Determination of molecular weight distribution of nylon 12 by gel permeation chromatography

Molecular weight distribution of Nylon 12 was determined with hexafluoroisopropanol/toluene mixture as eluent by gel permeation chromatography. Calibration curve for Nylon 12 was easily obtained from that of polystyrene because the method of universal calibration was applicable among these polymers. The molecular weight distributions of Nylon 12 were always broader than expected by the theory of polymerization, i.e., most probable distribution. This result was not caused by broadening effect in gel permeation chromatography, but by polymerization itself.     

Catalytic oxygenative degradation of 4-chlorocatechol by a nonheme iron(III) complex—Mechanism and prevention of catechol ester formation

We examined the oxygenative degradation of 4-chlorocatechol and 4-tert-butylcatechol catalyzed by iron(III)-tris(pyridin-2-yl)amine complex from the standpoint of repressing the formation of 4-chlorocatechol esters of the oxygenated products that causes the incomplete degradation of 4-chlorocatechol. Analysis of the products revealed that 4-chlorocatechol esters are formed by the reaction of muconic anhydride, which is the monooxygenated product, with catechols. It was found that the use of MeOH as the solvent instead of MeCN completely suppressed the catechol ester formation through the methanolysis of muconic anhydride, which greatly improves the degradation efficiency of 4-chlorocatechol.     

Total Synthesis of the Nonribosomal Peptide Surugamide B and Identification of a New Offloading Cyclase Family

The cathepsin B inhibitor surugamide B ( 2 ), along with structurally related derivatives (A and C–E), has previously been isolated from the marine actinomycete Streptomyces sp. JAMM992. The biosynthetic genes are unexpectedly part of a cluster of four non‐ribosomal peptide synthetase (NRPS) genes, two of which are responsible for the biosynthesis of the additional linear decapeptide surugamide F. However, the thioesterase domain required for the later stage of the biosynthesis of the cyclic peptides surugamides A–E is not present in any module architecture of the surugamide NRPSs. Herein, we report the first total synthesis of surugamide B ( 2 ) through the macrocyclization at the biomimetic position, which not only alleviated the Cα epimerization in the macrolactamization process, but also efficiently provided 2 in 34 % yield for 18 steps. Furthermore, both the chemical and enzymatic studies with the biosynthetic precursor mimics revealed that the stand‐alone enzyme SurE, which belongs to the penicillin‐binding protein family, is responsible for macrocyclization of the tethered octapeptidyl intermediate.     

Chemistry of the neopolyoxins,pyrimidine and imidazoline nucleoside peptide antibiotics

New chitin synthetase inhibitors, neopolyoxins A, B, and C were isolated from the culture filtrate of Streptomyces cacaoi subsp. asoensis. Their absolute structures have been established on the basis of chemical and spectroscopic evidence. They are structural analogs of the polyoxins. As a nucleobase, neopolyoxin C possesses uracil, while neopolyoxins A and B contain the imidazoline moiety. A ring contraction reaction of pyrimidine nucleoside into imidazoline nucleoside played a key role in the structure determination of the nucleoside moiety. A similar transformation was suggested for the biosynthesis of neopolyoxins A and B.     

Toroidal surgeries on hyperbolic knots

For a hyperbolic knot in , a toroidal surgery is Dehn surgery which yields a -manifold containing an incompressible torus. It is known that a toroidal surgery on is an integer or a half-integer. In this paper, we prove that all integers occur among the toroidal slopes of hyperbolic knots with bridge index at most three and tunnel number one.

     

Supramolecular graphyne: a C(sp)-H...N hydrogen-bonded unique network structure of 2,4,6-triethynyl-1,3,5-triazine

The crystallization of 2,4,6-triethynyl-1,3,5-triazine (2) leads to a pi-stacked layered structure of a C(sp)-H...N hydrogen-bonded unique hexagonal network structure, which may be regarded as a supramolecular analogue of a hitherto unknown graphyne network: in-plane intermolecular interactions are short and linear H...N contacts (2.31 and 2.34 A) and the interlayer separation is 3.23 A.     

Induction in linear logic

Linear logic, introduced by Girardet al., has a great power of expression, but no method for induction. This paper proposes a method of induction using knowledge represented by linear logical formulas. In linear logic, the number of propositions is controlled by logical operators. When a background theory and a hypothesis prove an example, the number of propositions on each side must be equivalent.     

Ultrasonic effects on electroorganic processes--Part 20. Photocatalytic oxidation of aliphatic alcohols in aqueous suspension of TiO2 powder

Ultrasonic effects in a suspension system were examined using the photocatalytic oxidation of 2-propanol to acetone and of ethanol to acetaldehyde in the aqueous suspension of TiO2 powder as a model reaction. The formation rate of acetone was significantly increased under ultrasonic irradiation. The oxidation reaction under ultrasonic irradiation was affected in a different manner from that in silence by reaction conditions such as ultrasonic power, stirring speed, amount of TiO2, concentration of 2-propanol, and pretreatment of the TiO2 powder. Furthermore, it was also observed that the particle size of the TiO2 photocatalyst powder was increased due to the particle agglomeration by ultrasonic irradiation, and consequently it was suggested that ultrasound activates the surface of the catalyst. These results are discussed on the basis of not only the activation of the photocatalyst but also ultrasonic enhancement of mass transport of 2-propanol molecules.     

Theoretical study of resonant tunneling in rectangular double-, triple-, quadruple-, and quintuple-barrier structures

The transmission coefficient and the resonance condition in the one-dimensional rectangular double-, triple-, quadruple-, and quintuple-barrier structures are derived theoretically under the assumption of the constant tunneling effective mass. It is found that the resonance energies are different from the eigenvalues in the quantum well due to coupling between wells in the multiple-barrier (much more than triple-barrier) structures. It is confirmed that the transmission spectrum is a Lorentzian near to energies of resonance.