Applied radiation research around a 15 MeV high-average-power linac

The Department of Subatomic and Radiation Physics of the University Gent is equipped with a 15 MeV 20 kW linear electron accelerator (linac) facility. In its present configuration the accelerator is used as a multipurpose apparatus for research in the fields of polymer chemistry, biomedical materials, medicine, food technology, dosimetry, solid state physics, agriculture and nuclear and radiation physics. We present an overview of both the various research projects around our linac facility involving radiation chemistry and physics and the specialised technologies facilitating this research.     

External damping losses in measuring the vibration damping properties in lightly damped specimens using transient time-domain methods

The contaminating effect of external damping sources to the overall measured damping of mechanical structures has always been an issue. Although these sources are qualitatively known, they are often not considered if damping properties are experimentally determined, yielding erroneous results. The aim of this paper is to quantify some of these undesired effects on the overall measured damping value. Free vibrations of steel plate specimens are used to list up several causes of external damping sources. As small modifications to the test setup may lead to totally different results, appropriate actions are offered to design a more accurate test setup. Known observations, such as the damping value’s dependence on the specimen size and the excitation level, are confirmed. Finally, it is shown that the damping capacity of one type of steel alloy can usually not be generalised to other steel alloys.     

Palladium‐Catalyzed Carbonylative α‐Arylation to β‐Ketonitriles

A carbonylative α‐arylation process employing unactivated nitriles for the first time is described. The reaction tolerates a range of (hetero)aryl iodides and several nitrile coupling partners. No prefunctionalization of the nitriles is necessary and the resulting β‐ketonitriles are obtained in good to excellent yields. The methodology also allows for a convenient ¹³C‐labelling of the generated carbonyl moiety.     

Cyclooctane Metathesis Catalyzed by Silica‐Supported Tungsten Pentamethyl [(SiO)W(Me)5]: Distribution of Macrocyclic Alkanes

Metathesis of cyclic alkanes catalyzed by the new surface complex [(?SiO)W(Me)₅] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula C_nH_2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.     

Electron paramagnetic resonance spectroscopy of Cr 3+ in hexagonal Cs 2 NaGaF 6 crystals

Powder samples of hydrothermally grown Cr 3+ -doped Cs 2 NaGaF 6 crystals have been investigated with electron paramagnetic resonance spectroscopy at X - (9.5 v GHz) and Q -band (34 v GHz). Analysis of the spectra clearly demonstrates that there are two distinct Cr 3+ centres in the Cs 2 NaGaF 6 crystal, having nearly identical g factors, but differing largely from the viewpoint of their zero field splitting. By using the 53 Cr hyperfine spectra observed with electron nuclear double resonance spectroscopy, it is deduced that these centres have opposite signs for the zero field splitting. The spectroscopic properties of the Cr 3+ centres in the isostructural Cs 2 NaGaF 6 and Cs 2 NaAlF 6 crystals are compared and discussed.     

Multi-frequency EPR study of radiation-induced radicals in tooth enamel

Human tooth enamel powders, unheated as well as heated prior to X -irradiation at room temperature, have been investigated by means of Q - and W -band Electron Paramagnetic Resonance (EPR). Upon irradiation of enamel, carbonate-derived radicals are generated. The simplest acquired EPR spectra in this study consist mainly of a group of three different \hbox{CO}_3^{3-} signals, with a very weak \hbox{CO}_2^{-} contribution. The characterisation of the paramagnetic species in enamel is quite important for the reliability of EPR applications ( e.g. , EPR retrospective dosimetry). The spectra from the heated samples reveal a striking resemblance with spectra from certain irradiated synthetic apatite powders. The spin Hamiltonian parameters obtained from the computer simulations of the Q - and W -band spectra are compared with those reported in the literature.     

Combined electron magnetic resonance and density functional theory study of 10 K X-irradiated beta-D-fructose single crystals

Primary free radical formations in fructose single crystals X-irradiated at 10 K were investigated at the same temperature using X-band Electron Paramagnetic Resonance (EPR), Electron Nuclear Double Resonance (ENDOR) and ENDOR induced EPR (EIE) techniques. ENDOR angular variations in the three principal crystallographic planes and a fourth skewed plane allowed the unambiguous determination of five proton hyperfine coupling tensors. From the EIE studies, these hyperfine interactions were assigned to three different radicals, labeled T1, T1* and T2. For the T1 and T1* radicals, the close similarity in hyperfine coupling tensors suggests that they are due to the same type of radical stabilized in two slightly different geometrical conformations. Periodic density functional theory calculations were used to aid the identification of the structure of the radiation-induced radicals. For the T1/T1* radicals a C3 centered hydroxyalkyl radical model formed by a net H abstraction is proposed. The T2 radical is proposed to be a C5 centered hydroxyalkyl radical, formed by a net hydrogen abstraction. For both radicals, a very good agreement between calculated and experimental hyperfine coupling tensors was obtained.     

The Growth of Co:ZnO/ZnO Core/Shell Colloidal Quantum Dots: Changes in Nanocrystal Size,Concentration and Dopant Coordination

We report a synthesis route for the growth of Co:ZnO/ZnO core/shell quantum dots. This procedure consists of successive steps, comprising the addition of diluted precursor salt solutions, and heat treatment at 50 °C. By deriving a relation between the extinction coefficient at 250 nm and the nanocrystal diameter, we are able to monitor changes in quantum dot concentration during shell growth. We found that a mechanism based on the nucleation of new particles after salt addition and subsequent Ostwald ripening during the heat treatment is responsible for the shell growth. Based on ligand‐field absorption spectroscopy, we demonstrate that the Co²⁺ ions adsorbed at the surface of Co:ZnO quantum dots are incorporated inside the ZnO shells. Finally, EPR spectroscopy indicates that the surface‐adsorbed Co²⁺ ions can be incorporated as substitutional as well as interstitial Co²⁺ ions.     

Radiation-induced radicals in glucose-1-phosphate. I. Electron paramagnetic resonance and electron nuclear double resonance analysis of in situ X-irradiated single crystals at 77 K

Electron magnetic resonance analysis of radiation-induced defects in dipotassium glucose-1-phosphate dihydrate single crystals in situ X-irradiated and measured at 77 K shows that at least seven different carbon-centered radical species are trapped. Four of these (R1-R4) can be fully or partly characterized in terms of proton hyperfine coupling tensors. The dominant radical (R2) is identified as a C1-centered species, assumedly formed by a scission of the sugar-phosphate junction and the concerted formation of a carbonyl group at the neighboring C2 carbon. This structure is chemically identical to a radical recently identified in irradiated sucrose single crystals. Radical species R1 and R4 most likely are C3- and C6-centered species, respectively, both formed by a net hydrogen abstraction. R3 is suggested to be chemically similar to but geometrically different from R4. Knowledge of the identity of the sugar radicals present at 77 K provides a first step in elucidating the formation mechanism of the phosphoryl radicals previously detected after X-irradiation at 280 K. In paper II, the chemical identity, precise conformation, and possible formation mechanisms of these radical species are investigated by means of DFT calculations and elementary insight into the radiation chemistry of sugar and sugar derivatives is obtained.