Polymerization of coordinated monomers. III. Copolymerization of acrylonitrile–zinc chloride,methacrylonitrile–zinc chloride or methyl methacrylate–zinc chloride complex with styrene

The 1:1 or 2:1 complex of acrylonitrile, methacrylonitrile, or methyl methacrylate with ZnCl₂ was copolymerized with styrene at the temperature of 0–30°C without any initiator. The structure of the copolymer from methyl methacrylate complex and styrene was examined by NMR spectroscopy. The complexes of acrylonitrile or methacrylonitrile with ZnCl₂ gave a copolymer containing about 50 mole-% styrene units. The complexes of methyl methacrylate yielded an alternating copolymer when the feed molar ratio of methyl methacrylate to styrene was small, but with increasing feed molar ratio the resulting copolymer consisted of about 2 moles of methyl methacrylate per mole of styrene. The formation of a charge-transfer complex of styrene with a monomer coordinated to zinc atom was inferred from the ultraviolet spectra. The regulation of the copolymerization was considered to be effected by the charge-transfer complex. The copolymer resulting from the 2:1 methyl methacrylate–zinc chloride complex had no specific tacticity, whereas the copolymer from the 1:1 complex was richer in coisotacticity than in cosyndiotacticity. The change of the composition of the copolymer and its specific tacticity in the polymerization of the methyl methacrylate complex is related to the structure of the complex.     

A synthetic approach to (+)-aldosterone and its relatives (2)- a stereoselective synthesis of (+)-trans-4,5-(4-methoxybenzo)- 1β , 7aβ - ( 2α-methoxymethyl- 5 -oxofuro) hydrindane

A stereoselectivity in an intramolecular cycloaddition of the olefinic $\text{o}$-quinodimethanes 13 and 23 generated $\text{in}$$\text{situ}$ from the thermolysis of optically active 4β-[2-(4-methoxybenzocyclobutenyl)ethyl] -5α-methoxymethyl-3-phenyl-thio-methylenefuran-2-ones 12 and 22, respectively, is studied and a stereoselective synthesis of (+)-$\text{trans}$-4,5-( 4-methoxybenzo) -1β,7aβ-(2α-methoxymethyl-5-oxofuro)hydrindane 1 is also described.     

Lewis acid mediated claisen-type rearrangement of aryl dienyl ethers

In the presence of BF₃·.OEt₂, aryl dienyl ethers were rearranged under mild conditions to afford dienyl phenols in good yields.     

Long-lived charge-separated state leading to DNA damage through hole transfer

The hole transfer causes the long-lived charge-separated state in DNA during the photosensitized one-electron oxidation of DNA. The combination of the transient absorption measurement and DNA damage quantification by HPLC clearly demonstrated that the yield of the DNA damage correlates well with the lifetime of the charge-separated state.     

Finding of remarkable synergistic effect on the aroxyl-radical-scavenging rates under the coexistence of α-tocopherol and catechins

Measurements of aroxyl radical (ArO^•)-scavenging rate constants () of antioxidants (AOHs) (α-tocopherol (α-TocH) and three catechins (CatHs) (ie, epicatechin (EC), epigallocatechin (EGC), and epigallocatechin gallate (EGCG)) were performed in ethanol solution, using stopped-flow spectrophotometry. values were measured not only for each AOH, but also for the mixtures of two AOHs (α-TocH and CatH). A notable synergistic effect that the value of α-TocH increases 1.29, 1.84, and 1.65 times under the coexistence of constant concentrations of EC, EGC, and EGCG, respectively, was observed for the solutions including α-TocH and CatH. Similarly, values of CatHs (EC, EGC, and EGCG) increased 1.72, 2.25, and 2.34 times under the coexistence of constant concentrations of α-TocH, respectively. UV-Vis absorption of α-tocopheroxyl radical (α-Toc^•) (λ_max = 428 nm), which had been produced by reaction of α-TocH with ArO^•, decreased remarkably under the coexistence of α-TocH and CatHs due to the fast α-TocH-regeneration reaction by CatHs. The result suggests that the prooxidant reaction due to α-Toc^• is suppressed by the coexistence of CatHs. By analyzing the formation and decay curves of α-Toc^•, it has been ascertained that one molecule of EGCG having three OH groups at B-ring may rapidly regenerate three molecules of α-Toc^• to α-TocH.     

Cross‐sectional structural characterization of the surface of exfoliated HOPG using HRTEM‐EELS

We analyzed the surface atomic structure of highly oriented pyrolytic graphite (HOPG) substrate exfoliated with adhesive tape, using high‐resolution transmission electron microscopy and scanning transmission electron microscopy‐electron energy‐loss spectroscopy (STEM‐EELS). The surface step height of the exfoliated HOPG substrate was determined using high‐angle annular dark‐field‐scanning transmission electron microscopy (HAADF‐STEM) images and the depth profiles of the EELS spectra of a cross‐sectioned thin foil specimen prepared via focused ion beam milling. The exfoliated surface of the HOPG substrate presented disordered and curved graphene layers. The STEM‐EELS measurements indicated that upon exfoliation, the surface of the HOPG substrate reacted with atmospheric water and oxygen molecules.