Synthesis and Chiroptical Properties of Quinoxaline-Fused Polyaza[5]–[7]helicenes with Orange-Color CPL Emissions

We achieved a two-type synthesis of quinoxaline-fused polyaza[5]- and [7]helicenes through consecutive N−H/C−H coupling with a hypervalent iodine reagent as a key reaction. By fusing electron-deficient quinoxaline, these polyazahelicenes constitute an efficient donor-acceptor type of molecule with absorption edges that reach up to approximately 650 nm. Evaluating the chiroptical properties reveals that the polyazahelicene exhibits a rare orange circularly polarized glow with a luminescence dissymmetry factor (g_lum value) of 0.003.     

Molecular Mobility of Polyrotaxane Surfaces Alleviates Oxidative Stress-Induced Senescence in Mesenchymal Stem Cells

Polyrotaxane is a supramolecular assembly consisting of multiple cyclic molecules threaded by a linear polymer. One of the unique properties of polyrotaxane is molecular mobility, cyclic molecules moving along the linear polymer. Molecular mobility of polyrotaxane surfaces affects cell spreading, differentiation, and other cell-related aspects through changing subcellular localization of yes-associated proteins (YAPs). Subcellular YAP localization is also related to cell senescence derived from oxidative stress, which is known to cause cancer, diabetes, and heart disease. Herein, the effects of polyrotaxane surface molecular mobility on subcellular YAP localization and cell senescence following H₂O₂-induced oxidative stress are evaluated in human mesenchymal stem cells (HMSCs) cultured on polyrotaxane surfaces with different molecular mobilities. Oxidative stress promotes cytoplasmic YAP localization in HMSCs on high-mobility polyrotaxane surfaces; however, low-mobility polyrotaxane surfaces more effectively maintain nuclear YAP localization, exhibiting lower senescence-associated β-galactosidase activity and senescence-related gene expression and DNA damage than that seen with the high-mobility surfaces. These results suggest that the molecular mobility of polyrotaxane surfaces regulates subcellular YAP localization, thereby protecting HMSCs from oxidative stress-induced cell senescence. Applying the molecular mobility of polyrotaxane surfaces to implantable scaffolds can provide insights into the prevention and treatment of diseases caused by oxidative stress.     

Copper-Catalyzed Enantioselective Reductive Aldol Reaction of α,β-Unsaturated Carboxylic Acids to Alkyl Aryl Ketones: Silanes as Activator and Transient Protecting Group

The first enantioselective reductive aldol reaction of unprotected α,β-unsaturated carboxylic acids was developed by employing a copper/bisphosphine catalyst. The reaction features in situ protection and activation of an α,β-unsaturated carboxylic acid by a hydrosilane. The copper enolate formed in situ reacts with an alkyl aryl ketone to afford the β-hydroxy carboxylic acid with excellent enantioselectivity (up to 99 % ee). The corresponding gram-scale reaction with a low catalyst loading and the derivatization of the β-hydroxy carboxylic acids highlight the practicality of this transformation.     

Near-Infrared Electrochromic Behavior of Dibenzothiepin Derivatives Attached with Two Michler's Hydrol Blue Units

10,11-Bis[bis(4-dimethylaminophenyl)methylene]dibenzo[bf]thiepin ( 1 ) and -oxepin ( 2 ) were prepared as stable yellow crystalline compounds, which are the cyclic analogues of electron-donating hexaarylbutadienes. Upon two-electron oxidation, they are reversibly transformed into the title dications ( 1 ²⁺ and 2 ²⁺) exhibiting near-infrared (NIR) absorptions, which were also isolated as stable salts. These redox pairs can serve as new entries into less well-explored organic NIR-electrochromic systems, and the separation of redox peaks (electrochemical bistability) was attained for 1 / 1 ²⁺ and 2 / 2 ²⁺, thanks to drastic geometrical changes between neutral and dicationic states, as revealed by a series of X-ray analyses. Thiepin-S,S-dioxide analogue ( 3 / 3 ²⁺) exhibits quite similar dynamic redox behavior due to nonaromatic nature of the dibenzothiepin and -oxepin unit in 1 ²⁺ and 2 ²⁺, whereas the thiepin-S-oxide derivative ( 4 / 4 ²⁺) does not exhibit bistability due to the smaller change in geometry upon electron transfer, showing that a subtle change of a bridging atom in the central seven-membered ring can modify the redox properties.     

Effect of omega-hydrogenation on the adsorption of fluorononanols at the hexane/water interface: Temperature effect on the adsorption of fluorononanols

The interfacial tensions (gamma) of the hexane solutions of 1H,1H-perfluorononanol (FDFC9OH) and its omega-hydrogenated analogue 1H,1H,9H-perfluorononanol (HDFC9OH) against water were measured as a function of temperature and concentration under atmospheric pressure in order to know the effect of omega-dipoles on the adsorption behavior of fluorononanols. The interfacial pressure (pi) versus mean area per adsorbed molecule (A) curves consist of two discontinuous changes among three different states: the gaseous, expanded, and condensed states. The A values at given pi in the gaseous and expanded states are larger for HDFC9OH than for FDFC9OH. The changes in partial molar entropy (s1(H) - s1(O)) and energy (u1(H) - u1(O)) of adsorption were evaluated. Their values are negative, and therefore, the alcohols have a smaller entropy and energy at the interface than in the bulk solution. Furthermore, the u1(H) - u1(O) value is more negative for HDFC9OH than for FDFC9OH in the expanded state and also in the condensed film just above the expanded-condensed phase transition point. This seems to be due to the following: (1) HDFC9OH may tilt from interface normal for omega-dipoles to interact effectively with water molecules in the interfacial region and to reduce their own repulsive interaction between neighbors arranging parallel in the adsorbed film. This leads to a lower value for HDFC9OH than for FDFC9OH. (2) The contact of omega-dipoles with hexane molecules in the bulk solution is energetically unfavorable, and thus, the u1(O) value of HDFC9OH is expected to be larger than that of FDFC9OH.     

Discotic liquid crystals stabilized by interionic interactions: imidazolium ion-anchored paraffinic triphenylene

Incorporation of imidazolium ion functionalities into the paraffinic side-chain termini of a triphenylene derivative resulted in stabilization of a columnar mesophase of its liquid crystalline assembly, which was retained over a wider temperature range down to 4 degrees C by an externally added imidazolium-based ionic liquid.     

ESR study on chemical crosslinking reaction mechanisms of polyethylene using a chemical agent. III. Effect of amine type antioxidants

The effect of antioxidant on the reaction mechanism of chemical crosslinking of polyethylene with dicumyl peroxide (DCP) at high temperatures was investigated by electron spin resonance (ESR). The crosslinking reactions were induced by the alkyl radicals in polyethylene (PE) formed by the thermal decomposition of DCP above 120°C. The type and the content of radicals were much changed for amine type antioxidants on PE crosslinking. It was confirmed that the radicals originated from DCP decomposition reacted preferentially with the amine type antioxidants to produce the nitroxyl radical and that the antioxidants retarded the initiation reaction of the PE crosslinking reaction. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 349–356, 1999     

Enantio‐ and Stereoselective Cyclopolymerization of Hexa‐1,5‐diene Catalyzed by Zirconium Complexes Possessing Optically Active Bis(phenolato) Ligands

Enantio‐ and stereoselective cyclopolymerization of hexa‐1,5‐diene was achieved by enantiomerically pure dichloro zirconium(IV) pre‐catalysts 2 possessing chiral [OSSO]‐type bis(phenolate) ligands (−)‐ 1 and (+)‐ 1 in combination with dried methylaluminoxane (dMAO) as an activator. The corresponding activities were recorded with quite high values up to 1,960 g mmol( 2 )^–1 h^–1, which are extremely larger than those of the related complexes. The microstructure analysis for the PMCPs furnished by pre‐catalysts (Λ,S,S)‐ 2 and (Δ,R,R)‐ 2 showed good isotacticity factors (α = 75−78%) and relatively high proportions of trans‐cyclopentane rings (σ = 14−21%). These enantiomeric PMCPs exhibited large specific optical rotations ([α]_D = +28 to +32° from (Λ,S,S)‐ 2 , −26 to −34° from (Δ,R,R)‐ 2 ).

     

Silver‐Catalyzed Efficient Synthesis of Oxindoles and Pyrroloindolines via α‐Aminoalkylation of N‐Arylacrylamides with Amino Acid Derivatives

α‐Aminoalkylation of N‐arylacrylamides with amino acid derivatives was achieved by silver‐catalysis in moderate to high yields. The reaction provides an efficient strategy for the synthesis of functionalized oxindoles, and is suitable for a wide range of N‐arylacrylamides and amino acids, both of which are inexpensive and readily available. The oxindoles obtained were readily transformed into densely functionalized pyrroloindolines by deprotection and cyclization in one pot.     

Electron spin resonance study on chemical‐crosslinking reaction mechanisms of polyethylene using a chemical agent. VI. Effect of α‐methyl styrene dimer

The effect of α‐methyl styrene dimer (AMSD), which is used as a scorch retarder, on the reaction mechanisms of the chemical crosslinking of polyethylene (PE) with dicumyl peroxide (DCP) at high temperatures was investigated using electron spin resonance. When AMSD was added to PE containing DCP, the AMSD radical was observed; however, the PE alkyl radical or allyl radical presence was not detected. At 145 °C, crosslinking was obstructed as a result of the reaction between AMSD and alkyl radicals. As the temperature increased, AMSD fragmented to form 2‐phenyl‐2‐propyl and double bonds in PE. This generation of double bonds, however, accelerated crosslinking at 180 °C and was more effective than when AMSD was not present. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2151–2156, 2001