Radiochemical methods in nuclear waste management

Radiochemical techniques play an important role in nuclear waste management studies at the Centre for Analytical Research in the Environment. Current research includes the measurement of atmospheric emissions from a reprocessing plant, modelling of environmental pathways, and evaluation of reactor materials for the prediction of releases from ultimate disposal sites. A radiochemical separation procedure has been developed for¹²⁹I, which has been applied to a study of emissions from the Sellafield nuclear reprocessing plant. Atmospheric emissions, rainfall, grass, milk and wild food are analysed to model the ultimate fate of¹²⁹I. A new procedure has been developed for measuring sub-ppm concentrations of chlorine in archive steel samples as part of programme to produce an inventory of arisings of³⁶Cl from nuclear power stations. The method has been extended to other reactor materials and this paper describes the application of the radiochemical method for Magnox alloys, mild steel and cast iron.     

Regioselective cyclomanganation of Schiff bases. An unexpected effect of chloro substituents

In this paper we describe the synthesis of new metallacycles by the cyclomanganation reaction of benzyl-benzylidene-amines by using [MnMe(CO)₅] as metallating agent. These ligands can undergo metallation on different aromatic carbon atoms but no important differences have been found in the regioselectivity of the process, that can be related to the electronic effect of the substituents, and in all the cases studied the endo-cyclomanganated complexes of para-substituted imines have been obtained. The corresponding exo-metallacycles were obtained by reaction of [MnMe(CO)₅] on the imine 2,6-Cl₂C₆H₃CHNCH₂Ph and 2,4,6-Me₃C₆H₂CHNCH₂Ph, derived from 2,6-dichlorobenzaldehyde and 2,4,6-trimethylbenzaldehyde, respectively.The results described suggest that the mechanism of the cyclomanganation is similar to that of cyclopalladation and it can be proposed that cyclomanganation takes place by the formation of a four-centered transition state, involving the C-H and Mn-C_acetyl bonds, in the acetyl coordination complex formed in the first step of the reaction.     

Bis(1,2-bis(diphenylphosphino)ethane)tungsten(0) Complexes Containing Electron-Saturated Metal Centers and Singly-Coordinated Bridging Ligands

Reaction of 1,4-diisocyanobenzene or 4-isocyanobenzonitrile with trans-W(N(2))(2)(DPPE)(2) (DPPE = 1,2-bis(diphenylphosphino)ethane) produced cis-WL(2)(DPPE)(2), where L = 1,4-diisocyanobenzene or 4-isocyanobenzonitrile. cis-(CNC(6)H(4)NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P&onemacr;, with a = 12.848(3) ?, b = 13.596(3) ?, c = 19.072(3) ?, alpha = 78.99(2) degrees, beta = 70.66(2) degrees, gamma = 65.26(2) degrees, V = 2849.8(11) ?(3), and Z = 2. cis-(NCC(6)H(4)NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P&onemacr;, with a = 12.712(3) ?, b = 13.700(3) ?, c = 19.109(3) ?, alpha = 77.91(2) degrees, beta = 70.63(2) degrees, gamma = 64.76(2) degrees, V = 2830.7(13) ?(3), and Z = 2. Both compounds possess a distorted octahedral geometry about the metal center, with the two isocyanide ligands cis to one another. The isocyanide ligands are substantially bent along the CNC axis of the isocyanide group coordinated to tungsten. For the complex containing the symmetric ligand, CNC(6)H(4)NC, the mean CNC angle for the coordinated end of the isocyanide is 139.1(11) degrees, the average W-C bond length is 1.86(1) ?, and the C&tbd1;N bond lengths have a mean value of 1.30(2) ?. These data indicate substantial back-donation from an electron-saturated tungsten atom. This is supported spectroscopically, with substantial shifts to lower wavenumbers for the C-N stretching frequencies of the coordinated isocyanide groups. Similar trends are observed in cis-(NCC(6)H(4)NC)(2)W(DPPE)(2). Both compounds contain electron-rich metals surrounded by large ligands which apparently protect the metals from atmospheric oxidation. The isocyanide ligands in both complexes contain a second coordinating group pointing away from the metal into the environment surrounding the molecules, providing the potential for polymetallic complexes containing metals in a variety of oxidation states.     

Study of the direct detection of crosslinks in hydrocarbons by 13C-NMR. I. Preparation and characterization of model compound 1,1,2,2-tetra(tridecyl) ethane

The present series of papers is the commencement of a study aimed at the direct detection and quantification of crosslinking in hydrocarbons with the ultimate objective of a precise study of radiation-induced crosslinking in polyethylene. The subject of the present paper is the synthesis of a model compound containing a crosslink in a well-defined position sufficiently remote from the chain ends to be representative of an average crosslink in polyethylene. Such a compound in the form of 1,1,2,2-tetra(tridecyl) ethane has been synthetized and isolated in pure form in the course of the present work. Melting points and x-ray spacings of the new compound have been determined, and a comparison with the corresponding linear paraffins has been made. Effects are noted relating to the influence of molecular shape on the GPC elution volume, in which context an observation on a cyclic paraffin is also quoted.     

Chemicals from forest products by supercritical fluid extraction

Supercritical acetone or methanol extraction of wood gave liquid products with a maximum yield of 74%. Approximately 5% of these complex products was identified as substituted guaiacols and levoglucosan. Acetone extract could substitute for 30% of the phenol in phenolic resins.

Resin and fatty acids were extracted from southern pine and waxes from Douglas-fir bark using supercritical carbon dioxide, nitrous oxide, propane or ethylene. Of these, propane and nitrous oxide gave the best yields.     

Biosynthesis of 4-methylproline in cyanobacteria: cloning of nosE and nosF genes and biochemical characterization of the encoded dehydrogenase and reductase activities

The biosynthesis of the unusual amino acid 4-methylproline in the Nostoc genus of cyanobacteria was investigated on the genetic and enzymatic level. Two genes involved in the biosynthesis were cloned and the corresponding enzymes, a zinc-dependent long-chain dehydrogenase and a Delta(1)-pyrroline-5-carboxylic acid (P5C) reductase homologue, were overexpressed in Escherichia coli and biochemically characterized. Putative substrates were synthesized to test enzyme substrate specificities, and deuterium labeling studies were carried out to reveal the stereospecificities of the enzymatic reactions with respect to the substrates as well as to the coenzymes.     

Synthesis of tricyclic phospholene oxides by cycloaddition of phosphorus halides with heterocyclic analogs of 1-vinyl-3,4-dihydronaphthalenes

Replacement of C-4 with a hetero substituent (NR,O,S) in the 1-vinyl-3,4-dihydronaphthalene system has provided a new type of diene for participation in the McCormack cycloaddition reaction with P(III) halides. The tricyclic phospholene oxides so obtained are the first to bear an additional heteroatom in the ring system. 1,2-Dihydro-7-methoxy-1-(p-toluenesulfonyl)-4-vinylquinoline is a stable solid that reacts with methylphosphonous dichloride to give, after hydrolysis of the cycloadduct, the 1,2,4,5-tetrahydro-1H-phospholo-[2,3-c]quinoline ring system. The dihydroquinoline moiety was aromatized by detosylation with potassium t-butoxide. The tendency of 4-vinyl-2H-benzopyran to dimerize was a serious complication in its use, and the cycloaddition with methylphosphonous dichloride proceeded only in low yield. The product, a 2,3,3a,4-tetra-hydrobenzo[3,2-d]pyran derivative, was a stable, easily purified and characterized substance. 4-Vinyl-2H-benzo[b]thiopyran was more stable than the pyran, but the phospholo derivative from reaction with methylphosphonous dichloride was more difficult to purify. All products were characterized by ¹³C-nmr spectroscopy.