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11.
Masahisa Wada Yoshiharu Nishiyama Giovanni Bellesia Trevor Forsyth S. Gnanakaran Paul Langan 《Cellulose (London, England)》2011,18(2):191-206
The hydrogen bond arrangement in a complex of cellulose with ammonia has been studied using neutron crystallography in combination
with molecular dynamics simulations. The O6 atom of the hydroxymethyl group is donor in a highly occupied hydrogen bond to
an ammonia molecule. This rotating ammonia molecule is donor in partially occupied and transient hydrogen bonds to the O2,
O3 and O6 atoms of the hydroxyl groups of other chains. The hydrogen atom bound to the O3 atom is disordered but it is almost
always involved in some type of hydrogen bonding. It is donated in a hydrogen bond most of the time to the O5 atom on the
same chain. However, it also rotates away from this O5 atom to be donated to an ammonia molecule part of the time. On the
other hand the hydrogen atom bound to the O2 atom is free from hydrogen bonding most of the time. It is donated in a hydrogen
bond to the O6 atom on a neighboring chain only with a relatively small probability. These results provide new insights into
how hydrogen bonds are rearranged during the conversion of cellulose I to cellulose IIII by ammonia treatment. 相似文献
12.
Yusuke Sasano Shota Nagasawa Mai Yamazaki Dr. Masatoshi Shibuya Prof. Dr. Jaiwook Park Prof. Dr. Yoshiharu Iwabuchi 《Angewandte Chemie (International ed. in English)》2014,53(12):3236-3240
The direct oxidation of unprotected amino alcohols to their corresponding amino carbonyl compounds has often posed serious challenges in organic synthesis and has constrained chemists to adopting an indirect route, such as a protection/deprotection strategy, to attain their goal. Described herein is a highly chemoselective aerobic oxidation of unprotected amino alcohols to their amino carbonyl compounds in which 2‐azaadamantane N‐oxyl (AZADO)/copper catalysis is used. The catalytic system developed leads to the alcohol‐selective oxidation of various unprotected amino alcohols, carrying a primary, secondary, or tertiary amino group, in good to high yield at ambient temperature with exposure to air, thus offering flexibility in the synthesis of nitrogen‐containing compounds. 相似文献
13.
Takanari Togashi Mitsuo Umetsu Takashi Naka Satoshi Ohara Yoshiharu Hatakeyama Tadafumi Adschiri 《Journal of nanoparticle research》2011,13(9):3991-3999
The assembly of metal oxide nanoparticles (NPs) on a biomolecular template by a one-pot hydrothermal synthesis method is achieved
for the first time. Magnetite (Fe3O4) nanoneedles (length: ~100 nm; width: ~10 nm) were assembled on cyclic-diphenylalanine (cFF) nanorods (length: 2–10 μm; width:
200 nm). The Fe3O4 nanoneedles and cFF nanorods were simultaneously synthesized from FeSO4 and l-phenylalanine by hydrothermal synthesis (220 °C and 22 MPa), respectively. The samples were analyzed by powder X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (IR), transmission electron microscopy (TEM), and superconducting quantum interference
device (SQUID) magnetometry. Experimental results indicate that Fe3O4 nanoneedles were assembled on cFF nanorods during the hydrothermal reaction. The composite contained 3.3 wt% Fe3O4 nanoneedles without any loss of the original magnetic properties of Fe3O4. 相似文献
14.
Pan Chen Yoshiharu Nishiyama Jean-Luc Putaux Karim Mazeau 《Cellulose (London, England)》2014,21(2):897-908
We have performed molecular dynamics calculations using a revised version of the Gromos56Acarbo force field to understand the consequences of the different potential hydrogen bonding patterns on the structural stability and thermal behavior of the Iα and Iβ forms of native cellulose. For each allomorph, we considered three patterns of hydrogen bonds: two patterns obtained from neutron diffraction data refinement and a regular mixture of the two. Upon annealing, the hydrogen bonding schemes of cellulose Iβ, irrespective of the starting structure, re-arranged into the main hydrogen bond pattern experimentally observed (pattern A). On the other hand, the Iα structures, irrespective of the starting hydrogen bonding pattern, converged to a non-experimental structure where the adjacent chains are shifted along the chain direction by 0.12 nm in the hydrogen-bonded plane, and the hydroxymethyl group conformation alternates between gt and tg along the chain. The exotic structure in Iα might be a consequence of a deficiency in force field parameters and/or potential molecular arrangement in less crystalline cellulose. 相似文献
15.
Sai Venkatesh Pingali Hugh M. O’Neill Yoshiharu Nishiyama Lilin He Yuri B. Melnichenko Volker Urban Loukas Petridis Brian Davison Paul Langan 《Cellulose (London, England)》2014,21(2):873-878
Morphological changes to the different components of lignocellulosic biomass were observed as they occurred during steam pretreatment by placing a pressure reaction cell in a neutron beam and collecting time-resolved neutron scattering data. Changes to cellulose morphology occurred mainly in the heating phase, whereas changes in lignin morphology occurred mainly in the holding and cooling phases. During the heating stage, water is irreversibly expelled from cellulose microfibrils as the elementary fibrils coalesce. During the holding phase lignin aggregates begin to appear and they increase in size most noticeably during the cooling phase. This experiment demonstrates the unique information that in situ small angle neutron scattering studies of pretreatment can provide. This approach could be useful in optimizing the heating, holding and cooling stages of pretreatments to allow the exact size and nature of lignin aggregates to be controlled in order to enhance enzyme accessibility to cellulose and therefore the efficiency of biomass conversion. 相似文献
16.
A simple copper- and base-free palladium-catalyzed Sonogashira-type cross-coupling by the use of triarylantimony dicarboxylates is described. Reaction of triarylantimony diacetates with terminal alkynes in the presence of 1 mol % of PdCl2(PPh3)2 catalyst led to the formation of cross-coupling products in good to excellent yields. The reaction proceeded effectively under an aerobic condition, in that two of the three aryl groups on antimony could be transferred to the coupling products, whereas only one of them was involved in the reaction in an argon atmosphere. The reaction is sensitive to the electronic nature of the diacetates, and those bearing an electron-withdrawing group on the aromatic ring showed higher reactivity than those having an electron-donating group. 相似文献
17.
Yoshihiko Nishimori Katsuhiko Kanaizuka Dr. Tomochika Kurita Toshiaki Nagatsu Yu Segawa Fumiyuki Toshimitsu Satoshi Muratsugu Dr. Mitsuya Utsuno Dr. Shoko Kume Dr. Masaki Murata Dr. Hiroshi Nishihara Prof. 《化学:亚洲杂志》2009,4(8):1361-1367
Electronic conductivity of molecular wires is a critical fundamental issue in molecular electronics. π‐Conjugated redox molecular wires with the superior long‐range electron‐transport ability could be constructed on a gold surface through the stepwise ligand–metal coordination method. The βd value, indicating the degree of decrease in the electron‐transfer rate constant with distance along the molecular wire between the electrode and the redox active species at the terminal of the wire, were 0.008–0.07 Å?1 and 0.002–0.004 Å?1 for molecular wires of bis(terpyridine)iron and bis(terpyridine)cobalt complex oligomers, respectively. The influences on βd by the chemical structure of molecular wires and the terminal redox units, temperature, electric field, and electrolyte concentration were clarified. The results indicate that facile sequential electron hopping between neighboring metal–complex units within the wire is responsible for the high electron‐transport ability. 相似文献
18.
Masahisa Wada Laurent Heux Yoshiharu Nishiyama Paul Langan 《Cellulose (London, England)》2009,16(6):943-957
X-ray crystallographic and cross-polarization/magic angle spinning 13C nuclear magnetic resonance techniques have been used to study an ethylenediamine (EDA)-cellulose I complex, a transient structure in the cellulose I to cellulose IIII conversion. The crystal structure (space group P2 1 ; a = 4.546 Å, b = 11.330 Å, c = 10.368 Å and γ = 94.017°) corresponds to a one-chain unit cell with one glucosyl residue in the asymmetric unit, a gt conformation for the hydroxymethyl group, and one EDA molecule per glucosyl residue. Unusually, there are no O–H···O hydrogen bonds between the cellulose chains; the chains are arranged in hydrophobic stacks, stabilized by hydrogen bonds to the amine groups of bridging EDA molecules. This new structure is an example of a complex in which the cellulose chains are isolated from each other, and provides a number of insights into the structural pathway followed during the conversion of cellulose I to cellulose IIII through EDA treatment. 相似文献
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