Extraordinary Destabilization of Silica Nanocolloids by Filtration.

After silica nanoparticles in solutions were filtered by a syringe filter with a much larger pore size than the particle diameter Dp, the filtrated effects on the rapid coagulation rate in 1 M KCl solution, the dynamic light scattering diameter, and the zeta potential at pH ∼ 6 were investigated by employing the particles of two different sizes: S particles (Dp ∼ 50 nm) of silica and latex and L particles (Dp ∼ 300 nm) of silica. It was found that the hydrodynamic diameters of silica particles became a little smaller and the absolute values of their zeta potentials decreased significantly by filtration, but that is not the case for latex particles. As for the rapid coagulation rate, the value of silica S particles increased more than 2 orders of magnitude by filtration, but no significant difference was found in the case of silica L and latex S particles. From these data, it was postulated that the gel-like layer was removed from the surface of silica S particles by filtration and the existence of the gel-like layer resulted into about 2 orders of magnitude reduction of the rapid coagulation rate. The extraordinary reduction of rapid coagulation of silica particles at Dp < 150 nm was successfully estimated by the revised Smoluchowski theory, which we call the Higashitani-Mori (HM) model. It was also found that the rapid coagulation rate of filtrated particles decreased slowly with a decreasing particle size at Dp < ca. 250 nm, which was also estimated properly by the HM model, neglecting the contribution of the redispersion of coagulated particles. Another finding in this study was that the gel-like layers were recovered with time even if they were removed by filtration, although the detailed mechanism of this recovering is not known at present and left as a future problem.

Ionic Specificity in Rapid Coagulation of Silica Nanoparticles.

The Smoluchowski theory has been widely accepted as the basic theory to estimate the rapid coagulation rate of colloidal particles in electrolyte solutions. However, because the size and specificity of molecules and ions are not taken into account, the theory is applicable only if the particle size is large enough to neglect the effects caused by the structured layers composed of water molecules, ions, and hydrated ions adsorbed on the colloidal surface. In the present study, the rapid coagulation rates of silica nanoparticles in concentrated chloride and potassium solutions were measured by using a low-angle light-scattering apparatus, and the dependence of the experimental value of rapid coagulation rate, KER, on the particle diameter, Dp, and also on the Gibbs free energy of hydration of ions, ΔGhyd, was investigated extensively. The following were found. (1) When the particle size was small enough, the value of KER reduced exponentially not only with the decreasing particle size but also with the increasing value of (-ΔGhyd) of cations (counterions) in the case of chloride solutions and with that of anions (coions) in the case of potassium solutions. (2) Silica nanoparticles of Dp ≲ 70 nm in 1 M KNO3 and KSCN solutions did not coagulate at all, although they coagulated at Dp ≳ 100 nm as in the other potassium solutions. These unexpected phenomena were explained by the proposed mechanisms.

Orders of Magnitude Reduction of Rapid Coagulation Rate with Decreasing Size of Silica Nanoparticles.

The modification of the classical Smoluchowski theory for the rapid coagulation rate of colloidal particles, which takes account of the effect of the squeezing flow between colliding particles, has been widely accepted because it predicts experimental results adequately. However, it is not clear whether the modified theory, in which the coagulation rate is independent of the particle size, is applicable even to nanoparticles in solutions. In the present study, the rapid coagulation rates of silica particles in various 2 M chloride and 1 M potassium solutions were measured by using a low-angle light-scattering apparatus, and the dependence of rapid coagulation rate on the particle diameter, Dp, was investigated extensively. It was clearly shown that the rapid coagulation rate of spherical silica particles reduces by the orders of magnitude with decreasing particle size at Dp ≤ 300 nm, whereas it coincides with the value predicted by the modified theory at Dp ≥ 300 nm. A possible mechanism is proposed, and an analytical equation, which predicts the dramatic reduction in the rapid coagulation rate with decreasing particle size, is derived.

Periodicity in ultrasonic atomization involving beads-fountain oscillations and mist generation: Effects of driving frequency.

Ultrasonic atomization induced by high driving frequency, generally on the order of 1 MHz or higher, could involve a liquid fountain in the form of a corrugated jet, or a chain of "beads" of submillimeter diameter in contact. This study concerns dynamics/instability of such beads fountain, observed under lower input power density (≤ 6 W/cm2) of the "flat" ultrasound transducer with a "regulating" nozzle equipped, exhibiting time-varying characteristics with certain periodicity. High-speed, high-resolution images are processed for quantitative elucidation: frequency analysis (fast Fourier transform) and time-frequency analysis (discrete wavelet transform) are employed, respectively, to evaluate dominant frequencies of beads-surface oscillations and to reveal factor(s) triggering mist emergence. The resulting time variation in the measured (or apparent) fountain structure, associated with the recurring-beads size scalable to the ultrasound wavelength, subsumes periodic nature predictable from simple physical modeling as well as principle. It is further found that such dynamics in (time-series data for) the fountain structure at given height(s) along a series of beads would signal "bursting" of liquid droplets emanating out of a highly deformed bead often followed by a cloud of tiny droplets, or mist. In particular, the bursting appears to be not a completely random phenomenon but should concur with the fountain periodicity with a limited extent of probability.

Physically unclonable functions taggant for universal steganographic prints.

Counterfeiting of financial cards and marketable securities is a major social problem globally. Electronic identification and image recognition are common anti-counterfeiting techniques, yet they can be overcome by understanding the corresponding algorithms and analysis methods. The present work describes a physically unclonable functions taggant, in an aqueous-soluble ink, based on surface-enhanced Raman scattering of discrete self-assemblies of Au nanoparticles. Using this stealth nanobeacon, we detected a fingerprint-type Raman spectroscopy signal that we clearly identified even on a business card with a pigment mask such as copper-phthalocyanine printed on it. Accordingly, we have overcome the reverse engineering problem that is otherwise inherent to analogous anti-counterfeiting techniques. One can readily tailor the ink to various information needs and application requirements. Our stealth nanobeacon printing will be particularly useful for steganography and provide a sensitive fingerprint for anti-counterfeiting.

Au nanorod arrays tailored for surface-enhanced Raman spectroscopy.

We have demonstrated surface-enhanced Raman spectroscopy (SERS) on arrays of Au nanorods aligned in line by a dynamic oblique deposition technique. For light polarized along the major axes of the nanorods, the plasma resonance of the Au nanorods has been tuned to a wavelength suitable for Raman spectroscopy. Raman scattering on the discrete nanorods is significantly enhanced compared with that on semicontinuous Au films. Since the preparation process is physically bottom-up, it is robust in its selection of the materials and is useful for providing SERS sensors at low cost.

Determination of the metabolites of the new designer drugs bk-MBDB and bk-MDEA in human urine.

This is the first report on identifying the specific metabolites of the new designer drugs 2-methylamino-1-(3,4-methylenedioxyphenyl)butan-1-one (bk-MBDB) and 2-ethylamino-1-(3,4-methylenedioxyphenyl)propan-1-one (bk-MDEA) in human urine using synthesized standards. Based on GC/MS and LC/MS, we identified N-dealkylation, demethylenation followed by O-methylation, and beta-ketone reduction as their major metabolic pathways. The quantitative analyses by LC/MS revealed that both demethylenation followed by O-methylation and beta-ketone reduction were superior to N-dealkylation and that both bk-MBDB and bk-MDEA were mainly metabolized into their corresponding 4-hydroxy-3-methoxy metabolites (4-OH-3MeO metabolites). After hydrolysis, the concentrations of 4-OH-3MeO metabolites and 3-hydroxy-4-methoxy metabolites of both bk-MBDB and bk-MDEA dramatically increased, suggesting that the metabolites mainly exist as their conjugates.

Self-assembled nanoscale architecture of TiO2 and application for dye-sensitized solar cells.

A single-crystal-like titania nanowire network was successfully synthesized by a surfactant assisted "oriented attachment" mechanism. Highly crystallized titania nanorods have been synthesized by hydrothermal process using block-copolymer F127 with ethylenediamine. It was observed from high resolution TEM image that titanium atoms aligned perfectly in titania anatase structure with no defect. A high light-to-electricity conversion yield (9.3%) was attained by applying these titania nanoscale materials for making an electrode of dye-sensitized solar cells.

Ag nanorod arrays tailored for surface-enhanced Raman imaging in the near-infrared region.

Using a dynamic oblique angle deposition technique, we demonstrate the direct formation of Ag nanorods with quasi-parallel major axes on a template layer of oxide having a strongly anisotropic surface morphology. The optical properties of the nanorods are tuned by varying the deposition conditions without any pre- or post-treatment, and the resulting Ag nanorod arrays exhibit high surface-enhanced Raman scattering (SERS) activity. In addition to high macroscopic uniformity over a large area, our nanorod arrays contain a high density of isolated nanorods. Using the optimum Ag nanorod arrays, the SERS imaging of the microdroplets of a rhodamine 6G solution is successfully demonstrated. The space resolution of the imaging is of the order of at least a few µm. These features are suitable for the SERS imaging of biomaterials.