Development of anchored oligothiophenes on substrates for the application to the tunable transparent conductive films

Bis(triethoxysilyl)-substituted oligothiophene with a moderate π-conjugation length was newly synthesized and polymerized to give a polysilsesquioxane network having oligothiophene units dispersed homogeneously without phase separation. The polymer was fixed on glass or ITO substrate by spin-coating and annealing. The resulting film exhibited a high mechanical strength due to the covalent bonding with the substrates, and was electrochemically stable even after 300 redox cycles in electrolyte solution. Chemical oxidation of the polymer films yielded electrically conductive and almost transparent films.     

The alkylation of biphenyl over three-dimensional large pore zeolites: The influence of zeolite structure and alkylating agent on the selectivity for 4,4′-dialkylbiphenyl

Catalytic properties of three-dimensional zeolites, Y (FAU), Beta (BEA), and CIT-1 (CON) zeolites were examined in the alkylation, isopropylation, sec-butylation, and tert-butylation, of biphenyl (BP), and compared to those of H-mordenite (MOR). The selectivities for 4,4′-dialkylbiphenyl (4,4′-DABP) varied with the types of zeolite and of alkylating agent. FAU, BEA, and CON gave only low selectivities for 4,4′-diisopropylbiphenyl (4,4′-DIPB) in the isopropylation, and predominant isomers were bulky and thermodynamically unstable 2,x′-DIPB (2,2′-, 2,3′-, and 2,4′-) at lower temperatures, and bulky and thermodynamically stable 3,4′- and 3,3′-DIPB at higher temperatures: this is quite different from catalytic features over MOR, which gave 4,4′-DIPB with high selectivities at moderate temperatures. These results suggest that FAU, BEA, and CON have no shape-selective nature in the isopropylation, and that the reaction is principally controlled kinetically at lower temperatures, and thermodynamically at higher temperatures. The sec-butylation gave similar results to the isopropylation. Although the selectivities for 4,4′-di-sec-butylbiphenyl (4,4′-DSBB) were higher than those in the isopropylation, predominant isomers were 2,x′-DSBB (2,2′-, 2,3′-, and 2,4′-) at lower temperatures, and 3,4′- and 3,3′-DSBB at higher temperatures. The tert-butylation gave 4,4′-di-tert-butylbiphenyl (4,4′-DTBB) in moderate to high selectivities over all zeolites at moderate temperatures: the selectivity for 4,4′-DTBB was higher than 80% over BEA and CON; however, it still remained at 50% over FAU. FAU channels with super cages are too large for selective formation of 4,4′-DTBB.

From these results, it is concluded that the selectivity for 4,4′-DABP in the alkylation over MOR, FAU, BEA, and CON is determined by the exclusion of bulky isomers at their transition states, and that the exclusion is caused by the steric restriction at the transition states of bulky isomers by the zeolite channels.     

Use of solid phase microextraction (SPME) for profiling the volatile metabolites produced by Glomerella cingulata

The profile of volatile organic compounds (VOCs) released from Glomerella cingulata using solid phase microextraction (SPME) with different fibers, Polydimethylsiloxane (PDMS), Polydimethylsiloxane/Divinylbenzene (PDMS/DVB), Carboxen/Polydimethylsiloxane (CAR/PDMS) and Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS), was investigated. C4-C6 aliphatic alcohols were the predominant fraction of VOCs isolated by CAR/PDMS fiber. Sesquiterpene hydrocarbons represented 20.3% of VOCs isolated by PDMS fiber. During the growth phase, Ochracin was produced in the large majority of VOCs. 3-Methylbutanol and phenylethyl alcohol were found in the log phase of it. Alcohols were found in cultures of higher age, while sesquiterpenes were found to be characteristic of initial growth stage of G. cingulata.     

HCl emission during co-pyrolysis of demolition wood with a small amount of PVC film and the effect of wood constituents on HCl emission reduction

In this study, HCl emission during the co-pyrolysis of demolition wood and a small amount of polyvinyl chloride (PVC) film (the Cl content of which ranged from 0.5% to 6% by weight) in an N₂ atmosphere at elevated temperatures of up to 600 °C was measured using a laboratory-scale cylindrical batch reactor. In the pyrolysis experiments, HCl emission was reduced by the presence of wood. The effect of the primary constituents of wood (cellulose, hemicellulose, and lignin) on HCl emission was investigated by not only measuring HCl emission and Cl distribution to various phases during the co-pyrolysis of each constituent with PVC film but also by conducting thermogravimetric analysis of the constituents. This investigation first revealed that hemicellulose significantly reduced HCl emission by fixing most of the Cl molecules in a sample into pyrolyzed residue.     

New polymerization of dienes and related monomers catalyzed by late transition metal complexes

This article reviews recent studies on the polymerization of 1,6-heptadienes and 2-aryl- and 2-alkoxy-1-methylenecyclopropanes catalyzed by Co, Fe, and Pd complexes. Co and Fe complexes with bis(imino)pyridine ligands catalyze the cyclopolymerization of 1,6-heptadiene in the presence of MMAO to produce the polymer, which contains five-membered rings in the monomer units. The polymers with cis- or trans-five-membered rings are obtained selectively, depending on the complex used in the polymerization. The catalyst, prepared from the Co complex having a bis(imino)pyridine ligand and MMAO, promotes the polymerization of 2-aryl-1-methylenecyclopropanes without ring-opening. The reaction under ethylene atmosphere produces alternating copolymer of the two monomers to yield the polymers composed of the C4 repeating unit with a 1,1-cyclopropanediyl group. The alternating copolymer of ethylene and 7-methylenebicyclo[4.1.0]heptane undergoes thermal rearrangement to afford the polymer with CC double bond in main chain. A radical pathway is proposed. Dinuclear π-allylpalladium complexes with bridging Cl ligands initiate living polymerization of 2-alkoxy-1-methylenecyclopropanes, which accompanies ring-opening of the monomer, to afford the polymers composed of the C₃ repeating units having alkoxy and vinylidene groups. A cyclic dinuclear π-allylpalladium complex reacts with 2-alkoxy-1-methylenecyclopropane in the presence of pyridine to produce the living polymer with macrocyclic structures. Block copolymerization of the two monomers that contain OR or O(CH₂CH₂O)R as the substituents on the three-membered ring, results in the polymers with hydrophobic and hydrophilic segments.     

Grafting polymer from poly(ethylene terephthalate) films by surface‐initiated ATRP

Surface‐initiated atom transfer radical polymerization (ATRP) from poly(ethylene terephthalate) (PET) film was studied. Poly(methyl methacrylate) (PMMA), poly (acrylamide) (PAAM), and their diblock copolymer (PMMA/PAAM) on the surface of PET film were successfully prepared by surface‐initiated ATRP. The structures and properties of the modified PET film were characterized by FT‐IR/ATR, X‐ray photoelectron spectroscopy (XPS), measurements of contact angles, and scanning electronic microscopy (SEM). The results indicate that the surface properties of PET film were greatly improved by grafted polymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Local Epidermal Endocrine Estrogen Protects Human Melanocytes against Oxidative Stress,a Novel Insight into Vitiligo Pathology

As the outermost barrier of the body, skin is a major target of oxidative stress. In the brain, estrogen has been reported synthesized locally and protects neurons from oxidative stress. Here, we explored whether estrogen is also locally synthesized in the skin to protect from oxidative stress and whether aberrant local estrogen synthesis is involved in skin disorders. Enzymes and estrogen receptor expression in skin cells were examined first by quantitative real-time PCR and Western blot analyses. Interestingly, the estrogen synthesis enzyme was mainly localized in epidermal keratinocytes and estrogen receptors were mainly expressed in melanocytes among 13 kinds of cultured human skin cells. The most abundant estrogen synthesis enzyme expressed in the epidermis was 17β-hydroxysteroid dehydrogenase 1 (HSD17β1) localized in keratinocytes, and the most dominant estrogen receptor expressed in the epidermis was G protein-coupled estrogen receptor 1 (GPER1) in melanocytes. To investigate whether keratinocyte-derived estradiol could protect melanocytes from oxidative stress, cultured human primary epidermal melanocytes (HEMn-MPs) were treated with H₂O₂ in the presence or absence of 17β estradiol or co-cultured with HSD17β1 siRNA-transfected keratinocytes. Keratinocyte-derived estradiol exhibited protective effects against H₂O₂-induced cell death. Further, reduced expression of HSD17β1 in the epidermis of skin from vitiligo patients was observed compared to the skin from healthy donors or in the normal portions of the skin in vitiligo patients. Our results suggest a possible new target for interventions that may be used in combination with current therapies for patients with vitiligo.     

Chemical Modification of Phage-Displayed Helix-Loop-Helix Peptides to Construct Kinase-Focused Libraries

Conformationally constrained peptides hold promise as molecular tools in chemical biology and as a new modality in drug discovery. The construction and screening of a target-focused library could be a promising approach for the generation of de novo ligands or inhibitors against target proteins. Here, we have prepared a protein kinase-focused library by chemically modifying helix-loop-helix (HLH) peptides displayed on phage and subsequently tethered to adenosine. The library was screened against aurora kinase A (AurA). The selected HLH peptide Bip - 3 retained the α-helical structure and bound to AurA with a K_D value of 13.7 μM. Bip - 3 and the adenosine-tethered peptide Bip - 3 - Adc provided IC₅₀ values of 103 μM and 7.7 μM, respectively, suggesting that Bip - 3 - Adc bivalently inhibited AurA. In addition, the selectivity of Bip - 3 - Adc to several protein kinases was tested, and was highest against AurA. These results demonstrate that chemical modification can enable the construction of a kinase-focused library of phage-displayed HLH peptides.     

Screening of Inhibitors Targeting Heat Shock Protein 47 Involved in the Development of Idiopathic Pulmonary Fibrosis

Heat shock protein 47 (HSP47), a collagen-specific molecular chaperone, is causally related to fibrotic diseases, including idiopathic pulmonary fibrosis. The identification of Compounds that interfere with the HSP47-collagen interaction is essential for the development of relevant therapeutics. Herein, we prepared human HSP47 as a soluble fusion protein expressed in E. coli and established an assay system for HSP47 inhibitor screening. We screened a natural and synthetic Compound library established at Nagasaki University. Among 1023 Compounds, 13 exhibited inhibitory activity against human HSP47, of which three inhibited its function in a dose-dependent manner. Epigallocatechin-3-O-gallate, one of these three Compounds, is a typical polyphenol Compound derived from tea leaves. Structurally related Compounds were synthesized and examined for their activity, revealing a hydroxyl group at A-ring position 5 as important for its activity. The present findings provide valuable insight for the development of natural product-derived therapeutics for fibrotic diseases, including idiopathic pulmonary fibrosis.     

MiR-10a in Pancreatic Juice as a Biomarker for Invasive Intraductal Papillary Mucinous Neoplasm by miRNA Sequencing

New biomarkers are needed to further stratify the risk of malignancy in intraductal papillary mucinous neoplasm (IPMN). Although microRNAs (miRNAs) are expected to be stable biomarkers, they can vary owing to a lack of definite internal controls. To identify universal biomarkers for invasive IPMN, we performed miRNA sequencing using tumor-normal paired samples. A total of 19 resected tissues and 13 pancreatic juice samples from 32 IPMN patients were analyzed for miRNA expression by next-generation sequencing with a two-step normalization of miRNA sequence data. The miRNAs involved in IPMN associated with invasive carcinoma were identified from this tissue analysis and further verified with the pancreatic juice samples. From the tumor-normal paired tissue analysis of the expression levels of 2792 miRNAs, 20 upregulated and 17 downregulated miRNAs were identified. In IPMN associated with invasive carcinoma (INV), miR-10a-5p and miR-221-3p were upregulated and miR-148a-3p was downregulated when compared with noninvasive IPMN. When these findings were further validated with pancreatic juice samples, miR-10a-5p was found to be elevated in INV (p = 0.002). Therefore, three differentially expressed miRNAs were identified in tissues with INV, and the expression of miR-10a-5p was also elevated in pancreatic juice samples with INV. MiR-10a-5p is a promising additional biomarker for invasive IPMN.