Catalytic specificity exhibited by p-sulfonatocalix[n]arenes in the methanolysis of N-acetyl-l-amino acids

Specific acid catalysis of p-sulfonatocalix[n]arenes (n = 4, Calix-S4; n = 6, Calix-S6; n = 8, Calix-S8) was observed in the alcoholysis of N-acetyl-l-amino acids in methanol. The methanolysis rates of basic amino acid substrates (His, Lys, and Arg) were markedly enhanced in the presence of Calix-Sn, as compared with rates observed with p-hydroxybenzenesulfonic acid (pHBS), which is a noncyclic analogue of Calix-Sn. This catalytic effect of Calix-Sn was not observed for the methanolysis of Phe, Tyr, and Trp substrates. On the other hand, (1)H NMR experiments following the effect of Calix-Sn on N-acetyl-l-amino acid substrates in CD(3)OD showed that the spectrum of a mixture of the His substrate with Calix-Sn was significantly different from the combined spectra of the respective compounds. These changes in spectra support the formation of an inclusion complex of Calix-Sn with basic amino acids. Furthermore, it was obvious that methanolysis of the His substrate catalyzed by Calix-S4 and Calix-S6 obeyed Michaelis-Menten kinetics. These results indicate that the catalytic activity of Calix-Sn originates from its forming a complex with specific substrates (basic amino acids), similar to enzymatic reactions.     

Genome Mining of Oxidation Modules in trans-Acyltransferase Polyketide Synthases Reveals a Culturable Source for Lobatamides

Bacterial trans-acyltransferase polyketide synthases (trans-AT PKSs) are multimodular megaenzymes that biosynthesize many bioactive natural products. They contain a remarkable range of domains and module types that introduce different substituents into growing polyketide chains. As one such modification, we recently reported Baeyer–Villiger-type oxygen insertion into nascent polyketide backbones, thereby generating malonyl thioester intermediates. In this work, genome mining focusing on architecturally diverse oxidation modules in trans-AT PKSs led us to the culturable plant symbiont Gynuella sunshinyii, which harbors two distinct modules in one orphan PKS. The PKS product was revealed to be lobatamide A, a potent cytotoxin previously only known from a marine tunicate. Biochemical studies show that one module generates glycolyl thioester intermediates, while the other is proposed to be involved in oxime formation. The data suggest varied roles of oxygenation modules in the biosynthesis of polyketide scaffolds and support the importance of trans-AT PKSs in the specialized metabolism of symbiotic bacteria.     

Genome Mining of Oxidation Modules in trans‐Acyltransferase Polyketide Synthases Reveals a Culturable Source for Lobatamides

Bacterial trans‐acyltransferase polyketide synthases (trans‐AT PKSs) are multimodular megaenzymes that biosynthesize many bioactive natural products. They contain a remarkable range of domains and module types that introduce different substituents into growing polyketide chains. As one such modification, we recently reported Baeyer–Villiger‐type oxygen insertion into nascent polyketide backbones, thereby generating malonyl thioester intermediates. In this work, genome mining focusing on architecturally diverse oxidation modules in trans‐AT PKSs led us to the culturable plant symbiont Gynuella sunshinyii, which harbors two distinct modules in one orphan PKS. The PKS product was revealed to be lobatamide A, a potent cytotoxin previously only known from a marine tunicate. Biochemical studies show that one module generates glycolyl thioester intermediates, while the other is proposed to be involved in oxime formation. The data suggest varied roles of oxygenation modules in the biosynthesis of polyketide scaffolds and support the importance of trans‐AT PKSs in the specialized metabolism of symbiotic bacteria.     

Ultrasonic butt welding of aluminum,aluminum alloy and stainless steel plate specimens

Welding characteristics of aluminum, aluminum alloy and stainless steel plate specimens of 6.0 mm thickness by a 15 kHz ultrasonic butt welding system were studied. There are no detailed welding condition data of these specimens although the joining of these materials are required due to anticorrosive and high strength characteristics for not only large specimens but small electronic parts especially. These specimens of 6.0 mm thickness were welded end to end using a 15 kHz ultrasonic butt welding equipment with a vibration source using eight bolt-clamped Langevin type PZT transducers and a 50 kW static induction thyristor power amplifier. The stainless steel plate specimens electrolytically polished were joined with welding strength almost equal to the material strength under rather large vibration amplitude of 25 microm (peak-to-zero value), static pressure 70 MPa and welding time of 1.0-3.0 s. The hardness of stainless steel specimen adjacent to a welding surface increased about 20% by ultrasonic vibration.     

One-dimensional longitudinal-torsional vibration converter with multiple diagonally slitted parts

For increasing the available vibration velocity of the one-dimensional longitudinal-torsional vibration converter, a new type of complex vibration converter with multiple slitted parts installed in the positions avoiding longitudinal nodal positions along the converter for decreasing the maximum vibration stress level at the vibration nodal part was studied. The free end of the converter vibrates in an elliptical or circular locus. Complex vibration systems with elliptical to circular or rectangular to square loci can be applied effectively for various high-power applications, including ultrasonic welding of metal or plastics, ultrasonic wire bonding of IC, LSI and electronic devices, and also ultrasonic motors. The converter with multiple slitted parts was improved in the vibration stress level and the quality factor compared with the converter with single slitted part.     

Improvement of S/N ratio of a proportional counter for depth selective conversion electron Mössbauer spectroscopy

The S/N ratio of a proportional counter for DCEMS of⁵⁷Fe was improved by introducing a lead slit which collimates incident γ-rays to hit only a sample. The background spectrum due to the 122 and 136 keV γ-rays was obtained and it was found that the fraction of the background noise of these γ-rays was 65% in the energy region of 2–5 keV. The S/N ratio for a natural iron foil was in good agreement with the calculated one.     

Molecular orientation and mechanical anisotropy of polypropylene sheet containing N,N′‐dicyclohexyl‐2,6‐naphthalenedicarboxamide

Effect of mixing and processing conditions at T‐die extrusion on the structure and mechanical properties is studied for isotactic polypropylene (PP) containing a small amount of β‐form nucleating agent, N,N′‐dicyclohexyl‐2,6‐naphthalenedicarboxamide. It is found that trigonal β crystals are predominantly formed in the extruded samples containing the nucleating agent irrespective of the mixing and processing conditions, leading to the marked mechanical toughness. On the contrary, the molecular orientation is significantly affected by the mixing and processing conditions. In particular, it should be noted that PP molecules in the extruded sheet which was mixed at high temperature (260 °C) and extruded at low temperature (200 °C) orient perpendicular to the applied flow direction. As a result, the sheet shows anomalous mechanical anisotropy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 424–433, 2009     

A Structurally Robust Chiral Borate Ion: Molecular Design,Synthesis, and Asymmetric Catalysis

Catalysis by chiral weakly‐coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non‐nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O‐tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins‐type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis.