A Novel Non-Phosgene Process for Polycarbonate Production from CO2: Green and Sustainable Chemistry in Practice

This paper focuses on the world’s first non-phosgene process using CO₂ as starting material succeeded in development and industrialization by Asahi Kasei Corp. The Asahi Kasei Process enables high-yield production of high-quality PC having excellent properties and high-purity monoethylene glycol (MEG), starting from ethylene oxide (EO), by-produced CO₂ and bisphenol-A without waste and waste water. The innovative reactive distillation technologies in the monomer production and the innovative gravity-utilized, non-agitation polymerization reactor in the melt polymerization, led the new process to success. The monomer process consists of 3 production steps, ethylene carbonate (EC) from CO₂ and EO, dimethyl carbonate (DMC) and MEG from EC and MeOH, and diphenyl carbonate (DPC) and MeOH from DMC and PhOH. All intermediates are recycled. The new type polymerization reactor perfectly overcomes the difficulty based on the extremely high viscosity in the melt polymerization of DPC with Bis-A. The by-produced PhOH is recycled to the monomer process. The reduction of CO₂ emissions (0.173t/PC 1t) is also achieved, because CO₂ used as raw material is utilized as the main chain components of the products. Four commercial plants (Taiwan: 150,000 t/y, Korea: 2 plants of 65,000 t/y, Russia: 65,000 t/y) using the Asahi Kasei Process are now successfully operating, and the plant of 260,000 t/y in Saudi Arabia will start in 2010.     

Synthesis of 2-substituted quinones, vitamin K3, and vitamin K1 from p-cresol. BF3·OEt2-catalyzed methyl migration of 4-tert-butyldioxycyclohexadienones

BF₃·OEt₂-catalyzed methyl group migration of 4-methyl-4-tert-butyldioxycyclohexadienone, which is obtained by ruthenium-catalyzed oxidation of p-cresol with tert-butyl hydroperoxide, in hexafluoro-2-propanol/toluene gave toluquinone efficiently. The reaction can be applied to the regio-selective short-step syntheses of vitamin K₃ and vitamin K₁ from p-cresol.     

Constricted hysteresis loops in Fe and Ni single crystals

Magnetic hysteresis loops reflect the variety of magnetic domain structures and have been considered to have normal rectangular or leaf-like shapes in standard ferromagnets such as Fe and Ni metals. We report on observations of constricted hysteresis loops in Fe and Ni single crystals with very low defect densities. The constricted loops were observed below T=150 K and in a medium temperature range from 150 to 430 K in Fe and Ni single crystals, respectively. These constricted loops disappear by weak plastic deformation for both single crystals. The origin of constricted hysteresis loops was explained by eddy current effects under less domain wall pinning due to dislocations.     

Study of carrier doping across the parent Mott insulator La2CuO4

Ce substituted La₂CuO₄ single crystals are investigated to try doping electrons into the parent Mott insulator. Transport properties of slightly Ce substituted La₂CuO₄ show that carriers are still holes activated from an impurity level of which activation energy is the same as the parent La₂CuO₄.     

Y443F mutation in the substrate-binding domain of extracellular PHB depolymerase enhances its PHB adsorption and disruption abilities

Extracellular poly[(R)-3-hydroxybutyrate] (PHB) depolymerase (PhaZ_RpiT1) from Ralstonia pickettii T1 adsorbs to the PHB surface via its substrate-binding domain (SBD) and cleaves the PHB chain using its catalytic domain. Our previous study (Biomacromolecules 2010; 11: 113-119) has suggested that the hydrophobic interaction between the amino acid residues at positions 441, 443, and 445 in the SBD and the PHB surface plays a crucial role in facilitating the association phase of the enzyme adsorption process. In the present study, in order to improve PhaZ_RpiT1 for effective PHB degradation, we targeted Tyr at position 443 for substitution with a more highly hydrophobic amino acid residue because its hydrophobicity shows medium to high degree compared to those of general naturally occurring amino acid residues. We designed a mutant enzyme with an amino acid substitution at this position, taking the following factors into consideration: (1) to achieve higher hydrophobicity than the original residue, (2) to retain the β-sheet structure, and (3) to change as little as possible the volume of the amino acid residue after the substitution. As a result, the substitution of Tyr443 with Phe (Y443F) was considered to be appropriate. The purified Y443F enzyme showed identical CD spectrum and hydrolysis activity for a water-soluble substrate with the wild type, indicating that the mutation had no influence on the structure and the ester bond cleavage activity. In contrast, the Y443F enzyme had higher PHB degradation activity than the wild type. Kinetic analysis of PHB degradation suggests that this amino acid substitution promoted not only the adsorption of the mutant enzyme to PHB, but also the disruption of the PHB surface to enhance the hydrolysis of the PHB polymer chain.     

Electronic inhomogeneity and breakdown of the universal thermal conductivity of cuprate superconductors

We report systematic, high-precision measurements of the low-T (down to 70 mK) thermal conductivity kappa of YBa2Cu3O(y), La(2-x)Sr(x)CuO4, and Bi2Sr2CaCu2O(8+delta). Careful examinations of the Zn- and hole-doping dependences of the residual thermal conductivity kappa0/T, as well as the in-plane anisotropy of kappa0/T in Bi2Sr2CaCu2O(8+delta), indicate a breakdown of the universal thermal conductivity, a notable theoretical prediction for d-wave superconductors. Our results point to an important role of electronic inhomogeneities, which are not considered in the standard perturbation theory for thermal conductivity, in the underdoped to optimally doped regime.     

Efficient synthesis of 1,3,5-trisubstituted (pyrrol-2-yl)acetic acid esters via dual nucleophilic reactions of sulfonamides or carbamate with 4-trimethyl-siloxy-(5E)-hexen-2-ynoates: Lewis acid catalyzed SN1 and intramolecular Michael addition

[reaction: see text] Carbamates or sulfonamides have proven to regioselectively attack 2-propynyl-allyl hybrid cations, generated by the action of TMSOTf on 4-(trimethylsioxy)hex-5-en-2-ynoates, to afford conjugated 6-aminohex-4-en-2-ynoates in which an intramolecular amino-Michael reaction took place, leading to pyrrole frameworks. In particular, the sulfonamides gave 1-sulfonylpyrroles in one pot.     

Selective One-Pot Synthesis of Allenyl Phenyl Selenide and 1-(Phenylseleno)Propyne. Role of Sodium Benzeneselenolate as a Base in Dmf

The reaction of excess sodium benzeneselenolate with propargyl bromide in DMR-THF at room temperature produced allenyl phenyl selenide or l-(phenylseleno)propyne selectively, depending only on the reaction time.     

Vaulted trans‐Bis(salicylaldiminato)platinum(II) Crystals: Heat‐Resistant,Chromatically Sensitive Platforms for Solid‐State Phosphorescence at Ambient Temperature

The synthesis, structure, and solid‐state emission of vaulted trans‐bis(salicylaldiminato)platinum(II) complexes are described. A series of polymethylene ( 1 : n=8; 2 : n=9; 3 : n=10; 4 : n=11; 5 : n=12; 6 : n=13) and polyoxyethylene ( 7 : m=2; 8 : m=3; 9 : m=4) vaulted complexes (R=H ( a ), 3‐MeO ( b ), 4‐MeO ( c ), 5‐MeO ( d ), 6‐MeO ( e ), 4‐CF₃O ( f ), 5‐CF₃O ( g )) was prepared by treating [PtCl₂(CH₃CN)₂] with the corresponding N,N′‐bis(salicylidene)‐1,ω‐alkanediamines. The trans coordination, vaulted structures, and the crystal packing of 1 – 9 have been unequivocally established from X‐ray diffraction studies. Unpredictable, structure‐dependent phosphorescent emission has been observed for crystals of the complexes under UV excitation at ambient temperature, whereas these complexes are entirely nonemissive in the solution state under the same conditions. The long‐linked complex crystals 4 – 6 , 8 , and 9 exhibit intense emission (Φ_77K=0.22–0.88) at 77 K, whereas short‐linked complexes 1 – 3 and 7 are non‐ or slightly emissive at the same temperature (Φ_77K<0.01–0.18). At 298 K, some of the long‐linked crystals, 4 a , 4 b , 5 c , 5 e , 6 c , 6 e , and 9 b , completely lose their high‐emission properties with elevation of the temperature (Φ_298K<0.01–0.02), whereas the other long‐linked crystals, 5 a , 6 a , 9 a , and 9 d , exhibit high heat resistance towards emission decay with increasing temperature (Φ_298K=0.21–0.38). Chromogenic control of solid‐state emission over the range of 98 nm can be performed simply by introducing MeO groups at different positions on the aromatic rings. Orange, yellow‐green, red, and yellow emissions are observed in the glass and crystalline state upon 3‐, 4‐, 5‐, and 6‐MeO substitution, respectively, whereas those with CF₃O substituents have orange emission, irrespective of the substitution position. DFT calculations (B3LYP/6‐31G*, LanL2DZ) showed that such chromatic variation is ascribed to the position‐specific influence of the substituents on the highest‐occupied molecular orbital (HOMO) and lowest‐unoccupied molecular orbital (LUMO) levels of the trans‐bis(salicylaldiminato)platinum(II) platform. The solid‐state emission and its heat resistance have been discussed on the basis of X‐ray diffraction studies. The planarity of the trans‐coordination sites is strongly correlated to the solid‐state emission intensities of crystals 1 – 9 at lower temperatures. The specific heat‐resistance properties shown exclusively by the 5 a , 6 a , 9 a , and 9 d crystals are due to their strong three‐dimensional hydrogen‐bonding interactions and/or Pt???Pt contacts, whereas heat‐quenchable crystals 4 a , 4 b , 5 c , 5 e , 6 c , 6 e , and 9 b are poorly bound with limited interactions, such as non‐, one‐, or two‐dimensional hydrogen‐bonding networks. These results lead to the conclusion that Pt???Pt contacts are an important factor in the heat resistance of solid‐state phosphorescence at ambient temperature, although the role of Pt???Pt contacts can be substituted by only higher‐ordered hydrogen‐bonding fixation.     

A sharp J-band-like electronic absorption peak observed for the chromonic liquid crystal of bisazo dye Ponceau SS in water

Abstract  

The bisazo dye Ponceau SS forms an acute oblique (V-type) dimer in dilute aqueous solution. In concentrated aqueous solution, these V-type dimers are considered to stack to form V-type blocks of chromonic liquid-crystalline (LC) columns. The weak interactions among these LC columnar V-type blocks have been spectroscopically investigated. On increasing the concentration of Ponceau SS at 25 °C, the V-type LC columnar blocks form a rhombus-type LC columnar block at 2 wt% concentration. These rhombus-type LC columnar blocks are further aligned at an acute angle at 5 and 10 wt% concentrations. The rapidly cooled 10 wt% LC sample shows an unusually sharp J-band-like peak in the electronic absorption spectrum. The emergence of this J-band-like peak has been analyzed from the viewpoint of an exciton model, suggesting that many nearest neighbor unique molecules belonging to many different rhombus-type LC columnar blocks are aligned in a head-to-tail manner to give a giant quasi-linear head-to-tail-type exciton.