A novel water-soluble Hantzsch 1,4-dihydropyridine compound that functions in biological processes through NADH regeneration

A novel Hantzsch 1,4-dihydropyridine derivative could function in an organic solvent-free solution, and thus it could function in biological systems. These functions can be accomplished through regeneration of the reduced form of nicotinamine adenine dinucleotide (NADH), an essential compound for living organisms. The results obtained here demonstrate the usefulness of a water-soluble Hantzsch 1,4-dihydropyridine derivative and its wide applicability as a chemical energy source, which drives various biological processes efficiently.     

Structure of single-wall carbon nanotubes purified and cut using polymer

Following on from our previous report that a monochlorobenzene solution of polymethylmethacrylate is useful for purifying and cutting single-wall carbon nanotubes (SWNTs) and thinning SWNT bundles, we show in this report that polymer and residual amorphous carbon can be removed by burning in oxygen gas. The SWNTs thus obtained had many holes (giving them a worm-eaten look) and were thermally unstable. Such severe damage caused by oxidation is unusual for SWNTs; we think that they were chemically damaged during ultrasonication in the monochlorobenzene solution of polymethylmethacrylate. Received: 28 March 2001 / Accepted: 2 August 2001 / Published online: 17 October 2001     

Free-radical polymerizations initiated by triethylaluminum–cuprous chloride mixtures

Methyl methacrylate was polymerized by triethylaluminum—cuprous chloride catalyst. A study of the polymerization kinetics indicated that the overall rate was represented by the equation, R_p = K[AlEt₃] [CuCl]^½ [M]². The overall activation energy was 16.5 kcal/mole. From ESR measurement and the results of copolymerization of methyl methacrylate with styrene, it was suggested that the catalytic system has the character of a radical initiator. A polymerization scheme was also proposed.     

Cp2TiCl2-Catalyzed Grignard exchange reactions with acetylenes. A convenient method for preparation of E-alkenyl Grignard reagents

Disubstituted acetylenes react with isobutylmagnesium halide in the presence of a catalytic amount of Cp₂TiCl₂ in ether to afford E-alkenyl Grignard reagents selectively and in almost quantitative yields. The regiochemistry of this hydromagnesation reaction is high for alkylarylacetylenes and silylacetylenes giving E-ArC(MgBr)CHR from alkylarylacetylenes, E-ArC(MgBr)CH(SiMe₃) from arylsilylacetylenes, and ECHRC(MgBr)(SiMe₃) from alkylsilylacetylenes, respectively. Thanks to the high reactivity of the Grignard reagent, the present reaction offers a novel, selective and operationally simple route for preparation of trisubstituted olefins.     

Peptide synthesis in water IV. Preparation of N-ethanesulfonylethoxycarbonyl (Esc) amino acids and their application to solid phase peptide synthesis

A new N-protecting group, ethanesulfonylethoxycarbonyl (Esc), was designed to perform peptide synthesis in both aqueous and organic solvents. Esc-amino acids were prepared by the reaction of Esc-Cl and amino acids. Although Esc-Cl was a highly reactive reagent, it was not stable and decomposed during the purification procedure. A more stable reagent, ethanesulfonylethyl-4-nitrophenyl carbonate (Esc-ONp), was designed for preparation of Esc-amino acids. Esc-ONp was a stable reagent and could be purified by silica gel column chromatography or recrystallization. Esc-amino acids were prepared by the reaction of Esc-ONp and amino acids in good yield. To evaluate Esc-amino acids, Leu-enkephalin amide was synthesized using Esc-amino acids by the solid phase method in water. Removal of the Esc group was performed with 0.025 mol/l NaOH in 50% aqueous ethanol. Leu-enkephalin amide was successfully synthesized on a poly(ethylene glycol)-grafted polystyrene resin. Esc-amino acids have moderate solubility in organic solvents (such as dimethylformamide and acetonitrile). Leu-enkephalin amide was synthesized using Esc-amino acids by the solid phase method in dimethylformamide. Removal of the Esc group was performed with 0.05 mol/l tetrabutylammonium fluoride in dimethylformamide. Synthesis of Leu-enkephalin amide using Esc-amino acids in dimethylformamide was also successful. The yields of synthesis of Leu-enkephalin amide in water and dimethylformamide were 71% and 67%, respectively.     

A novel propargyltitanation of acetylenes. Heteroatom substituent-dependent manifold in intermolecular coupling of allene and acetylene

Titanium alkoxide-mediated coupling of functionalized allenes and acetylenes afforded various types of products, and the first propargyltitanation of acetylenes was achieved by the appropriate choice of allenes.     

A family of new boron-containing free radicals

The first spectroscopic evidence for the existence of the HBX and DBX (X = F, Cl, Br) free radicals has been obtained from laser-induced fluorescence and wavelength-resolved emission spectra. The vibrational frequencies measured in emission are in excellent agreement with our ab initio (CCSD(T)/aug-cc-pVTZ) predictions. The patterns of resolved rotational sub-band structure and deuterium isotope effects have been used to positively identify the radicals. The experimental data and ab initio predictions will be useful in searches for the matrix infrared and microwave spectra of these new radicals.