The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 1. Thieno[3′,2′:4,5]thieno[2,3-c]quinoline and thieno[2′,3′:4,5]thieno[2,3-c]quinoline

The synthesis of two previously unknown heterocyclic ring systems, namely, thieno[3′,2′:4,5]thieno[2,3-c]-quinoline and thieno[2′,3′:4,5]thieno[2,3-c]quinoline is reported. These two novel ring systems were assembled by photocyclization of the appropriate anilides.     

Synthesis,characterization, and properties of polyurethanes containing 1,4:3,6‐dianhydro‐D‐sorbitol

Two‐ and three‐component polyurethanes containing 1,4:3,6‐dianhydro‐D ‐sorbitol (isosorbide) derived from glucose were synthesized using n‐BuSn(?O)OH·H₂O as a catalyst, and the thermal properties (T_g, T_d) of the polymers were investigated by differential scanning calorimetry and thermogravimetric analysis. We carried out molds for polyurethanes, the molds of polyurethanes were obtained. The dynamic mechanical analyzes showed that the storage modulus values of the three‐component polymers were constant to a higher temperature than those of the two‐component polymers. The storage moduli (E′), loss moduli (E″), and values of tan δ for the polymers were obtained. The rigidity of three‐component polymers was increased by the introduction of bisphenol A and diphenylmethane group to two‐component polymer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6025–6031, 2009     

Concerted proton-electron transfer in the oxidation of hydrogen-bonded phenols

Three phenols with pendant, hydrogen-bonded bases (HOAr-B) have been oxidized in MeCN with various one-electron oxidants. The bases are a primary amine (-CPh(2)NH(2)), an imidazole, and a pyridine. The product of chemical and quasi-reversible electrochemical oxidations in each case is the phenoxyl radical in which the phenolic proton has transferred to the base, (*)OAr-BH(+), a proton-coupled electron transfer (PCET) process. The redox potentials for these oxidations are lower than for other phenols, predominately from the driving force for proton movement. One-electron oxidation of the phenols occurs by a concerted proton-electron transfer (CPET) mechanism, based on thermochemical arguments, isotope effects, and DeltaDeltaG(++)/DeltaDeltaG degrees . The data rule out stepwise paths involving initial electron transfer to form the phenol radical cations [(*)(+)HOAr-B] or initial proton transfer to give the zwitterions [(-)OAr-BH(+)]. The rate constant for heterogeneous electron transfer from HOAr-NH(2) to a platinum electrode has been derived from electrochemical measurements. For oxidations of HOAr-NH(2), the dependence of the solution rate constants on driving force, on temperature, and on the nature of the oxidant, and the correspondence between the homogeneous and heterogeneous rate constants, are all consistent with the application of adiabatic Marcus theory. The CPET reorganization energies, lambda = 23-56 kcal mol(-)(1), are large in comparison with those for electron transfer reactions of aromatic compounds. The reactions are not highly non-adiabatic, based on minimum values of H(rp) derived from the temperature dependence of the rate constants. These are among the first detailed analyses of CPET reactions where the proton and electron move to different sites.     

Indonesian medicinal plants. XXIV. Stereochemical structure of perseitol x K+ complex isolated from the leaves of Scurrula fusca (Loranthaceae)

A complex of perseitol (D-glycero-D-galacto-heptitol) and K+ ions in a molar ratio of 20:1 was isolated from the leaves of Scurrula fusca (Loranthaceae), which has been traditionally used for the treatment of cancer in Sulawesi Island, Indonesia. The stereochemical structure of the complex in H2O solution has been elucidated by use of several kinds of NMR techniques. Furthermore, it has been found that the complex exhibits a potent inhibitory effect on [3H]-leucine incorporation for protein synthesis in Ehrlich ascites tumor cells in mice.     

Molecular-length and chiral discriminations by beta-structural poly(L-alanine) on silica

Poly(L-alanine)-grafted porous silica (Sil-Ala22) was prepared by polymerization of N-carboxyanhydride of L-alanine initiated by 3-aminopropylated silica. Its selective interaction with aromatic guest molecules was evaluated by the retention time in liquid chromatography using the column packed with Sil-Ala22. Sil-Ala22 showed a specific selective retention with discriminating molecular shapes, such as molecular length, linearity and planarity. This selectivity can be explained by a multiple pi-pi interaction with the carbonyl groups one dimensionally-aligned on the rigid beta-form structure in the peptide main chain. Chiral separation with Sil-Ala22 was also described.     

Pattern Classification by Linear Goal Programming and its Extensions

Pattern classification is one of the main themes in pattern recognition, and has been tackled by several methods such as the statistic one, artificial neural networks, mathematical programming and so on. Among them, the multi-surface method proposed by Mangasarian is very attractive, because it can provide an exact discrimination function even for highly nonlinear problems without any assumption on the data distribution. However, the method often causes many slits on the discrimination curve. In other words, the piecewise linear discrimination curve is sometimes too complex resulting in a poor generalization ability. In this paper, several trials in order to overcome the difficulties of the multi-surface method are suggested. One of them is the utilization of goal programming in which the auxiliary linear programming problem is formulated as a goal programming in order to get as simple discrimination curves as possible. Another one is to apply fuzzy programming by which we can get fuzzy discrimination curves with gray zones. In addition, it will be shown that using the suggested methods, the additional learning can be easily made. These features of the methods make the discrimination more realistic. The effectiveness of the methods is shown on the basis of some applications.     

Viscoelasticity and birefringence of polyisobutylene

The complex Young's modulus, E*(ω), and the complex strain-optical coefficient, O*(ω), were measured for polyisobutylene (PIB) over a wide temperature range near and above its glass transition temperature. The master curves could be constructed well for each function with the method of reduced variables. The shift factor, a_T, for E*(ω) is the same as that for O*(ω). The ratio of the imaginary parts of O*(ω) and E*(ω), O″(ω)/E″(ω), takes an extremum, which has never been observed for other polymers. The relation between O*(ω) and E*(ω) cannot be described by a modified stress-optical rule (MSOR) which has been found valid for various polymers. The basic concept of the MSOR. i.e., the chain orientation and the orientation of flat monomer units in the stretch direction, is not sufficient to describe the behavior of PIB and another origin of stress, presumably due to the fluctuation of local stress, should be included. This term does not contribute to the birefringence. The main maximum of tan δ is ascribed to the relaxation of the chain orientation in contrast with many other polymers, such as polyisoprene and polycarbonate, for which the maximum of tan δ is ascribed to the rotational relaxation of monomer units. © 1995 John Wiley & Sons, Inc.