Synthesis of (±)‐Kempa‐6,8‐dien‐3‐ol (=(2aRS,3SR,4aSR,7RS,7aSR,10bSR,10cSR)‐2,2a,3,4,4a,5,6,7,7a,8,10b,10c‐Dodecahydro‐2a,7,10,10c‐tetramethylnaphth[2,18‐cde]azulen‐3‐ol)

The synthesis of kempa‐6,8‐dien‐3β‐ol ( 4a ), as a synthetic leading model of the natural product 4b , was carried out starting from intermediate 12 , the synthetic route of which has been developed previously (Scheme 1). The conversion of 12 to the model compound 4a involved the elaboration of three structure modifications by three processes, Tasks A, B, and C (see Scheme 2). Task A was achieved by epoxy‐ring opening of 41 with Me₃SiCl (Scheme 9), and Task B being performed by oxidation at the 13‐position, followed by hydrogenation, and then epimerization (Schemes 4 and 5). The removal of the 2‐OH group from 12 (Task C) was achieved via 30b according to Scheme 6, whereby 30b was formed exclusively from 30a / 31a 1 : 1 (Scheme 7). In addition, some useful reactions from the synthetic viewpoint were developed during the course of the present experiments.     

Dynamics and thermodynamics of dimerization of parallel G-quadruplexed DNA formed from d(TTAGn) (n=3-5)

Parallel G-quadruplexes formed from oligonucleotide sequences, d(TTAGn), where n = 3-5, have been shown to form a dimer through end-to-end stacking of 3'-terminal G-tetrads. The monomers and dimers of the G-quadruplexes are in dynamic equilibrium with an exchange rate of approximately 1 s-1. A thermodynamic study demonstrated that the dimerization of the G-quadruplexes is largely enthalpic in origin.     

Application of Hot Press Sintering to Na2O-B2O3-SiO2 Gels Containing Quantum Dots for Lowering of Densification Temperature

Na₂O-B₂O₃-SiO₂ (NBS) gels containing a large amount of CdS quantum-dots (10 wt%) were densified using the hot press (HP) sintering method. By HP treatment, full-densification temperature could be lowered by about 40°C than that of the normal non-pressing (NP) heat treatment. Exciton absorption of CdS quantum-dots in HP-sample showed a large blue shift compared with that in the NP sample, and the size-distribution of CdS dots remained very sharp, with a mean particle diameter d = 3.66 nm and a standard deviation of = 0.72. HP pressure had a large effect on the reduction of sintering temperature and time, resulting in the suppression of the aggregation and growth of CdS quantum-dots in NBS glasses.     

Endo- and aminopeptidase activities of rat cathepsin H.

Employing soluble denatured protein substrates and their derivatives, the proteolytic activity of rat cathepsin H was investigated. The enzyme showed aminopeptidase activity which sequentially released amino acid from the N-terminal of the substrate. The aminopeptidase activity did not act on N alpha-acetylated peptides and showed moderate ionic-strength dependence when methionyl-methylcoumarylamide was employed as a substrate. These results indicate that the activity essentially requires an N-terminal free amino group of the substrate and recognizes it electrostatically to some extent. On the other hand, the enzyme was also indicated to exhibit endopeptidase activity by employing appropriate N alpha-acetylated peptide substrates. In contrast to the aminopeptidase activity, the endopeptidase activity showed rather strict specificity, preferring hydrophobic residues at P2 and P3 sites. Because of the broad specificity and high efficiency of the aminopeptidase activity, it was difficult to directly observe endopeptidase activity in the digestion of large peptide substrates with a free alpha-amino terminal. Thus, this is the first experimental evidence that indicates endopeptidase activity by assigning internal peptide bonds cleaved by this activity. From this data, we proposed a model of the binding site of this enzyme.     

Template-directed DNA photoligation via alpha-5-cyanovinyldeoxyuridine

[reaction: see text] We describe an efficient template-directed photoligation of oligodeoxynucleotides (ODNs) using alpha-5-cyanovinyldeoxyuridine (alpha(C)U). An efficient photoligation was produced by photoirradiation of an ODN containing alpha(C)U at the 3' end with an ODN containing thymine at the 5' end in the presence of a template ODN. This photoligation method is a new and efficient way to synthesize branched ODNs.     

Cationic polymerization behavior of hydroxystyrenes

Solution polymerizations of o-, m- and p-hydroxystyrene with boron trifluoride etherate were investigated. The results of infrared and ultraviolet spectroscopic investigations of the polymers thus obtained indicate that p-hydroxystyrene polymer consisted mainly of the structure formed through the normal vinyl polymerization mechanism, whereas o- and m-hydroxystyrene polymers contained considerable portions of the structures due to the reaction of the vinyl group with the phenol nucleus. The rate of polymerization and the intrinsic viscosity of the polymer decreased in the order p-hydroxystyrene ? o-hydroxystyrene > m-hydroxystyrene. It was of interest that on the cationic polymerization only p-hydroxystyrene gave polymer of high molecular weight. Plausible polymerization mechanisms were considered. Solid-state polymerization of p-hydroxystyrene at solid carbon dioxide temperature with the use of boron trifluoride etherate was also investigated. Appreciable polymerization occurred only at fairly high catalyst concentrations.     

Gas-phase reactions of organic radicals and diradicals with ions

Reactions of polyatomic organic radicals with gas phase ions have been studied at thermal energy using a flowing afterglow-selected ion flow tube (FA-SIFT) instrument. A supersonic pyrolysis nozzle produces allyl radical (CH2CHCH2) and ortho-benzyne diradical (o-C6H4) for reaction with ions. We have observed: [CH2CHCH2 + H3O+ --> C3H6+ + H2O], [CH2CHCH2 + HO- --> no ion products], [o-C6H4 + H3O+ --> C6H5+ + H2O], and [o-C6H4 + HO- --> C6H3- + H2O]. The proton transfer reactions with H3O+ occur at nearly every collision (kII approximately with 10(-9) cm3 s(-1)). The exothermic proton abstraction for o-C6H4 + HO- is unexpectedly slow (kII approximately with 10(-10) cm3 s(-1)). This has been rationalized by competing associative detachment: o-C6H4 + HO- --> C6H5O + e-. The allyl + HO- reaction proceeds presumably via similar detachment pathways.     

Dependence of phase behavior of some non-ionic surfactants at the air-water interface on micellization in the bulk

The temperature-dependent surface phase behavior of two sparingly soluble surfactants, namely, ethylene glycol n-dodecyl ether (EGDE) and ethylene glycol n-tetradecyl ether (EGTE), at the air-water interface was investigated by film balance and Brewster angle microscopy (BAM). A cusp point followed by a pronounced plateau region in the surface pressure-time (pi-t) adsorption isotherms of the amphiphiles measured by film balance indicates the first-order phase transition. Bright two-dimensional condensed phase domains in a dark background are observed by BAM just after the phase transition. In both cases the critical surface pressure necessary for the phase transition increases with increasing temperature. The domains are found to be circular up to 5 and 27 degrees C for EGDE and EGTE, respectively, above which they show a fingering pattern. Condensed domains are observed up to 23 and 37 degrees C for EGDE and EGTE, respectively. The surface properties of the amphiphiles are found to be markedly affected by their tendency to aggregate in the bulk as micelles. The CMC values of both the amphiphiles show a maximum at a definite temperature, T(max), that corresponds well to their respective maximum temperatures of domain formation. An increase in temperature beyond T(max) results in an increasing trend for the formation of micelles. Consequently the system suffers from a shortage of two-dimensional surface concentration of the molecules to attain the surface pressure necessary for phase transition. With increasing temperature, the enthalpy, DeltaH(m) degrees , and entropy, DeltaS(m) degrees , of micellization change from negative to positive in both cases. An enthalpy-entropy compensation effect is found to hold for both the amphiphiles over the entire temperature range. The thermodynamic quantities reveal that the increase in temperature is favorable for micellization when the temperature exceeds the corresponding T(max) of the amphiphiles.     

Highly chemo- and regioselective phosphitylation of unprotected 2′-deoxyribonucleosides

We have developed the chemo- and regioselective phosphitylation of unprotected 2′-deoxyribonucleosides by the use of di-tert-butyl N,N-diethylphosphoramidite, a sterically hindered phosphoramidite. Both N/O- and primary hydroxy group-selectivities were simultaneously achieved, and the selectivity for the 5′-hydroxy groups was up to 97% regardless of the base moiety of the 2′-deoxyribonucleosides. The 3′-O-isomers and the 5′-O-isomers were easily separated by silica gel column chromatography or crystallization to give the pure 2′-deoxyribonucleoside 5′-phosphites in moderate to good yields.