Synthesis and characterization of isotopically enriched methylmercury (CH3201Hg+)

A simple procedure for the synthesis of an important standard, isotopically enriched methylmercury, which is not commercially available, has been established successfully. The isotopically enriched standard synthesized is utilized in conventional isotope dilution mass spectrometry (IDMS), as well as in speciated IDMS (SIDMS), for determination of the true concentration of methylmercury in environmental samples. The CH₃²⁰¹Hg⁺ standard has been synthesized from commercially available ²⁰¹HgO and tetramethyltin. The synthesis time required is 1 h at 60°C. The product is highly pure, yielding more than 90% as ²⁰¹Hg in CH₃²⁰¹Hg⁺. Hazardous dimethylmercury does not occur during this synthesis procedure. The product synthesized was analyzed using high‐performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (ICP‐MS) and ICP‐MS alone in order to determine its concentration, isotopic composition and purity. The stability of the product was also evaluated for over 6 months and found to be stable at 4°C in the dark. The isotopically enriched methylmercury synthesized can be used in SIDMS and IDMS analyses as a standard. Copyright © 2003 John Wiley & Sons, Ltd.     

Entropy production per site in (nonreversible) spin-flip processes

Entropy production per site in a (nonreversible) spin-flip process is studied. We give it a useful expression, from which a property stronger than affinity of the entropy production per site follows. Furthermore, quasi-invariance of nonequilibrium measures in the spin-flip processes is discussed via entropy production.     

Catalytic property of Europium supported on alumina from its ammoniacal solution

Europium supported on alumina (Eu/Al₂O₃) was prepared by impregnation from an ammoniacal solution of the metal. The catalytic activity of Eu/Al₂O₃ for the isomerization of 2,3-dimethylbut-1-ene to 2,3-dimethylbut-2-ene was examined. Eu/Al₂O₃ showed the highest catalytic activity for the isomerization when heated under a vacuum at 523 K, the yield of 2,3-dimethylbut-2-ene in 20 min being 81.6% at 314 K. IR spectrum shows the presence of two kinds of Eu amides. The change of the IR spectra and the catalytic activities with evacuation temperature suggest that only one of the two Eu amides is catalytically active for this base-catalyzed isomerization.     

Subtilisin catalysis of substrate anchored in cyclodextrin

The N-benzoyl-l-tyrosine ethyl ester (BTEE) anchored in cyclodextrin (β and β-methyl CD) serves as an excellent substrate for subtilisin Carlsberg catalysis. The rate of hydrolysis was found to be approximately twofold higher than that of the methanolic substrate. The K_mapp and V_max values for the CD anchored substrates were significantly higher than the methanol-solubilized BTEE.     

Photografting of vinyl polymers onto ultrafine inorganic particles: Photopolymerization of vinyl monomers initiated by AZO groups introduced onto these surfaces

The photografting of polymers onto ultrafine inorganic particles, such as silica and titanium oxide, initiated by azo groups introduced onto these surfaces was investigated. The introduction of azo groups onto the particles was achieved by the reaction of 4,4′-azobis(4-cyanopentanoic acid) with surface isocyanate groups, which were introduced by the treatment with tolylene 2,4-diisocyanate. It was found that the photopolymerization of vinyl monomers, such as methyl methacrylate (MMA), styrene, and N-vinylcarbazole, is initiated by ultrafine particles having azo groups. The corresponding polymers were effectively grafted onto these surfaces through the propagation of the polymer from the surface radicals formed by the photodecomposition of the azo groups: e.g., the percentage of grafting of PMMA and polystyrene onto silica was reached to 112 and 176%, respectively. The percentage of grafting onto silica in the graft polymerization initiated by photodecomposition of surface azo groups was much larger than that initiated by thermal decomposition. Polymer-grafted ultrafine particles thus obtained gave a stable colloidal dispersion in good solvents for the grafted chain. © 1994 John Wiley & Sons, Inc.     

Peptides-XXXXVI: Studies in the synthesis of an analogue of hen egg white lysozyme

The previously synthesised (1–37), (38–75), (76–93), (94–104), (105–117) and (118–129) fragments of the analogue were combined making extensive use of the DCCI/HONSu method. The final coupling involved the (1–75) and (76–129) sub-fragments. Aggregation of the latter fragment caused problems in purification by routine gel filtration methods employing Enzacryl K2 or Sephadex LH60. The fully protected (1–129) product was partially purified by washing, then deprotectcd and purified by gel filtration and ion exchange chromatography. Satisfactory removal of the acetamidomethyl group used for cysteine protection could not be achieved.     

Gamma,delta-unsaturated beta-diketones by acylation of ketones

[reaction: see text] Gamma,delta-unsaturated beta-diketones have been prepared by the acylation of ketones with N-acylbenzotriazoles of various aliphatic and aromatic alpha,beta-unsaturated carboxylic acids.