Collection of mercury from artificial sea-water with activated carbon

Nanogram amounts of mercury(II) and methylmercury in artificial sea-water containing mineral acids as preserving reagents were shown to be collected quantitatively with activated carbon. Mercury concentrated on activated carbon was determined directly by combustion, trapping on gold and electrothermal atomic-absorption spectrophotometry. The activated carbon was purified by heating at 350 degrees for 2 hr. Sulphuric acid and hydrochloric acid were purified by treatment with activated carbon. Interference from iodide was eliminated by using a carbonate buffer wash before the atomic-absorption measurement. Less than 4 ng of mercury in 200-300 ml of artificial sea-water, whether acidified or not (with sulphuric, hydrochloric or nitric acid), was satisfactorily collected with 100 mg of activated carbon. Mercury was also collected quantitatively after oxidative treatment of artificial sea-water.     

Photopolymerization of cyclohexene oxide by use of o-nitrobenzyl triphenylsilyl ether/aluminum compound catalyst. Dependence of catalyst activity on the structure of the silyl ether

o-Nitrobenzyl triphenylsilyl ehther/aluminum compound has been previously shown by the authors to act as catalyst in the photopolymerization of epoxides. The dependence of the structure of the silyl ether on the catalyst activity was examined. There were two steps in the photopolymerization. The first step (“Step 1”) is photodecomposition of the silyl ether to silanol. The second step (“Step 2”) is the initiation of polymerization by silanol and the aluminum compound. The introduction of an electron withdrawing group, Cl, CF₃, on the benzene ring bonded to Si made the quantum yield of Step 1 low, however, the rate of Step 2 was increased. The low quantum yield of Step 1 was explained in terms of the rate of electron transfer that is controlled by the relative electron density between the CH₂ and NO₂ in the o-nitrobenzyl group. The acceleration of Step 2 was explained in terms of an increase in silanol acidity that was promoted by the introduction of an electron withdrawing group. The overall rate of the photopolymerizatiol depends to a greater degree on the rate of Step 2 than on that of Step 1.     

Investigation of the detection limit for the determination,by pyrolysis-capillary GC,of the thickness of ultra thin PMMA layers coated on to PET film

The determination of nanometer thick layers of poly(methyl methacrylate) coated on to the surface of poly(ethylene terephthalate) film has been investigated by high resolution pyrolysis gas chromatography without sample pretreatment or modification of the instrumentation used. A good linear relationship was observed between the quantity of the characteristic pyrolysate and the thickness of the poly(methyl methacrylate) layer; the detection limit was sufficient to enable the quantitation of poly(methyl methacrylate)-to-poly(ethylene terephthalate) film thickness ratios of 1:20000 in composite materials.     

Super acid-induced Pummerer-type cyclization reaction: improvement in the synthesis of chiral 1,3-dimethyl-1,2,3,4-tetrahydroisoquinolines

Improved synthesis of four stereoisomeric chiral 1,3-dimethyl-1,2,3,4-tetrahydroisoquinolines (1a, b, ent-1a, b) was achieved via the super acid-induced cyclization of chiral N-[1-methyl-2-(phenylsulfinyl)ethyl]-N-(1-phenylethyl)formamides (4a, b, ent-4a, b) using the Pummerer-type cyclization reaction as a key step. The cyclization leading to the isoquinoline ring proceeded in a quantitative manner when trifluoromethane sulfonic acid (TFSA) was used as the super acid, although Friedel-Crafts-type alkylation of 4-phenylsulfanyl TIQ derivatives (5) with benzene used as the solvent accompanied cyclization to yield the 4-phenyl-TIQs (7). The byproduct (7) was exclusively formed when a large excess amount of TFSA was used.     

Reaction of 3,4-disubstituted 1,2,5-oxadiazole 2-oxides with dipolarophiles : Substituent and solvent effect on the reaction courses

A variety of symmetrically or unsymmetrically 3,4-disubstituttd furoxans such as dicyano, dialkyl, diacyl, bis(phenylsulfonyl), N.N'-dialkyldicarbamoyl, 3(or 4)-methyl-4(or -3)-phenyl(or nitro, ethoxy, phenoxy, phenylthio, pyrrolidinyl, phenylsulfonyl), 3(or 4)-ethyl-4(or -3)phcnyl, and 3(or 4)-ethoxy-4(or -3)-phenylsulfonylruroxan reacted with dipolarophiles in toluene or xylene at the refluxing temperature to give nitrone-type 1,3-dipolar cycloadducts, 5-substituted 1-aza-2,8-dioxabicyclo-[3.3.0]octanes and/or 3-substituted 2-isoxazoline 2-oxides. On the other hand, some of the furoxans gave 2-isoxazolines via nitrile oxide 1,3-dipolar cycloaddition in a toluene (or xylene)-DMF solvent at the refluxing temperature.     

Detection of the His-heme Fe2+-NO species in the reduction of NO to N2O by ba3-oxidase from thermus thermophilus

Reaction pathways in the enzymatic formation and cleavage of the N-N and N-O bonds, respectively, are difficult to verify without the structure of the intermediates, but we now have such information on the heme a(3)(2+)-NO species formed in the reaction of ba(3)-oxidase with NO from resonance Raman spectroscopy. We have identified the His-heme a(3)(2+)-NO/Cu(B)(1+) species by its characteristic Fe-NO and N-O stretching frequencies at 539 and 1620 cm(-)(1), respectively. The Fe-NO and N-O frequencies in ba(3)-oxidase are 21 and 7 cm(-)(1) lower and higher, respectively, than those observed in Mb-NO. From these results and earlier Raman and FTIR measurements, we demonstrate that the protein environment of the proximal His384 that is part of the Q-proton pathway controls the strength of the Fe-His384 bond upon ligand (CO vs NO) binding. We also show by time-resolved FTIR spectroscopy that Cu(B)(1+) has a much lower affinity for NO than for CO. We suggest that the reduction of NO to N(2)O by ba(3)-oxidase proceeds by the fast binding of the first NO molecule to heme a(3) with high-affinity, and the second NO molecule binds to Cu(B) with low-affinity, producing the temporal co-presence of two NO molecules in the heme-copper center. The low-affinity of Cu(B) for NO binding also explains the NO reductase activity of the ba(3)-oxidase as opposed to other heme-copper oxidases. With the identification of the His-heme a(3)(2+)-NO/Cu(B)(1+) species, the structure of the binuclear heme a(3)-Cu(B)(1+) center in the initial step of the NO reduction mechanism is known.     

A synthesis of chiral 1,1,3-trisubstituted 1,2,3,4-tetrahydro-beta-carbolines by the Pictet-Spengler reaction of tryptophan and ketones: conversion of (1R,3S)-diastereomers into their (1S,3S)-counterparts by scission of the C(1)-N(2) bond

The Pictet-Spengler cyclization of the imines (3) prepared by the condensation of L-tryptophan methyl ester (1) and aryl methyl ketones (2), using titanium(IV) isopropoxide as an iminating reagent, quantitatively proceeded, when treated with trifluoroacetic acid (TFA) or formic acid, to provide two diastereomers, that is (1S,3S)-1-aryl-3-isopropoxycarbonyl-1-methyl-1,2,3,4-tetrahydro-beta-carbolines (4) and their (1R,3S)-diastereomers (5), of which the diastereomer ratios varied from 1 to 5 depending on the reaction conditions. The (1R,3S)-diastereomers (5) are thermodynamically more stable than their (1S,3S)-congeners (4), as shown by equilibration experiments in TFA. The conversion of 4 to 5 (also 5 to 4) should occur under acidic conditions by cleavage of the C(1)-N(2) bond with complete retention of configuration at the C-3 chiral center. The low diastereo-selectivity observed in the Pictet-Spengler reaction of 1 and 2 is concluded to be a stereochemical outcome under conditions of kinetic control (lower temperature, shorter reaction time), while the high diastereo selectivity with preferential formation of the more stable isomer (5) is the result of thermodynamically controlled experiments (higher temperature, longer reaction time).     

Spectrophotometric determination of zirconium, uranium, thorium and rare earths with arsenazo III after extractions with thenoyltrifluoroacetone and tri-n-octylamine

A method is described for the spectrophotometric determination of microgram amounts of zirconium, uranium(VI), thorium and rare earths with Arsenazo III after systematic separation by extraction. First zirconium is extracted into a xylene solution of thenoyltrifluoroacetone (TTA) from about 4M hydrochloric acid. Uranium(VI) is then extracted into a xylene solution of tri-n-octy lamine from about 4M hydrochloric acid. Thorium is next extracted into TTA solution at pH about 1.5, and finally rare earths are extracted into TTA solution at pH about 4.7. Each metal is back-extracted from the organic phase before determination.     

A New Convenient Synthesis of α-Arylpropionic Acid Esters and α-Arylpropionitriles

Various types of α-arylpropionic acid esters were effectively obtained by the coupling reaction of aryl Grignard reagents and α-bromopropionic acid esters in the presence of nickel catalysts. α-Arylpropionitriles, precursors of α-arylpropionic acids, were also synthesized by the reaction of α-methanesulfonyloxypropionitrile and arylcopper reagents prepared from equimolar amount of arylmagnesium halides and copper(I) bromide.     

High-quality lowest-loss-mode lasing in GaAs quasi-stadium laser diodes having unstable resonators

We obtained high-quality lowest-loss-mode lasing in quasi-stadium laser diodes having unstable resonators that consisted of two curved end mirrors and two straight sidewall mirrors. The laser diodes were fabricated by applying a reactive ion etching technique to a metal-organic chemical-vapor deposition-grown graded-index separate-confinement heterostructure single-quantum-well GaAs/AlGaAs structure. The electrode contact area of the laser diodes was formed along unstable periodic orbits, along which the optical beams are localized. Highly directional fan-out beams corresponding to the numerically obtained lowest loss mode were emitted from the end mirrors under CW operation at room temperature.