Structure and dynamics of a complex of cellulose with EDA: insights into the action of amines on cellulose

The neutron structure of a complex of EDA with cellulose has been determined to reveal the location of hydrogen atoms involved in hydrogen-bonding. EDA disrupts the hydrogen-bonding pattern of naturally occurring cellulose by accepting a strong hydrogen-bond from the O6 hydroxymethyl group as the conformation of this group is rotated from tg to gt. The O3-H·O5 intrachain hydrogen-bond commonly found in cellulose allomorphs is observed to be disordered in the neutron structure, and quantum chemistry and molecular dynamics calculations show that O3 prefers to donate to EDA. The hydrogen-bonding arrangement is highly dynamic with bonds continually being formed and broken thus explaining the difficulty in locating all of the hydrogen atoms in the neutron scattering density maps. Comparison with other polysaccharide-amino complexes supports a common underlying mechanism for amine disruption of cellulose.     

One-step production of nanofibrillated bacterial cellulose (NFBC) from waste glycerol using Gluconacetobacter intermedius NEDO-01

A major by-product of biodiesel production is waste glycerol, which has numerous potential applications. In this study, we isolated a novel bacterium capable of producing cellulose from waste glycerol, and identified it as a novel strain (named NEDO-01) of Gluconacetobacter intermedius. Scanning electron microscopy revealed that the morphology of the pellicle produced by NEDO-01 was similar to that of cellulose produced by Gluconacetobacter hansenii ATCC23769. Furthermore, X-ray diffraction and solid-state nuclear magnetic resonance spectroscopic analyses suggested that cellulose produced by NEDO-01 had molecular and crystalline structures similar to those of cellulose produced by ATCC23769. After the optimization of cultivation conditions, NEDO-01 mediated the one-step production of nanofibrillated bacterial cellulose (NFBC) from waste glycerol in a medium supplemented with carboxymethyl cellulose. Transmission electron microscopic analysis revealed that the NFBC was composed of relatively uniform fibers with diameters of approximately 20 nm. NFBC was produced as uniform water suspensions, the yield of which was 3.4 g/L from cultivation in 7.5 L medium in a 10-L jar fermenter. The bioconversion of waste glycerol to NFBC, which has superior fluidity, moldability, and miscibility, has a wide variety of applications, including potential uses in the medical and materials engineering fields.     

3-Nitro-l,2,4-triazol-l-yl-tris(pyrrolidin-1-yl)phosphonium hexafluorophosphate (PyNTP) as a condensing reagent for solid-phase peptide synthesis

Solid-phase oligopeptide synthesis has been well developed and most short oligopeptides can now be easily synthesized. However, when a desired oligopeptide forms a secondary structure or includes less reactive amino acids such as aminoisobutyric acid, its terminal amino groups become less reactive and synthesis of the desired oligopeptides becomes difficult. To expand the number of synthetic peptide sequences, we have developed efficient coupling conditions using 3-nitro-l,2,4-triazol-l-yl-tris(pyrrolidin-1-yl)phosphonium hexafluorophosphate (PyNTP) as a highly reactive condensing reagent on an unswellable solid support. PyNTP demonstrated higher reactivity than conventional condensing reagents and the optical purity of the synthesized oligopeptides was sufficiently high for application to general oligopeptide synthesis.     

Laboratory and practical synthesis of Suvorexant,a selective dual orexin receptor antagonist

The development of a laboratory and practical synthesis of Suvorexant 1, using intramolecular Mitsunobu cyclization reaction of intermediate 5 as the key reaction, has been reported. Compound 5 was obtained from known chiral ester 2 in three steps, and the key cyclization proceeded smoothly to provide the core seven-membered ring compound 6, which was transformed into 1 by an additional four-step sequence. The procedure described here needs no chiral-HPLC separation, no classical resolution, and no unique enzyme reactions, and offers an alternative practical synthesis of 1.     

Wide band gap and p‐type conductive Cu–Nb–O films

Cu–Nb–O films with a thickness of ca. 150 nm were prepared on borosilicate glass substrates using CuNbO₃ ceramic target at substrate temperature of 500 °C by pulsed laser deposition. The X‐ray diffraction patterns showed that the Cu–Nb–O films were amorphous or an aggregation of fine crystals. The post‐annealed film at 300 °C in N₂ gas showed 80% transmission in visible light (band gap = 2.6 eV) and high p‐type conductivity of 21 S cm^–1. The Cu–Nb–O film with a thickness of 100 nm, fabricated from the target with a composition of Cu/Nb = 0.9, showed the highest p‐type conductivity of 116 S cm^–1. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Secondary sonochemical effect on Mo-catalyzed bromination of aromatic compounds

The Molybdate-catalyzed bromination of various aromatic compounds in the presence of KBr/H(2)O(2) in an aqueous/chloroform biphasic system occurred under ultrasonic irradiation, whereas the reaction did not take place under conventional mechanical stirring (1400 rpm). The sonochemical activation was found to be of secondary effect, attributed to lowering pH by sonolysis of CHCl(3)-H(2)O solvents mixture.     

Rapid programmable/code-length-variable, time-domain bit-by-bit code shifting for high-speed secure optical communication

We propose and experimentally demonstrate a time-domain bit-by-bit code-shifting scheme that can rapidly program ultralong, code-length variable optical code by using only a dispersive element and a high-speed phase modulator for improving information security. The proposed scheme operates in the bit overlap regime and could eliminate the vulnerability of extracting the code by analyzing the fine structure of the time-domain spectral phase encoded signal. It is also intrinsically immune to eavesdropping via conventional power detection and differential-phase-shift-keying (DPSK) demodulation attacks. With this scheme, 10 Gbits/s of return-to-zero-DPSK data secured by bit-by-bit code shifting using up to 1024 chip optical code patterns have been transmitted over 49 km error free. The proposed scheme exhibits the potential for high-data-rate secure optical communication and to realize even one time pad.     

Developments at the SLOWRI facility at RIKEN: precision optical spectroscopy of 7,9,10,11Be+ ions

Precision optical spectroscopy of radioactive Be isotopes produced in projectile fragmentation has been performed for the first time at the prototype SLOWRI facility of RIKEN RI-Beam Factory. The ground state hyperfine constants of ⁷Be⁺ and ¹¹Be⁺ were determined with relative accuracies of 6 × 10^?7 and 3 × 10^?8, respectively, by laser-microwave double resonance spectroscopy of laser-cooled ions in a trap. The optical transition energies from the ground S-state to the excited P-state of Be isotope ions were also measured to determine the nuclear charge radii from the isotope shifts. Development of the universal slow RI-beam facility??SLOWRI??based on the rf-carpet ion guide technique is progressing at RIKEN RI-beam factory. An additional capability of providing parasitic slow RI-beams from the projectile fragment separator BigRIPS is also discussed.     

Efficient Light‐Harvesting Antennae Resulting from the Dense Organization of Dyes into DNA Junctions through d‐Threoninol

Herein we report the construction of efficient light‐harvesting antennae by hybridization of DNA oligonucleotides containing high densities of fluorophores into DNA junctions through d ‐threoninol. Six pyrene donors could be incorporated into each arm without self‐quenching. A perylene acceptor was located at the center of the junction. Antenna effects of a duplex and three‐ to eight‐way junctions were systematically compared. Six‐ and eight‐way junctions had the highest antenna effects, and their effective absorption coefficients were 8.5 times higher than that of perylene. Interestingly, even‐numbered junctions had higher efficiencies than odd‐numbered junctions. Nondenaturing gel analyses and fluorescence lifetime measurements demonstrated that the strong odd–even effects were derived from differences in the stability of junctions. The results presented will guide the design of efficient artificial photosynthetic systems.