Gold-Catalyzed Enantioselective Synthesis, Crystal Structure, and Photophysical/Chiroptical Properties of Aza[10]helicenes.

The enantioselective synthesis of an aza[10]helicene, possessing two pyridone units, has been achieved by the gold-catalyzed intramolecular quadruple hydroarylation of a tetrayne. This aza[10]helicene was successfully converted into a fully aromatic aza[10]helicene, possessing two pyridine units. Structure-photophysical and chiroptical properties relationship in a series of azahelicene isomers has also been disclosed.

Arachidonic acid-dependent carbon-eight volatile synthesis from wounded liverwort (Marchantia polymorpha).

Eight-carbon (C8) volatiles, such as 1-octen-3-ol, octan-3-one, and octan-3-ol, are ubiquitously found among fungi and bryophytes. In this study, it was found that the thalli of the common liverwort Marchantia polymorpha, a model plant species, emitted high amounts of C8 volatiles mainly consisting of (R)-1-octen-3-ol and octan-3-one upon mechanical wounding. The induction of emission took place within 40min. In intact thalli, 1-octen-3-yl acetate was the predominant C8 volatile while tissue disruption resulted in conversion of the acetate to 1-octen-3-ol. This conversion was carried out by an esterase showing stereospecificity to (R)-1-octen-3-yl acetate. From the transgenic line of M. polymorpha (des6(KO)) lacking arachidonic acid and eicosapentaenoic acid, formation of C8 volatiles was only minimally observed, which indicated that arachidonic and/or eicosapentaenoic acids were essential to form C8 volatiles in M. polymorpha. When des6(KO) thalli were exposed to the vapor of 1-octen-3-ol, they absorbed the alcohol and converted it into 1-octen-3-yl acetate and octan-3-one. Therefore, this implied that 1-octen-3-ol was the primary C8 product formed from arachidonic acid, and further metabolism involving acetylation and oxidoreduction occurred to diversify the C8 products. Octan-3-one was only minimally formed from completely disrupted thalli, while it was formed as the most abundant product in partially disrupted thalli. Therefore, it is assumed that the remaining intact tissues were involved in the conversion of 1-octen-3-ol to octan-3-one in the partially disrupted thalli. The conversion was partly promoted by addition of NAD(P)H into the completely disrupted tissues, suggesting an NAD(P)H-dependent oxidoreductase was involved in the conversion.

Behavioral and clinical correlates of serum bilirubin concentrations in Japanese men and women.

BACKGROUND: A considerable interest has been drawn to potential protective effects of bilirubin against oxidative stress-related diseases. Smoking is known to be associated with lower concentrations of serum bilirubin, but other behavioral correlates of serum bilirubin have not been well studied. In this cross-sectional study, we examined the associations of behavioral and clinical factors with serum total bilirubin in Japanese men and women. METHOD: The study subjects comprised of 4802 men and 6414 women aged 49-76 years who participated in the baseline survey of an ongoing cohort study on lifestyle-related diseases in Fukuoka, Japan. With consideration to time of the day of blood sampling and fasting hours, the associations with smoking, alcohol intake, body mass index, physical activity, coffee, tea, blood pressure, glycated hemoglobin (HbA1c), HDL cholesterol and non-HDL cholesterol with serum bilirubin were evaluated by analysis of covariance and multiple linear regression analysis. RESULTS: While smoking was negatively associated with serum bilirubin, alcohol consumption was positively associated with serum bilirubin in both men and women. Coffee consumption was associated with lower bilirubin concentrations in both sexes. In the multiple linear regression analysis, HDL cholesterol was positively and HbA1c was negatively associated with bilirubin in both men and women, and the associations were more evident in women. CONCLUSION: Smoking, alcohol use and coffee consumption were important behavioral correlates of serum bilirubin in Japanese men and women. Serum HDL cholesterol was a measurable clinical correlate of bilirubin in women.

Roles of focal adhesions and fibronectin-mediated cohesion in proliferation of confluent fibroblasts.

Multilayered fibroblast sheets have applications as cell transplants for tissue engineering. One way to increase their therapeutic efficacy is to increase cell numbers in a graft, but the factors influencing multilayered growth remain poorly understood. In this study, we investigated the roles of focal adhesion (FA) assembly and intercellular cohesion through fibronectin (FN) in the proliferation of normal human fibroblasts at confluence. Density-dependent growth-arrested fibroblasts resumed DNA synthesis when cultured in multilayer formation medium (MFM) containing transforming growth factor-beta1, ascorbic acid, and serum. This proliferation depended on alpha 5 beta 1-integrin-mediated cell-FN-cell interactions because blocking them with antibodies inhibited DNA synthesis. However, cell-FN-cell cohesion operated well regardless of exposure to MFM, judging from several parameters, including FN matrix deposition, activated beta1 integrin expression, and stress fiber development. Density-arrested cells formed few FAs at the cell center. Exposure of the cells to MFM induced the formation of vinculin-, paxillin-, and phosphotyrosine-containing FAs throughout the ventral cell-surface, indicating ROCK-mediated actomyosin contractile force generation. When the assembly of FAs was inhibited with either the ROCK inhibitor Y-27632 or the myosin II inhibitor blebbistatin, the up-regulation of DNA synthesis by MFM was suppressed. The drugs did not impair FN matrix deposition, activated beta1 integrin expression, and stress fiber development. Thus, these results indicate that the formation of FAs promotes the proliferation of confluent fibroblasts with the support of alpha 5 beta 1-integrin-mediated cell-FN-cell cohesion. The present findings provide insights into the rational design of high-density fibroblast transplants.