A novel phenyl–bromine ligand exchange reaction on germanium by boron tribromide

A novel phenyl–bromine ligand exchange reaction by BBr₃ on germanium was investigated that proceeds without breaking Ge CH₂Ar bond. Typically, the reaction between (PhCH₂)₃PhGe and BBr₃ resulted exclusively in the formation of (PhCH₂)₃GeBr. Copyright © 2005 John Wiley & Sons, Ltd.     

Evaluation of osmium(II) complexes as electron transfer mediators accessible for amperometric glucose sensors.

In order to lower the redox potentials of Os(III/II) complexes, the mixed ligand complexes of Os(II) were synthesized. The redox potentials of Os(III/II) complexes could be lowered by the use of 4,4'-dimethyl-2,2'-bipyridine (dmbpy), imidazole (Him) or its derivatives, and chloride ion as ligands, e.g., values of the redox (formal) potentials of 628 mV vs. Ag/AgCl for [Os(bpy)3]3+/2+ (bpy: 2,2'-bipyridine) and -6 mV for [OsCl(Him)(dmbpy)2]2+/+ were given in deaerated 0.1 mol dm-3 phosphate buffer (pH 7.0). The evaluation of Os(II) complexes as electron transfer mediators accessible for amperometric glucose sensors was examined according to the determination of the redox potentials of Os(III/II) complexes and the second-order rate constants for electron transfer between glucose oxidase (GOx) in reduced form and the Os(III) complex. Although the Os(II) complexes with lower redox potentials tended to decrease the second-order rate constants ks, the ks values for the majority of Os(II) complexes synthesized in this study were greater than that for ferrocenecarboxylic acid. Acceleration of the electron-transfer reaction is attributable to the hydrogen bonding and/or the electrostatic interaction between the Os(II) complexes and GOx. It may be consequently concluded that the mixed ligand complexes of Os(II) with bpy (dmbpy), Him (its derivatives), and Cl- can act as more efficient electron transfer mediators for the fabrication of amperometric glucose sensors.     

Generation of debris in the femtosecond laser machining of a silicon substrate

A mechanism of debris accumulation around the hole created on a silicon substrate with a femtosecond laser is experimentally studied. The hole created by the laser pulses has an edge consisting of pillared structures. However, no solid or liquid materials with similar dimensions as the pillared structures were ejected from the hole as the laser machining was performed in vacuum or in the presence of various gases. When the target was placed in a gas under 100 Torr, a thick layer of cotton-like material formed around the hole. Laser irradiation of a vertically placed target resulted in re-solidified material that formed after dripping from the hole edge, showing that substrate was partially melted. The surface morphology features suggest that the debris was formed as a result of aggregation of small particles such as atoms or atomic clusters on the substrate surface instead of large-scale droplets or fragments, which are commonly observed with nanosecond lasers. PACS 78.67.Bf; 81.15.Fg; 81.16.Mk; 81.20.Wk; 81.65.Cf     

Biometric Identification Systems with Noisy Enrollment for Gaussian Sources and Channels

In the present paper, we investigate the fundamental trade-off of identification, secret-key, storage, and privacy-leakage rates in biometric identification systems for remote or hidden Gaussian sources. We use a technique of converting the system to one where the data flow is in one-way direction to derive the capacity region of these rates. Also, we provide numerical calculations of three different examples for the system. The numerical results imply that it seems hard to achieve both high secret-key and small privacy-leakage rates simultaneously.     

First observation of natural circular dichroism spectra in the extreme ultraviolet region using a polarizing undulator‐based optical system and its polarization characteristics

Natural circular dichroism (CD) spectra in the extreme ultraviolet (EUV) region down to a wavelength of 80 nm have been observed for the first time, using an alanine thin film deposited on sodium salicylate coated glass as a sample. Calibrated EUV‐CD spectra of l ‐alanine exhibited a large negative peak at around 120 nm and a positive CD signal below 90 nm, which were roughly predicted by theoretical calculations. A CD measurement system with an Onuki‐type polarizing undulator was used to obtain the EUV‐CD spectra. This CD system, the development of which took five years, can be used to observe even weak natural CD spectra. The polarization characteristics of this system were also evaluated in order to calibrate the recorded CD spectra.     

Redox reactions of nitrite ions on the surface of colloidal magnetite particles coated with chondroitin sulfate

Colloidal magnetite particles coated with chondroitin sulfate (abbreviated as Fe/CS) were prepared under conditions of varying Fe(II) fractions at a fixed Fe concentration and a given concentration of CS. The average size of the magnetite core region was estimated as 7 nm from transmittance electron microscopy measurements, while the size of the Fe/CS particles ranged 155–175 nm, as estimated using Rayleigh scattering measurements by reference to a control size derived from the dynamic light scattering. The reaction of various Fe/CS with NO⁻ ₂ in aqueous solutions was determined by fluorometry using 2,3-diaminonaphthalene as a probe and by gas chromatography–mass spectrometry. The concentrations of NO⁻ ₂ in the reaction mixtures decreased in the presence of Fe/CS to a greater extent under Ar compared with aerobic conditions. The reactivity of Fe/CS toward NO⁻ ₂ under aerobic conditions increased with decreasing the size of Fe/CS particles or with increasing content of Fe(III) in the Fe/CS solutions, but was independent of the Fe(II) fraction in the preparation process. While CS molecules had no influence on the NO⁻ ₂ decomposition, those coated with the magnetite core may prevent the diffusion of NO⁻ ₂ to be adsorbed on the core surfaces. NO⁻ ₂ was concluded to undergo redox reactions with Fe(II) and Fe(III) located on the core surface of magnetite crystalline structures of Fe/CS. Received: 12 April 2000/Accepted: 9 August 2000     

Spectrocyclic Voltammetry of Ruthenium Purple Electrodeposited on a WO3/Tris(2,2′-bipyridine)-ruthenium(II)/Polymer Hybrid Film

Summary: Electrochemical reactions of Ruthenium purple, Feequation/tex2gif-stack-1.gif[Ru^II(CN)₆]₃ (RP; Fe^III-Ru^II) were studied using a spectrocyclic voltammetry (SCV) technique. The SCV measurement for an RP film coated on an ITO electrode showed a reversible redox between RP and Ruthenium white (RW; Fe^II-Ru^II) at 0.14 V vs saturated calomel reference electrode (SCE). An RP film was electrodeposited on a hybrid film of tungsten trioxide (WO₃)/tris(2,2′-bipyridine)ruthenium(II) ([Ru(bpy)₃]²⁺; bpy = 2,2′-bipyridine)/poly(sodium 4-styrenesulfonate) (PSS) (denoted as WRP film) from a colloidal solution containing 0.5 mM FeCl₃, 0.5 mM K₄[Ru(CN)₆] and 40 mM KCl using a potentiodynamic multi-sweep technique. In a cyclic voltammogram (CV) of a WRP/RP film, a redox response was observed at 0.61 V in addition to essential redox responses of WRP hybrid film (a [Ru(bpy)₃]²⁺/[Ru(bpy)₃]³⁺ redox at 1.03 V and a H_xWO₃/WO₃ redox below 0.09 V), but a redox response of RW/RP was not observed at 0.14 V. The SCV measurement for the WRP/RP film suggested that the redox response at 0.61 V is attributed to a redox of [Ru(bpy)₃]²⁺/[Ru(bpy)₃]³⁺ interacted electrostatically with RP. It also showed that RW is oxidized to RP via [Ru(bpy)₃]²⁺/[Ru(bpy)₃]³⁺ redox and RP is reversibly reduced to RW via H_xWO₃/WO₃ redox. This unique geared electrochemical reaction for the WRP/RP film leads to a hysteresis property of an RW/RP redox.     

Total synthesis of piericidin A1 and B1 and key analogues

Full details of the total synthesis of piericidin A1 and B1 and its extension to the preparation of a series of key analogues are described including ent-piericidin A1 (ent-1), 4'-deshydroxypiericidin A1 (58), 5'-desmethylpiericidin A1 (73), 4'-deshydroxy-5'-desmethylpiericidin A1 (75), and the corresponding analogues 51, 59, 76, and 77 bearing a simplified farnesyl side chain. The evaluation of these key analogues, along with those derived from their further functionalizations, permitted a scan of the key structural features providing new insights into the role of the substituents found in both the pyridyl core as well as the side chain. A strategic late stage heterobenzylic Stille cross-coupling reaction of the pyridyl core with the fully elaborated side chain permitted ready access to the analogues in which each half of the molecule could be systematically and divergently modified. The pyridyl cores were assembled enlisting inverse electron demand Diels-Alder reactions of N-sulfonyl-1-azabutadienes, while key elements of side chain syntheses include an anti selective asymmetric aldol to install the C9 and C10 relative and absolute stereochemistry (for natural and ent-1) and a modified Julia olefination for formation of the C5-C6 trans double bond with convergent assemblage of the side chains.