Ru(II)-catalyzed chemo- and regioselective cyclotrimerization of three unsymmetrical alkynes through boron temporary tether. One-pot four-component coupling via cyclotrimerization/Suzuki-Miyaura coupling

The Ru(II)-catalyzed [2+2+2] cyclotrimerization of alkynylboronates, propargyl alcohol, and terminal alkynes proceeded chemo- and regioselectively to give rise to arylboronates, which were subjected to Suzuki-Miyaura cross-coupling with aryliodides to afford highly substituted biaryls in 53-76% yields.     

Measurement of attachment force of microbial cells

A parallel-plate flow chamber consisting of two transparent electro-conductive glass plates was constructed. The two glass plates were set parallel to each other and connected to a potentiostat apparatus to regulate the strength of the electric field between the plates. A microbial cell suspension was flowed through the chamber. This system enabled the application of an electrostatic force to suspend charged particles, e.g. microbial cells, existing between the two plates. The time course of the cell attachment of Pseudomonas syringae pv. atropurpurea NIAES 1309 suspended in 10 mM phosphate buffer solution (pH 7.0) to the glass plate was investigated at various electric field strengths ranging from −4.2 to +4.1 V cm⁻¹. The attachment rate and the maximum number of attached cells increased linearly with the increase in the strength of the positive electric field. In contrast, the rate and the number of cells decreased linearly with the decrease in the strength of the negative electric field. These linear relations gave a specific value for the strength of the electric field (−5.9 ± 0.7 V cm⁻¹) where the electrostatic repulsion and the microbial attachment force were thought to be equal, resulting in no cell attachment. From this value, the electrostatic repulsion, i.e. the microbial attachment force, was calculated to be 5.0 × 10⁻¹¹ N cell⁻¹ for cells of average size.     

Modified normal pulse polarography of alkali-metal ions in acid solution

Well-defined polarograms of five alkali-metal ions in 0.01M hydrochloric acid were obtained by means of modified normal pulse polarography. The method uses the procedure of anodic stripping chronoamperometry during the life-time of a drop from a dropping mercury electrode, namely preparation of electrode, accumulating step and anodic stripping step of a metal. The instantaneous polarographic currents were sampled only once per mercury drop after the fall of each pulse. The wave heights for alkali-metal ions by the present method are free from the interference caused by 0.01M hydrochloric acid. The present method is applicable to monitoring of alkali-metal ions in fluid acid streams.     

High-performance liquid chromatography of apolipoproteins in serum high-density lipoproteins

A simple and rapid method for apolipoprotein analysis in serum high-density lipoproteins (HDL) has been developed using high-performance liquid chromatography (HPLC) with sodium phosphate buffer (pH 7.0) containing 0.1% sodium dodecyl sulphate (SDS) as eluent. In contrast to the use of urea solution as an eluent, apolipoproteins can be analysed by applying an incubation mixture of HDL and the eluent buffer. A TSK-GEL column of G3000SW was found to be more profitable than G2000SW or G4000SW for analysis of HDL apolipoproteins. Elution patterns monitored by absorbance at 280 nm using a G3000SW column can give precise quantitative as well as qualitative information about apolipoproteins of molecular weight between 10(4) and 10(5). HPLC patterns of HDL apolipoproteins were compared between individual human subjects with various diseases. Elution profiles for lipid components in an incubation mixture were also examined.     

Regioselective allylzincation of alkenylboronate

[reaction: see text] Boryl substitution on an olefin activates the olefinic double bond toward addition of an organozinc reagent. Addition of an allylic zinc reagent to an alkenylboronate thus takes place smoothly to afford a variety of gem-zincio/boryl species. Theoretical studies with density functional calculations on the reaction pathway revealed that the reaction proceeds via a zincio-ene reaction rather than a bora-Claisen rearrangement.     

High frequency titrations involving chelation with ethylenediaminetetra-acetic acid. II. quantitative determination of some divalent metals

The high frequency oscillator provides an excellent means of detecting the end-points of titrations performed with ethylenediaminetetraacetic acid or its salts. The determination of various divalent metals is reported, based on both direct and indirect titrations. Because of the great sensitivity of the method it is possible to determine cobalt, nickel, copper (II), zinc, cadmium, lead and manganese (II) in concentration ranges of 1/1000 to 1/6000M.     

THE CONFORMATIONAL ANALYSIS AND PHOTOISOMERIZATION OF RETINOCHROME ANALOGS WITH POLYENALS

Abstract— 3, 7-Dimethyl-2, 4, 6, 8, 10-dodecapentaenal was synthesized for reconstitution of the retinochrome analog. Its opsin shift was 1000 cm ¹ smaller than that of native retinochrome, whose chromophore contains the same number of double bonds. The conformational change from 6-s-trans to 6-s-cis , as figured in a retinal molecule, plays an important role in the formation of the retinochrome analog, based on the estimation of opsin shifts for retinal analogs locked in the 6-s conformation. Thus the conformation of the 6–7 single bond in the native retinochrome was suggested to be 6 -cis . Analysis of the circular dichroic spectra of retinochrome analogs revealed that the 6-s conformation is independent of the appearance of the β-band. The stereoselectivity in the photoisomerization of the retinal analogs by a retinochrome template depends on the hydrophobic binding in the region of the β-ionone ring.     

Alternative copolymerization of aziridines and carbon monoxide by γ-ray irradiation

The copolymerization of carbon monoxide and aziridines such as ethylenimine and propylenimine was carried out by γ-ray irradiation. Aziridines and carbon monoxide were allowed to copolymerize under γ-ray irradiation from a Co⁶⁰ source and gave a crystalline solid copolymer. The yield of the copolymer increased with reaction temperature. The composition of copolymers obtained did not depend on the feed ratio of monomers and was found to be almost equimolar. The copolymer of ethylenimine and carbon monoxide melted at about 322–335°C. with decomposition and has an infrared spectrum identical with that of poly-β-alanine obtained by the hydrogen-migration polymerization of acrylamide. The hydrolyzed product of the ethylenimine–carbon monoxide copolymer was confirmed to be β-alanine by paper chromatography. These results lead to the conclusion that the copolymerization of aziridines and carbon monoxide took place alternatively by γ-ray irradiation, and produced crystalline poly-β-alanines.     

Coenzyme models. 32. Catalytic activity of polymer-bound thiazolium ions as estimated by flavin trapping technique

Three thiazolium-containing polymers, Th-7, Th-33, and Th-18-Py [where Th-x and Py mean x mol % thiazolium unit and pyridinium unit (54 mol %), respectively], were synthesized from partially p-chloromethylated polystyrene. The catalytic activities of these polymer catalysts in acyloin condensation of aldehydes and decarboxylation of α-keto acids were estimated kinetically by oxidative trapping of the key intermediate by flavin (flavin-trapping technique). In aqueous solution at 30°C, the catalytic activity of Th-18-Py and Th-33 in condensation of p-chlorobenzaldehyde was comparable with that of the cationic-micelle-bound thiazolium ion, whereas Th-7 and a monomeric thiazolium compound (N-benzylthiazolium bromide) scarcely exhibited any catalytic activity. The catalysis of the polymer-bound thiazolium ions was sensitively suppressed by increased ionic strength. These results suggest that the pendent thiazolium ion is activated by the relatively high charge density along the polymer chain: the cationic environment is able to facilitate dissociation of the thiazolium ion to the ylid form and deprotonation of the thiazolium-aldehyde adduct to the key intermediate.     

Cidep study of radical-ion pair systems: Photooxidation reactions of carbazoles by maleic anhydride in alcohol solution

Photooxidation (charge transfer) reactions of carbazole derivatives by maleic anhydride (MA) in alcoholic media are studied by a time-resolved cw-ESR (TRESR) and Fourier transform ESR (FTESR) techniques. The CIDEP spectra observed in the systems (methyl-, ethyl-, and phenyl-substituted carbazoles with MA) remarkably depend on the MA concentration. Under the high concentration conditions, an emissive TM (triplet mechanism) polarization with a slight A/E (absorption/emission) pattern of the RPM (radical pair mechanism) is observed. In the low concentration of MA, a TM-like absorptive polarization is superimposed on the A/E pattern of the RPM. Since this reaction takes place exclusively through the triplet state, this spectral phase reveals that the singlet state of the radical-ion pair (RIP) has an energy higher than that of the triplet state, in other words, the sign of the apparent exchange interaction of the present RIP systems is positive. The total absorptive polarization observed in the low concentration of MA is tentatively explained by the polarization transfer from the excited triplet state of carbazoles in thermal equilibrium.