Synthesis and ion selectivity of macrocyclic metacyclophanes analogous to spherand-type calixarenes

Novel macrocyclic compounds, hexahydroxy[1.0.1.0.1.0]- (2b) and octahydroxy[1.0.1.0.1.0.1.0]metacyclophane (2c) have been prepared in 50–70% yield by base-catalyzed condensation of 5,5-di-tert-butyl-2,2-dihydroxybiphenyl (1) with formaldehyde in refluxing xylene. An attempted alkylation of the flexible macrocycles2b and2c with ethyl bromoacetate in the presence of Cs₂CO₃ under acetonitrile reflux gave only one pure stereoisomer3 and4, respectively, while other possible isomers were not observed. The structural characterization of these products is also discussed. The two-phase solvent extraction data indicated that hexaethyl ester3 and octaethyl ester4 show strong metal affinity, comparable with that of the corresponding calix[n]arenes, and a high K⁺ selectivity was observed for octaethyl ester4.¹H-NMR titration of hexaethyl ester3 and octaethyl ester4 with KSCN clearly demonstrate that a 11 complex is formed which is stable on the NMR time scale.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Microdetermination of fluorine in organic compounds by oxygen flask combustion and conductometric titration

For the conductometric titration of fluoride with calcium acetate, solvent system in sample solution and titrant, concentration, and acidity of sample solution were examined to establish the titration conditions. Results of these examinations were transferred to the microdetermination of fluorine in organic compounds using oxygen flask combustion method.Comparative examination between quartz and Pyrex flasks for the combustion of fluorine samples indicated that good results were obtained by the use of the former flask, whereas the use of the latter one gave negative values of 1.0–1.6% due to the formation of boron fluoride during the combustion.     

Hair analysis of nicotine and cotinine for evaluating tobacco smoke exposure by liquid chromatography-mass spectrometry

A simple liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method for the determination of nicotine and cotinine in human hair was established. In the procedure, a hair sample (10 mg) was washed with dichloromethane and digested in 2.5 M sodium hydroxide. The digest was extracted with dichloromethane and then 25 mM hydrochloric acid in methanol was added to the extract, to prevent loss of analytes. The solution was evaporated and redissolved in the mobile phase, methanol/10 mM ammonium acetate (30/70, v/v). A 20 microL aliquot of redissolved solution was subjected to analysis. Nicotine and cotinine in human hair were quantified by using deuterated analytes as internal standards. The quantification limits were 8 microg/L for nicotine and 0.9 microg/L for cotinine. The proposed method was applied to measure the concentrations of nicotine and cotinine in hair of smokers and non-smokers to evaluate their self-reported smoking and exposure to environmental tobacco smoke. In both cases, the method provided good selectivity, accuracy and precision.     

Involvement of human small fragment nuclease in the resistance of human cells to UV-C-induced cell death

Human small fragment nuclease (Sfn) is one of the cellular proteins that were reported to degrade small, single-stranded DNA and RNA. However, the biological role of Sfn in cellular response to various stressors such as UV-C (mainly 254 nm wavelength ultraviolet ray) remains unclear. We have examined whether modulation of human SFN gene expression affects cell survival capacity against UV-C-induced cell death, analyzing colony survival ability in UV-C-sensitive human RSa cells treated with short double-stranded RNA (siRNA) specific for SFN messenger RNA (mRNA). The expression levels of SFN mRNA in the siRNA-treated RSa cells decreased to about 15% compared with those in the control siRNA-treated cells. The siRNA-treated RSa cells showed lower colony survival and higher activity of caspase-3 after UV-C irradiation than the control siRNA-treated RSa cells. Furthermore, the removal capacity of cyclobutane pyrimidine dimers (CPD) in the siRNA-treated RSa cells decreased compared with the control siRNA-treated RSa cells. There was no difference in the colony survival and CPD removal capacity after UV-C irradiation between the control siRNA-treated RSa cells and mock-treated RSa cells. These results suggest that SFN expression is involved in resistance of RSa cells to UV-C-induced cell death through the roles it plays in the DNA repair process.     

Spectrophotometric determination of boron with an azomethine H derivative

Summary An azomethine H derivative, 1-(2,4-dihydroxybenzylidene-amino)-8-hydroxynaphthalene-3,6-disulphonic acid (azomethine HR) was examined and proposed as a spectrophotometric reagent for boron, as compared with azomethine H. Azomethine HR reacts with boron in aqueous solution (pH 7.5) to form a yellow complex having an absorption maximum at 425 nm. The sensitivity is 3.5-fold greater than with azomethine H when the same reagent concentration is applied. Basic conditions for the determination of boron have been worked out. The method is applicable to sea and hot spring waters. The standard deviation is ±2.1%.

---

Spektralphotometrische Borbestimmung mit einem Azomethin H-Derivat

     

Silica sol-gel/organic hybrid material for protein encapsulated column of capillary electrochromatography

A new-type of sol-gel/organic hybrid composite material using gelatin or chitosan with tetramethoxysilane was developed for the bovine serum albumin (BSA)-encapsulated monolithic column for capillary electrochromatography (CEC). The composite monolith was used to immobilize BSA in a fused-silica capillary. The addition of gelatin and chitosan to the alkoxysilane enabled the enantioseparation of Trp. A very small amount of these polymers were effective for the enantioseparation. Especially, the monolithic column prepared from chitosan with tetramethoxysilane showed a high enantioselectivity for Trp enantiomers and the value (alpha' = t2/t1, t1: fast eluted enantiomer, t2: second eluted enantiomer) reached 1.15 on CEC mode. Furthermore, the composite materials exhibited a higher stability compared to the silica sol-gel column. These results showed that the sol-gel/organic hybrid composite was useful as a monolithic matrix for the BSA-encapsulated column for CEC.     

Origin of the Landau-Lifshitz hydrodynamic fluctuations in nonequilibrium systems and a new method for reducing the Boltzmann equation

The Landau-Lifshitz fluctuating fluxes in fluctuating hydrodynamics are derived from the deterministic Boltzmann equation with the aid of a reduction method developed by Fujisaka and Mori. Thus it is shown that the hydrodynamic fluctuations innonequilibrium systems are generated by the reduction of variables from the-space distribution function to its five momentum moments, i.e., the hydrodynamic variables. This differs from the Bixon-Zwanzig and Fox-Uhlenbeck theories, in which the Landau-Lifshitz fluctuating fluxes are derived from the molecular fluctuating force in thestochastic Boltzmann-Langevin equation, which is, however, negligible in nonequilibrium systems. Thus the present method improves the Chapman-Enskog reduction method so as to include the hydrodynamic fluctuations generated by the reduction of variables.Supported in part by the Scientific Research Fund of the Ministry of Education.     

Molecular structure of 1,1-difluoroethylene as determined by gas phase electron diffraction and microwave data

The structure of 1,1-difluoroethylene was determined, from gas phase electron diffraction data obtained independently in Leiden and Tokyo and the rotational constants of F₂CCH₂, F₂CCHD and F₂CCD₂ derived from the microwave study by Chauffoureaux. The two electron diffraction data agreed without significant discrepancy. From a joint least squares analysis of the diffraction and microwave data, the following r_g bond distances and r_z bond angles were derived: CC = 1.340 ± 0.006 Å, C-F = 1.315 ± 0.003 Å, C-H = 1.091 ± 0.010 Å, ∠C-C-F = 124.7 ± 0.3°, ∠C-C-H = 119.0 ± 0.4°, where the uncertainties represent estimated limits of error.     

Total synthesis of (+)-benzastatin E via diastereoselective Grignard addition to 2-acylindoline

[reaction: see text] A stereoselective total synthesis of (+)-benzastatin E (1) is described. The synthesis involves a diastereoselective Grignard addition to 2-acylindoline 2, which is derived from commercially available (S)-2-indolinecarboxylic acid (3). The unknown absolute configuration of (+)-1 is determined as (9S,10R).