Structural analysis of amylose tris(3,5-dimethylphenylcarbamate) by NMR relevant to its chiral recognition mechanism in HPLC

The structural analysis of amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) was performed by NMR spectroscopy using a sample with a lower degree of polymerization in order to understand the chiral recognition mechanism when it was used as a chiral stationary phase (CSP) in high-performance liquid chromatography (HPLC). ADMPC exhibited chiral discrimination for many enantiomers, including 1-(9-anthryl)-2,2,2-trifluoroethanol (1) and 1,1'-bi-2-naphthol (2) in both NMR and HPLC. A good agreement was observed between the HPLC and NMR results when chloroform was employed as the common solvent. The structure of ADMPC in solution was investigated by NMR using the 2D NOESY technique coupled with computer modeling, and a left-handed 4/3 helical structure was obtained as the most probable one. The binding geometry between ADMPC and the enantiomers of 1 was also investigated by (1)H NMR titration. On the basis of these results combined with molecular modeling, a rational model to explain the chiral discrimination mechanism of 1 on ADMPC was proposed.     

Copolymerization of vinylsilanes with styrene

New vinylsilanes (M₂), i. e. phenylvinylsilane (I), allylmethylsilane (II), allylphenylsilane (III), and p-vinylphenylmethylsilane (IV), were prepared and copolymerized with styrene (M₁). The monomer reactivity ratios were r₁ = 5.7 and r₂ = 0, r₁ = 36 and r₂ = 0, r₁ = 29 and r₂ = 0₁, and r₁ = 0.91 and r₂ = 1.1, respectively. From the results of infrared and NMR spectra it was indicated that the vinylsilanes participated in copolymerization in the form of a vinyl type of polymerization and not in the form of a hydrogen-transfer type of polymerization. The reaction of copolymer with alcohols and methyl methacrylate and appropriate catalysts was investigated.     

Analytical application and spectrophotometric study of the scandium-indoferron complex

A new spectrophotometric method for microgram amounts of scandium with indoferron is described. The molar absorptivity is 960 l.mole⁻¹.mm⁻¹ at 600 nm. Uranium and the rare earths do not interfere, if present in amounts less than 50 μg. Scandium in silicate rocks can be determined by the procedure after separation of the scandium by a three-stage ion-exchange Chromatographic technique. The acid dissociation constants of indoferron and conditional formation constants of the 1:2 complex have been determined spectrophotometrically.     

Insulating tubular BN sheathing on semiconducting nanowires

An effective method was developed for generation of insulating tubular boron nitride (BN)-sheathed nanostructures. ZnS nanowires and multilayered Si-SiO2 nanowires were successfully sheathed with insulating tubular BN-forming nanocables. Both the semiconductor nanowire cores and the BN sheaths are crystalline with well-uniform morphologies.     

A mesoporous non-precious metal boride system: synthesis of mesoporous cobalt boride by strictly controlled chemical reduction

Generating high surface area mesoporous transition metal boride is interesting because the incorporation of boron atoms generates lattice distortions that lead to the formation of amorphous metal boride with unique properties in catalysis. Here we report the first synthesis of mesoporous cobalt boron amorphous alloy colloidal particles using a soft template-directed assembly approach. Dual reducing agents are used to precisely control the chemical reduction process of mesoporous cobalt boron nanospheres. The Earth-abundance of cobalt boride combined with the high surface area and mesoporous nanoarchitecture enables solar-energy efficient photothermal conversion of CO₂ into CO compared to non-porous cobalt boron alloys and commercial cobalt catalysts.

Generating high surface area mesoporous transition metal boride is challenging but interesting because incorporation of boron atoms can generate lattice distortion to form amorphous metal boride which has unique properties in catalysis.     

Studies on the syntheses of heterocylic compounds—762: Synthesis of 3-benzyl-6-methyl-2-oxo-3,6-diazabicyclo[3.1.0]hexane as a synthetic intermediate of mitomycins

(±)-1-Benzyl-3α-hydroxy-4β-methylamino-2-oxopyrrolidine (15) and its cis-isomer (16) were synthesised from 1-benzyl-4-ethoxycarbonyl-2,3-dioxopyrrolidine (2) in several steps. The former (15) was converted to 3-benzyl-6-methyl-2-oxo-3,6-diazabicyclo[3.1.0]hexane (17) with a mixture of triphenylphosphine, carbon tetrachloride and triethylamine.