Metal-Induced Structural Switching of a Folded Quinone-Sandwiched Porphyrin

We report the synthesis of a novel quinone-sandwiched porphyrin in which two benzoquinones are connected oppositely at the meso positions of a porphyrin through rigid 3-amido 2,2′-bipyridine linkers. ¹H-NMR and single crystal X-ray analyses revealed that the quinone-sandwiched porphyrin has a folded structure in which the porphyrin unit was inserted into the two quinone moieties via π-stacking. Insertion of a Zn(II) ion into the porphyrin center induced a drastic conformational change which is resulted in coordination of the oxygen atoms of both benzoquinone moieties to the Zn-porphyrin to afford a 6-coordinated structure.     

Novel Structures for Porous Silicon Light-Emitting Diodes

In this paper, two novel structures of porous silicon (PS) light-emitting diodes (LEDs) are proposed aiming at the reduction of series resistance, R_s. The basic idea of the novel structures is to suppress the excessive growth of nanoporous silicon (nano-PS) layer that is electroluminescence- (EL-) active but highly resistive. The initial wafer of the first structure consists of a lightly-doped layer stacked on a highly-doped substrate. As a consequence of anodization, nano-PS layer is formed only in the lightly-doped layer, while meso-PS layer with moderate resistivity is formed in the highly-doped substrate. The second structure consists of alternately stacked nano- and meso-PS layers, since it is expected that multiple thin nano-PS layers connected in series are less resistive than a single thick nano-PS layer. Preliminary experimental results proved the effectiveness of these novel structures on the reduction of R_s.     

Hepatic Expression of Long-Chain Acyl-CoA Synthetase 3 is Upregulated in Hyperlipidemic Hamsters

Members of the mammalian long-chain acyl-CoA synthetase (ACSL) family are key enzymes for cellular fatty acid metabolism that catalyze the initial step in activation of long-chain fatty acids. However, the specificity of individual isoforms of ACSL to the lipid metabolic process is not well studied. In addition, the regulation of expression of individual ACSL isoforms under hyperlipidemic conditions is largely unknown. We cloned the hamster ACSL3 cDNA coding region and generated specific antibodies recognizing the ACSL3 protein. We next observed the changes in ACSL3 mRNA and protein expression in hamsters fed a standard chow diet or a high fat and high cholesterol (HFHC) diet. HFHC feeding significantly increased ACSL3 mRNA and protein expression in liver and to a lesser extent in muscle but not in adipose, brain, heart, or testis. Additionally, ACSL3 mRNA abundance was differentially regulated by the nutritional status in different tissues with liver, muscle, and adipose being the most sensitive tissues. Importantly, the hepatic ACSL3 mRNA expression pattern in response to fasting and refeeding in hyperlipidemic hamsters differed from that observed in normal chow-fed hamsters. Together, these results provide the first in vivo evidence of altered regulation of hepatic ACSL3 expression under hyperlipidemic conditions and suggest important regulatory roles for this enzyme in lipid metabolism.     

Hydrogen bond network in the distal site of peroxidases: spectroscopic properties of Asn70 --> Asp horseradish peroxidase mutant

The distal His in peroxidases forms a hydrogen bond with the adjacent Asn, which is highly conserved among many plant and fungal peroxidases. Our previous work [Nagano, S., Tanaka, M., Ishimori, K., Watanabe, Y., & Morishima, I. (1996) Biochemistry 35, 14251-14258] has revealed that the replacement of Asn70 in horseradish peroxidase C (HRP) by Val (N70V) and Asp (N70D) discourages the oxidation activity for guaiacol, and the elementary reaction rate constants for the mutants was decreased by 10-15-fold. In order to delineate the structure-function relationship of the His-Asn couple in peroxidase activity, heme environmental structures of the HRP mutant, N70D, were investigated by CD, 1H NMR, and IR spectroscopies as well as Fe2+/Fe3+ redox potential measurements. While N70D mutant exhibited quite similar CD spectra and redox potential to those of native enzyme, the paramagnetic NMR spectrum clearly showed that the hydrogen bond between the distal His and Asp70 is not formed in the mutant. The disappearance of the splitting in the 1H NMR signal of heme peripheral 8-methyl group observed in 50% H2O/50% D2O solution of N70D-CN suggests that the hydrogen bond between the distal His and heme-bound cyanide is also disrupted by the mutation, which was supported by the low C-N vibration frequency and large dissociation constant of the heme-bound cyanide in the mutant. Together with the results from various spectroscopies and redox potentials, we can conclude that the improper positioning of the distal His induced the cleavages of the hydrogen bonds around the distal His, resulting in the substantial decrease of the catalytic activity without large structural alterations of the enzyme. The His-Asn hydrogen bond in the distal site of peroxidases, therefore, is essential for the catalytic activity by controlling the precise location of the distal His.     

Performance evaluation of iterative geometric fitting algorithms

The convergence performance of typical numerical schemes for geometric fitting for computer vision applications is compared. First, the problem and the associated KCR lower bound are stated. Then, three well-known fitting algorithms are described: FNS, HEIV, and renormalization. To these, we add a special variant of Gauss-Newton iterations. For initialization of iterations, random choice, least squares, and Taubin's method are tested. Simulation is conducted for fundamental matrix computation and ellipse fitting, which reveals different characteristics of each method.     

Phase diagram and Raman spectroscopy of EuCl2---NaCl binary mixtures

A phase diagram of the EuCl₂---NaCl system was determined by differential scanning calorimetry (DSC) and the activity coefficients of EuCl₂ and NaCl in this system were estimated under some assumptions. According to DSC measurement, it was found that there were two phase transitions at 1123.9 K and 1016.8 K. In order to specify the melting point of EuCl₂ we did Raman spectroscopy experiments. Thus, the melting point of EuCl₂ was evaluated to be 1016.8 K which was detected as the lower peak in the DSC curve. Raman spectroscopy of this system suggested that complex species were not formed clearly in the EuCl₂ poor system and the estimated activity coefficients of EuCl₂ also supported this suggestion.     

Three-Dimensional Measurement of Ice Crystals in Frozen Materials by Near-Infrared Imaging Spectroscopy

A novel technique was developed to recognize ice crystals in biological materials and to analyze their three-dimensional morphology using a Cryogenic Micro-Slicer Spectral Imaging System with a micro-slicer unit and a near-infrared spectral imaging unit. Consecutive cross-sections of a frozen sample were exposed by the multi-slicing operations with a minimum thickness of 1 µm, and their images were taken by the imaging unit. Spectroscopic analysis using a near-infrared spectrum meter showed an absorption peak at 1460 nm for pure water. Based on the observations of the absorption band of ice crystals in the wavelength range of 1450–1570 nm and its peak at 1495 nm, a commodity-type bandpass filter with a central wavelength of 1500 nm was adopted to identify ice crystals in near-infrared images. The absorption peak of water exhibited a tendency to move toward longer wavelengths with decreasing sample temperature from 25 °C to ?15 °C. The filtered images of ice crystals in frozen samples were darker than the other components at the peak wavelength of ice crystals. The three-dimensional reconstructed morphology of ice crystals revealed that they were formed along the direction of heat transfer while freezing. The proposed method provides a novel tool to investigate the effects of freezing conditions on the size, morphology and distribution of ice crystals.     

Adjunctive Application of Antimicrobial Photodynamic Therapy in Nonsurgical Periodontal Treatment: A Review of Literature

Periodontal disease is caused by dental plaque biofilms, and the removal of these biofilms from the root surface of teeth plays a central part in its treatment. The conventional treatment for periodontal disease fails to remove periodontal infection in a subset of cases, such as those with complicated root morphology. Adjunctive antimicrobial photodynamic therapy (aPDT) has been proposed as an additional treatment for this infectious disease. Many periodontal pathogenic bacteria are susceptible to low-power lasers in the presence of dyes, such as methylene blue, toluidine blue O, malachite green, and indocyanine green. aPDT uses these light-activated photosensitizer that is incorporated selectively by bacteria and absorbs a low-power laser/light with an appropriate wavelength to induce singlet oxygen and free radicals, which are toxic to bacteria. While this technique has been evaluated by many clinical studies, some systematic reviews and meta-analyses have reported controversial results about the benefits of aPDT for periodontal treatment. In the light of these previous reports, the aim of this review is to provide comprehensive information about aPDT and help extend knowledge of advanced laser therapy.     

Site‐Selective Iron(III) Chloride‐Catalyzed Arylation of 4‐Aryl‐4‐methoxy‐2,5‐cyclohexadienones for the Synthesis of Polyarylated Phenols

The iron(III) chloride‐catalyzed Friedel–Crafts arylation of 4‐aryl‐4‐methoxy‐2,5‐cyclohexadienones, which were easily prepared by the phenyliodine(III) diacetate (PIDA)‐mediated oxidation of 4‐arylphenols in methanol, proceeded site‐selectively to form meta‐terphenyl (2,4‐diarylphenol) derivatives in good yields. The subsequent PIDA‐mediated oxidation and iron(III) chloride‐catalyzed Friedel–Crafts arylation of the resulting products gave the corresponding 2,4,6‐triarylphenol derivatives. The present method provides useful highly substituted polyarylated compounds.

     

Decreasing resistances of membrane-electrode assemblies containing hydrocarbon-based ionomers for improving their anodic performances

To improve methanol-oxidation performances of membrane-electrode assemblies composed of a hydrocarbon-based ionomers, the resistances involved in the reaction were decreased. Electrochemical impedance spectroscopy revealed that the proton-conductive resistance (R_i) in the anode was decreased from 0.54 to 0.40 Ω cm² by increasing a loading ratio of platinum-ruthenium to carbon support of anode catalyst from 54 to 73 wt.%. In addition, R_i was decreased to be 0.25 Ω cm² by increasing ion-exchange capacity (IEC) of the ionomer from 1.4 to 2.9 mequiv. g⁻¹. Consequently, the polarization resistance of the anode was significantly decreased, in turn, increasing current density of methanol oxidation at the potential of 0.45 V from 0.110 to 0.244 A cm⁻².