Flow-injection determination of hydrogen peroxide based on fluorescence quenching of chromotropic acid catalyzed with Fe(II)

Flow-injection analysis system (FIA system), which was based on Fe(II)-catalyzed oxidation of chromotropic acid with hydrogen peroxide, was developed for the determination of hydrogen peroxide. The chromotropic acid has a fluorescence measured at λ_em = 440 nm (emission wavelength) with λ_ex = 235 nm (excitation wavelength), and the fluorescence intensity at λ_em = 440 nm quietly decreased in the presence of hydrogen peroxide and Fe(II), which was caused by Fe(II)-catalyzed oxidation of chromotropic acid with hydrogen peroxide. By measuring the difference of fluorescence intensity, hydrogen peroxide (1.0 × 10⁻⁸-1.0 × 10⁻³ mol L⁻¹) could be determined by the proposed FIA system, whose analytical throughput was 40 samples h⁻¹. The relative standard deviation (RSD) was 1.03% (n = 10) for 4.0 × 10⁻⁸ mol L⁻¹ hydrogen peroxide. The proposed FIA technique could be applied to the determination of hydrogen peroxide in rain water samples.     

The axial methionine ligand may control the redox reorganizations in the active site of blue copper proteins

Structural and energetic reorganizations in redox reaction of type 1 copper proteins are studied by density functional and ab initio molecular orbital calculations. Model complexes of the active site with varying number of ligands, from Cu(SCH(3))(0/+) to Cu(SCH(3))(Im)(2)(S(CH(3))(2))(0/+), where Im denotes imidazole, are investigated. Following the findings of structural instability in Cu(I)(SCH(3))(Im)(2) and its stabilization by the addition of the axial methionine (Met) ligand model, the structure and energetics are examined as functions of the Cu-S(Met) distance in the range of 2.1-3.3 A?. The reorganization energies in both redox states exhibit a minimum at the Cu-S(Met) distance of ～2.4?A?, whereas the ionization potential increases monotonically. The changes of reorganization energies correlate well with one of the Cu-N(His) distances rather than the Cu-S(Cys) distance. The estimated Arrhenius factor for oxidation of plastocyanin by P700(+) (in photosystem I) changes by an order of magnitude when the Cu-S(Met) distance fluctuates between 2.4 and 3.0 A?, whereas the factor for reduction of plastocyanin by cytochrome f is nearly constant. Together with the data from our previous classical molecular dynamics simulation of solvated protein, we argue that the electron transfer rate is affected, and thus may be controlled, by the fluctuation of a weakly bound axial Met ligand. We also present the assessment of various exchange-correlation functionals, including those with the long-range correction, against the CCSD(T) reference and on the basis of a perturbative adiabatic connection model. For Cu(SCH(3)) and Cu(SCH(3))(Im), simple correlations have been found between the reorganization energies and the amount of Hartree-Fock exchange.     

Analytical investigations of the behavior of silole-core dendrimers with peripheral globotriaose in water and acetone/water mixed solvent

A new compound having a 2,3,4,5-tetraphenylsilole derivative on the center silicon of Dumbbell(1)6Gb3; Silole-Dumbbell(1)6Gb3 (1) was previously reported. It was found that 1 exhibited strongly increased fluorescence both in water and in a 96% acetone/water mixed solvent. The physical behavior of 1 in water and in the 96% acetone/water mixed solvent was investigated, and analyses including fluorescence quantum yields, dynamic-light-scattering (DLS), atomic-force-microscopy (AFM), and fluorescence microscopy were carried out. It was clarified that 1 dynamically formed different types of aggregates in water and in higher acetone concentrations to yield high aggregation-induced emission (AIE) effects due to the formation of micelle-like particles in water and inversion-type micelles in the acetone/water mixed solvent, respectively.     

Effect of suspended particles on spreading of volatile droplet on solid substrate

Abstract  

We have been interested in behaviors of suspended particles in a volatile droplet placed on a smooth substrate. It is known that the particles gather and deposit in the vicinity of the macroscopic contact line of the droplet, which is generally called ‘coffee stain problem’. A convective flow induced by non-uniform evaporation through the interface brings suspended particles toward the pinned contact line in the drying droplet, which forms a ring stain. We have focused on the dynamics of the droplet with/without suspended particles spreading on the solid substrate and on the behaviors of particles in the evaporating droplet. Spreading process of the droplet is significantly affected by the suspended particles. We indicate flow patterns in the droplet, in which the flow exhibits a modal structure with a mode number in the azimuthal direction, and indicate particles depositions after the dryout of the droplet. Three-dimensional particle tracking velocimetry is applied to reconstruct such unique flow patterns in the spreading process of the droplet. Resultant patterns of the particles depositing on the substrate are introduced.     

Voice Analysis of Postlingually Deaf Adults Pre- and Postcochlear Implantation

Objectives

To ascertain whether cochlear implantation (CI), without specific vocal rehabilitation, is associated with changes in perceptual and acoustic vocal parameters in adults with severe to profound postlingual deafness.

Hypothesis

Merely restoring auditory feedback could allow the individual to make necessary adjustments in vocal pattern.

Study Design

Prospective and longitudinal.

Methods

The experimental group composed of 40 postlingually deaf adults (20 males and 20 females) with no previous laryngeal or voice disorders. Participants’ voices were recorded before CI and 6–9 months after CI. To check for chance modifications between two evaluations, a control group of 12 postlingually deaf adults, six male and six female, without CI was also evaluated. All sessions composed of the recording of read sentences from Consensus Auditory-Perceptual Evaluation of Voice and sustained vowel /a/. Auditory and acoustic analyses were then conducted.

Results

We found a statistically significant reduction in overall severity, strain, loudness, and instability in auditory analysis. In vocal acoustic analysis, we found statistically significant reduction fundamental frequency (F0) values (in male participants) and F0 variability (in both genders). The control group showed no statistically significant changes in most vocal parameters assessed, apart from pitch and F0 (in female participants only). On comparing the interval of variation of results between the experimental and control groups, we found no statistically significant difference in vocal parameters between CI recipients and nonrecipients, with the exception of F0 variability in male participants.

Conclusions

The patients in our sample showed changes in overall severity, strain, loudness, and instability values, and reductions in F0 and its variability. On comparing the variation of results between the groups, we were able to prove in our study that implant recipients postlingually deaf adults (experimental group), without specific vocal rehabilitation, differed from nonrecipients (control group) in loudness and F0 variability sustained vowel /a/ in male participants.     

Evolution of the Kondo effect in a quantum dot probed by shot noise

We measure the current and shot noise in a quantum dot in the Kondo regime to address the nonequilibrium properties of the Kondo effect. By systematically tuning the temperature and gate voltages to define the level positions in the quantum dot, we observe an enhancement of the shot noise as temperature decreases below the Kondo temperature, which indicates that the two-particle scattering process grows as the Kondo state evolves. Below the Kondo temperature, the Fano factor defined at finite temperature is found to exceed the expected value of unity from the noninteracting model, reaching 1.8±0.2.     

What we have learned from studies on chemical properties of amorphous alloys?

Amorphous alloys have many attractive characteristics including extremely high corrosion resistance if the sufficient amounts of corrosion-resistant elements are added. The superiority of amorphous alloys is based on the homogeneous single phase nature without any chemical and physical heterogeneities. Although there are processing limitations to avoid the formation of heterogeneous crystalline structure in addition to no welding technology without crystallization, the application of corrosion-resistant amorphous alloys is expected particularly to the very aggressive environments, where any conventional crystalline metallic materials cannot be used. Some amorphous bulk alloys showed zero corrosion mass loss due to spontaneous passivation even in 12 M HCl. Production of amorphous bulk alloys became possible for selected compositions. The homogeneous single phase nature is also effective to form useful catalysts with unique composition and structure. An example of catalysts is for carbon dioxide methanation useful for supply of renewable energy in the form of methane.     

A microfluidic chip integrated with a microoptical lens fabricated by femtosecond laser micromachining

We report on the integration of microlens and microfluidic channels in fused silica glass chip using femtosecond laser micromachining. The main process includes three procedures: (1) femtosecond laser scanning for forming a hemispherical surface and a Y-shaped channel in the fused silica glass; (2) chemical etching of the sample for removal of the modified areas; and (3) oxyhydrogen (OH) flame polish for smoothening the surface of the microlens. In addition, we demonstrate that the fabricated microlens exhibits good imaging performance with a 5× magnification, showing great potential in future lab-on-a-chip applications.     

Synthesis of carbazole‐based light‐emitting polymers incorporating 2,5‐bis(phenylethenyl)‐4‐decyloxyanisole as collateral fluorophore

The Suzuki coupling polymerization between bis(carbazole) monomer ( CzDB ) and 9,9‐dihexylfluorene‐2,7‐diboronic acid was carried out to obtain PFCz‐PEDA0 having the number‐averaged molecular weight of 7000. The absorption and emission maximum wavelengths were observed at 344 and 408 nm, respectively. The quantum yield (QY) was relatively low (0.12) because of the photo‐induced electron transfer. Subsequently, CzPEDA ‐bearing 2,5‐bis(phenylethenyl)‐4‐decyloxyanisole (PEDA) segment sandwiched with 3‐bromocarbazole units was copolymerized to give PFCz‐PEDAn (n = 05, 10, 20, 35, and 50). The content of PEDA segment in polymer could be controlled by the monomer feed ratio. In CHCl₃ solution, the absorbance at around 400 nm became larger with one isosbestic point at 370 nm, and the emission peak at 448 nm became prominent with increasing the PEDA content. The QY of polymer was increased as the PEDA content, which was a consequence of the fluorescence resonance energy transfer from carbazole‐containing chromophore (energy donor) to PEDA fluorophore (energy acceptor). In spin‐coated film, the maximum QY was obtained in PFCz‐PEDA05 having the most appropriate molar balance of energy donor and acceptor units. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8141–8148, 2008