Trans-cis Photoisomerization of 1-Methyl-4-(4′-hydroxystyryl)pyridinium in inclusion complexes ofβ-cyclodextrin and its derivatives

The effects of -cyclodextrin (-CyD), heptakis(2,6-di-O-methyl)--cyclodextrin (DMCyD) and heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TMCyD) ontrans-cis photoisomerization of 1-ethyl-4-(4-hydroxystyryl)pyridinium (POH) have been studied in aqueous solutions. The ratio of [cis]/[trans] for POH in the photostationary state at pH 8.54 was remarkably reduced by the presence of CyD or DMCyD. The reduction of the [cis]/[trans] ratio in the photostationary state was explained in terms of the shift of the equilibrium of POH ₊ ^trans PO _trans + H^– toward PO _trans formation. The binding constants of CyD and DMCyD for PO _trans were 2.00- and 1.36-fold larger than those for POH ₊ ^trans , respectively. The binding constants of TMCyD for both species are much smaller than those of CyD and DMCyD. This result indicates that PO _trans , which has a betain structure, forms stable complexes with CyD and DMCyD with its hydrophobic parts inside and the charged parts outside the CyD cavities.     

NMR studies of conformations and molecular recognition of pyridinio-appended and nicotinamide-appended β-cyclodextrin

Abstract

The conformations of pyridinio-appended β-cyclodextrin (CDP⁺) and nicotinamide-appended β-cyclodextrin (CDNA⁺) were studied by NMR spectroscopy. The orientations of the pyridine residue of CDP⁺ and the nicotinamide residue of CDNA⁺ were determined by using a combination of NMR spectroscopic techniques. NMR spectra indicate that the shapes of the cavities of CDP⁺ and CDNA⁺ were changed after forming complexes. This change depended on the shape of the guest. CDNA⁺ could separate the ¹H resonances at the Cβ position of racemic tryptophan into two sets of resonances for each enantiomer.     

A Convenient General Access to α-Sulfenylated Acetophenones and Alkanones

Friedel-Crafts acylation of arenes with methylthio- (1) or phenylthio-acetyl chloride (2) provides ready access to α-methylthio- or α-phenylthio-substituted acetophenones. The acyl chlorides 1 and 2 reacted also with organoaluminum reagents to give α-sulfenylated alkanones.     

Elongation method with intermediate mechanical and electrostatic embedding for geometry optimizations of polymers

The elongation method with intermediate mechanical and electrostatic embedding (ELG-IMEE) is proposed. The electrostatic embedding uses atomic charges generated by a charge sensitivity analysis (CSA) method and parameterized for three different population analyses, namely, the Merz–Singh–Kollman scheme, the charge model 5, and the atomic polar tensor. The obtained CSA models were tested on two model systems. Test calculations show that the electrostatic embedding provides several times of decrease in the difference of energies of testing and reference calculations in comparison with the conventional elongation approach (ELG). The mechanical embedding is implemented in a combination of the conventional elongation method and the ONIOM approach. Moreover, it was demonstrated that the geometry optimization with the ELG-IMEE reduces the errors in the optimized structures by about one order in root-mean-square deviation, when compared to ELG.     

Polyaddition reaction of pseudoxazolones with dimercaptans

Polymers having thioether, thiolester, and amide linkages in each repeating unit of a polymer main chain were prepared by the polyaddition reaction of pseudoxazolones (2-isopropylidene-4-alkyl-3-oxazolin-5-ones) and dimercaptans. The polymers had inherent viscosities in a range of 0.08–0.22 and gave transparent films by solution casting.     

Synthesis and reactivity of β-cyclodextrin-histamine as enzyme model

Cyclodextrin (CD) has a hydrophobic cavity which acts like a binding site of an actual enzyme. But enzymatic turnover reaction did not occur in CD-catalyzed reactions. -CD was modified by a histamine group to attach a reactive functional group. -CD-histamine accelerates the hydrolysis of p-nitrophenyl acetate. Catalytic rate constant of this reaction is close to an actual enzyme, -chymotrypsin. Enzymatic turnover reaction is realized with this compound at around neutral pH value.     

Long-term effects of UV light on contractility of rat arteries in vivo

Several studies have shown that UV irradiation may be effective for preventing vascular restenosis or vasopasm. However, the long-term effects of UV light on the physiological properties of vessels such as arterial tension have not been elucidated. We therefore studied the long-term effects of UV using rat carotid arteries treated with UV-B light (wavelength = 313 nm, total energy = 14 mJ/mm2). The animals were sacrificed at 1, 7 and 14 days after UV light exposure, and the carotid arteries were studied by light microscopy and the contractile responses of isolated arterial rings were recorded under isometric tension. UV treatment had induced a substantial loss of smooth muscle cells (SMC) along the entire circumference of the media on days 7 and 14, whereas loss of SMC on day 1 was negligible. Contractile responses of arteries that had been exposed to UV light were significantly reduced on days, 1, 7 and 14. The susceptibility of UV-treated arteries to phenylephrine and prostaglandin F2 alpha was significantly decreased on days 1 and 7, but decreased susceptibility was not seen on day 14. Acetylcholine-induced relaxations were not altered by UV treatment. These results suggest that the long-term effect of UV light is an attenuation of smooth muscle contractility without impairment of endothelial function.