The identification of selenium species in biological samples

Selenium is an essential component of glutathione peroxidase and other enzyme systems and is therefore essential for animal metabolism. It is, however, toxic at concentrations little above those required for health. Some plants accumulate selenium from seleniferous soils and constitute a toxic hazard to grazing stock. The more complex organic selenium compounds that occur naturally in plants, animals and microorganisms have been characterized following their isolation or partial isolation, and have often been identified by their similarity to analogous sulphur compounds. The occurrence and identification ­of selenium compounds in biological samples and methods for their analysis are reviewed. Copyright © 2000 John Wiley & Sons, Ltd.     

Hetero-Type Benzannulation Leading to Substituted Benzothio-Phenes

TiCl₄ (or SnCl₄)-promoted hetero-type benzannulation reactions using various (2,2-dichlorocyclopropyl)(thiophen-2-yl)methanols proceeded smoothly to produce uniquely substituted 4-chlorobenzothiophenes (five examples). The present approach involves the first distinctive thiophene formation from thiophene cores, in contrast to traditional methods of thiophene formation from benzene cores. The stereocongested (less reactive) Cl position in the obtained 4-chlorobenzothiophenes functioned successfully as the partners of three cross-coupling reactions: (i) a Suzuki–Miyaura cross-couplings using Pd(OAc)₂/SPhos/K₃PO₄ catalysis (seven examples; 63–91%), (ii) a hydroxylation using KOH/Pd(dba)₂/tBu-XPhos catalysis (85%), and (iii) a borylation using a B₂(pin)₂/Pd(dba)₂/XPhos/NaOAc catalysis-provided 4-(pin)B-benzothiophene (58%).     

Isomerization polymerization and copolymerization of glycidyl alkanoates catalyzed by methylaluminum bis(2,6‐di‐t‐butyl‐4‐methylphenoxide)

The isomerization polymerizations of glycidyl propionate (1b), octanoate (1c), and stearate (1d) with methylaluminum bis(2,6‐di‐tert‐butyl‐4‐methylphenoxide) (3) were investigated. The polymerizations selectively gave poly(2‐alkyl‐1,3‐dioxolane‐4,2‐diyloxymethylene)s (2), although the polymer yield as well as the polymer molecular weight significantly decreased as the acyl chain of 1 was lengthened. These polymers readily hydrolyzed to glycerin and the corresponding fatty acids under mild conditions. The copolymerizations of glycidyl acetate (1a) with these monomers were also examined. In any combination, the composition of the obtained copolymer was essentially identical with the feed ratio, while both copolymer yield and molecular weight decreased as the feed of 1a was decreased. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 435–444, 1999 (See graphics.)     

Unique Participation of Unprotected Internucleotidic Phosphodiester Residues on Unexpected Cleavage Reaction of the Si?O Bond of the Diisopropylsilandiyl Group Used as a Linker for the Solid‐Phase Synthesis of 5′‐Terminal Guanylated Oligodeoxynucleotides

In connection with the synthesis of guanosine‐capped oligodeoxynucleotides on polymer supports, we found an unprecedented Si O bond cleavage reaction, which occurred when polymer‐linked oligodeoxynucleotides having unprotected internucleotidic phosphate groups were allowed to react with the guanosine 5′‐phosphorimidazolide derivative 18 in the presence of 4‐nitro‐6‐(trifluoromethyl)‐1H‐benzotriazol‐1‐ol (Ntbt‐OH) as an effective activator in pyridine. This side reaction was confirmed by the fact that the liquid‐phase reaction of DMTrTpT O Si(iPr₂)OEt 42 with a simpler model compound, methyl phosphorimidazolide 34 , in the presence of Ntbt‐OH gave DMTrTpT 43 . It turned out that the side reaction hardly occurs without unprotected internucleotidic phosphate groups on oligodeoxynucleotides. The detailed study of this side reaction disclosed that Ntbt‐OH directly attacks the Si‐atom to release oligonucleotides from the resin. It is likely that Ntbt‐OH serves as a very strong nucleophile in pyridine, especially to the Si‐atom of the linker.     

Arsenic Compounds in Zoo- and Phyto-plankton of Marine Origin

Major water-soluble arsenic compounds accumulated in some zoo- and phyto-plankton were identified. Zooplankton were collected at sampling stations in the Sea of Japan by a Norpac net towed from 600 m depth to the surface. Phytoplankton were cultivated under axenic conditions. Water-soluble arsenic compounds were extracted repeatedly from plankton tissues by aqueous methanol. The arsenic compounds in the extracts were analyzed by HPLC–ICP/MS. Among zooplankton analyzed in the present study, two carnivorous species, i.e. Amphipoda ( Themisto sp.) and Sagittoidea ( Sagitta sp.), contained arsenobetaine as the dominant arsenic species. Arsenobetaine was the major species in Euphausiacea ( Euphausia sp.), also. The most abundant arsenic compound in the herbivorous Copepoda species ( Calanus sp.), on the other hand, was an arsenic-containing ribofuranoside with a sulfate ester group, and arsenobetaine was only a minor component. Phytoplankton contained arsenic-containing ribofuranosides apparently in a species-speific manner. The arsenic compounds in zooplankton seem to reflect their feeding habit; i.e. carnivorous species eating zooplankton or other small animals accumulate arsenobetaine, while herbivorous ones eating phytoplankton accumulate arsenic-containing ribofuranosides as major arsenic compounds.     

Ring-opening polymerization of six- and seven-membered cyclic pseudoureas

The cationic ring-opening polymerization of six-membered cyclic pseudoureas, 2-(1-pyrrolidinyl)- ( 2a ) and 2-morpholino-5,6-dihydro-4H-1,3-oxazine ( 2b ), was examined, which proceeded in two different ways, depending on the nature of initiator. The polymerization of 2 with methyl p-toluenesulfonate or trifluoromethanesulfonate (MeOTf) produced poly[(N-carbamoylimino)trimethylene], while that with benzyl chloride or bromide or methyl iodide gave a polymer consisting of 1,3-diazin-2-one-1,3-diylalkylene unit (the main component) and (N-carbamoylimino)trimethylene unit. The cationic ring-opening polymerization of seven-membered cyclic pseudourea, 2-(1-pyrrolidinyl)-4,5,6,7-tetrahydro-4H-1,3-oxazepine ( 3 ) was also examined. The polymerization of 3 with MeOTf as initiator gave poly{[N-(1-pyrrolidinycarbonyl)imino]tetra-methylene}. With benzyl chloride, on the other hand, no polymerization of 3 proceeded but, instead, the quantitative isomerization of 3 to 1,1′-carbonyldipyrrolidine took place. The polymerization mechanism of 2 and 3 as well as the isomerization mechanism of 3 were discussed with comparing them to the polymerization mechanism of five-membered pseudoureas. © 1977 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 933–945, 1997