Cobalt activation of Bacillus BR449 thermostable nitrile hydratase expressed in Escherichia coli

Expression of nitrile hydratase enzymes utilized in a new “green” process for acrylamide production has proven difficult in Escherichia coli owing to lack of a cobalt transport system to introduce the required cobaltion into this host. We describe the expression of a thermostable nitrile hydratase from a moderatethermophile Bacillus sp. BR449 in E. coli in which the cobaltrequired for enzyme activation is introduced by incubation, of the apoenzyme in the presence of Co⁺⁺ ion at 50°C, yielding active and thermostable, enzyme.     

Photoreaction of 2-halo-N-pyridinylbenzamide: intramolecular cyclization mechanism of phenyl radical assisted with n-complexation of chlorine radical

The photochemical behavior of 2-halo-N-pyridinylbenzamide (1-4 in Chart 1) was studied. The photoreaction of 2-chloro-N-pyridinylbenzamides 1a, 2a, 3a, and 4 afforded photocyclized products, benzo[c]naphthyridinones (6-9 and 16), in high yield, whereas the bromo analogues 1b, 2b, and 3b produced extensively photoreduced products, N-pyridinylbenzamides (1c, 10, and 11), with minor photocyclized product. Since the photocyclization reaction of 2-chloro-N-pyridinylbenzamide is retarded by the presence of oxygen and sensitized by the presence of a triplet sensitizer, acetone or acetophenone, a triplet state of the chloro analogue is involved in the reaction. Since several radical intermediates, particularly n-complexes of chlorine radical, are identified in the laser flash photolysis of 2-chloro-N-pyridinylbenzamide, an intramolecular cyclization mechanism of phenyl radical assisted with n-complexation of chlorine radical for the cyclization reaction is proposed: the triplet state (78 kcal/mol) of the chloro analogue (1a), which is populated by the excitation of 1a undergoes a homolytic cleavage of the C-Cl bond to give phenyl and chlorine radicals; while chlorine radical holds the neighbor pyridinyl ring with its n-complexation, the intramolecular arylation of the phenyl radical with the pyridinyl ring proceeds to produce a conjugated 2,3-dihydropyridinyl radical and then the conjugated radical aromatizes to afford a cyclized product, benzo[c]naphthyridinone by ejecting a hydrogen. The photoreduction product can be formed by hydrogen atom abstraction of the phenyl sigma radical from the environment.     

Influences of Heating Condition and Substrate-Surface Roughness on the Characteristics of Sol-Gel-Derived Hydroxyapatite Coatings

A prepared transparent HA solution was coated on Ti6Al4V substrates by a spin-coating technique. The crystallization of the sol-gel-derived HA coated on the metallic substrates could be done at relatively low firing temperatures (as low as 600°C). The characteristics of the HA-coated layer were dependent on the surface roughness of substrates and heating conditions such as firing temperature, holding time, heating rate, and atmosphere. The heat treatment at a slow heating rate (<2°C/min.) and a long heating time (>10 hrs) at 600°C in air produced the uniform surface and improved the crystallinity. The HA layer coated on 20 m grit-blasted substates was more uniform and had fever cracks after firing, compared with that coated on 100 m grit-blasted rougher substrates.     

Synthesis of optically active 2-alkyl-3,4-iminobutanoic acids. Beta-amino acids containing an aziridine heterocycle

All four stereoisomers of 2-alkyl-3,4-iminobutanoic acid, a novel class of beta-amino acids bearing a chemically versatile aziridine ring, were synthesized starting with aspartic acid. The synthetic strategy involves the introduction of an alkyl group at the beta-position of fully protected optically active aspartic acid followed by the construction of an aziridine ring making use of the alpha-carboxylate and alpha-amino groups. The alpha-carboxylate was reduced to the corresponding alcohol, which was then subjected to cyclization to form an aziridine ring with the N-protected amino group. Removal of the protection groups yielded the target compounds.     

Antimalarial and cytotoxic activities of bicycl

Biological evaluations of bicyclo[6.4.0]dodecenone derivatives on antimalarial activity in vitro against Plasmodium falciparum and cytotoxicity against human KB cells were made. (+/-)-(1R*,4S*,7R*,8S*)-4-tert-Butyl-dimethylsiloxy-5,5-dimethyl-1-methyl-9-methylene-7-phenylsulfonylbicyclo[6.4.0]dodec-2,11-dien-10-one (15) exhibited potent antimalarial activity, whereas (+/-)-(1R*,7R*,8S*)-1-methyl-9-methylene-7-phenylsulfonylbicyclo[6.4.0]dodec-2,11-dien-10-one (14) showed significant cytotoxic activity in human KB cells. Both 14 and 15 possess, as a structural character, the exo-methylene moiety in their 6-membered ring of the 8-6 fused ring system.     

The effect of surface polarity of glass on liquid crystal alignment

The effects of the surface polarity of a glass substrate on the orientation of nematic liquid crystals (LCs) were studied using the polarised optical microscope and Fourier-transform infrared spectroscopy. On the surface of oxygen plasma treated glass, a homeotropic alignment of LCs was induced for LCs with negative dielectric anisotropy. This suggests that vertical orientation of LCs could be induced on a polar glass substrate without using an LC alignment layer. Upon cooling towards the isotropic–nematic transition, E7 with positive dielectric anisotropy changes its LC arrangement to isotropic, homeotropic, planar orientations in order. The nematic LC anchoring transition of E7 was interpreted by considering the competition between van der Waals forces and dipole interactions that control the alignment of LC molecules on a polar glass surface.     

Peripheral chain length-dependent complex phase behaviour in C3-symmetric hexa-alkylated liquid crystals

We report the thermal and self-assembly properties of C₃-symmetric liquid crystalline (LC) molecules consisting of a conformationally tunable triazole-based mesogen and six-fold alkyl chains. Unlike the LC compound (1) based on non-crystallisable octyl chains, 2 and 3, which have crystallisable dodecyl and tetradecyl chains, respectively, exhibit a cold crystallisation which only takes place under slow heating conditions (2°C/min). In contrast with the vertically interdigitated lamellar crystalline phase of 1, a laterally interdigitated bilayered lamellar structure driven by the crystallisation of the dodecyl or tetradecyl chains is observed in the cold crystallisation temperature range. In addition to their crystalline morphology, 2 and 3 show LC morphological behaviour distinct from that of 1, 2 and 3 exhibit a hexagonal columnar LC phase consisting of T-shaped conformers rather than the lamellar LC phase of 1. The morphological transformation from the lamellar (1) to the columnar phase (2 and 3) can be rationalised by the alleviation of the conformational energy of the longer alkyl chains. Consequently, the simple variation of alkyl chain length in the C₃-symmetric LC system results in contrasting thermal and assembly properties in the crystalline and LC phases.     

Enhancement of flexoelectric ratio of nematic liquid crystal by doping calamitic ferroelectric liquid crystal

We measured the flexoelectric ratio e* of a nematic liquid crystal (NLC) doped with a calamitic ferroelectric liquid crystal (FLC). We doped two kinds of commercial FLC into the pure NLC at a weight concentration of 5 wt%. The absolute value of the flexoelectric ratio was increased up to 49% compared to the pure NLC. The greater transverse dipole moment and the elastic constant of FLC are thought to be related to the increase of the flexoelectric ratio.     

Polyvinyl alcohol-borate hydrogel containing Prussian blue for surface decontamination

A polyvinyl alcohol (PVA)-borate hydrogel-based strippable surface decontaminant containing an ammonium salt and Prussian blue (PB) was developed for the removal of ¹³⁷Cs from various surfaces. This surface decontaminant can be easily prepared by the simple mixing of commercially available materials, such as PVA, borax, NH₄Cl and PB, in water, and the decontaminant can be peeled off surfaces due to its high elastic property after surface decontamination. The hydrogel displayed an effective removal performance for Cs from painted cement, aluminum, stainless steel, and cement surfaces and a potential for reusability. Therefore, the PB/PVA-borate hydrogel has good potential as a new surface decontaminant.     

Measurement of <Superscript>99</Superscript>Mo production cross-section from the <Superscript>100</Superscript>Mo(n,2n) reaction with quasi monoenergetic neutron based on the <Superscript>9</Superscript>Be(p,n) reaction

The production cross-section of the medical isotope, ⁹⁹Mo from the enriched ¹⁰⁰Mo(n,2n) reaction with the average neutron energies of 21.9 and 26.5 MeV has been determined for the first time by using an off-line γ-ray spectrometric technique. The average neutron energies were generated by using the ⁹Be(p,n) reaction with the proton energies of 35 and 45 MeV from the MC50 cyclotron of the Korea Institute of Radiological and Medical Sciences (KIRAMS) at Seoul, South Korea. The ¹⁰⁰Mo(n,2n) reaction cross-section as a function of neutron energy was also calculated theoretically by using the computer code TALYS-1.8 and EMPIRE-3.2 Malta. The experimental results are in close agreement with the theoretical values from TALYS-1.8. However, the present data at the neutron energy of 21.9 MeV is slightly lower and at 26.5 MeV is higher than the values from EMPIRE-3.2 Malta.