. These sessions included the following areas.

• Fundamentals: thermodynamics at the nanoscale; applications of nanostructured fluids; transport properties in nanophase and nanoscale systems; molecular modelling methods; self and directed assembly at the nanoscale; nanofabrication and nanoscale processing; manipulation of nanophases by external fields; nanoscale systems; adsorption and transport in carbon nanotubes; nanotribology; making the transition from materials and phenomena to new technologies; operation of micro-and nano-systems. • Materials: nanoparticle synthesis and stabilization; nanoscale structure in polymers; nanotemplating of polymers; synthesis of carbon nanotubes and nanotube-based materials; nanowires; nanoparticle assemblies and superlattices; nanoelectronic materials; self-assembly of templated inorganic materials; nanostructured hybrid organic/inorganic materials; gas phase synthesis of nanoparticles; multicomponent structured particles; nano energetic materials; liquid-phase synthesis of nanoparticles. • Energy: synthesis and characterization of nanostructured catalytic materials; nanomaterials and devices for energy applications. • Biotechnology: nanobiotechnology; nanotechnology for the biotechnology and pharmaceuticals industries; nanotechnology and nanobiotechnology for sensors; advances in biomaterials, bionanotechnology, biomimetic systems and tissue engineering; nanotechnology for drug delivery and imaging; bionanotechnology in cancer and cardiovascular disease; nanostructured biomaterials; nanotechnology in bioengineering; nanofabrication of biosensing devices.

We are pleased to present a selection of research papers in this special issue of Nanotechnology on behalf of the Nanoscale Science and Engineering Forum (NSEF). NSEF was established in 2001 as a new division of AIChE to promote nanotechnology efforts in chemical engineering. The chemical engineering discipline deals with the production and processing of chemicals and materials, and does so through a fundamental understanding of the core issues of transport, thermodynamics, and kinetics that exist at multiple length scales. Thus, it should come as no surprise that chemical engineers have been pursuing nanotechnology research for the last fifty years. For example, fuel production has benefited immensely from improved catalysts in which their pore structure is controlled with nanoscale precision, and polymer properties have been improved by controlling the polymer supramolecular structure at the nanometre scale. Chemical engineering will continue to make important contributions to nanotechnology, and will play a critical role in the transition from basic science and engineering research to commercial applications.

We would like to thank all of the authors who contributed to this special issue; the three NSEF poster presentation award winners for their papers (Sureshkumar, Sunkara, and Rinaldi groups); Dr Nina Couzin, Publisher of Nanotechnology, for her support and enthusiasm for this project; Drs Sharon Glotzer and Dan Coy who chaired the topical conference; and Drs Meyya Meyyappan and Brett Cruden (NASA Ames Research Center) for their assistance in the initial planning stages. We also take this opportunity to thank the many people and organizations who have supported the 2004 topical conference along the way, which include all the session chairs, Hyperion Catalysis International, Inc., Nanophase Technologies, Inc., and the executive board of the NSEF.

A two-dimensional computational model is developed to describe electrochemical nanostructuring of conducting materials with ultrashort voltage pulses. The model consists of (1) a transient charging simulation to describe the evolution of the overpotentials at the tool and workpiece surfaces and the resulting dissolution currents and (2) a feature profile evolution tool which uses the level set method to describe either vertical or lateral etching of the workpiece. Results presented include transient currents at different separations between tool and workpiece, evolution of overpotentials and dissolution currents as a function of position along the workpiece, and etch profiles as a function of pulse duration.

Nucleic acid engineers have created nanoscale fluorescent labels that are uniquely identifiable by the number of conjugated fluorophores, and with binding characteristics that permit recognition of individual specific biomolecules. The viability of this technology for use in multi-analyte homogeneous assays depends on the ability to optically detect individual labels, and distinguish the fluorescence emission of each label. We describe the use of fluidic channels with submicrometre dimensions to rapidly detect individual labels in solution. Labels with small differences in fluorophore composition were differentiated with varying degrees of accuracy. Labels were synthesized at the molecular level from dendrimer-like DNA, with the identity encoded into the number of Alexa Fluor 488 and BODIPY 630/650 fluorophores conjugated with the structure. To explore the decoding resolution limit, labels with a single fluorophore of each colour were detected, and were found to be distinguishable as a group, but not individually, from labels with one additional red fluorophore. Labels with one green and three red fluorophores were individually distinguishable with greater than 80% accuracy from labels with one red and three green fluorophores. Photon counting histograms were analysed to differentiate the various labels, and fluorescence correlation spectroscopy was used to measure their mobilities. Fluidic channels were fabricated in fused silica with a 500 nm square cross section, resulting in a focal volume of approximately 500 al. Because the entire channel width was illuminated, every fluorescent molecule in solution passing through the channel was uniformly excited and analyzed. Flow control enabled a balance of rapid data acquisition and efficient fluorescence collection with these nanoscale systems.

We report a method to fabricate high-quality patterned magnetic dot arrays using block copolymer lithography, metal deposition, and a dry lift-off technique. Long-range order of cylindrical domains oriented perpendicular to the substrate and in hexagonal arrays was induced in the block copolymer films by prepatterning the substrate with topographic features and chemically modifying the surface to exhibit neutral wetting behaviour towards the blocks of the copolymer. The uniformity of the domain size and row spacing of block copolymer templates created in this way was improved compared to those reported in previous studies that used graphoepitaxy of sphere-forming block copolymers. The pattern of block copolymer domains was transferred to a pattern of magnetic metal dots, demonstrating the potential of this technology for the fabrication of patterned magnetic recording media.

Simulations of material architectures in polymer–liquid crystal blends driven by phase separation–phase ordering–texturing processes are presented. The study shows that mixtures of polymers and liquid crystals result in blend morphologies that organize at several scales. For thermally driven instabilities, morphologies of polymer droplets embedded in a liquid crystal matrix show colloidal crystallinity. Large polymer drops strongly affect the orientation of the matrix, producing textures consisting of defect lattices. This work shows that thermally driven phase separation–phase ordering–texturing processes can result in multiscale materials, with length scales cascading down from droplets to interfaces, and finally to nanoscale defects.

This paper presents a simple approach for forming anti-reflective film stacks on plastic substrates employing aqueous colloidal dispersions of metal oxide nanoparticles. Results demonstrate that it is possible to fabricate a polymeric thin film of continuously tunable refractive index over a wide range by loading the film with varying concentrations of metal oxide nanoparticles. Specifically, the refractive index for the polymer film was tuned from 1.46 to 1.54 using silica nanoparticle loadings from 50 to 0 wt% and from 1.54 to 1.95 using ceria nanoparticle loadings from 0 to 90 wt%, respectively. The low and high refractive index layers are then combined to create an anti-reflective coating which exhibits a reflectance spectrum, abrasion resistance, haze and transmission values that compare well with those produced using state-of-the-art vacuum based techniques. Furthermore, the results show that it is possible to begin with aqueous dispersions and then dilute them with organic solvents for use in a spin coating method to prepare the polymer–metal oxide nanoparticle composite films.

Gold nanoparticles with an average diameter in the range 5–20 nm have been synthesized from hydrogen tetrachloroaureate (III) hydrate (HAuCl₄·3H₂O) in air-saturated aqueous PEO–PPO–PEO block copolymer solutions at ambient temperature in the absence of any other reducing agent (PEO: poly(ethylene oxide), PPO: poly(propylene oxide)). The particle size was controlled by the block copolymer concentration and PEO and PPO block lengths. Our findings indicate that longer PEO blocks lead to an increase in particle size because of an increase in reaction activity. Adsorption of PO segments on gold nanoparticles seems to prevent particle growth from aggregation, and results in small particle size and high colloidal stability. An increase of the HAuCl₄ concentration causes a change in the particle shape from spherical to triangular or hexagonal nanoplates.

The size distributions of nanoparticles in flames are measured using a novel particle mass spectrometer (PMS), which is developed for the size range between 0.3 and 50 nm and for number concentrations between 10⁹ and 10¹³. Using this instrument the particles are sampled without prior dilution from the flame into a molecular beam. The charged nanoparticles are then deflected by an electric field, to determine the mass according to the time-of-flight principle. The PMS is installed in a low pressure combustion chamber operated at 30 mbar. Measurements are made on primary soot particles and iron oxide particles in a laminar, premixed acetylene/oxygen flame. The soot particles increase in size as a function of the height above the burner and the C/O ratio from 2 up to 10 nm. Iron oxide particles of 3–5 nm are detected as a function of burner height. The soot particles form more rapidly than the iron oxide particles. A model calculation for the formation of silica and iron oxide in hydrogen/oxygen flames is developed, based on previously published reaction mechanisms. On adding a mono-disperse particle coagulation scheme, the time history of the particle number concentration and the particle size is calculated. In agreement with experimental data, the calculations show that iron oxide particles are formed more slowly than silica particles.

In this paper, we report a synthesis strategy for a new class of hollow, curved carbon morphologies, 'carbon microtubes' (CMTs), with absolute control over their conical angles and internal diameters. Our synthesis methodology employs nitrogen or oxygen dosing to change the wetting behaviour of gallium metal with the growing carbon walls to tune the conical angles. Increasing N₂ concentrations in the gas phase during growth increases the conical angles of CMTs from +25° to about −20°. A methodology using the timing of oxygen or nitrogen dosing during CMT growth is shown to tune the internal diameters anywhere from a few nanometres to a few microns. The walls of the carbon microtubes are characterized using transmission electron microscopy (TEM) and Raman spectroscopy and are found to consist of aligned graphite nanocrystals (2–5 nm in size). Furthermore, dark field images of CMTs showed that the graphite nanocrystals are aligned with their c-axes perpendicular to the wall surface and that the crystals themselves are oriented with respect to the wall surface depending upon the conical angle of the CMT.

A simple, direct synthesis method was used to grow core–shell SiC–SiO₂ nanowires by heating NiO-catalysed silicon substrates. A carbothermal reduction of WO₃ provided a reductive environment and carbon source to synthesize crystalline SiC nanowires covered with SiO₂ sheaths at the growth temperature of 1000–1100 °C. Transmission electron microscopy showed that the SiC core was 15–25 nm in diameter and the SiO₂ shell layer was an average of 20 nm in thickness. The thickness of the SiO₂ shell layer could be controlled using hydrofluoric acid (HF) etching. Field emission results of core–shell SiC–SiO₂ and bare SiC nanowires showed that the SiC nanowires coated with an optimum SiO₂ thickness (10 nm) have a higher field emission current than the bare SiC nanowires.

Primary zirconia nanoparticles were conformally coated with alumina ultrathin films using atomic layer deposition (ALD) in a fluidized bed reactor. Alternating doses of trimethylaluminium and water vapour were performed to deposit Al₂O₃ nanolayers on the surface of 26 nm zirconia nanoparticles. Transmission Fourier transform infrared spectroscopy was performed ex situ. Bulk Al₂O₃ vibrational modes were observed for coated particles after 50 and 70 cycles. Coated nanoparticles were also examined with transmission electron microscopy, high-resolution field emission scanning electron microscopy and energy dispersive spectroscopy. Analysis revealed highly conformal and uniform alumina nanofilms throughout the surface of zirconia nanoparticles. The particle size distribution and surface area of the nanoparticles are not affected by the coating process. Primary nanoparticles are coated individually despite their high aggregation tendency during fluidization. The dynamic aggregation behaviour of zirconia nanoparticles in the fluidized bed plays a key role in the individual coating of nanoparticles.

We have developed a unique approach for the fabrication of enzyme aggregate coatings on the surfaces of electrospun polymer nanofibres. This approach employs covalent attachment of seed enzymes onto nanofibres consisting of a mixture of polystyrene and poly(styrene-co-maleic anhydride), followed by a glutaraldehyde (GA) treatment that cross-links additional enzyme molecules and aggregates from the solution onto the covalently attached seed enzyme molecules. These cross-linked enzyme aggregates, covalently attached to the nanofibres via the linkers of seed enzyme molecules, are expected to improve the enzyme activity due to increased enzyme loading, and also the enzyme stability. To demonstrate the principle, we coated α-chymotrypsin (CT) on nanofibres electrospun from a mixture of polystyrene and poly(styrene-co-maleic anhydride). The initial activity of CT-aggregate-coated nanofibres was nine times higher than nanofibres with just a layer of covalently attached CT molecules. The enzyme stability of CT-aggregate-coated nanofibres was greatly improved with essentially no measurable loss of activity over a month of observation under rigorous shaking conditions. This new approach of enzyme coating on nanofibres, yielding high activity and stability, creates a useful new biocatalytic immobilized enzyme system with potential applications in bioconversion, bioremediation, and biosensors.

Germanium nanocrystals were synthesized in supercritical (sc) CO₂ by thermolysis of diphenylgermane (DPG) or tetraethylgermane (TEG) with octanol as a capping ligand at 500 °C and 27.6 MPa. The Ge nanocrystals were characterized with high resolution transmission electron microscopy (HRTEM), energy-dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD). On the basis of TEM, the mean diameters of the nanocrystals made from DPG and TEG were 10.1 and 5.6 nm, respectively. The synthesis in sc-CO₂ produced much less organic contamination compared with similar reactions in organic supercritical fluids. When the same reaction of DPG with octanol was performed in the gas phase without CO₂ present, bulk Ge crystals were formed instead of nanocrystals. Thus, the solvation of the hydrocarbon ligands by CO₂ was sufficient to provide steric stabilization. The presence of steric stabilization in CO₂ at a reduced temperature of 2.5, with a reduced solvent density of only 0.4, may be attributed to a reduction in the differences between ligand–ligand interactions and ligand–CO₂ interactions relative to thermal energy.

Deposition of small Pt nanoparticles of the order of 2–2.5 nm on carbon nanotubes (CNTs) grown directly on carbon paper is demonstrated in this work. Sulfonic acid functionalization of CNTs is used as a means to facilitate the uniform deposition of Pt on the CNT surface. The organic molecules attached covalently to the CNT surface via electrochemical reduction of corresponding diazonium salts are treated with concentrated sulfuric acid and the sulfonic acid sites thus attached are used as molecular sites for Pt ion adsorption, which are subsequently reduced to yield the small Pt nanoparticles. Cyclic voltammograms reveal that, after removal of the organic groups during high temperature reduction, these Pt nanoparticles are in electrical contact with the carbon paper backing. A typical Pt loading of 0.09 mg cm⁻² is achieved, that shows higher specific surface area of Pt than an E-TEK electrode with Pt loading of 0.075 mg cm⁻². A membrane and electrode assembly (MEA) is prepared with a Pt/CNT electrode as cathode and an E-TEK electrode as anode, and it offers better performance than a conventional E-TEK MEA.

The low thermal stability of nanoparticles typically restricts their use in catalytic and other applications to low- to moderate-temperature conditions. We present a novel approach to the stabilization of nanosized noble metal particles by embedding them in a high-temperature stabilized hexa-aluminate matrix. The simple 'one-pot' approach is based on a microemulsion-templated sol–gel synthesis and yields mesoporous nanocomposite materials with pure textural porosity and excellent high-temperature stability up to about 1200 °C. To our knowledge, this is the first time that metal nanoparticles have been stabilized to such high temperatures. We furthermore find that the microemulsion templating allows a tailoring of the ceramic matrix without influencing the size of the embedded Pt particle. This opens up the possibility of a true multiscale engineering of nanocomposite materials. We see these novel materials therefore not only as very promising candidates for a broad range of high-temperature catalytic applications, but generally view this versatile synthesis route as a first step towards expanding the parameter range for nanoparticle applications.

A Brownian dynamics simulation was carried out for a spherical nanoparticle with polymer chains tethered to its surface. These simulations are relevant to understanding the transport properties of polymer-stabilized nanoparticles in environmental and other applications. Hydrodynamic interactions (HI) were taken into account to properly describe the diffusion properties of a stabilized particle. HI are important in this context because of the close proximity of the surface-tethered polymer chains. HI were implemented using a method introduced by Fixman (1986 Macromolecules19 1204), which uses a Chebyshev polynomial expansion to calculate the square root of the diffusion tensor. Simulation predictions were compared to published experimental data for the hydrodynamic radius of a silica particle stabilized by polystyrene tethered chains, and good agreement was achieved. A relationship that allows polymer-stabilized particles with arbitrary polymer-chain densities to be modelled is developed.

Multivalent molecules, i.e. scaffolds presenting multiple copies of a suitable ligand, constitute an emerging class of nanoscale therapeutics. We present a novel approach for the design of multivalent ligands, which allows the biofunctionalization of polymers with proteins or peptides in a controlled orientation. It consists of the synthesis of water-soluble, activated polymer scaffolds of controlled molecular weight, which can be biofunctionalized with various thiolated ligands in aqueous media under mild conditions. These polymers were synthesized by ring-opening metathesis polymerization (ROMP) and further modified to make them water-soluble. The incorporation of chloride groups activated the polymers to react with thiol-containing peptides or proteins, and the formation of multivalent ligands in aqueous media was demonstrated. This strategy represents a convenient route for synthesizing multivalent ligands of controlled dimensions and valency.

The layer-by-layer (LbL) deposition of poly(sodium 4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) over cotton fibres is reported. Cotton fibres offer unique challenges to the deposition of nanolayers because of their unique cross section as well as the chemical heterogeneity of their surface. Cationic cotton substrates were produced by using 2,3-epoxypropyltrimethylammonium chloride. Attenuated total reflectance FTIR, x-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were used to validate the presence of the nanolayers as well as to corroborate their self-organized structure. TEM images indicated conformal and uniform coating of the cotton fibres. XPS spectral data were found to be in quantitative agreement with previous published work that studied the LbL deposition of PSS and PAH over synthetic substrates.

A Monte Carlo simulation approach for BaSO₄ nanoparticle precipitation in microemulsions has been applied to a semi-batch reactor experiment. The simulation includes two technical process parameters, the feed rate and the initial volume ratio of the two reactants. A set of experiments with different initial reactant concentrations of BaCl₂ and K₂SO₄ showed a significant change in the particle size. It was compared to the simulated final particle size and with an adaptation of one internal parameter of the Monte Carlo simulation a good agreement between simulated and experimental data was achieved. Using this set of parameters the feed rate and the initial volume ratio is varied. It is shown how these process parameters influence the particle size and the size distribution. The simulation results may help in finding appropriate control parameters in a scale-up approach of the microemulsion technology for nanoparticle production.

Improved depositions of various metal clusters onto a biomolecular template were achieved using a genetically engineered tobacco mosaic virus (TMV). Wild-type TMV was genetically altered to display multiple solid metal binding sites through the insertion of two cysteine residues within the amino-terminus of the virus coat protein. Gold, silver, and palladium clusters synthesized through in situ chemical reductions could be readily deposited onto the genetically modified template via the exposed cysteine-derived thiol groups. Metal cluster coatings on the cysteine-modified template were more densely deposited and stable than similar coatings on the unmodified wild-type template. Combined, these results confirm that the introduction of cysteine residues onto the outer surface of the TMV coat protein enhances the usefulness of this virus as a biotemplate for the deposition of metal clusters.

The Maxwell–Stefan (MS) formulation, as applied to zeolites that contain both weak and strong adsorption sites, such as ZSM-5, is compared to dynamic Monte Carlo simulations, for the limiting case of single-component self-diffusion. This study is intended as a consistency check, and as a step towards an analytical or semi-analytical theory for self-diffusion in zeolites with multiple types of sites. In its original form, when it is assumed that ζ, the ratio of the self-exchange coefficient to the corrected diffusivity, is equal to 1, the MS formulation performs well for silicalite, the all-Si version of ZSM-5. However, when there are lattice heterogeneities or the topology of the pore network differs from that of silicalite, it is necessary to assume . Because ζ is generally occupancy dependent, the theory is unsuited as a fully predictive theory for self-diffusion in heterogeneous microporous solids, unless a theory for ζ is derived. However, since several studies have demonstrated that the MS formulation is able to predict multi-component diffusivities from single-component diffusivities for zeolites with one type of site, an extension to zeolites with multiple types of sites would be very valuable.

Nanobiotechnology is a growing area of research, primarily due to the potentially numerous applications of new synthetic nanomaterials in engineering/science. Although various definitions have been given for the word 'nanomaterials' by many different experts, the commonly accepted one refers to nanomaterials as those materials which possess grains, particles, fibres, or other constituent components that have one dimension specifically less than 100 nm. In biological applications, most of the research to date has focused on the interactions between mammalian cells and synthetic nanophase surfaces for the creation of better tissue engineering materials. Although mammalian cells have shown a definite positive response to nanophase materials, information on bacterial interactions with nanophase materials remains elusive. For this reason, this study was designed to assess the adhesion of Pseudomonas fluorescens on nanophase compared to conventional grain size alumina substrates. Results provide the first evidence of increased adhesion of Pseudomonas fluorescens on alumina with nanometre compared to conventional grain sizes. To understand more about the process, polymer (specifically, poly-lactic-co-glycolic acid or PLGA) casts were made of the conventional and nanostructured alumina surfaces. Results showed similar increased Pseudomonas fluorescens capture on PLGA casts of nanostructured compared to conventional alumina as on the alumina itself. For these reasons, a key material property shown to enhance bacterial adhesion was elucidated in this study for both polymers and ceramics: nanostructured surface features.

This contribution summarizes investigations of organic–inorganic hybrid materials wherein the inorganic phase is ordered mesoporous silica such as MCM-41 and SBA-15. The review, which covers work performed in the last three years, emphasizes studies of: (1) covalently attached functional groups, (2) new approaches to functionalization, (3) approaches for achieving high densities of uniform functional groups, (4) periodic mesoporous organosilicas (PMOs) with hierarchical ordering, (5) new functional chemistries, and (6) the application of new materials to enantioselective catalysis and emerging areas. The review concludes with the authors outlining some outstanding problems in the field.

Both Ni- and Co-MCM-41 may be used for the synthesis of single-wall carbon nanotubes (SWNT). We present a comparative investigation that demonstrates that smaller diameter SWNT with a narrower distribution of diameters are produced using Co-MCM-41. Temperature-programmed reduction and x-ray absorption spectroscopy were used to measure the reducibility and metal cluster growth of Ni- and Co-MCM-41 in He, H₂ and under CO disproportionation reaction. The differences between these two catalysts can be attributed to a greater reducibility of and a greater CO affinity for Ni relative to Co.

Nanoscale carriers of active compounds, especially drugs, need not be spherical in shape. Worm micelles as blends of degradable polylactic acid (PLA) and inert block copolymer amphiphiles were prepared for controlled release and initial study of carrier transport through nano-porous media. The loading capacity of a typical hydrophobic drug, Triamterene, and the release of hydrophobic dyes were evaluated together with morphological changes of the micelles. Degradation of PLA by hydrolysis led to the self-shortening of worms and a clear transition towards spherical micelles, correlating with the release of hydrophobic dyes. Perhaps equally important for application is the flexibility of worm micelles, which we show allows them to penetrate nanoporous gels where 100 nm sized vesicles cannot enter. Such gels have served as tissue models, and so the results here collectively suggest a new class of hydrophobic drug nano-carriers that are capable of tissue permeation as well as controlled release.

In this work, we use AFM measurements in conjunction with dialysis experiments to study the synthesis mechanism and physical state of dendrimer-stabilized platinum nanoparticles. For characterizing particle size distributions by high resolution transmission electron microscopy and AFM, sample preparation by drop evaporation presumably minimizes the risk of sample bias that might be found in spin coating or dip-and-rinse methods. However, residual synthesis by-products (mainly salts) must be removed from solutions of dendrimer-stabilized metal nanoparticles prior to AFM imaging. Purification by dialysis is effective for this purpose. We discovered, by UV–visible spectrophotometry and atomic absorption (AA) spectroscopy, that dialysis using 'regular' cellulose dialysis tubing (12 000 Da cut-off) used in all previous work leads to substantial losses of poly(amidoamine) (PAMAM) dendrimer (G4OH), PAMAM–Pt(+2) complex, and PAMAM-stabilized Pt nanoparticles. Use of benzoylated dialysis tubing (1200 Da cut-off) shows no losses of G4OH or G4OH–Pt mixtures. We use AFM to see whether selective filtration during dialysis introduces sampling bias in the measurement of particle size distributions. We compare results (UV–visible spectra, AA results, and AFM-based particle size distributions) for a sample of G4OH–Pt₄₀ divided into two parts, one part dialysed with regular dialysis tubing and the other with benzoylated tubing. Exhaustive dialysis using benzoylated tubing may lead to the loss of colloidal Pt nanoparticles stabilized by adsorbed dendrimer, but not Pt nanoparticles encapsulated by the dendrimer. The comparisons also lead to new insights concerning the underlying synthesis mechanisms for PAMAM-stabilized Pt nanoparticles.

A cationic partially fluorinated surfactant with four carbons in the chain 1-(3,3,4,4,4-pentafluorobutyl)pyridinium chloride is employed as a structure-directing agent to synthesize nanoporous silica. Samples are prepared in dilute ammonia solutions at room temperature with a range of surfactant:Si ratios. The sample with the largest surfactant:Si ratio forms particles with wormhole-like micropores with an average diameter of 1.6 nm, which corresponds to the anticipated small size of the surfactant aggregates. On the other hand, the sample with the smallest surfactant:Si ratio forms a gel that, upon drying, has uniform 11.1 nm pores. The formation and stabilization of the latter large-mesopore structure is unusual for a sample prepared and dried under ambient conditions, and may reflect favourable roles of the surfactant both in inducing gelation and in stabilizing the pore structure during drying.

The electrical properties of Bi₂S₃ nanowire bundles were investigated. The nanowires were synthesized using a solventless reaction involving a single-source bismuth thiolate precursor and stabilizing organic ligands. For electrical testing, nanowires were dispersed in solution and drop cast onto a substrate with gold contact pads patterned by electron beam lithography techniques (EBL). Electrical connections were made by depositing platinum interconnect lines between the nanowires and the gold pads by focused ion beam (FIB) chemical vapour deposition. Current–voltage (I–V) curves were measured under nitrogen as a function of temperature. The data revealed activated transport that followed a Meyer–Neldel relationship. Annealing under vacuum decreased the nanowire resistance by nearly four orders of magnitude. The annealed nanowires followed an inverse Meyer–Neldel relationship. Illumination with UV light increased the current, and air exposure decreased the current under constant applied bias.

The melt-state viscoelastic properties of exfoliated in situ polymerized and intercalated solution-blended polystyrene (PS) and organically modified montmorillonite nanocomposites were investigated and compared. The PS nanocomposites prepared by nitroxide-mediated polymerization (NMP) exhibit a stable exfoliated structure whereas the PS nanocomposites prepared by solution mixing exhibit an intercalated structure. The linear viscoelastic properties were strongly correlated with the dispersion state of the nanocomposites. On the other hand, the non-linear oscillatory shear properties exhibited shear thinning character and were consistent with the weak interactions between the polymer and the layered silicate.

The dynamics of water and sodium counter-ions (Na⁺) in a C222₁ orthorhombic β-lactoglobulin crystal is investigated by means of 5 ns molecular dynamics simulations. The effect of the fluctuation of the protein atoms on the motion of water and sodium ions is studied by comparing simulations in a rigid and in a flexible lattice. The electrostatic interactions of sodium ions with the positively charged LYS residues inside the crystal channels significantly influence the ionic motion. According to our results, water molecules close to the protein surface undergo an anomalous diffusive motion. On the other hand, the motion of water molecules further away from the protein surface is normal diffusive. Protein fluctuations affect the diffusion constant of water, which increases from 0.646 ± 0.108 to 0.887 ± 0.41 nm² ns⁻¹, when protein fluctuations are taken into account. The pore size (0.63–1.05 nm) and the water diffusivities are in good agreement with previous experimental results. The dynamics of sodium ions is disordered. LYS residues inside the pore are the main obstacles to the motion of sodium ions. However, the simulation time is still too short for providing a precise description of anomalous diffusion of sodium ions. The results are not only of interest for studying ion and water transport through biological nanopores, but may also elucidate water–protein and ion–protein interactions in protein crystals.

This work investigated the effects of the use of a surfactant or the functionalization of single-walled carbon nanotubes (SWNTs) on their dispersion in uncrosslinked poly(propylene fumarate) (PPF) and the mechanical reinforcement of crosslinked composites as a function of the SWNT concentration. Rheological measurements showed good dispersion of SWNTs in uncrosslinked PPF at low concentrations of 0.05 wt% and SWNT aggregation for higher concentrations for all formulations examined. Mechanical testing demonstrated significant reinforcement in the compressive and flexural mechanical properties of crosslinked nanocomposites which peaked for low SWNT concentrations of the order of 0.05 wt%. For example, a 74% increase was recorded for the compressive modulus and a 69% increase for the flexural modulus of nanocomposites with functionalized SWNTs at a 0.05 wt% loading. Nevertheless, this reinforcement was not related to the use of a surfactant or the functionalization of the SWNTs tested. Scanning electron microscopy examinations of fractured nanocomposite surfaces revealed the formation of SWNT aggregates at higher concentrations corroborating the rheological and mechanical data. These results suggest that the dispersion of individual SWNTs in a uncrosslinked formulation is pivotal to the development of injectable nanocomposites for bone tissue engineering applications.

A two-step process is utilized for cutting single-walled carbon nanotubes (SWNTs). The first step requires the breakage of carbon–carbon bonds in the lattice while the second step is aimed at etching at these damage sites to create short, cut nanotubes. To achieve monodisperse lengths from any cutting strategy requires control of both steps. Room-temperature piranha and ammonium persulfate solutions have shown the ability to exploit the damage sites and etch SWNTs in a controlled manner. Despite the aggressive nature of these oxidizing solutions, the etch rate for SWNTs is relatively slow and almost no new sidewall damage is introduced. Carbon–carbon bond breakage can be introduced through fluorination to ∼C₂F, and subsequent etching using piranha solutions has been shown to be very effective in cutting nanotubes. The final average length of the nanotubes is approximately 100 nm with carbon yields as high as 70–80%.

Brownian dynamics simulations (BDSs) are performed to investigate the influence of interfacial electrochemical reaction rate on the evolution of coating morphology on circular fibres. The boundary condition for the fluid phase concentration, representing the balance between the rates of interfacial reaction and transport of ions by bulk diffusion, is incorporated into the BDS by using a reaction probability, P_s. Different modes of growth, ranging from diffusion limited () to reaction controlled , are studied. It is found that, consistent with experimental observations, two distinct morphological regimes exist, with a dense and uniform structure for (reaction limited deposition (RLD)) and an open and porous one as (diffusion limited deposition (DLD)). An analysis of the fractal dimension indicates that this morphological transition occurs at P_s≈0.3. Long-time power-law scalings for the evolution of thickness and roughness (ξ) of the coating exist, i.e.  with 0.86≤α≤0.91 and 0.56≤β≤0.93 for 0.01≤P_s≤1. These values are different from those reported for sequential, pseudo-time lattice simulations on planar surfaces, signifying the importance of multiparticle dynamics and surface curvature. The internal structure and porosity of the coating are characterized quantitatively by the radial density profile, pair correlation function, two-point probability function, void distribution function and pore area distribution. For RLD the radial density, ρ_n, remains nearly constant, while for DLD ρ_n follows a power law, . The coating exhibits short ranged order in the RLD regime while a long range order is created by DLD. The void distribution function becomes broader with increasing P_s, indicating that in the RLD regime the coating consists of small and spherical pores, while in the DLD regime large and elongated pores are obtained. The pore area distribution shows narrower distributions in DLD for small pores, while the area of the largest pore increases by nearly three orders of magnitude as one moves from the RLD to the DLD regime. Such morphological diversity could be potentially exploited for applications such as percolation, catalysis and surface protection.

This paper presents a systematic study on the generation of iron platinum-containing magnetic nanocomposites and alloys from Pt@Fe₂O₃ core–shell nanoparticle precursors. These core–shell nanoparticles were made using a sequential synthetic approach. They could form FePt alloys and alloy-containing nanocomposites through a solid-state reaction at >400 °C. The chemical compositions of FePt alloys were controllable by using Pt@Fe₂O₃ core–shell nanoparticles that had the designed Pt core diameter and iron oxide shell thickness. We show that face-centred tetragonal (fct) FePt@Fe core–shell nanoparticles could be made from Pt@Fe₂O₃ core–shell nanoparticles with 5% hydrogen in argon (v/v). Furthermore, various FePt alloys and alloy-containing nanocomposites including metastable intermediate phases could be obtained. The materials were characterized by high resolution scanning transmission electron microscopy (HR-STEM), energy dispersive x-ray (EDX) spectroscopy, powder x-ray diffraction (PXRD), parallel electron energy loss spectroscopy (PEELS), and superconducting quantum interference device (SQUID) magnetometry. These materials could have potential applications as permanent hard magnets and data storage media.

This work focuses on the modelling, simulation and control of a batch protein crystallization process that is used to produce the crystals of tetragonal hen egg-white (HEW) lysozyme. First, a model is presented that describes the formation of protein crystals via nucleation and growth. Existing experimental data are used to develop empirical models of the nucleation and growth mechanisms of the tetragonal HEW lysozyme crystal. The developed growth and nucleation rate expressions are used within a population balance model to simulate the batch crystallization process. Then, model reduction techniques are used to derive a reduced-order moments model for the purpose of controller design. Online measurements of the solute concentration and reactor temperature are assumed to be available, and a Luenberger-type observer is used to estimate the moments of the crystal size distribution based on the available measurements. A predictive controller, which uses the available state estimates, is designed to achieve the objective of maximizing the volume-averaged crystal size while respecting constraints on the manipulated input variables (which reflect physical limitations of control actuators) and on the process state variables (which reflect performance considerations). Simulation results demonstrate that the proposed predictive controller is able to increase the volume-averaged crystal size by 30% and 8.5% compared to constant temperature control (CTC) and constant supersaturation control (CSC) strategies, respectively, while reducing the number of fine crystals produced. Furthermore, a comparison of the crystal size distributions (CSDs) indicates that the product achieved by the proposed predictive control strategy has larger total volume and lower polydispersity compared to the CTC and CSC strategies. Finally, the robustness of the proposed method (achieved due to the presence of feedback) with respect to plant-model mismatch is demonstrated. The proposed method is demonstrated to successfully achieve the task of maximizing the volume-averaged crystal size in the presence of plant-model mismatch, and is found to be robust in comparison to open-loop optimal control strategies.

Classical molecular dynamics simulations using a reactive force field, which allows simulation of bond-breaking and bond-forming, are carried out to investigate the several stages of a catalysed synthesis process of single-wall carbon nanotubes. The simulations assume instantaneous catalysis of a precursor gas on the surface of metallic nanoclusters, illustrating how carbon atoms dissolve in the metal cluster and then precipitate on its surface, evolving into various carbon structures, finally forming a cap which eventually grows to a single-wall nanotube. The results are discussed in the context of experimental synthesis results.

The uptake of platinum and copper tetra-ammine (PTA and CTA, [(NH₃)₄Pt]²⁺ and [(NH₃)₄Cu]²⁺) into zeolites was compared over silica and three zeolites (Y, MOR and MFI) with different points of zero charge and aluminium content. Adsorption was determined as a function of pH at several metal concentrations, and pH shifts relative to metal free control experiments were carefully monitored.

The uptake of both metal ammine complexes onto silica is well described by electrostatic adsorption. We suggest that the metal cations interact with zeolites by two mechanisms, ion exchange at the Al exchange sites and electrostatic adsorption at silanol groups. The former is the dominant mechanism at low to mid pH, and the latter at high pH. This effect is most clearly manifested in zeolites with low aluminium content such as ZSM5; electrostatic adsorption at high pH in ZSM5 yields metal loadings much in excess of the ion exchange capacity and so gives rise to 'overexchange'.

Differences between PTA and CTA can be explained by the weaker stability of the CTA complex and its response to the decrease in local pH near the adsorption plane of low PZC zeolites. This change in local pH near oxide surfaces is characteristic of electrostatic adsorption. As the local pH decreases, the CTA ion is probably converted to a dimerized copper complex, perhaps Cu₂(OH)₂²⁺. A portion of the released ammonia is protonated, increasing the solution pH. In high PZC, high aluminium zeolites with high ion exchange capacity, there is relatively little contribution from electrostatic adsorption.

The initial stage of the reaction between sodium stearate (NaSt) and AgNO₃ produces silver stearate (AgSt) micelles, [(C₁₈H₃₅O₂)_x(Na_x−y)(Ag_y)(H₂O)_z], and aggregations of these AgSt micelles in the form of cubic pre-AgSt crystals. When cubic grains of 50 nm AgBr are added to the NaSt dispersion prior to the AgNO₃, the reaction proceeds to form the silver stearate micelles, but not the aggregation of those micelles. Instead, the {111} silver ion planes of the cubic AgBr crystal corners provide nucleation sites for silver stearate micelle deposition and crystal growth. After nucleation, the AgSt micelles evolve into nanostructured bud-like formations via an epitaxial interface on one or several corners of each AgBr cubic crystal. Over time, additional AgSt micelle deposition enables the buds to grow longer into strand-like structures, which then connect to form the beginnings of the ultimate silver stearate crystal plates.

The design of nanophase titania/poly-lactic-co-glycolic acid (PLGA) composites offers an exciting approach to combine the advantages of a degradable polymer with nano-size ceramic grains to optimize physical and biological properties for bone regeneration. Importantly, nanophase titania mimics the size scale of constituent components of bone since it is a nanostructured composite composed of nanometre dimensioned hydroxyapatite well dispersed in a mostly collagen matrix. For these reasons, the objective of the present in vitro study was to investigate osteoblast (bone-forming cell) adhesion and long-term functions on nanophase titania/PLGA composites. Since nanophase titania tended to significantly agglomerate when added to polymers, different sonication output powers were applied in this study to improve titania dispersion. Results demonstrated that the dispersion of titania in PLGA was enhanced by increasing the intensity of sonication and that greater osteoblast adhesion correlated with improved nanophase titania dispersion in PLGA. Moreover, results correlated better osteoblast long-term functions, such as alkaline phosphatase activity and calcium-containing mineral deposition, on nanophase titania/PLGA composites compared to plain PLGA. In fact, the greatest collagen production by osteoblasts occurred when cultured on nanophase titania sonicated in PLGA at the highest powers. In this manner, the present study demonstrates that PLGA composites with well dispersed nanophase titania can enhance osteoblast functions necessary for improved bone tissue engineering applications.

Homogeneous yttria-stabilized zirconia (YSZ) with 8–31 nm average crystallite and particle diameter containing 3–10 mol% yttria are made by flame spray pyrolysis (FSP) of various yttrium and zirconium precursors at production rates up to 350 g h⁻¹. Product particles are characterized by N₂ adsorption (BET), transmission electron microscopy (TEM), energy-dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD). The effect of liquid precursor composition on product particle morphology, composition and crystallinity is investigated. The yttria content does not affect the product primary particle and crystal sizes of homogeneous YSZ. These are determined, in turn, by the process enthalpy content and overall metal concentration. Flame-made YSZ nanoparticles of homogeneous composition and morphology are formed when using either only organometallic zirconium and yttrium precursors or 2-ethylhexanoic acid as solvent and inexpensive zirconium carbonate and yttrium nitrate hexahydrate as precursors. In contrast, and consistent with the literature, hollow or inhomogeneous YSZ particles are made when organometallic zirconium and yttrium nitrate precursors of high water content are employed, especially at high production rate. The ratio of XRD-determined small to large sizes for inhomogeneous crystalline particles is an effective quantitative measure of their degree of inhomogeneity. For such inhomogeneous particles nitrogen adsorption is not a reliable technique for the average grain size as it relies on integral properties of the particle size distribution.

Reverse micelles prepared in the system water, sodium bis-(2-ethylhexyl) sulfoccinate (AOT), and isooctane were investigated as a templating system for the production of gold nanoparticles from Au(III) and the reducing agent sulfite. A core–shell Mie model was used to describe the optical properties of gold nanoparticles in the reverse micelles. Dynamic light scattering of gold colloids in aqueous media and in reverse micelle solution indicated agglomeration of micelles containing particles. This was verified theoretically with an analysis of the total interaction energy between pairs of particles as a function of particle size. The analysis indicated that particles larger than about 8 nm in diameter should reversibly flocculate. Transmission electron microscopy measurements of gold nanoparticles produced in our reverse micelles showed diameters of 8–10 nm. Evidence of cluster formation was also observed. Time-correlated UV–vis absorption measurements showed a red shift for the peak wavelength. This was interpreted as the result of multiple scattering and plasmon interaction between particles due to agglomeration of micelles with particles larger than 8 nm.

Previous studies in our laboratory have shown that individual nanoparticle chain aggregates (NCAs) exhibit unusual mechanical behaviour when under strain inside the transmission electron microscope. NCAs made of various materials (e.g. carbon, metal oxides and metals) were strained by as much as 100% under tension. The nanoparticles that compose the chains were 5–10 nm in diameter and the chains of the order of 1 µm in length. Such aggregates are of technological importance in the manufacture of nanocomposite materials (e.g. rubber), aggregate break-up (e.g. sampling diesel emissions) and chemical–mechanical planarization.

The goal of this study was to simulate the mechanical behaviour of chain aggregates with morphological properties similar to those of technological interest. Molecular dynamics (MD) and energy minimization computer simulations are employed to investigate, at the atomic scale, the behaviour of short nanoparticle aggregates under strain and to obtain quantitative information on the forces involved in aggregate straining and fracturing. The interaction potential used is that of copper obtained with the embedded atom method (EAM). Two seven-nanoparticle aggregates are studied, one linear and the other kinked. The seven nanoparticles in both aggregates are single crystals and about 2.5 nm in diameter each. The aggregates are strained along their longest dimension, to the breaking point, at strain rates spanning from 2.5 × 10⁷ to 8.0 × 10⁸ s⁻¹ (MD simulations). The linear aggregate yield strain is about 0.1. The kinked aggregate elastic limit is also about 0.1, but only one-third of the stress develops along the straining direction compared to the linear aggregate. The kinked aggregate breaks at a strain of about 0.5, five times higher than the breaking strain of the linear aggregate. The ability of the kinked aggregate to straighten through combined nanoparticle interface sliding and rotation accounts for the extra strain accommodation. Simulation strain rates are orders of magnitude higher than the experimental ones. However, aggregate behaviour is independent of strain rates over the range studied here. The MD and energy minimization straining gave very similar results. In the elastic regime, the 1/S₁₁ modulus for the seven-nanoparticle kinked aggregate is about one-fifth of the bulk value. This is due to a combined effect of the small primary particle diameter and the aggregate kinked structure. If this softening behaviour also occurs for nanoparticle aggregates of other materials (e.g. carbon, silica), nanoparticle aggregates, in some cases, may be strained along with the nanocomposite they reinforce.