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111.
Dr. R. Fernando Martínez Zilei Liu Dr. Andreas F. G. Glawar Dr. Akihide Yoshihara Prof. Ken Izumori Prof. George W. J. Fleet Dr. Sarah F. Jenkinson 《Angewandte Chemie (International ed. in English)》2014,53(4):1160-1162
The scarcity and expense of access to L ‐sugars and other rare sugars have prevented the exploitation of their biological potential; for example D ‐psicose, only recently available, has been recognized as an important new food. Here we give the definitive and cheap synthesis of 99.4% pure L ‐glucose from D ‐glucose which requires purification of neither intermediates nor final product other than extraction into and removal of solvents; a simple crystallization will raise the purity to >99.8%. 相似文献
112.
Dr. Masaki Yoshida Dr. Mio Kondo Prof. Toshikazu Nakamura Prof. Ken Sakai Prof. Shigeyuki Masaoka 《Angewandte Chemie (International ed. in English)》2014,53(43):11519-11523
A series of [{(terpy)(bpy)Ru}(μ‐O){Ru(bpy)(terpy)}]n+ ( [RuORu]n+ , terpy=2,2′;6′,2′′‐terpyridine, bpy=2,2′‐bipyridine) was systematically synthesized and characterized in three distinct redox states (n=3, 4, and 5 for RuII,III2 , RuIII,III2 , and RuIII,IV2 , respectively). The crystal structures of [RuORu]n+ (n=3, 4, 5) in all three redox states were successfully determined. X‐ray crystallography showed that the Ru? O distances and the Ru‐O‐Ru angles are mainly regulated by the oxidation states of the ruthenium centers. X‐ray crystallography and ESR spectra clearly revealed the detailed electronic structures of two mixed‐valence complexes, [RuIIIORuIV]5+ and [RuIIORuIII]3+ , in which each unpaired electron is completely delocalized across the oxo‐bridged dinuclear core. These findings allow us to understand the systematic changes in structure and electronic state that accompany the changes in the redox state. 相似文献
113.
Libo Li Ken A. Dill Christopher J. Fennell 《Journal of computer-aided molecular design》2014,28(3):259-264
Here, we test a method, called semi-explicit assembly (SEA), that computes the solvation free energies of molecules in water in the SAMPL4 blind test challenge. SEA was developed with the intention of being as accurate as explicit-solvent models, but much faster to compute. It is accurate because it uses pre-simulations of simple spheres in explicit solvent to obtain structural and thermodynamic quantities, and it is fast because it parses solute free energies into regionally additive quantities. SAMPL4 provided us the opportunity to make new tests of SEA. Our tests here lead us to the following conclusions: (1) The newest version, called Field-SEA, which gives improved predictions for highly charged ions, is shown here to perform as well as the earlier versions (dipolar and quadrupolar SEA) on this broad blind SAMPL4 test set. (2) We find that both the past and present SEA models give solvation free energies that are as accurate as TIP3P. (3) Using a new approach for force field parameter optimization, we developed improved hydroxyl parameters that ensure consistency with neat-solvent dielectric constants, and found that they led to improved solvation free energies for hydroxyl-containing compounds in SAMPL4. We also learned that these hydroxyl parameters are not just fixing solvent exposed oxygens in a general sense, and therefore do not improve predictions for carbonyl or carboxylic-acid groups. Other such functional groups will need their own independent optimizations for potential improvements. Overall, these tests in SAMPL4 indicate that SEA is an accurate, general and fast new approach to computing solvation free energies. 相似文献
114.
Suzuka Kinoshita Ryota Yamano Dr. Yu Shibata Yusuke Tanaka Kyoichi Hanada Dr. Takashi Matsumoto Prof. Dr. Kazunori Miyamoto Dr. Atsuya Muranaka Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Tanaka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):11113-11120
An S-shaped double helicene-like molecule (>99 % ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex-catalyzed highly diastereo- and enantioselective intramolecular double [2+2+2] cycloaddition of a 2-naphthol- and benzene-linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S-shaped double helicene-like molecule, but the introduction of two additional fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100 °C. The enantiopure S-shaped double helicene-like molecule forms a trimer through the multiple C−H⋅⋅⋅π and C−H⋅⋅⋅O interactions in the solid-state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S-shaped double helicene-like molecule enhanced the chiroptical properties. 相似文献
115.
Pia Rönfeldt Helge Reinsch Erik Svensson Grape A. Ken Inge Huayna Terraschke Norbert Stock 《无机化学与普通化学杂志》2020,646(16):1373-1379
A new scandium naphthalenedicarboxylate with the framework composition [Sc2(1,4-NDC)3] (H2-1,4-NDC = 1,4-naphthalenedicarboxylic acid) was obtained under hydrothermal synthesis conditions. A structure model could be developed by a combination of 3D electron diffraction measurements and computationally assisted structure determination, which was further validated by a good agreement with the experimental powder X-ray diffraction pattern. The structure consists of isolated ScO6 octahedra interconnected by the carboxylate groups of linker molecules to form chains. These chains are connected by the naphthalene-moieties to form a three-dimensional framework with square-shaped pores and the organic group pointing into the pores. Although very similar synthesis conditions were chosen, [Sc2(1,4-NDC)3] is not isostructural to aluminum naphthalenedicarboxylate [Al(OH)(1,4-NDC)], which crystallizes in a MIL-53 type structure. This can be traced back to the different inorganic building units that are observed. The compound was thoroughly characterized by elemental analysis, IR spectroscopy, sorption measurements, thermogravimetric analysis and luminescence measurements. [Sc2(1,4-NDC)3] exhibits a high thermal stability and a ligand-based blue luminescence in the solid state at room temperature. 相似文献
116.
Quantum tunneling effects play an important role in a variety of chemical reactions considerably affecting the reaction rates via opening the classically forbidden paths and emerging as highly efficient or selective processes. However, in the case of electrochemical reactions, quantum tunneling effects are less investigated due to complicated nature of chemical interactions at the electrified interfaces. In this review, we summarize the experimental/theoretical concept of electrochemical quantum proton tunneling (EQPT), which is a key element in microscopic electrode processes. First, we review the experimental observations of EQPT, and next, we discuss possible theoretical pictures of the process. This review shows that a combination of a wide spectrum of scientific efforts is required to understand microscopic mechanism of EQPT including development of the precise electrochemistry-oriented experimental techniques and methodologies, formulation of the appropriate theoretical models for specific systems, and performance of the advanced computational simulations. 相似文献
117.
Doaa H. M. Alsaadi Aedla Raju Ken Kusakari Faruk Karahan Nazim Sekeroglu Takashi Watanabe 《Molecules (Basel, Switzerland)》2020,25(23)
The growth and quality of licorice depend on various environmental factors, including the local climate and soil properties; therefore, its cultivation is often unsuccessful. The current study investigated the key factors that affect the contents of bioactive compounds of Glycyrrhiza glabra L. root and estimated suitable growth zones from collection sites in the Hatay region of Turkey. The contents of three bioactive compounds (glycyrrhizic acid, glabridin, and liquiritin), soil factors (pH, soil bearing capacity, and moisture content), and geographical information (slope, aspect, curvature, elevation, and hillshade) were measured. Meteorological data (temperature and precipitation) were also obtained. An analysis of variance (ANOVA) and multivariate analysis of variance (MANOVA) were performed on the data. The soil bearing capacity, moisture content, slope, aspect, curvature, and elevation of the study area showed statistically significant effects on the glycyrrhizic acid and liquiritin contents. A habitat suitability zone map was generated using a GIS-based frequency ratio (FR) model with spatial correlations to the soil, topographical, and meteorological data. The final map categorized the study area into four zones: very high (15.14%), high (31.50%), moderate (40.25%), and low suitability (13.11%). High suitability zones are recommended for further investigation and future cultivation of G. glabra. 相似文献
118.
Hiroshi Takikawa Arata Nishii Hiromu Takiguchi Hirotoshi Yagishita Masato Tanaka Keiichi Hirano Masanobu Uchiyama Ken Ohmori Keisuke Suzuki 《Angewandte Chemie (International ed. in English)》2020,59(30):12440-12444
An intramolecular benzyne–phenolate [4+2] cycloaddition is reported. Benzyne precursors, having vicinal halogen‐sulfonate functionalities, linked with a phenol(ate) by various tether groups undergo efficient intramolecular [4+2] cycloaddition by treatment with either Ph3MgLi or nBuLi for halogen–metal exchange to form various benzobarrelenes. 相似文献
119.
Hiroshi Fujimoto Ken Sakata Kenichi Fukui 《International journal of quantum chemistry》1996,60(1):401-408
Electron delocalization between the reagent and reactant molecules is the principal driving force of chemical reactions. It brings about the formation of new bonds and the cleavage of old bonds. By taking the aromatic substitution reaction as an example, we have shown the orbitals participating in electron delocalization. The interacting orbitals obtained are localized around the reaction sites, showing the chemical bonds that should be generated and broken transiently along the reaction path. By projecting a reference orbital function that has been chosen to specify the bond being formed on to the MOs of the reactant molecules, the reactive orbitals that are very similar to the interacting orbital have been obtained. The local potential of the reaction site for electron donation estimated for substituted benzene molecules by using these projected orbitals shows a fair correlation with the experimental scale of the electron-donating and -withdrawing strength of substituent groups. The reactivity is shown to be governed by local electronegativity and local chemical hardness and also by the localizability of interaction on the reaction site. © 1996 John Wiley & Sons, Inc. 相似文献
120.
Jrg Kressler Bernd Rudolf Ken Shimomai Toshiaki Ougizawa Takashi Inoue 《Macromolecular rapid communications》1995,16(8):631-636
Pressure, volume, temperature (PVT) measurements reveal that during the intramolecular cyclization reaction of poly(acrylonitrile) (PAN) and poly(styrene-co-acrylonitrile) (SAN) the volume decreases. This volume contraction becomes smaller with increasing styrene content in the random copolymers and should be related to the simultaneous decrease of longer acrylonitrile homo-sequences. The onset temperature of the cyclization reaction is raised with higher styrene contents in the random copolymers. Thus, it can be excluded that the cyclization reaction has a major influence on the discoloration process of SAN samples having relatively small acrylonitrile contents (less than 50 mol-%) during thermal annealing below 300°C. 相似文献