Surface plasmon resonance and electrochemistry for detection of small molecules using catalyzed deposition of metal ions on gold substrate

Small molecules are difficult to detect by conventional surface plasmon resonance (SPR) spectroscopy due to the fact that the changes in the refractive index resulted from the binding process of small biomolecules are quite small. Here, we report a simple and effective method to detect small biomolecule using SPR spectroscopy and electrochemistry by catalyzed deposition of metal ions on SPR gold film. As an example, the ascorbic acid-mediated deposition of Ag on gold film was monitored by in situ SPR spectrum. The deposition of Ag atom on gold film resulted in an obvious decrease of depth in SPR angular scan curves of reflectance intensity and minimum reflectivity angle. The depth change of the SPR reflectance intensity and minimum reflectivity angle curves mainly relied on the amount of Ag atom deposited on gold film that can be controlled by the concentration of ascorbic acid. By monitoring the deposition of Ag atom on gold film, ascorbic acid was detected in the concentration range of 2 × 10⁻⁵ M to 1 ×  10⁻³ M. After each of detections, the SPR sensor surface was completely regenerated by a potential step that stripped off the Ag atom. Furthermore, the regeneration process of the sensor surface provides the feasibility for detecting the concentration of ascorbic acid by electrochemical method.     

L X-ray emission from fast highly charged Cu ions in collisions with gaseous targets: Saturation effect in excitation and transfer

We have measured L X-ray production cross sections for highly charged 156 MeV Be-like Cu ions in collisions with gaseous targets of H₂, Ne, Ar, Kr and Xe. In the present collision systems, measured projectile L X-ray intensity is contributed by the excitation as well as electron transfer processes. The projectile L X-ray production cross sections are found to increase initially and then saturate with increasing target atomic number. The charge state dependence of projectile L X-ray production cross sections have been measured with Kr target.     

Mitochondria-targeted ratiometric fluorescent probes for micropolarity and microviscosity and their applications

Two fluorescent "off-on" probes YYH1 and YYH2 were used for bioimaging mitochondrial polarity and viscosity.     

Preparation and voltammetric characterisation of bismuth-modified mesoporous platinum microelectrodes. Application to the electrooxidation of formic acid

In this paper mesoporous platinum microeletrodes (Pt-ME) modified with submonolayers of adsorbed bismuth (Bi-PtME) were prepared and characterised by cyclic voltammetry (CV). The mesoporous platinum films were electrodeposited from hexachloroplatinic acid dissolved in the aqueous domain of the lyotropic liquid crystalline phase of Brij 78^®, to form metal films with hexagonal arrays of nanometer-sized channels. Bismuth deposition was performed by different procedures involving either the spontaneous adsorption of bismuth onto the Pt surface from Bi³⁺ solutions, or by under potential deposition (UPD) of bismuth from Bi³⁺ solutions, by cycling the potential over an useful range, or applying a constant potential for a given time. The latter procedures provided high bismuth coverage (θ_Bi), whereas only small amounts of bismuth could be adsorbed from the simple immersion of the Pt-ME at open circuit. The coverage by irreversibly adsorbed bismuth was checked in a 0.5 M H₂SO₄ solution free of Bi³⁺ ions and exploiting the charge involved in the hydrogen adsorption/desorption, which decreased in proportion to the amount of platinum sites covered by bismuth. The ability of the prepared Bi-PtME towards the oxidation of formic acid was also investigated. It was found that Bi-PtME with θ_Bi = 0.6 provided stationary voltammograms characterised by a low hysteresis between the anodic and cathodic scans. The onset of the waves resulted shifted by about 150 mV towards less positive potentials with respect to that of the corresponding Pt-ME. At 0.1 M HCOOH current densities of about 70 mA cm⁻² were achieved. These results were discussed in terms of high tolerance towards the intermediate poisons of the Bi-PtME investigated here. Bi-PtME with much lower real surface area and bismuth coverage displayed both lower catalytic activity and tolerance to poisons.     

Amphiphilic miktoarm star copolymers can self-assemble into micelle-like aggregates in nonselective solvents: a case study of polyoxometalate based miktoarm stars

It is well-known that amphiphilic star-shaped copolymers can self-assemble in selective solvents to form complicated micellar constructs as a synergistic result of both the topological constraints and relative volume fractions of the arms. Although the association phenomena of amphiphilic stars have been observed in nonselective solvents, both the structural detail and formation mechanism of these associates are not clear yet. Moreover, these experimental observations are controversial with respect to molecularly dispersed starlike copolymers in nonselective solvents as is popularly believed. To clarify these issues, we have synthesized a series of polyoxometalate-based polystyrene-poly(ethylene glycol)(PS-PEG) miktoarm star supramolecular copolymers(SEW-1–5) by coupling a Keggin-type polyoxometalate of K_4[α-SiW_(12)O_(40)] with 1,2,3-triazolium bridged block copolymers of-PS_n-b~+-PEG_mI~-(n=17, 26, 39, 57, 81; m=45) through ionic exchange reactions, respectively. TEM imaging,contact angle and ~1H NMR studies reveal that SEW-2–5 self-assemble in chloroform, THF, and toluene to create micellelike aggregates ranging from cylinder to sphere with a PS corona and a PEG core, while for SEW-1, reverse bilayers are captured with a PEG corona and a PS core. Among these aggregates, the Keggin clusters of [α-SiW_(12)O_(40)]~(4-) localize at the core-corona interfaces between PS and PEG. In terms of solvent quality, chloroform, THF, and toluene are only slightly poorer for PEG than that for PS with a relative order of chloroformTHFtoluene. These unexpected aggregates originate from the topological constraints of the chemically different arms of PS and PEG in the miktoarm stars, where the weak incompatibility between the PS and PEG arms is intensified appropriately. The presence of the reverse bilayered structures of SEW-1 is due to the magnified steric hindrance of the PEG45 arm with decreasing the molecular weight of the PS17 arm. However, to the best of our knowledge,these are the first examples clearly indicating that miktoarm star copolymers can self-assemble in common good solvents or slightly selective solvents to generate micellelike aggregates. This scenario is not only in sharp contrast to the intuitively considered behavior of unimolecular miktoarm stars in nonselective solvents, but also rather different from the conventional selfassembly behavior of amphiphilic star copolymers in selective solvents.     

Study of transition metal oxide doped LaGaO3 as electrode materials for LSGM-based solid oxide fuel cells

Transition metal oxide doped lanthanum gallates, La_0.9Sr_0.1Ga_0.8M_0.2O₃ (where M=Co, Mn, Cr, Fe, or V), are studied as mixed ionic-electronic conductors (MIECs) for electrode applications. The electrochemical properties of these materials in air and in H₂ are characterized using impedance spectroscopy, open cell voltage measurement, and gas permeation measurement. Three single cells based on La_0.9Sr_0.1Ga_0.8 Mg_0.2O₃ (LSGM) electrolyte (1.13 to 1.65 mm thick) but with different electrode materials are studied under identical conditions to characterize the effectiveness of the lanthanum gallate-based MIECs for electrode applications. At 800 °C, a single cell using La_0.9Sr_0.1- Ga_0.8Co_0.2O₃ as the cathode and La_0.9Sr_0.1Ga_0.8Mn_0.2O₃ as the anode shows a maximum power density of 88 mW/cm², which is better than that of a cell using Pt as both electrodes (20 mW/cm²) and that of a cell using La_0.6Sr_0.4CoO₃ (LSC) as the cathode and CeO₂-Ni as the anode (61 mW/cm²) under identical conditions. The performance of LSGM-based fuel cells with MIEC electrodes may be further improved by reducing the electrolyte thickness and by optimizing the microstructures of the electrodes through processing. Received: 9 January 1998 / Accepted: 1 May 1998     

Properties of nanobelts and nanotubes measured by in situ TEM.

Characterizing the physical properties of individual nanostructures is challenging because of the difficulty in manipulating the objects of sizes from nanometers to micrometers. Most nanomeasurements have been carried using scanning probe microscopy. In this article, we demonstrate that transmission electron microscopy can be a powerful tool for quantitative measurements of the mechanical and electrical properties of a single nanostructure. Dual-mode resonance of an oxide nanobelt has been observed, and its bending modulus has been measured. An in situ technique was demonstrated for measuring the work function at the tip of a carbon nanotube. The ballistic quantum conductance of a multiwalled carbon nanotube was observed at room temperature using the setup in TEM. It is concluded that in situ measurement by directly linking structure with property is a future direction of electron microscopy.     

Electrochemical formation of self-organized zirconium titanate nanotube multilayers

The present work reports the formation of multilayers of self-organized zirconium titanate nanotubes by anodizing a Ti–35Zr alloy in 1 M (NH₄)₂SO₄ + 0.5 wt% NH₄F electrolytes. It was found that multilayers consisting of different diameter nanotubes can be produced by repeated anodization steps under different conditions. Formation of new nanotubes starts in the gaps between the existing tubes. The process allows the formation of multilayer stacks consisting of layers of several 100 nm in length and adjustable nanotube diameters in a range from 50 to 180 nm.     

1,3,8,10-Tetrahydro-2,9-diazadibenzo[cd,lm]perylenes: synthesis of reduced perylene bisimide analogues

A unique family of 1,3,8,10-tetrahydro-2,9-diazadibenzo[cd,lm]perylenes (THDAP) was prepared through a new synthetic strategy. Completion of the synthesis was achieved in several steps from commercially available perylene-3,4,9,10-tetracarboxylic dianhydride via reactions between 3,4,9,10-tetra(chloromethyl)perylene and primary amines. The successful use of a variety of primary amines in the reactions indicated that the synthetic approach provides a rich opportunity to produce new functionalized perylene derivatives.