In situ deposition of Pd nanoparticles on carbon paper and their electroactivity for ethanol oxidation

Ionics - In this work, Pd and PdNi nanostructured particles have been deposited on the carbon paper (CP) by a novel and simple method of in situ deposition. The prepared catalysts were named as...     

The development of multivalent ion conductors and their application for chemical sensors

New types of multivalent ion conducting solid electrolytes have been extensively developed and their applications for chemical sensors were investigated. Among the trivalent ion conductors, the highest ion conductivity was realized with the (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃ solid electrolyte and the value reaches the region between yttria stabilized zirconia (YSZ) and calcia stabilized zirconia (CSZ) of the representative oxide anion conductors. The above described Al³⁺ ion conducting (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃ solid electrolyte was combined with YSZ, with accompanying the Y₂O₃-KNO₂ solid solution as an auxiliary electrode for nitrogen monoxide (NO) gas sensing. The sensor response was rapid and a reproducible output was continuously observed obeying the Nernst theoretical relationship in a typical NO gas content region in exhaust gases. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

In situ deposition behavior of silica-based layers and its effect on thermal degradation of IN713 turbine blades during operation of a micro-gas turbine

This study examined the in situ deposition behavior of silica-based layers on IN713 turbine blades during the operation of a 13 kgf-class gas turbine at a rotation speed of 20,000/min as well as its effect on the degradation of the metallic substrate. Tetraethylorthosilicate (TEOS) was mixed with the fuel (liquid petroleum gas, LPG) and burned to generate silica-based coating precursors for deposition from the flame. Two deposition conditions were adopted. For condition 1 (C1), the silicon-to-carbon ratio in the mixed fuel was set at 0.1 mol% for the first 5 min and at zero mol% for the final 95 min in a 100-min operation. For condition 2 (C2), the ratio was set at 0.005 mol% during the entire 100 min operation. The total TEOS feed was the same under both conditions. C1 resulted in a rather uniform and thicker (5-10 μm on the pressure side) porous silica-based coating on the blade than C2. The in situ deposited layer of C1 was well preserved on the blade and protected the underlying metallic substrate from oxidation during the entire 100 min operation. The layer on the C2 blades was ∼5 μm thick at the region near to root, but was too thin in the other areas on the blade to be protective. The early build-up of a porous layer to an effective thickness on the blades produced a thermal barrier toward the substrate as well as a diffusion barrier toward the oxidizing elements during operation.     

Formation of gold nanoparticles and their aggregates in a liquid at magnetron deposition

The influence of magnetron deposition conditions on the size of Au nanoparticles and their aggregates obtained by condensation in a neutral liquid is studied experimentally. A model is suggested in which the nanoparticles and aggregates form in a thin subsurface layer, which becomes oversaturated by atoms and resulting nanoparticles when the liquid flows through a localized deposition zone. The process stops when the products leave this zone because of stirring. The size of nanoparticles and aggregates depends on the particle flux density and exposure time in the deposition zone. The final size of nanoparticles depends on the exposure time only slightly, while that of aggregates significantly depends on the exposure time. This allows one to prepare a concentrated solution of almost monodisperse nanoparticles with a low degree of aggregation by properly selecting deposition conditions and multiply passing the liquid through the deposition zone.     

In situ derivatization-liquid liquid extraction as a sample preparation strategy for the determination of urinary biomarker prolyl-4-hydroxyproline by liquid chromatography-tandem mass spectrometry

Polar analytes that possess protic functional groups have often been treated with alkyl chloroformates to decrease their polarity and increase their volatility prior to gas chromatography-mass spectrometry analysis. This derivatization reaction has two distinct advantages. It proceeds smoothly in aqueous media, and the desired reaction products are efficiently separated from interfering ionic components by their extraction into a water-immiscible organic phase. In the present work, the derivatization-liquid liquid sample preparation was examined in detail for analysis of a potential urinary dipeptide biomarker L-prolyl-4-L-hydroxyproline (PHP) by downstream liquid chromatography coupled to electrospray mass spectrometry. PHP was treated with a series of alkyl and fluoroalkyl chloroformates in aqueous media, and the detected reaction products were investigated. Smooth conversion of PHP into the N-isobutyloxycarbonyl isobutyl ester was accomplished by the coupled action of isobutanol, isobutyl chloroformate and the pyridine catalyst. This derivative afforded a highest detector response from all the derivatized forms examined, including the nonderivatized PHP. A simple isocratic elution on a common RP-C18 HPLC column coupled with tandem mass spectrometry, and use of the synthesized heptadeuterated analog (D7-PHP) as an internal standard, enabled validation of the method and determination of PHP in human urine in less than 5?min. The in situ derivatization-liquid liquid extraction has thus been demonstrated to be a useful sample preparation strategy for the analysis of polar metabolites by liquid chromatography-tandem mass spectrometry in the complex urine matrix.     

In situ characterization of liquid network structures at high pressure and temperature using X-ray absorption spectroscopy coupled with the Paris-Edinburgh press

ABSTRACT

We review recent progress in studying structural properties of liquids using X-ray absorption spectroscopy coupled with the Paris-Edinburgh press at third-generation synchrotron facilities. This experimental method allows for detecting subtle changes in atomic arrangements of melts over a wide pressure–temperature range. It has been also employed to monitor variations of the local coordination environment of diluted species contained in glasses, liquids and crystalline phases as a function of the pressure and temperature. Such information is of great importance for gaining deeper insights into the physico-chemical properties of liquids at extreme condition, including the understanding of such phenomena as liquid–liquid phase transitions, viscosity drops and various transport properties of geological melts. Here, we describe the experimental approach and discuss its potential in structural characterization on selected scientific highlights. Finally, the current ongoing instrumental developments and future scientific opportunities are discussed.     

Observation of nonlinear saturable and reverse-saturable absorption in silver nanowires and their silica gel glass composite

Silver nanowires (Ag NWs) and their silica gel glass composite were produced. Their nonlinear optical (NLO) properties, mainly saturable absorption (SA) and reverse-saturable absorption (RSA), were investigated at 532 and 1064 nm, using the open aperture z-scan technique and a nanosecond-pulsed laser. We found that Ag NWs demonstrate rather different NLO behaviors in liquid and solid-state matrices. The Ag NWs suspension exhibited only RSA, whereas a transformation from SA to RSA occurred in the silica gel glass composite. The underlying mechanism was proposed from the viewpoint of different environments and electronic dynamics of Ag NWs in the liquid and solid-state matrices.     

In situ synthesis of silicon-substituted biphasic calcium phosphate and their performance in vitro

In situ preparation of silicon (Si) substituted biphasic calcium phosphate (BCP) of hydroxyapatite (HAp)/ β-tricalcium phosphate (β-TCP) were carried out through aqueous co-precipitation method. The concentrations of added silicon were varied with the phosphor in order to obtain constant Ca/(P+Si) ratios of 1.602. X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) spectroscopy were used to characterize the structure of synthesized silicon substituted BCP powders. The characterization revealed that the formation of biphasic mixtures of different HAp/ β-TCP ratios was dependent on the content of silicon. After immersing in Hanks' balanced salt solution (HBSS) for 1 week, 3 wt% silicon substituted BCP powders were degraded and precipitation started to be formed with small granules consisting of number of flake-like crystal onto the surface of synthesized powders. In the case of 1 wt% silicon substituted BCP powders, the degradation behavior was detected after immersion in HBSS for 3 weeks. On the other hand, silicon unsubtituted BCP powders were not degraded even after that duration. On the basis of these results, silicon substituted BCP is able to develop a new apatite phase on the surface in contact with physiological fluids faster than BCP does. This enhanced reactivity resulted in reduction for the stability of the β-TCP structure due to SiO₄ tetrahedral distortion and disorder at the hydroxyl site when silicon incorporates into BCP.     

In situ observation and analysis of multiple cracking phenomena in thin glass layers deposited on polymer films

The multiple cracking phenomena in thin SiO_x films deposited on 12 μm-thick polyethylene terephthalate (PET) substrates during the tensile test are investigated. Thicknesses of SiO_x films ranged from 43 to 320 nm. The multiple cracking progress is observed in situ by optical microscopy and from which the crack density in SiO_x films is measured. The predicted crack density by the shear lag analysis including residual strains, explains reasonably well the experimental results. The critical energy release rate, G_c, for the first film cracking is also evaluated from simple energy balance arguments. Although it depends on the analytical model, G_c is estimated to be a constant value of about 1.0 J/m² regardless of the thickness.     

Novel ionic liquid supported on Fe3O4 nanoparticles and its application as a catalyst in Mannich reaction under ultrasonic irradiation

A family of novel ionic liquid with l-alanine and choline chloride as environmentally benign materials have been synthesized and grafted on Fe₃O₄ nanoparticles using easy preparation techniques. The structure of ionic liquid supported on Fe₃O₄ nanoparticles (IL-Fe₃O₄ NPs) characterized by various analyses such as FE-SEM, EDX, XRD, NMR, FTIR and VSM. The catalytic activities of this catalyst are examined in the Mannich reaction for synthesis of β-aminocarbonyl compounds under ultrasonic irradiation. The recyclability of catalyst is investigated, and the results have indicated that the catalyst can be recycled six times without obvious activity decreasing.     

Synthesis of colloidal gold nanobones with tunable negative curvatures at end surface and their application in SERS

In this work, gold nanobones with the length from 50 to 70 nm were synthesized by a seed-mediated method. The plasmonic optical properties and the roles of gold seed amount in regulating the negative curvatures of the end surfaces of the gold nanobones have also been studied. Compared with the gold nanorods, a new middle surface plasmon resonance (SPR) peak appears in the absorption spectra due to the negative curvatures on the end surfaces of the gold nanobones. What is more, the surface enhanced Raman scattering (SERS) activities of gold nanobones are much stronger than that of gold nanorods. By controlling the amount of the gold seed, the wavelength of the middle SPR peak can be adjusted between 560 and 650 nm, and the corresponding negative curvature of the end surfaces could also be fine tuned. When the amount of gold seed reaches saturation, the end surfaces of nanobones have the strongest negative curvature, which results in the greatest SERS activity. This improved SERS has been attributed to the negative curvature-induced formation of the antenna dimers. The orientation of plasmon coupling between the antenna dimers is perpendicular to the nanobones. Thus, the hot spots at the ends of nanobones could always be created when the excitation beam polarization is either parallel or perpendicular to the nanobones. This negative curvature-dependent SERS enhancement lays the foundation for the extensive application of gold nanobones in SERS.     

Production of nanosized aluminum powders and their application as fillers for composite materials based on ultrahigh molecular weight polyethylene (UHMWPE)

A modified levitation-in-flow Gen-Miller technique is developed to produce nanodisperse aluminum particles 40–200 nm in size with a barrier coating of controlled thickness made of aluminum oxides and (oxy)nitrides for the use as a dielectric filler in composite materials. The polymerization filling technique (in situ polymerization) is used to synthesize new highly filled nanocomposite materials based on UHMWPE and nanodisperse aluminum with the barrier coating combining dielectric, heat-conducting, and plastic properties, which can replace brittle ceramics in a number of fields. The samples of such nanocomposites with a content of nanoaluminum ranging from 20 to 80 wt % were synthesized and characterized by electron microscopy and X-ray diffraction analysis.     

Development of mesoporous structures of composite silica particles with various organic functional groups in the presence and absence of ammonia catalyst

Development of mesoporous structures of composite silica particles with various organic functional groups was investigated by using a two-step process, consisting of one-pot sol-gel process in the presence and absence of ammonium hydroxide and a selective dissolution process with an ethanol-water mixture. Five different organosilanes, including methyltrimethoxysilane (MTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), phenyltrimethoxysilane (PTMS), vinyltrimethoxysilane (VTMS), and 3-aminopropyltrimethoxysilane (APTMS) were employed. The mesoporous (organically modified silica) ORMOSIL particles were obtained even in the absence of ammonium hydroxide when the reaction mixture contained APTMS. The morphology of the particles, however, were different from those prepared with ammonia catalyst and the same organosilane mixtures, probably because the overall hydrolysis/condensation rates became slower. Co-existence of APTMS and VTMS was essential to prepare mesoporous particles from ternary organosilane mixtures. The work presented here demonstrates that organosilica particles with desired functionality and desired mesoporous structures can be obtained by selecting proper types of organosilane monomers and performing a facile and mild process either with or without ammonium hydroxide.     

Improving colloidal properties of quantum dots with combined silica and polymer coatings for in vitro immuofluorenscence assay

Semiconductor quantum dots (QDs) are promising fluorescence probes for immuofluorescence assay in the biological applications. However, water solubilization and non-specific binding are two critical issues to be addressed for the practical uses. Here, we reported a new type of QDs with combined silica and polymer coating. QDs with excellent colloidal properties were prepared via carboxylation of the amino groups on the surface of silica-coated QDs by reacting with multi-carboxyl poly (acrylic acid) (PAA). Hydrodynamic size of PAA-functionalized silica-coated QDs was around 40 nm. They were highly fluorescent (about 47.8% quantum yield). No precipitate of QDs was observed after 3 month storage at 4 °C. When cancer cells (HeLa) were used, the functionalized QDs exhibited little or no non-specific cellular binding. The results from in vitro experiments indicated that PAA-functionalized silica-coated QDs-antibody bioconjugates had excellent antigen-capture ability and exhibited little or no non-specific binding to polystyrene spheres which were used to immobilize the antigen for immuoflurescence assay. The PAA-functionalized silica-coated QDs with improved colloidal properties could serve as excellent alternative fluorescent probes for biodetection.     

In situ observation of dynamics of plasma self-channeling and bulk modification in silica glasses induced by a high-intensity femtosecond laser

The time-resolved dynamics of plasma self-channeling and refractive index bulk modification in silica glasses were first observed in situ using a high-intensity femtosecond (110 fs) Ti:sapphire laser (λ_p=790 nm). Plasma channeling is induced in silica glass at an irradiation higher than an input intensity of 1.5×10¹² W/cm² and photoinduces either the refractive-index modification or optical crack modification. In the domain of refractive-index modification, the lifetime of induced plasma self-channeling was 20 ps and the structural transition time for forming the refractive-index change was 10 ps. In the domain of optical cracks, however, the lifetime of induced plasma formation was 30 ps and the structural transition time for forming the optical cracks was 40 ps. According to electron spin resonance spectroscopic (ESP) measurement, it was found that the defect concentration of the SiE^′ center increased significantly in the refractive index modification region. A maximum value of the refractive-index change Δn was measured to be 1.6×10^-2. The intensity profile of the output beam transmitted through the refractive-index modification showed that the bulk modification produced a permanent optical waveguide. Received: 8 April 2002 / Accepted: 12 April 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +81-48/462-4682, E-mail: shcho@riken.go.jp     

Voltammetric determination of uric acid in the presence of ascorbic acid and dopamine using chitosan/ionic liquid composite electrode

A chitosan/ionic liquid composite electrode was prepared and used to determine uric acid (UA) in the presence of a large excess of ascorbic acid (AA) and dopamine (DA) by linear sweep voltammetry (LSV). The modified electrode shows large peak separations between DA, AA, and UA. Due to the existence of chitosan and ionic liquid in the composite, the modified electrode exhibits strong electrochemical catalytic activity toward the oxidation of UA. Under optimal conditions, the peak current is linearly dependent on the UA concentration in the range of 5?×?10^?7–2?×?10^?4 M in the presence of 5?×?10^?4 M AA and 5?×?10^?5 M DA with a correlation coefficient of 0.9978, and the detection limit is 5?×?10^?8 M at a signal-to-noise ratio of 3. With good sensitivity and stability, the constructed sensor was applied in the determination of UA in human serum samples and satisfactory results were obtained.     

Semiconducting In2S3 quantum dots in thin film form: sonochemical versus conventional chemical synthesis and investigation of their structural and optical properties

Indium(III) sulfide quantum dots were deposited in thin film form using both a conventional chemical bath deposition method and a sonochemical route. The developed routes allow deposition of cubic α-In₂S₃ nanocrystals in thin film form. The as-deposited films produced by the conventional and sonochemical approaches are highly nanocrystalline, with average crystal sizes of 2.5 and 2.0 nm correspondingly (as determined from the Scherrer formula), which increase to 4.1 nm upon annealing treatment, due to coalescence and crystal-growth processes. Refinement of the lattice-constant value in the case of as-deposited and annealed films was performed using linear regression analysis. Blue-shifted band-gap energy values of as-deposited films with respect to those corresponding to bulk specimen, accompanied with the red shift of absorption onset upon annealing, strongly indicate the quantum-dot behavior of the synthesized nanocrystals. The detected three-dimensional quantum-confinement effects in the synthesized nanocrystals were discussed in terms of the Brus model. On the basis of optical spectroscopic data, we estimated the Bohr's excitonic radius value in this semiconductor. Presented at the X-th Symposium on Suface Physics, Prague, Czech Republic, July 11–15, 2005.     

Dynamics of rough interfaces in chemical vapor deposition: experiments and a model for silica films

We study the surface dynamics of silica films grown by low pressure chemical vapor deposition. Atomic force microscopy measurements show that the surface reaches a scale invariant stationary state compatible with the Kardar-Parisi-Zhang (KPZ) equation in three dimensions. At intermediate times the surface undergoes an unstable transient due to shadowing effects. By varying growth conditions and using spectroscopic techniques, we determine the physical origin of KPZ scaling to be a low value of the surface sticking probability, related to the surface concentration of reactive groups. We propose a stochastic equation that describes the qualitative behavior of our experimental system.     

Vacuum-deposited wave-guiding layers on STW resonators based on LiTaO3 substrate as love wave sensors for chemical and biochemical sensing in liquids

A promising approach to apply the Love wave concept to commercially available low-loss surface acoustic wave (SAW) devices of the type Murata SAF 380 is presented. Thin wave-guiding layers of variable thickness are coated on the piezoelectric substrate of the devices. Two different layer materials were used: sputtered SiO₂ and a new polymer in this field, parylene C (poly-[2-chloro-p-xylylene]). Insertion loss, resonance frequency, frequency changes during protein precipitation and noise of the devices are discussed as a function of the thickness of the wave-guiding layer. It is demonstrated that the application of an optimized wave-guiding layer increases the sensitivity. When using SiO₂ as wave-guiding layer, an optimum layer thickness of 4 μm leads to a detection limit of 1.7 pg/mm². Therefore, the detection limit is improved by factor 7.7 as compared to uncoated SAW devices. Parylene-coated devices reach a detection limit of 2.9 pg/mm² at an optimum layer thickness of 0.5 μm. This corresponds to an improvement by factor 4.3. As the SAW devices used in this study are commercially available at low costs, applying appropriate wave-guiding layers permits an application as chemical or biochemical sensors with excellent sensitivities. Moreover, parylene-coated devices combine the sensitivity increase by excitation of Love waves with an excellent protective effect against corrosive attacks by the surrounding medium. Therefore, these sensors are most suitable for biosensing in conducting buffer solutions.     

Drastic change in shape of tetragonal TeO2 nanowires and their application to transparent chemical gas sensors

We have synthesized one-dimensional structures of tellurium dioxide (TeO₂) by heating of tellurium powders. Their morphology was drastically changed as the growth temperature increased in the range of 400-500 °C, in which high-temperature process facilitated the thickening of the stem nanowires, as well as the growth of secondary branches on the stems. The obtained TeO₂ products were crystalline with tetragonal structure. The TeO₂ nanowire film exhibited a high transmission rate of about 73%. We have investigated the NO₂ sensing properties of the as-fabricated TeO₂ nanowires, in which a linear relationship between sensitivity and the NO₂ gas concentration was observed. Thus, the TeO₂ nanowires demonstrated their potential application to transparent chemical sensors.