Enantioselective synthesis utilizing enantiomorphous organic crystal of achiral benzils as a source of chirality in asymmetric autocatalysis

Chiral crystals of achiral benzils act as efficient chiral initiators of asymmetric autocatalysis to afford highly enantioenriched pyrimidyl alkanols whose absolute configurations depend upon the enantiomorph of the crystal used in conjunction with asymmetric autocatalysis with amplification of enantiomeric excess.     

Curve-structured phenalenyl chemistry: synthesis, electronic structure, and bowl-inversion barrier of a phenalenyl-fused corannulene anion

We have demonstrated the features of curve-structured phenalenyl chemistry, for the first time. A phenalenyl-fused corannulene anion has been designed by the annelation of a six-memberd ring across peri-positions of corannulene and generated as a stable species in a degassed solution. The 1H and 13C NMR spectra have shown the highly symmetrical structure and high-field shifts of protons and carbons at the asterisked positions in the chemical structure, indicating the occurrence of large negative charge densities at these positions. These results well agree with the HOMO picture and the electrostatic potential surface, demonstrating the phenalenyl anion-type electronic structure is retained in the curved-surface pi-system. The calculated bowl-inversion barrier of the anion (11.3 kcal/mol) is larger than that of corannulene (9.2 kcal/mol) because of peri-annelation of the corannulene skeleton. The calculations of the barriers of the neutral radical (12.6 kcal/mol), radical dianion (8.1 kcal/mol), and trianion (5.4 kcal/mol) of the phenalenyl-fused corannulene have exhibited a stepwise flattening of the curvature with increase in negative charge. Therefore, we have revealed that the bowl-inversion barrier of the anion is governed by the setoff of the peri-annelation and negative charge effects.     

Light Absorption Properties and Electronic Band Structures of Lead‐Vanadium Oxyhalide Apatites Pb5(VO4)3X (X=F,Cl, Br,I)

The Pb‐V oxyhalide apatite compounds Pb₅(VO₄)₃X (X=F, Cl, Br, I) were successfully synthesized using a facile solution method and studied with respect to their structural/optical characteristics and electronic band structures. UV‐visible diffuse reflectance spectroscopy, electrochemical analysis and first‐principles calculations showed that the synthesized apatites behaved as n‐type semiconductors, with absorption bands in the UV‐visible region that could be assigned to electron transitions from the valence band to a conduction band formed by hybridized V 3d and Pb 6p orbitals. Among the apatites examined, Pb₅(VO₄)₃I had the smallest band gap of 2.7 eV, due to an obvious contribution of I 5p orbitals to the valence band maximum. Based on its visible light absorption capability, Pb₅(VO₄)₃I generated a continuous anodic photocurrent under visible light (λ>420 nm) in a solution of 0.1 m NaI in acetonitrile.     

Reaction of 6‐aryl‐ or styryl‐4‐methylsulfanyl‐2‐oxo‐2H‐pyrans with active methylene compounds and fluorescence properties of the products

New 2‐pyrone derivatives, dialkyl 3‐cyano‐6‐phenyl‐2‐oxo‐2H‐pyran‐4‐ylmalonates and alkyl 3‐cyano‐6‐phenyl‐2‐oxo‐2H‐pyran‐4‐ylacetates, which were easily prepared by the reaction of 6‐aryl‐4‐methyl‐sulfanyl‐2‐oxo‐2H‐pyran‐3‐carbonitriles with active methylene compounds in the presence of potassium carbonate, show fluorescence emission radiation. The light‐emitting region of dimethyl 3‐cyano‐6‐(4‐N,N‐dimethylamino)styryl‐2‐oxo‐2H‐pyran‐4‐ylmalonate ( 7h ) was 620 nm in dichloromethane, making this compound a typical red fluorescent compound. Methyl 8‐hydroxy‐6‐methyl‐1‐oxo‐3‐phenyl‐1H‐pyrano‐[3,4‐c]pyridine‐5‐carboxylate deriv‐atives also showed fluorescence in the solid state. This is the first example of fluorescence in fused 2‐pyrone derivatives.     

Preparation and formation mechanism of three-dimensionally ordered macroporous (3DOM) MgO, MgSO4, CaCO3, and SrCO3, and photonic stop band properties of 3DOM CaCO3

Three-dimensionally ordered macroporous (3DOM) magnesium (Mg) oxide (MgO), MgSO₄, calcium (Ca) carbonate (CaCO₃), and strontium (Sr) carbonate (SrCO₃) were prepared using a colloidal crystal of polymer spheres as a template. Ethanol or ethanol-water solution of metal salts (acetate or nitrate) and citric acid was infiltrated into the void of the colloidal crystal template of a monodispersed poly(methyl methacrylate) (PMMA) sphere. Heating of this PMMA-metal salt-citric acid composite produced the desired well-ordered 3DOM materials with a high pore fraction, which was confirmed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and ultraviolet-visible (UV-vis) diffuse reflectance spectra. The presence of citric acid is crucial for production of the 3DOM structures. Reaction of citric acid with metal salt produces metal citrate solid in the void of PMMA spheres, which is necessary to maintain the 3DOM structure during the calcination process. 3DOM CaCO₃ shows opalescent colors because of it's photonic stop band properties.     

Structural changes in the molecular sheets along (hk0) planes derived from cellulose Iβ by molecular dynamics simulations

We studied the stability of molecular sheets with four cellotetraoses in an aqueous environment by molecular dynamics simulation to identify the molecular details of first structure as one of the possibilities in the course of crystallization of cellulose I. After simulation, the molecular sheets formed by van der Waals forces along the (11?0) and (110) crystal plane did not change their structures in an aqueous environment, whereas the other ones formed by hydrogen bonds along the (100) and (200) crystal plane changed into a van der Waals associated molecular sheet, similar to the former. These simulated molecular sheets formed by van der Waals forces were structurally stable in water because of their hydrophilic exterior and hydrophobic interior. Therefore, if the molecular sheet structures are formed in the real system, the sheets formed by van der Waals forces are probably the initial structure of crystallization. A close analysis indicated that these sheets could be classified into two groups in terms of the hydrogen bonding networks, camber angle, and main and side chain conformations. One group was the molecular sheets corresponding to the (110) after simulation. This sheet is probably rigid because intramolecular hydrogen bonds of the chains in the sheet are highly developed. The other group was the molecular sheets corresponding to (200), (100), and (11?0) crystal plane: the chains in these sheets seemed to be rather flexible due to their moderately developed intramolecular hydrogen bonds.     

Synthesis, characterization and formation process of transition metal oxide nanotubes using carbon nanofibers as templates

Mono and binary transition metal oxide nanotubes could be synthesized by the immersion of carbon nanofiber templates into metal nitrate solutions and removal of the templates by heat treatment in air. The transition metal oxide nanotubes were composed of nano-crystallites of metal oxides. The functional groups on the carbon nanofiber templates were essential for the coating of these templates: they acted as adsorption sites for the metal nitrates, ensuring a uniform metal oxide coating. During the removal of the carbon nanofiber templates by calcination in air, the metal oxide coatings promoted the combustion reaction between the carbon nanofibers and oxygen.     

Measuring the optical chirality of molecular aggregates at liquid–liquid interfaces

Some new experimental methods for measuring the optical chirality of molecular aggregates formed at liquid–liquid interfaces have been reviewed. Chirality measurements of interfacial aggregates are highly important not only in analytical spectroscopy but also in biochemistry and surface nanochemistry. Among these methods, a centrifugal liquid membrane method was shown to be a highly versatile method for measuring the optical chirality of the liquid–liquid interface when used in combination with a commercially available circular dichroism (CD) spectropolarimeter, provided that the interfacial aggregate exhibited a large molar absorptivity. Therefore, porphyrin and phthalocyanine were used as chromophoric probes of the chirality of itself or guest molecules at the interface. A microscopic CD method was also demonstrated for the measurement of a small region of a film or a sheet sample. In addition, second-harmonic generation and Raman scattering methods were reviewed as promising methods for detecting interfacial optical molecules and measuring bond distortions of chiral molecules, respectively.