Self-assembly of nanoparticles onto the surfaces of polystyrene spheres with a tunable composition and loading.

Functional colloidal materials were prepared by design through the self-assembly of nanoparticles (NPs) on the surfaces of polystyrene (PS) spheres with control over NP surface coverage, NP-to-NP spacing, and NP composition. The ability to control and fine tune the coating was extended to the first demonstration of the co-assembly of NPs of dissimilar composition onto the same PS sphere, forming a multi-component coating. A broad range of NP decorated PS (PS@NPs) spheres were prepared with uniform coatings attributed to electrostatic and hydrogen bonding interactions between stabilizing groups on the NPs and the functionalized surfaces of the PS spheres. This versatile two-step method provides more fine control than methods previously demonstrated in the literature. These decorated PS spheres are of interest for a number of applications, such as catalytic reactions where the PS spheres provide a support for the dispersion, stabilization, and recovery of NP catalysts. The catalytic properties of these PS@NPs spheres were assessed by studying the catalytic degradation of azo dyes, an environmental contaminant detrimental to eye health. The PS@NPs spheres were used in multiple, sequential catalytic reactions while largely retaining the NP coating.

Modulation of the Aß peptide aggregation pathway by KP1019 limits Aß-associated neurotoxicity.

Alzheimer's disease (AD) is a neurodegenerative disorder that is increasing worldwide due to increased life expectancy. AD is characterized by two pathological hallmarks in the brain: amyloid-ß (Aß) plaque deposits and neurofibrillary tangles. A focus of AD research has concentrated on either inhibiting Aß peptide aggregation that leads to plaque formation or breaking down pre-formed Aß peptide aggregates. An alternative approach is to modulate the Aß aggregation profile by facilitating the formation of Aß species that are off-pathway and non-toxic. Herein, we report the re-purposing of the widely studied Ru(iii) anti-cancer complex KP1019, towards regulating the aggregation profile of the Aß peptide. Using electron paramagnetic resonance (EPR) spectroscopy, we conclude that KP1019 binds to histidine residues, located at the N-terminus of the peptide, in a rapid and robust fashion. Native gels and transmission electron microscopy (TEM) analyses have provided insight into the species and structures that are generated by KP1019-Aß interactions. Finally, incubation in an in vitro human neuronal cell model has demonstrated that the formation of KP1019-Aß species rescues cell viability from Aß-associated neurotoxicity. Modulation of the Aß aggregation pathway via covalent interactions with small molecules is thus a promising AD therapeutic strategy.

Simultaneous patterning of two different types of nanoparticles into alternating domains of a striped array of a polymer blend in a single spin-casting step.

A fast and convenient method is developed for simultaneously patterning inorganic nanoparticles with different optical, electronic or magnetic functionality to specific surface regions, by spin-casting onto microcontact printed substrates blend solutions in which the two nanoparticle types are functionalized with surface polymer brush layers of different surface energies. The process is based on phase separation of different nanoparticles based on their immiscible brush layers during spin-casting, with the underlying surface energy heterogeneity of the patterned substrate directing the different NP types to domains of different surface energies. Here, we specifically demonstrate the simultaneous localization of cadmium sulfide quantum dots (CdS QDs), addressed with a surface layer of polystyrene (PS), and silver nanoparticles (Ag NPs), addressed with a surface layer of poly(methyl methacrylate) (PMMA), onto the non-polar and polar surface domains, respectively, of hydrophilic glass patterned with hydrophobic octadecyltrichlorosilane (OTS) stripe arrays with micron-scale periodicities. In order to prevent gelation of solvent-swollen polymer-brush coated NPs during spin casting, which effects strong kinetic constraints on phase separation and localization, PS, PMMA or PS/PMMA homopolymer blends of sufficiently high Mw were added to the NP blends to increase the free volume between approaching NPs. The process parameters were fine-tuned to obtain control over defects in the obtained patterns.

8-Hydroxyquinoline Schiff-base compounds as antioxidants and modulators of copper-mediated Aß peptide aggregation.

One of the hallmarks of Alzheimer's disease (AD) in the brain are amyloid-ß (Aß) plaques, and metal ions such as copper(II) and zinc(II) have been shown to play a role in the aggregation and toxicity of the Aß peptide, the major constituent of these extracellular aggregates. Metal binding agents can promote the disaggregation of Aß plaques, and have shown promise as AD therapeutics. Herein, we describe the syntheses and characterization of an acetohydrazone (8-H2QH), a thiosemicarbazone (8-H2QT), and a semicarbazone (8-H2QS) derived from 8-hydroxyquinoline. The three compounds are shown to be neutral at pH7.4, and are potent antioxidants as measured by a Trolox Equivalent Antioxidant Capacity (TEAC) assay. The ligands form complexes with Cu(II), 8-H2QT in a 1:1 metal:ligand ratio, and 8-H2QH and 8-H2QS in a 1:2 metal:ligand ratio. A preliminary aggregation inhibition assay using the Aß1-40 peptide showed that 8-H2QS and 8-H2QH inhibit peptide aggregation in the presence of Cu(II). Native gel electrophoresis/Western blot and TEM images were obtained to give a more detailed picture of the extent and pathways of Aß aggregation using the more neurotoxic Aß1-42 in the presence and absence of Cu(II), 8-H2QH, 8-H2QS and the drug candidate PBT2. An increase in the formation of oligomeric species is evident in the presence of Cu(II). However, in the presence of ligands and Cu(II), the results match those for the peptide alone, suggesting that the ligands function by sequestering Cu(II) and limiting oligomer formation in this assay.

Colloidal core-shell materials with 'spiky' surfaces assembled from gold nanorods.

A series of core-shell materials with 'spiky' surfaces are prepared through the self-assembly of gold nanorods onto polystyrene microspheres. Loading of the nanorods is finely tuned and the assemblies exhibit surface plasmon resonance properties. The 'spiky' surface topography of the assembled structures could serve as a versatile substrate for surface-enhanced Raman spectroscopy based sensing applications.

Tuning ligand electronics and peripheral substitution on cobalt salen complexes: structure and polymerisation activity.

A series of cobalt salen complexes, where salen represents an N2O2 bis-Schiff-base bis-phenolate framework, are prepared, characterised and investigated for reversible-termination organometallic mediated radical polymerisation (RT-OMRP). The salen ligands contain a cyclohexane diimine bridge and systematically altered para-substituted phenoxide moieties as a method to examine the electronic impact of the ligand on complex structure and reactivity. The complexes are characterised by single crystal X-ray diffraction, cyclic voltammetry, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy and computational methods. Structural studies all support a tailorable metal centre reactivity altered by the electron-donating ability of the salen ligand. RT-OMRP of styrene, methyl methacrylate and vinyl acetate is reported and suggests that cobalt-carbon bond strength varies with the ligand substitution. Competing ß-hydrogen abstraction affords long-chain olefin-terminated polymer chains and well controlled vinyl acetate polymerisations, contrasting with the lower temperature associative exchange mechanism of degenerative transfer OMRP.

Tunable loading of single-stranded DNA on gold nanorods through the displacement of polyvinylpyrrolidone.

A quantitative and tunable loading of single-stranded (ss-DNA) molecules onto gold nanorods was achieved through a new method of surfactant exchange. This new method involves the exchange of cetyltrimethylammonium bromide surfactants for an intermediate stabilizing layer of polyvinylpyrrolidone and sodium dodecylsulfate. The intermediate layer of surfactants on the anisotropic gold particles was easily displaced by thiolated ss-DNA, forming a tunable density of single-stranded DNA molecules on the surfaces of the gold nanorods. The success of this ligand exchange process was monitored in part through the combination of extinction, X-ray photoelectron, and infrared absorption spectroscopies. The number of ss-DNA molecules per nanorod for nanorods with a high density of ss-DNA molecules was quantified through a combination of fluorescence measurements and elemental analysis, and the functionality of the nanorods capped with dense monolayers of DNA was assessed using a hybridization assay. Core-satellite assemblies were successfully prepared from spherical particles containing a probe DNA molecule and a nanorod core capped with complementary ss-DNA molecules. The methods demonstrated herein for quantitatively fine tuning and maximizing, or otherwise optimizing, the loading of ss-DNA in monolayers on gold nanorods could be a useful methodology for decorating gold nanoparticles with multiple types of biofunctional molecules.

Surface-initiated atom transfer radical polymerization-induced transformation of selenium nanowires into copper selenide@polystyrene core-shell nanowires.

This Article reports the first preparation of cuprous and cupric selenide nanowires coated with a ∼5 nm thick sheath of polystyrene (copper selenide@polystyrene). These hybrid nanostructures are prepared by the transformation of selenium nanowires in a one-pot reaction, which is performed under ambient conditions. The composition, purity, and crystallinity of the copper selenide@polystyrene products were assessed by scanning transmission electron microscopy, electron energy-loss spectroscopy, X-ray powder diffraction, and X-ray photoelectron spectroscopy techniques. We determined that the single crystalline selenium nanowires are converted into polycrystalline copper selenide@polystyrene nanowires containing both cuprous selenide and cupric selenide. The product is purified through the selective removal of residual, non-transformed selenium nanowires by performing thermal evaporation below the decomposition temperature of these copper selenides. Powder X-ray diffraction of the purified copper selenide nanowires@polystyrene identified the presence of hexagonal, cubic, and orthorhombic phases of copper selenide. These purified cuprous and cupric selenide@polystyrene nanowires have an indirect bandgap of 1.44 eV, as determined by UV-vis absorption spectroscopy. This new synthesis of polymer-encapsulated nanoscale materials may provide a method for preparing other complex hybrid nanostructures.

Comprehensive structural, surface-chemical and electrochemical characterization of nickel-based metallic foams.

Nickel-based metallic foams are commonly used in electrochemical energy storage devices (rechargeable batteries) as both current collectors and active mass support. These materials attract attention as tunable electrode materials because they are available in a range of chemical compositions, pore structures, pore sizes, and densities. This contribution presents structural, chemical, and electrochemical characterization of Ni-based metallic foams. Several materials and surface science techniques (transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), focused ion beam (FIB), and X-ray photoelectron spectroscopy (XPS)) and electrochemical methods (cyclic voltammetry (CV)) are used to examine the micro-, meso-, and nanoscopic structural characteristics, surface morphology, and surface-chemical composition of these materials. XPS combined with Ar-ion etching is employed to analyze the surface and near-surface chemical composition of the foams. The specific and electrochemically active surface areas (As, Aecsa) are determined using CV. Though the foams exhibit structural robustness typical of bulk materials, they have large As, in the range of 200-600 cm(2) g(-1). In addition, they are dual-porosity materials and possess both macro- and mesopores.

Dual-function triazole-pyridine derivatives as inhibitors of metal-induced amyloid-ß aggregation.

Dysregulated metal ions are hypothesized to play a role in the aggregation of the amyloid-ß (Aß) peptide, leading to Alzheimer's disease (AD) pathology. In addition to direct effects on Aß aggregation, both Cu and Fe can catalyze the generation of reactive oxygen species (ROS), possibly contributing to significant neuronal toxicity. Therefore, disruption of metal-Aß interactions has become a viable strategy for AD therapeutic development. Herein, we report a new series of dual-function triazole-pyridine ligands [4-(2-(4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl)ethyl)morpholine (L1), 3-(4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl)propan-1-ol (L2), 2-(4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl)acetic acid (L3), and 5-(4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl)pentan-1-amine (L4)] that interact with the Aß peptide and modulate its aggregation in vitro. Metal chelation and Aß interaction properties of these molecules were studied by UV-vis, NMR spectroscopy and X-ray crystallography. In addition, turbidity and transmission electron microscopy (TEM) were employed to determine the anti-aggregation properties of L1-L4. All compounds demonstrated an ability to limit metal-induced Aß aggregation. Overall, our studies suggest the utility of the triazole-pyridine framework in the development of chemical reagents toward inhibitors for metal-triggered Aß aggregation.

Synthesis of selenium nano-composite (t-Se@PS) by surface initiated atom transfer radical polymerization.

Selenium nanostructures, which are otherwise susceptible to oxidative damage, were encapsulated with a thin layer of polystyrene. The thin layer of polystyrene was grafted onto the surfaces of selenium by a surface initiated atom transfer radical polymerization reaction. These encapsulated nanostructures demonstrate an enhanced resistance towards corrosion.

Optimizing the quality of monoreactive perfluoroalkylsilane-based self-assembled monolayers.

Self-assembled monolayers (or SAMs) created from monoreactive perfluoroalkylsilanes by deposition from a toluene solution are investigated for the dependence of their quality on processing conditions. Surface-sensitive spectroscopic techniques are used to provide feedback on the processing conditions in which solution temperature, silane concentration, and reaction time are optimized to improve the quality of these SAMs. For these analyses, monolayers are formed at 20, 40, 60, or 80 °C from solutions containing between 0.5 and 5 mM perfluoroalkylsilane over a period of up to 5 h. Physically adsorbed molecules are removed from these surfaces by extraction to determine the quality of the covalently bound monolayer. Water contact angle measurements, spectroscopic ellipsometry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM), respectively, are used in combination to assess the uniformity of the surface hydrophobicity, monolayer thickness, composition of the assembled perfluoroalkylsilane molecules, and topography of these monolayers. A comparison is also presented for two approaches to fill defects within these solvent extracted monolayers with more perfluoroalkylsilane molecules, aiming to improve the quality of these SAMs. A detailed XPS analysis is used to assess both the relative changes in density and average tilt of molecules within the monolayers as the process temperature is increased in increments from 20 to 80 °C. The observed differences in quality of the SAMs are attributed to temperature- and time-dependent organization and reactivity of the silane molecules. Although the assembly of these monoreactive perfluoroalkylsilanes is driven by thermodynamics, the quality of the monolayer is ultimately limited by the kinetics and mass transport during this assembly process. Lessons from these studies can be exploited for improving the quality of monolayers composed of other alkylsilane molecules that are covalently bound to the surfaces of oxides.

Directed polystyrene/poly(methyl methacrylate) phase separation and nanoparticle ordering on transparent chemically patterned substrates.

We investigate the surface-directed phase separation of spin-coated polystyrene/poly(methyl methacrylate) (PS/PMMA) blends on prepatterned octadecyltrichlorosilane (OTS)-glass substrates under various experimental conditions. As a result of tandem processes of spinodal decomposition and selective wetting of polymer components during spin-coating, low-energy OTS stripes and high-energy glass surfaces laterally arrange the phase-separated polymers according to the chemical pattern on the substrate. Optimal pattern replication was achieved when the length scale of phase separation, controlled via the polymer concentration of the spin-coating solution, matched the smallest feature dimension in a striped chemical pattern possessing two alternating distances between stripes. It was also shown that polymer blend patterns were most closely registered with the underlying substrate when the PS/PMMA composition ratio (30/70, w/w) matched the areal fraction of OTS on the glass surface (∼30%). The influence of solvents demonstrated that a solvent with a relatively low volatility, such toluene, was required for patterning so that domain feature sizes were able to coarsen to the size of the patterned features before film vitrification. As well, we showed that the technique and optimized conditions developed in this study could be applied to pattern photoluminescent CdS quantum dots into microscale arrays of parallel lines via spin-coating onto transparent OTS-glass substrates.

Electrokinetic assembly of selenium and silver nanowires into macroscopic fibers.

Solution-phase synthesized nanowires with high aspect ratios can be a challenge to assemble into desired structures. As synthesized, these nanostructures readily bend and entangle with each other to form larger aggregates. This manuscript reports a general procedure for directing the assembly of semiconducting and metallic nanowires into fibers that can easily span distances >1 cm. Dispersions of these nanostructures in a low dielectric solution are organized by electrokinetic techniques into fibers that can be isolated from solution. Theoretical studies suggest that the assembled fibers adopt an orientation along electric field lines in the solution. The number of assembled fibers is a function of the duration of the assembly process, the magnitude of the electric potential, and the initial concentration of nanowires dispersed in solution. These findings offer a general method for the assembly of nanowires into macroscopic fibers of tunable dimensions. Fibers of selenium nanowires isolated from solution can reversibly bend in response to a source of electrostatic charges positioned in close proximity to the free-standing fiber. These flexible selenium fibers also exhibit a photoconductive response when illuminated with white light.

Patterning block copolymer aggregates via Langmuir-Blodgett transfer to microcontact-printed substrates.

We demonstrate a new strategy for producing hierarchical polymer nanostructures, which combines nanoscale self-assembly of amphiphilic block copolymers at the air-water interface with microscale templated assembly of the resulting aggregates on chemically patterned substrates. Aggregates are formed via interfacial self-assembly of 141k polystyrene-b-poly(ethylene oxide) (PS-b-PEO, MW = 141k, 11.4 wt % PEO) or a blend of 185k PS-b-PEO (MW = 185k, 18.9 wt % PEO) and PS-coated CdS nanoparticles to form strandlike copolymer or copolymer-nanoparticle aggregates. Using Langmuir-Blodgett (LB) techniques, the aggregates are then transferred to patterned substrates possessing alternating hydrophilic/hydrophobic stripes, obtained by microcontact printing octadecyltrichlorosilane (OTS) on glass. The aggregates are transferred under various conditions of surface pressure, orientation of the patterned substrate, and withdrawal speed. Templated assembly of aggregates into the hydrophilic substrate domains is achieved when the hydrophilic/hydrophobic stripes are oriented perpendicular to the water surface during LB transfer; this is explained by surface energy heterogeneities along the subphase-substrate contact line, which induce selective dewetting and concomitant monolayer rearrangement at the drying front. In contrast, parallel orientation of stripes results in nonselective transfer of the monolayer without registration to the underlying surface pattern. By studying the effect of surface pressure, we show that packing constraints imposed by compression of aggregates to high surface densities prevent the formation of patterned LB films that match the established periodicity of the OTS-patterned glass. As well, it is shown that efficient transfer of aggregates to the patterned glass requires slower substrate withdrawal speeds compared to transfer to unpatterned hydrophilic glass.