Information theory of miniaturization advantages of column liquid chromatography for quantitative analysis

Summary The influences of decreasing column diameter and length on two analytical goals, the precision and solvent efficiency, in reversed-phase liquid-chromatography are studied. Low solvent consumption is one of analytical advantages of miniaturized columns and is shown to be quantitatively evaluated by the precision and solvent efficiency which are defined to be the total Shannon mutual information obtained from an assay and the information obtained in a unit solvent volume, respectively. Analysis of paraben food additives on a microbore column is taken as an example. In trace analysis, the relative standard deviation (RSD) of measurements theoretically derived from the precision is shown to approach to the observed ones.     

Intramolecular Nucleophilic Acyl Substitution Reaction of 3,4-Alkadienyl Carbonates Mediated by Ti(O-i-Pr)(4)/2 i-PrMgCl Reagent. Efficient Synthesis of Optically Active beta,gamma-Unsaturated Esters with an alpha-Substituent

Treatment of 3,4-alkadienyl carbonates 2a-i with a low-valent titanium reagent diisopropoxy(eta(2)-propene)titanium (1), readily generated by the reaction of Ti(O-i-Pr)(4) with 2 i-PrMgCl, resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford vinyltitanium compounds 3 which, in turn, reacted with H(3)O(+), D(2)O, or iodine to give alpha-substituted beta,gamma-unsaturated esters 4 in good to excellent yields. The olefin moiety of the hydrolysis product 4 has (Z)-geometry mainly except for 4h. Starting from chiral 2f or 2g, the reaction proceeded stereospecifically to give optically active alpha-substituted beta,gamma-unsaturated ester 4f or 4g having (Z)-olefin geometry exclusively.     

'Non-covalent synthesis' of a chiral host of calix[6]arene and enantiomeric discrimination

'Non-covalent synthesis' of novel chiral hosts (calix[6]arene-chiral amine complexes) and its application to enantiomeric discrimination was investigated by (1)H NMR spectroscopy. The topology of a ternary complex was proposed for the calix[6]arene-amine-sulfoxide to rationalize the chiral recognition.     

Photoinduced electron-transfer systems consisting of electron-donating pyrenes or anthracenes and benzimidazolines for reductive transformation of carbonyl compounds

Photoinduced electron-transfer reactions of several ketone substrates were studied to evaluate the utilities of 1,6-bis(dimethylamino)pyrene (BDMAP), 1,6-dimethoxypyrene (DMP), 9,10-bis(dimethylamino)anthracene (BDMAA), and 9,10-dimethoxyanthracene (DMA) as electron-donating sensitizers cooperating with 2-aryl-1,3-dimethylbenzimidazolines. BDMAP and DMP generally led higher conversion of ketones and better yield of reduction products compared to BDMAA and DMA.     

Efficient and widely applicable method of constructing neo-proteoglycan utilizing copper(I) catalyzed 1,3-dipolar cycloaddition

Efficient constructions of two types of neo-proteoglycan are described. Enzymatically prepared alkyne containing chondroitin 6-sulfate chains and chemically synthesized azido group having compounds are linked by utilizing the copper(I) catalyzed 1,3-dipolar cycloaddition.     

GaCl(3)-catalyzed ortho-ethynylation of phenols

Phenols are ethynylated at the ortho position with silylated chloroethyne in the presence of a catalytic amount of GaCl3 and lithium phenoxide. The lithium salt is essential for the catalysis, and addition of 2,6-di(tert-butyl)-4-methylpyridine inhibits desilylation and hydration of the products. The reaction can be applied to various substituted phenols giving the ortho-ethynylated products in high yields, and the turnover numbers based on GaCl3 are between 8 and 10. The reaction mechanism involves addition of in situ formed phenoxygallium to the haloethyne followed by the elimination of GaCl3.     

Extraction-spectrophotometric determination of anionic surfactants with a flow-injection system

Anionic surfactants are preconcentrated from 5-ml samples by extraction as the ion-pair with ethyl violet into toluene. The absorbance of aliquots of the toluene phase is measured at 610 nm in a flow-injection system. A phase converter is located prior to the injection valve to convert a water stream to, pumped with ordinary pump tubing, to a toluene stream. The working range was 0.01–1.0 mg l^?1 and the reproductibility (r.s.d, n = 10) was 2% for 0.4 mg l^?1 sodium dodecyl sulphate. The non-aqueous flow-injection system serves to miniaturize the extraction from separatory funnel (200 ml) to test tube (10 ml) scale without loss of precision or validity.