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.     

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.     

Catalytic flow-injection determination of copper at nanogram levels by using color formation of N-phenyl-p-phenylenediamine with m-phenylenediamine in the presence of pyridine and ammonia as activators

A spectrophotometric flow-injection method for determining copper(II) has been developed. It is based on the catalytic effect of copper(II) on the oxidative coupling of N-phenyl-p-phenylenediamine with m-phenylenediamine in the presence of hydrogen peroxide. Pyridine and ammonia as activators increased the absorbance for the copper(II)-catalyzed coloration, and the dye formed was stabilized by adding a non-ionic surfactant. The working range of the method was 0.1-2.0 ng ml(-1) of cooper(II) with a relative standard deviation 2.4% at a sampling rate of 30 h(-1). Interference from iron(III) was effectively suppressed by citric acid. Copper in natural water samples can be determined easily.     

Reactivity control of an allylsilane bearing a 2-(phenylazo)phenyl group by photoswitching of the coordination number of silicon

Photoswitching of the coordination number of silicon between four and five in allyldifluoro[2-(phenylazo)phenyl]silane, which was confirmed by X-ray analysis and multinuclear NMR spectroscopy, caused multistep reactions to proceed or stop, yielding tetrafluoro[2-(1-allyl-2-phenylhydrazino)phenyl]silicate without altering other reaction conditions.     

Self-crosslinkable polymers. I. Copolymerization of glycidyl methacrylate with 2-vinylpyridine and 2-vinyl-5-ethylpyridine

A soluble and self-crosslinkable linear copolymer with pendant epoxy and pyridyl groups was obtained from glycidyl methacrylate (M₁) and 2-vinylpyridine (M₂) or 2-vinyl-5-ethylpyridine (M₂) by the action of azobisisobutyronitrile. The monomer reactivity ratios were determined in tetrahydrofuran at 60°C: r₁ = 0.510, r₂ = 0.620 with 2-vinylpyridine and r₁ = 0.57, r₂ = 0.62 with 2-vinyl-5-ethylpyridine. These were consistent with the calculated values with the reported Q and e values for these monomers. The intrinsic viscosities of the copolymers with 2-vinylpyridine and with 2-vinyl-5-ethylpyridine were found to be 0.17–0.19 and 0.26–0.38, respectively, in tetrahydrofuran at 30°C; they were independent of the copolymer composition. The copolymers were amorphous, had no clear melting points, and became insoluble crosslinked polymers under heating without further addition of any curing agents.