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When studying hazardous materials such as spent nuclear fuel (SNF), the minimisation of sample volumes is essential, together with the use of chemically-similar surrogates where possible. For example, the bulk behaviour of urania (UO2) can be mimicked by appropriately-engineered thin films of sufficient thickness, and inactive materials such as ceria (CeO2) can be used to study the effects within radioactive systems used to fuel nuclear fission. However, thin film properties are sensitive to the preparative method, many of which require the use of highly toxic precursors and specialised apparatus (e.g., chemical vapour deposition). To address this, we present the development of a flexible, tuneable, scalable method for the preparation of thin-film CeO2 SIMFUEL models with a thickness of ≈5 μm. The effects of γ irradiation (up to 100 kGy) and dopants including trivalent lanthanides (Ln3+) and simulant ε-particles on the structure and long-term leaching of these systems under SNF storage conditions were explored, alongside the context of this within further work. It was found that the sensitivity of CeO2 films to reduction upon irradiation, particularly in the presence of simulant ε-particles, resulted in increased leaching of Ce (as CeIII), while trivalent lanthanides (Nd3+ and Eu3+) had a minimal effect on Ce leaching.

Molecular mechanisms based on photo-physical processes involving dietary carotenoids, their radicals, and the role of oxygen are discussed and used to suggest explanations of the poorly understood and often contradictory results related to mainly skin and vision. Differing and conflicting efficiencies of singlet oxygen reactions with carotenoids of biological importance are discussed in environments from ‘simple’ organic solvents to single He La cells. A range of free radical reactions with carotenoids, and the corresponding radicals of the carotenoids themselves, are compared and used to explain the switch from beneficial to deleterious processes involving dietary carotenoids and to unravel their differing functions; of particular interest is a possible role for vitamin C.

In the retina, retinoids involved in vision are under constant threat of oxidation, and their oxidation products exhibit deleterious properties. Using pulse radiolysis, this study determined that the bimolecular rate constants of scavenging cation radicals of retinoids by taurine are smaller than 2 × 107 M−1s−1 whereas lutein scavenges cation radicals of all three retinoids with the bimolecular rate constants approach the diffusion-controlled limits, while zeaxanthin is only 1.4–1.6-fold less effective. Despite that lutein exhibits greater scavenging rate constants of retinoid cation radicals than other antioxidants, the greater concentrations of ascorbate in the retina suggest that ascorbate may be the main protectant of all visual cycle retinoids from oxidative degradation, while α-tocopherol may play a substantial role in the protection of retinaldehyde but is relatively inefficient in the protection of retinol or retinyl palmitate. While the protection of retinoids by lutein and zeaxanthin appears inefficient in the retinal periphery, it can be quite substantial in the macula. Although the determined rate constants of scavenging the cation radicals of retinol and retinaldehyde by dopa-melanin are relatively small, the high concentration of melanin in the RPE melanosomes suggests they can be scavenged if they are in proximity to melanin-containing pigment granules.

This article describes the radiation facilities and associated sample preparation, management, and analysis equipment currently in place at the Dalton Cumbrian Facility, a facility which opened in 2011 to support the UK’s nuclear industry. Examples of measurements performed using these facilities are presented to illustrate their versatility and the breadth of research they make possible. Results are presented from research which furthers our understanding of radiation damage to polymeric materials, radiolytic yield of gaseous products in situations relevant to nuclear materials, radiation chemistry in light water reactor cooling systems, material chemistry relevant to immobilization of nuclear waste, and radiation-induced corrosion of fuel cladding elements. Applications of radiation chemistry relevant to health care are also described. Research concerning the mechanisms of radioprotection by dietary carotenoids is reported. An ongoing open-labware project to develop a suite of modular sample handling components suited to radiation research is described, as is the development of a new neutron source able to provide directional beams of neutrons.

Carotenoid pigments, particularly β-carotene and lycopene, are consumed in human foodstuffs and play a vital role in maintaining health. β-carotene is known to quench singlet oxygen and can have strong antioxidant activity. As such, it was proposed that β-carotene might reduce the risk of cancer. Epidemiological studies found inverse relationships between cancer risk and β-carotene intake or blood levels. However, clinical trials failed to support those findings and β-carotene supplementation actually increased lung cancer incidence in male smokers. Early experimental animal studies found dietary β-carotene inhibited UV-induced skin cancers. Later studies found that β-carotene supplementation exacerbated UV-carcinogenic expression. The discrepancies of these results were related to the type of diet the animals consumed. Lycopene has been associated with reduced risk of lethal stage prostate cancer. Other carotenoids, e.g., lutein and zeaxanthin, play a vital role in visual health. Numerous studies of molecular mechanisms to explain the carotenoids’ mode of action have centered on singlet oxygen, as well as radical reactions. In cellular systems, singlet oxygen quenching by carotenoids has been reported but is more complex than in organic solvents. In dietary β-carotene supplement studies, damaging pro-oxidant reactivity can also arise. Reasons for this switch are likely due to the properties of the carotenoid radicals themselves. Understanding singlet oxygen reactions and the anti-/pro-oxidant roles of carotenoids are of importance to photosynthesis, vision and cancer.

Retinoids are present in human tissues exposed to light and under increased risk of oxidative stress, such as the retina and skin. Retinoid cation radicals can be formed as a result of the interaction between retinoids and other radicals or photoexcitation with light. It has been shown that such semi-oxidized retinoids can oxidize certain amino acids and proteins, and that α-tocopherol can scavenge the cation radicals of retinol and retinoic acid. The aim of this study was to determine (i) whether β-, γ-, and δ-tocopherols can also scavenge these radicals, and (ii) whether tocopherols can scavenge the cation radicals of another form of vitamin A—retinal. The retinoid cation radicals were generated by the pulse radiolysis of benzene or aqueous solution in the presence of a selected retinoid under oxidizing conditions, and the kinetics of retinoid cation radical decays were measured in the absence and presence of different tocopherols, Trolox or urate. The bimolecular rate constants are the highest for the scavenging of cation radicals of retinal, (7 to 8) × 109 M−1·s−1, followed by retinoic acid, (0.03 to 5.6) × 109 M−1·s−1, and retinol, (0.08 to 1.6) × 108 M−1·s−1. Delta-tocopherol is the least effective scavenger of semi-oxidized retinol and retinoic acid. The hydrophilic analogue of α-tocopherol, Trolox, is substantially less efficient at scavenging retinoid cation radicals than α-tocopherol and urate, but it is more efficient at scavenging the cation radicals of retinoic acid and retinol than δ-tocopherol. The scavenging rate constants indicate that tocopherols can effectively compete with amino acids and proteins for retinoid cation radicals, thereby protecting these important biomolecules from oxidation. Our results provide another mechanism by which tocopherols can diminish the oxidative damage to the skin and retina and thereby protect from skin photosensitivity and the development and/or progression of changes in blinding retinal diseases such as Stargardt’s disease and age-related macular degeneration (AMD).

The caesium radioisotopes 134Cs, 135Cs, and 137Cs are highly problematic medium-lived species produced during nuclear fission, due to their high radioactivity and environmental mobility. While many ion exchange materials can readily isolate Cs+ ions from neutral or basic aqueous solutions, only ammonium phosphomolybdate (AMP) functions effectively in acidic conditions, removing caesium even down to trace levels. Composites of AMP in a porous polymeric support such as polyacrylonitrile (PAN) can be used to selectively remove Cs+ ions from acidic aqueous decontamination liquors as well as other liquid wastes, and are promising for the isolation of Cs+ isotopes in spent fuel reprocessing. While both AMP and PAN have demonstrable acid stability, and PAN has known resistance to gamma radiation, AMP-PAN composites have received only a limited analysis of their physiochemical and ion exchange performance following irradiation. In this publication, we explore the effect of high levels of gamma irradiation on the ion exchange properties of AMP and AMP-PAN as a Cs+-selective adsorbent under spent fuel dissolver liquor concentrations and acidity. We demonstrate no significant reduction in performance with respect to uptake kinetics or capacity upon irradiation, abiding by the same absorption mechanism observed in the established literature.

The first examples of vinylidene complexes of the cycloheptatrienyl tungsten system [W(CCHR)(dppe)(η-C7H7)]+(dppe = Ph2PCH2CH2PPh2; R = H, 3; Ph, 4; C6H4-4-Me, 5) have been synthesised by reaction of [WBr(dppe)(η-C7H7)], 1, with terminal alkynes HCCR; a one-pot synthesis of 1from [WBr(CO)2(η-C7H7)] facilitates its use as a precursor. The X-ray structure of 4[PF6] reveals that the vinylidene ligand substituents lie in the pseudo mirror plane of the W(dppe)(η-C7H7) auxiliary (vertical orientation) with the phenyl group located synto the cycloheptatrienyl ring. Variable temperature 1H NMR investigations on [W(CCH2)(dppe)(η-C7H7)][PF6], 3, estimate the energy barrier to rotation about the WCαbond as 62.5 ± 2 kJ mol−1; approximately 10 kJ mol−1greater than for the molybdenum analogue. Deprotonation of 4and 5with KOButyields the alkynyls [W(CCR)(dppe)(η-C7H7)] (R = Ph, 6; C6H4-4-Me, 7) which undergo a reversible one-electron oxidation at a glassy carbon electrode in CH2Cl2with E½values approximately 0.12 V negative of Mo analogues. The 17-electron radicals [6]+and [7]+have been investigated by spectroelectrochemical IR, UV-visible and EPR methods. The electronic structures of representative vinylidene (3) and alkynyl (6) complexes have been investigated at the B3LYP/Def2-SVP level. In both cases, electronic structure is characterised by a frontier orbital with significant metal dz2character and this dominates the structural and spectroscopic properties of the system. [ABSTRACT FROM AUTHOR]

In situ31P NMR spectroscopic studies of the reaction of the primary diphosphine 1,2-(PH2)2-C6H4with the mixed-metal base system nBuLi/Sb(NMe2)3, combined with X-ray structural investigations, strongly support a mechanism involving a series of deprotonation steps followed by antimony-mediated reductive C–P bond cleavage. The central intermediate in this reaction is the tetraphosphide dianion [C6H4P2]22−([4]) from which the final products, the 1,2,3-triphospholide anion [C6H4P3]−(3) and [PhPHLi] (8·Li), are evolved. An EPR spectrocopic study suggests that homolytic C–P bond cleavage is likely to be involved in this final step. [ABSTRACT FROM AUTHOR]

The 2c–2e−P–P bonded dimers [(CH)2(NR)2P]2dissociate in solution to give the persistent new 7π radicals [(CH)2(NR)2P], which are isoelectronic with the well known S/N thiazolyl radicals. [ABSTRACT FROM AUTHOR]