Identification of Nanoparticles via Plasmonic Scattering Interferometry

The development of optical imaging techniques has led to significant advancements in single‐nanoparticle tracking and analysis, but these techniques are incapable of label‐free selective nanoparticle recognition. A label‐free plasmonic imaging technology that is able to identify different kinds of nanoparticles in water is now presented. It quantifies the plasmonic interferometric scattering patterns of nanoparticles and establishes relationships among the refractive index, particle size, and pattern both numerically and experimentally. Using this approach, metallic and metallic oxide particles with different radii were distinguished without any calibration. The ability to optically identify and size different kinds of nanoparticles can provide a promising platform for investigating nanoparticles in complex environments to facilitate nanoscience studies, such as single‐nanoparticle catalysis and nanoparticle‐based drug delivery.     

Stabilization of the Suspension of Zirconia Microparticle Using the Nanoparticle Halos Mechanism: Zeta Potential Effect

An experimental study has been conducted to investigate the effect of silica nanoparticle halos on the stability of the zirconia aqueous suspension. The results of turbidity measurements showed that addition of nanoparticles to the suspension increases the stability of the zirconia suspension for all pH values. The achieved stability refers to the formation of nanoparticle halos around the microparticles that can be observed by scanning electron microscopy (SEM) imaging. The best stabilization is achievable when zirconia microparticles are at the isoelectric point. The minimum stabilization occurs when microparticles have relatively high zeta potential and the force between micro and nanoparticles is repulsive. Addition of a volume fraction of nanoparticles results in the increase in stability up to a certain value. Since then, the emergence of depletion force causes the instability of the suspension.     

Bottom-up assembly of colloidal gold and silver nanostructures for designable plasmonic structures and metamaterials

We report on bottom-up assembly routes for fabricating plasmonic structures and metamaterials composed of colloidal gold and silver nanostructures, such as nanoparticles ("metatoms") and shape-controlled nanocrystals. Owing to their well-controlled sizes/shapes, facile surface functionalization, and excellent plasmonic properties in the visible and near-infrared regions, these nanoparticles and nanocrystals are excellent building blocks of plasmonic structures and metamaterials for optical applications. Recently, we have utilized two kinds of bottom-up techniques (i.e., multiple-probe-based nanomanipulation and layer-by-layer self-assembly) to fabricate strongly coupled plasmonic dimers, one-dimensional (1D) chains, and large-scale two-dimensional/three-dimensional (2D/3D) nanoparticle supercrystals. These coupled nanoparticle/nanocrystal assemblies exhibit unique and tunable plasmonic properties, depending on the material composition, size/shape, intergap distance, the number of composing nanoparticles/nanocrystals (1D chains), and the nanoparticle layer number in the case of 3D nanoparticle supercrystals. By studying these coupled nanoparticle/nanocrystal assemblies, the fundamental plasmonic metamaterial effects could be investigated in detail under well-prepared and previously unexplored experimental settings.     

Interaction of polyethyleneimine-functionalized ZnO nanoparticles with bovine serum albumin

In biological fluids, nanoparticles are always surrounded by proteins. As the protein is adsorbed on the surface, the extent of adsorption and the effect on the protein conformation and stability are dependent on the chemical nature, shape, and size of the nanoparticle (NP). We have carried out a detailed investigation on the interaction of bovine serum albumin (BSA) with polyethyleneimine-functionalized ZnO nanoparticles (ZnO-PEI). ZnO-PEI was synthesized using a wet chemical method with a core size of ~3-7 nm (from transmission electron microscopy). The interaction of BSA with ZnO-PEI was examined using a combination of calorimetric, spectroscopic, and computational techniques. The binding was studied by ITC (isothermal titration calorimetry), and the result revealed that the complexation is enthalpy-driven, indicating the possible involvement of electrostatic interaction. To investigate the nature of the interaction and the location of the binding site, a detailed domain-wise surface electrostatic potential calculation was performed using adaptive Poisson-Boltzmann software (APBS). The result shows that the protein surface can bind the nanoparticle. On binding ZnO-PEI, the protein gets destabilized to some extent, as displayed by CD (circular dichroism) and FTIR (Fourier transform infrared) spectroscopy. Chemical and thermal denaturation of BSA, when carried out in the presence of ZnO-PEI, also indicated a small perturbation in the protein structure. A comparison of the enthalpy and entropy components of binding with those derived for the interaction of BSA with ZnO nanoparticles explains the effect of hydrophilic cationic species attached on the NP surface. The effect of the NP surface modification on the structure and stability of BSA would find useful applications in nanobiotechnology.     

Dynamic Color‐Switching of Plasmonic Nanoparticle Films

The fast and reversible switching of plasmonic color holds great promise for many applications, while its realization has been mainly limited to solution phases, achieving solid‐state plasmonic color‐switching has remained a significant challenge owing to the lack of strategies in dynamically controlling the nanoparticle separation and their plasmonic coupling. Herein, we report a novel strategy to fabricate plasmonic color‐switchable silver nanoparticle (AgNP) films. Using poly(acrylic acid) (PAA) as the capping ligand and sodium borate as the salt, the borate hydrolyzes rapidly in response to moisture and produces OH^? ions, which subsequently deprotonate the PAA on AgNPs, change the surface charge, and enable reversible tuning of the plasmonic coupling among adjacent AgNPs to exhibit plasmonic color‐switching. Such plasmonic films can be printed as high‐resolution invisible patterns, which can be readily revealed with high contrast by exposure to trace amounts of water vapor.     

Preparation of sterically stabilized gold nanoparticles for plasmonic applications

Plasmonic nanoparticles such as those of gold or silver have been recently investigated as a possible way to improve light absorption in thin film solar cells. Here, a simple method for the preparation of spherical plasmonic gold nanoparticles in the form of a colloidal solution is presented. The nanoparticle diameter is controlled in the range from several nm to tens of nm depending on the synthesis parameters with the size dispersion down to 14 %. The synthesis is based on thermal decomposition and reduction of the chloroauric acid in the presence of a stabilizing capping agent (surfactant) that is very slowly injected into the hot solvent. The surfactant prevents uncontrolled nanoparticle aggregation during the growth process. The nanoparticle size and shape depend on the type of the stabilizing agent. Surfactants with different lengths of the hydrocarbon chains such as Z-octa-9-decenylamine (oleylamine) with AgNO₃ and polyvinylpyrrolidone with AgNO₃ were used for the steric stabilization. Hydrodynamic diameter of the gold nanoparticles in the colloidal solution was determined by dynamic light scattering while the size of the nanoparticle metallic core was found by small-angle X-ray scattering. The UV-VIS-NIR spectrophotometer measurements revealed a plasmon resonance absorption in the 500–600 nm range. Self-assembled nanoparticle arrays on a silicon substrate were prepared by drop casting followed by spontaneous evaporation of the solvent and by a modified Langmuir-Blodgett deposition. The degree of perfection of the self-assembled arrays was analyzed by scanning electron microscopy and grazing-incidence small-angle X-ray scattering. Homogeneous close-packed hexagonal ordering of the nanoparticles stretching over large areas was evidenced. These results document the viability of the proposed nanoparticle synthesis for the preparation of high-quality plasmonic templates for thin film solar cells with enhanced power conversion efficiency, surface enhanced Raman scattering, and other applications.     

Molecular dynamics simulation of nanoparticle self-assembly at a liquid-liquid interface

We have used molecular dynamics simulations to investigate the in situ self-assembly of modified hydrocarbon nanoparticles (mean diameter of 1.2 nm) at a water-trichloroethylene (TCE) interface. The nanoparticles were first distributed randomly in the water phase. The MD simulation shows the in situ formation of nanoparticle clusters and the migration of both single particles and clusters from the water phase to the trichloroethylene phase, possibly due to the hydrophobic nature of the nanoparticles. Eventually, the single nanoparticles or clusters equilibrate at the water-TCE interface, and the surrounding liquid molecules pack randomly when in contact with the nanoparticle surfaces. In addition, the simulations show that the water-TCE interfacial thickness analyzed from density profiles is influenced by the presence of nanoparticles either near or in contact with the interface but is independent of the number of nanoparticles present. The nanoparticles, water molecules, and TCE molecules all exhibit diffusion anisotropy.     

Homogeneous functional Ni-P/ceramic nanocomposite coatings via stable dispersions in electroless nickel electrolytes

Stable nanoparticle dispersions in concentrated electrolytes are prerequisite for a variety of advanced nanocomposites prepared by deposition techniques. In this work we investigate the synthesis of electroless Ni-P/functional ceramic coatings from concentrated electrolytes containing functional nanoparticles such as TiO(2), α-Fe(2)O(3), ITO, and CeO(2). Stable nanoparticle dispersions in both low and high phosphorus electrolytes are achieved at plating temperatures (80-90 °C) by a generalized scheme employing comb-polyelectrolyte and antifreeze additives. Dispersion stability at room temperature is achieved in both low and high phosphorus EN media using anionic comb-polyelectrolyte surfactants with polyether side chain of 1100 g/mol. The optimal surfactant concentration is determined by zeta-potential and thermo-gravimetric analysis. Without additives the dispersions flocculate and sediment between 65 and 80 °C. Such phenomenon is believed to be associated with a critical flocculation temperature (CFT). The CFT is also weekly dependent on the particle type and the high ionic strength media. Addition of antifreeze additives such as propylene glycol and urea to the dispersions restores stability and increase the CFT for all particles. We estimate an average increase of the CFT by 1.5-2 °C per 1% additive for all particles and electrolytes. While the particle stabilization scheme is generalized in this work, the composite EN plating proved highly dependent on particle type. Baths containing ITO nanoparticles showed no plating reactions and those containing α-Fe(2)O(3) no nanoparticle co-deposition. In contrast, homogeneous Ni-P/TiO(2) and Ni-P/CeO(2) nanocomposites with up to 22 vol.% nanoparticles are produced. The possible application of the stabilization principles developed here for other functional nanocomposite systems is discussed.     

Surface-enhanced Raman nanoparticle beacons based on bioconjugated gold nanocrystals and long range plasmonic coupling

We have developed a new class of surface-enhanced Raman scattering beacons (SERS beacons) that can be turned on and off by long-range plasmonic coupling, induced by biomolecular recognition and binding events. The beacons are based on colloidal gold nanocrystals in two sizes (40 and 60 nm) and are prepared by spectral encoding with a Raman reporter molecule, functionalized with thiolated DNA probes, and stabilized and protected by low molecular weight poly(ethylene glycol)s (PEGs). The results show the SERS signal intensities increase by 40-200-fold when the nanoparticle beacons are activated by plasmonic coupling, much higher than the bright-to-dark intensity ratios reported for traditional molecular beacons. Multivalent gold nanoparticles also have exquisite specificity and are able to recognize single-base mismatches or mutations. This class of SERS nanoparticle beacons has novel mechanisms for molecular detection and signal amplification, and its long-range coupling nature raises new opportunities in developing plasmonic probes to detect proteins, cells, and intact viruses.     

Water-induced interactions between carbon nanoparticles

Molecular dynamics simulations were carried out in order to study the hydration of C60 fullerenes, carbon nanotubes, and graphene sheets in aqueous solution and the nature of water-induced interactions between these carbon nanoparticles. The hydration of these nonpolar carbon nanoparticles does not exhibit classical hydrophobic character due to the high density of surface atoms (carbon) resulting in strong water-surface dispersion interactions. Water was found to wet the nanoparticle surfaces independent of nanoparticle surface curvature, with the decrease in the extent of water-water hydrogen bonding with decreasing surface curvature being offset by stronger water-surface interactions. While all carbon nanoparticles investigated are anticipated to aggregate in water due to strong direct nanoparticle-nanoparticle interactions, the water-induced interactions between nanoparticles were found to be repulsive and, in contrast to the wetting behavior, were observed to exhibit strong dependence on surface curvature. The strength of the water-induced interaction between carbon nanoparticles was found to correlate well with the number of hydration water molecules displaced upon particle aggregation, which, relative to the amount of direct nanoparticle-nanoparticle contact engendered upon aggregation, decreases with decreasing surface curvature.     

Effective interactions in mixtures of silica microspheres and polystyrene nanoparticles

We investigate the effect of small concentrations of highly charged nanoparticles on the stability of uncharged colloidal microspheres using large-scale simulations. Employing pair potentials that accurately represent mixtures of silica microspheres and polystyrene nanoparticles as studied experimentally, we are able to demonstrate that nanoparticle-induced stabilization can arise from a relatively weak van der Waals attraction between the colloids and nanoparticles. This demonstrates that the nanoparticle haloing mechanism for colloidal stabilization is of considerable generality and potentially can be applied to large classes of systems. The range of optimal nanoparticle concentrations can be tuned by controlling the attraction between colloids and nanoparticles.     

均一取向等离子体二聚体的制备及光学机理

以单层SiO₂胶体微球为模板, 利用Au/SiO₂/Au交替沉积结合后退火处理的方法, 制备了一种垂直堆叠且均一取向的等离子体二聚体结构. 该方法具有很大的自由度, 可以通过调节实验流程来制备大面积取向相同的同质或异质纳米粒子二聚体. 所制备的纳米粒子的等离子体杂化效应明显, 在消光光谱中可以观察到成键及反键共振峰. 由于所得纳米粒子二聚体具有垂直堆叠的特殊规整取向, 还可以观察到所得样品等离子体吸收峰的角度依赖特性. 此外, 还探讨了Au/SiO₂/Au同质二聚体和Au/SiO₂/Ag异质二聚体的光学特性差异, 发现与Au/SiO₂/Au同质二聚体相比, Au/SiO₂/Ag异质二聚体由于Ag偶极等离子体模式与Au带间吸收的耦合而呈现Fano共振峰. 所得结果提供了一个调节贵金属等离子体光学共振峰位、 强度和波形的策略, 在纳米光子学领域有着广阔的应用前景, 对今后的实验和理论研究具有重要参考价值.     

Electrostatically tuned interactions in silica microsphere-polystyrene nanoparticle mixtures

We explore the generality of nanoparticle haloing as a novel colloidal stabilization mechanism in binary mixtures of silica microspheres and polystyrene nanoparticles. By selectively tuning their electrostatic interactions, both the initial microsphere stability and the role of nanoparticle additions are varied. Adsorption isotherm and zeta potential measurements indicate that highly charged nanoparticles exhibit a weak (haloing) association with negligibly charged microspheres, whereas they either strongly adsorb onto oppositely charged or are repelled by like-charged microsphere surfaces, respectively. Bulk sedimentation and confocal scanning fluorescence microscopy reveal that important differences in system stability emerge depending on whether the added nanoparticles serve as haloing, bridging, or depletant species.     

Logical regulations of the aggregation/dispersion of gold nanoparticles via programmed chemical interactions

Nanoparticles that respond to various chemical and physical stimuli form the basis for various conceivable applications including sensors, chemical logic, biomedical imaging, and therapies. In this work, we demonstrate that the electrostatic and chemical (complexing and gold-thiol bonding) interactions existing in a gold nanoparticle/Zn(2+)/dithiothreitol-based ternary chemical system is "programmable" and can be utilized to regulate the aggregation and dispersion of nanoparticles via XOR and INHIBIT logics. The resulting solutions alter their colors according to different input combinations because of the well-controlled aggregation or dispersion of plasmonic gold nanoparticles, opening up new possibilities for the developments of advanced sensors and nanobiomedical devices based on the coupling, gating, and signaling of different chemical stimuli.     

Emerging advances in plasmonic nanoassemblies for biosensing and cell imaging

Integrating discrete plasmonic nanoparticles into assemblies can induce plasmonic coupling that produces collective plasmonic properties, which are not available for single nanoparticles. Theoretical analysis revealed that plasmonic coupling derived from assemblies could produce stronger electromagnetic field enhancement effects. Thus, plasmonic assemblies enable better performance in plasmon-based applications,such as enhanced fluorescence and Raman effects. This makes them hold great potential...     

Quantitative data on the effects of alkyl substituents and Li-O and Li-N chelation on the stability of secondary alpha-oxy-organolithium compounds

A DeltaG(eq) stability scale of secondary alpha-oxy-organolithium compounds was established from measurements of tin-lithium exchange equilibria in THF, and the quantitative effects of substituents at the anionic center on carbanion stability are presented. A new lead-lithium exchange equilibrium reaction was also investigated and shown to be a very useful alternative for the determination of the relative stability of the more sterically hindered organolithium compounds. Alkyl groups adversely affect the stability of organolithium compounds when attached to the carbon bearing the negative charge, but the extent of this effect is highly dependent on the nature of the rest of the substituents attached to the anionic center. Quantitative data on the stabilization imparted to organolithium compounds by Li-O and Li-N chelation have been determined for a variety of systems. The formation of four- and five-membered chelate rings leads to a considerable stabilization of the organolithium compound, while chelation through the formation of six-membered rings affords no extra stabilization to this type of organometallics. Multinuclear NMR experiments carried out on several alpha-oxy-organolithium compounds to determine their aggregation state are supportive of these species being monomers in THF solution.     

Chiral Gold Nanorods with Five-Fold Rotational Symmetry and Orientation-Dependent Chiroptical Properties of Their Monomers and Dimers

Chiral plasmonic nanoparticles have attracted much attention because of their strong chiroptical responses and broad scientific applications. However, the types of chiral plasmonic nanoparticles have remained limited. Herein we report on a new type of chiral nanoparticle, chiral Au nanorod (NR) with five-fold rotational symmetry, which is synthesized using chiral molecules. Three different types of Au seeds (Au elongated nanodecahedrons, nanodecahedrons, and nanobipyramids) are used to study the growth behaviors. Different synthesis parameters, including the chiral molecules, surfactant, reductant, seeds, and Au precursor, are systematically varied to optimize the chiroptical responses of the chiral Au NRs. The chiral scattering measurements on the individual chiral Au NRs and their dimers are performed. Intriguingly, the chiroptical signals of the individual chiral Au NRs and their end-to-end dimers are similar, while those of the side-by-side dimers are largely reduced. Theoretical calculations and numerical simulations reveal that the different chiroptical responses of the chiral NR dimers are originated from the coupling effect between the plasmon resonance modes. Our study enriches chiral plasmonic nanoparticles and provides valuable insight for the design of plasmonic nanostructures with desired chiroptical properties.     

Enhanced two-photon emission in coupled metal nanoparticles induced by conjugated polymers

Interactions between noble metal (Ag and Au) nanoparticles and conjugated polymers as well as their one- and two-photon emission have been investigated. Ag and Au nanoparticles exhibited extraordinary quenching effects on the fluorescence of cationic poly(fluorinephenylene). The quenching efficiency by 37-nm Ag nanoparticles is ～19 times more efficient than that by 13-nm Au nanoparticles, and 9-10 orders of magnitude more efficient than typical small molecule dye-quencher pairs. On the other hand, the cationic conjugated polymers induce the aggregate formation and plasmonic coupling of the metal nanoparticles, as evidenced by transmission electron microscopy images and appearance of a new longitudinal plasmon band in the near-infrared region. The two-photon emissions of Ag and Au nanoparticles were found to be significantly enhanced upon addition of conjugated polymers, by a factor of 51-times and 9-times compared to the isolated nanoparticles for Ag and Au, respectively. These studies could be further extended to the applications of two-photon imaging and sensing of the analytes that can induce formation of metal nanoparticle aggregates, which have many advantages over the conventional one-photon counterparts.     

Thiophene dendron jacketed poly(amidoamine) dendrimers: nanoparticle synthesis and adsorption on graphite

The peripheral functionalization of amine-terminated fourth-generation poly(amidoamine) (PAMAM) with thiophene dendrons and the preparation of dendrimer-encapsulated metal nanoparticles are described. Interesting nanoparticle stabilization and energy-transfer properties were observed with these hybrid materials. The synthesis involved imine coupling of the dendron derivatives to the peripheral amine groups of PAMAM followed by reduction. The formation of these metal-organic nanoparticle hybrid materials was monitored by UV-vis spectroscopy. The complexation of metal ions and the stabilization effect of PAMAM on metal nanoparticles were investigated by FT-IR. Energy transfer was observed between the metal surface plasmon absorption and fluorescence of the terthiophene dendrons. Noncontact magnetic-AC mode AFM imaging revealed the formation of monodispersed and very stable nanoparticles adsorbed on an HOPG flat substrate.     

Comparison of the migration behavior of nanoparticles based on polyethylene glycol and silica using micellar electrokinetic chromatography

Nanoparticles, spherical particles with diameters less than 100 nm, are promising theranostic devices for noninvasive diagnosis and therapy. In this study, nanoparticles composed of polyethylene glycol and silica were prepared, and their migration behavior was examined using capillary electrophoresis. The effects of the sodium dodecyl sulfate concentration in the electrolyte, the nanoparticle size, and the encapsulated molecule on the migration were examined. The addition of sodium dodecyl sulfate into the electrolyte had a significant effect on the electrophoretic mobility of polyethylene glycol nanoparticles, but a small effect on that of silica nanoparticles. As for the size effect, the mobility became a little faster for smaller nanoparticle sizes for both polyethylene glycol and silica nanoparticles. The encapsulated molecule affected the mobility of the nanoparticles through interactions between the encapsulated molecules and sodium dodecyl sulfate. We propose that the large effect of sodium dodecyl sulfate on the migration of the polyethylene glycol nanoparticles was due to the large spaces within the nanoparticles. These results indicate that nanoparticle migration is mainly determined by the nanoparticle components.