Metallocene bis(perfluoroalkanesulfonate)s as air-stable cationic Lewis acids

Zirconocene and titanocene bis(perfluorooctanesulfonate)s were synthesized. In contrast to the corresponding triflates and perchlorates, these compounds are air- and water-stable. They were proved to be ionic on the basis of conductivity measurements and X-ray analysis, allowing these complexes to be stored for months. The strong Lewis acidity of these cationic metallocene species, which was proved by ESR study, enabled catalytic glycosylation.     

Tactile impression and friction of water on human skin

Water has a unique touch as well as characteristic physical properties. However, nobody knows the real identity of its touch. Here, we show that water creates a stick-slip feel when a small amount is rubbed using fingertip on an artificial skin that mimics the structure of human skin. The results of frictional analyses predict that this stick-slip feel is caused by a drastic change in frictional resistance. The present result is valuable for biologists and robot engineers as well as cognitive scientists and tribologists, because it is a new example of stick-slip phenomena on biological surfaces. The tactile texture of this most familiar material could also be applied to consumer products or virtual reality systems.     

The effect of the N‐substituent s‐trans to the carbonyl group of N‐methylacrylamide derivatives on the stereospecificity of radical polymerizations

Radical polymerization of N‐methylacrylamide (NMAAm), N,N‐dimethylacrylamide (DMAAm), and N‐methyl‐N‐phenylacrylamide (MPhAAm) was investigated in toluene at low temperatures. Atactic, isotactic, and syndiotactic polymers were obtained by the polymerization of NMAAm, DMAAm, and MPhAAm, respectively, indicating that the stereospecificity of the radical polymerization of acrylamide derivatives depended on the N‐substituents of the monomer used. From the viewpoint of monomer structure, the origin of the stereospecificity of radical polymerization of NMAAm derivatives is discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6534–6539, 2009     

Electronic structures of newly designed two-dimensional high-spin organic polymers

Practical two-dimensional high-spin organic polymers are newly designed and the electronic structures are examined on the basis of the ab initio two-dimensional unrestricted Hartree–Fock crystal orbital (UHF-CO) method. The present polymers can be oxidized up to six electrons per unit cell, and it is predicted that the three-electron and six-electron oxidations per unit cell lead to the high-spin organic polymers having superdegenerate band structures originating from the characteristic non-bonding crystal orbital patterns.     

Facile synthesis, crystal structures, and high-spin cationic states of all-para-brominated oligo(N-phenyl-m-aniline)s.

Syntheses of both the dimer (3) and the trimer (4) of all-para-brominated poly(N-phenyl-m-aniline)s (2c) were achieved in a one-pot procedure from the parent nonbrominated oligomers and benzyltrimethylammonium tribromide [(BTMA)Br(3)]. An X-ray crystallographic analysis revealed that 4 has a U-shaped structure, suggesting that 2c easily adopts helical structures. Furthermore, the redox properties were investigated by the UV-vis and EPR measurements. It was confirmed that the both 3 and 4 can be oxidized into the dications 3(2+) and 4(2+) with triplet spin-multiplicity.     

Effects of OH concentration and temperature on NO emission characteristics of turbulent non-premixed CH4/NH3/air flames in a two-stage gas turbine like combustor at high pressure

This study examined the effects of OH concentration and temperature on the NO emission characteristics of turbulent, non-premixed methane (CH₄)/ammonia (NH₃)/air swirl flames in two-stage combustors at high pressure. Emission data were obtained using large-eddy simulations with a finite-rate chemistry method from model flames based on the energy fraction of NH₃ (E_NH3) in CH₄/NH₃ mixtures. Although NO emissions at the combustor exit were found to be significantly higher than those generated by CH₄/air and NH₃/air flames under both lean and stoichiometric primary zone conditions, these emissions could be lowered to approximately 300 ppm by employing far-rich equivalence ratios (?) of 1.3 to 1.4 in the primary zone. This effect was possibly due to the lower OH concentrations under far-rich conditions. An analysis of local flame characteristics using a newly developed mixture fraction equation for CH₄/NH₃/air flames indicated that the local temperature and NO and OH concentration distributions with local ? were qualitatively similar to those in NH₃/air flames. That is, the maximum local NO and OH concentrations appeared at local ? of 0.9, although the maximum temperature was observed at local ? of 1.0. Both the temperature and OH concentration were found to gradually decrease with the partial replacement of CH₄ with NH₃. Consequently, NO emissions from CH₄/NH₃ flames were maximized at E_NH3 in the range of 20% to 30%, after which the emissions decreased. Above 2100 K, the NO emissions from CH₄/NH₃ flames increased exponentially with temperature, which was not observed in NH₃/air flames because of the lower flame temperatures in the latter. But, the maximum NO concentration in CH₄/NH₃ flames was occurred at a temperature slightly below the maximum temperature, just as in NH₃/air flames. The apparent exponential increase in NO emissions from CH₄/NH₃ flames is attributed to a similar trend in the OH concentration at high temperatures.     

Influence of wall heat loss on the emission characteristics of premixed ammonia-air swirling flames interacting with the combustor wall

The influence of wall heat loss on the emission characteristics of ammonia-air swirling flames has been investigated employing Planar Laser-Induced Fluorescence imaging of OH radicals and Fourier Transform Infrared spectrometry of the exhaust gases in combustors with insulated and uninsulated walls over a range of equivalence ratios, ?, and pressures up to 0.5 MPa. Strong influence of wall heat loss on the flames led to quenching of the flame front near the combustor wall at 0.1 MPa, resulting in large unburned NH₃ emissions, and inhibited the stabilization of flames in the outer recirculating zone (ORZ). A decrease in heat loss effects with an increase in pressure promoted extension of the fuel-rich stabilization limit owing to increased recirculation of H₂ from NH₃ decomposition in the ORZ. The influence of wall heat loss resulted in emission trends that contradict already reported trends in literature. NO emissions were found to be substantially low while unburned NH₃ and N₂O emissions were high at fuel-lean conditions during single-stage combustion, with values such as 55 ppmv of NO, 580 ppmv of N₂O and 4457 ppmv of NH₃ at ? = 0.8. In addition, the response of the flame to wall heat loss as pressure increased was more important than the effects of pressure on fuel-NO emission, thereby leading to an increase in NO emission with pressure. It was found that a reduction in wall heat loss or a sufficiently long fluid residence time in the primary combustion zone is necessary for efficient control of NH₃ and N₂O emissions in two-stage rich-lean ammonia combustors, the latter being more effective for N₂O in addition to NO control. This study demonstrates that the influence of wall heat loss should not be ignored in emissions measurements in NH₃-air combustion, and also advances the understanding of previous studies on ammonia micro gas turbines.     

Synthesis and characterization of a biphenyl-linked hemicryptophane and an endohedral cobalt(II) complex

Hemicryptophanes are covalent molecular cages, constructed from a cyclotriveratrylene-based host unit and a functional unit linked by covalent spacers, which have been designed to accommodate endohedral functionalities in the cavity. In this study, the synthesis and characterization of the rigid, biphenyl-linked hemicryptophane 1 were investigated by NMR, ESI-MS, and X-ray crystallography. The structure of the inclusion complex, in which a dichloromethane molecule was constructed encapsulated within 1, was characterized by X-ray crystallography. An endohedral, cobalt(II) hemicryptophane complex 2 was also synthesized and characterized ESI-MS and X-ray crystallography. The X-ray crystal structure of 2 showed that the biphenyl-linked hemicryptophane had three components—a molecule each of chloroform and acetonitrile, and a cobalt(II) ion—within its cavity.     

Heterocyclic effect for optical properties of naphthoquinone-based pigment: 2-methyl-3-heteroarylthio-1,4-naphthalenedione

Three novel naphthoquinone-based heterocyclic pigments, 2-methyl-3-[(1-methyl-1H-imidazol-2-yl)thio-1,4-naphthalenedione, (4-methyl-4H-1,2,4-triazol-3-yl)thio-1,4-naphthalenedione, and (1-methyl-1H-tetrazol-5-yl)thio]-1,4-naphthalenedione, are synthesized, and their optical properties in both solution and solid states are investigated. Depending on the heteroarylthio ring in the pigment, variation in optical properties is observed, e.g. characteristic colours for each pigment in the solution and solid states. The achiral pigment containing the 1-methyl-1H-tetrazol-5-yl ring exhibits a chiral space group and a CD signal in the solid state.     

Toward the assembly of heparin and heparan sulfate oligosaccharide libraries: efficient synthesis of uronic acid and disaccharide building blocks

The monosaccharide moieties found in heparin (HP) and heparan sulfate (HS), glucosamine and two kinds of uronic acids, glucuronic and iduronic acids, were efficiently synthesized by use of glucosamine hydrochloride and glucurono-6,3-lactone as starting compounds. In the synthesis of the disaccharide building block, the key issues of preparation of uronic acids (glucuronic acid and iduronic acid moieties) were achieved in 12 steps and 15 steps, respectively, without cumbersome C-6 oxidation. The resulting monosaccharide moieties were utilized to the syntheses of HP/HS disaccharide building blocks possessing glucosamine-glucuronic acid (GlcN-GlcA) or iduronic acid (GlcN-IdoA) sequences. The disaccharide building blocks were also suitable for further modification such as glycosylation, selective deprotection, and sulfation.