The application of synchrotron radiation and in particular X-ray absorption spectroscopy to matrix isolated species

This review provides comprehensive coverage of the application of X-ray absorption spectroscopy (XAS, XAFS, EXAFS, and XANES) to matrix isolated species. As X-ray absorption spectroscopy provides structural data without the need for long range order it has been applied to a large number of systems to yield unique structural data about both the matrix isolated species, and their interactions with the matrix host. To put the work into perspective there is a tutorial introduction to the theoretical background of X-ray absorption spectroscopy, data content, processing and analysis. In addition there is brief coverage of the use of other synchrotron radiation techniques for the study of matrix isolated species, and a consideration of future perspectives

Structure and electronic properties of the quasi-one-dimensional Ba₂Co₁₋ₓZnₓS₃ series

This work focuses on the structure and physical properties of the solid solution Ba₂Co₁₋ₓZnₓS₃ (0 ≤ x ≤ 1), a family of quasi-one-dimensional sulfides with end members Ba₂CoS₃ and Ba₂ZnS₃. The structure of selected compounds with increasing Zn²⁺ content has been analysed using, neutron diffraction, TEM and EXAFS and the physical properties via magnetic susceptibility and resistivity measurements. The progressive substitution of the non-magnetic Zn²⁺ cation for Co²⁺ rapidly destroys the antiferromagnetic transition present at 46 K in the quasi one-dimensional Ba₂CoS₃, leading to paramagnetic behaviour down to the lowest investigated temperature (5K) for compounds with x > 0.25. For compounds with x ≥ 0.4, a pure CW regime is recovered around 300 K, yielding effective moments consistent with the g factor of the tetrahedrally coordinated Co²⁺ previously determined for Ba₂CoS₃. The Zn²⁺/Co²⁺ substitution also removes the metallic-like behaviour of Ba₂CoS₃ causing an increase in the value of the resistivity with all the Ba₂Co₁₋ₓZnₓS₃ compounds showing semiconducting behaviour. The negative magnetoresistance of Ba₂CoS₃ is improved by the Zn²⁺/Co²⁺ substitution, with values of – 6% for Ba₂Co₀.₇₅Zn₀.₂₅S₃, – 9% for Ba₂Co₀.₅Zn₀.₅S₃ and – 8% for Ba₂Co₀.₂₅Zn₀.₇₅S₃. However, there does not seem to be a correlation between the values of the resistivity and the magnetoresistance and the content of Zn²⁺, leading to the hypothesis that transport properties may be linked more closely to extrinsic properties

Experimental evidence for the molecular molybdenum fluorides MoF to MoF6: a matrix isolation and DFT investigation

All of the molecular molybdenum fluorides, MoF to MoF6, have been synthesised from the reaction of thermally evaporated molybdenum atoms with fluorine molecules and atoms, trapped in argon matrices, and characterised by matrix isolation IR spectroscopy in conjunction with DFT calculations. This includes the first spectroscopic characterisation of MoF and MoF2, the latter of which is very bent with a bond angle of ca. 133°, the reassignment of the IR spectral data for trigonal planar MoF3, the observation of tetrahedral MoF4, the assignment of new features to MoF5 which displays a Jahn-Teller distorted trigonal bipyramidal structure, and octahedral MoF6. When the reaction of fluorine molecules and heated molybdenum is allowed to take place, MoF6, MoF4 and (MoF5)3 are observed

A matrix isolation and computational study of molecular palladium fluorides : does PdF₆ exist?

Palladium atoms generated by thermal evaporation and laser ablation were reacted with and trapped in F₂ /Ar, F₂ /Ne, and neat F₂ matrices. The products were characterized by electronic absorption and infrared spectroscopy, together with relativistic density functional theory calculations as well as coupled cluster calculations. Vibrational modes at 540 and 617 cm⁻¹ in argon matrices were assigned to molecular PdF and PdF₂ , and a band at 692 cm⁻¹ was assigned to molecular PdF₄ . A band at 624 cm⁻¹ can be assigned to either PdF₃ or PdF₆, with the former preferred from experimental considerations. Although calculations might support the latter assignment, our conclusion is that in these detailed experiments there is no convincing evidence for PdF₆

A review of co-morbidity between infectious and chronic disease in Sub Saharan Africa: TB and Diabetes Mellitus, HIV and Metabolic Syndrome, and the impact of globalization

BACKGROUND: Africa is facing a rapidly growing chronic non-communicable disease burden whilst at the same time experiencing continual high rates of infectious disease. It is well known that some infections increase the risk of certain chronic diseases and the converse. With an increasing dual burden of disease in Sub Saharan Africa the associations between diseases and our understanding of them will become of increased public health importance. AIMS: In this review we explore the relationships reported between tuberculosis and diabetes mellitus, human immunodeficiency virus, its treatment and metabolic risk. We aimed to address the important issues surrounding these associations within a Sub Saharan African setting and to describe the impact of globalization upon them. FINDINGS: Diabetes has been associated with a 3-fold incident risk of tuberculosis and it is hypothesised that tuberculosis may also increase the risk of developing diabetes. During co-morbid presentation of tuberculosis and diabetes both tuberculosis and diabetes outcomes are reported to worsen. Antiretroviral therapy for HIV has been associated with an increased risk of developing metabolic syndrome and HIV has been linked with an increased risk of developing both diabetes and cardiovascular disease. Globalization is clearly related to an increased risk of diabetes and cardiovascular disease. It may be exerting other negative and positive impacts upon infectious and chronic non-communicable disease associations but at present reporting upon these is sparse. CONCLUSION: The impact of these co-morbidities in Sub Saharan Africa is likely to be large. An increasing prevalence of diabetes may hinder efforts at tuberculosis control, increasing the number of susceptible individuals in populations where tuberculosis is endemic, and making successful treatment harder. Roll out of anti-retroviral treatment coverage within Sub Saharan Africa is an essential response to the HIV epidemic however it is likely to lead to a growing number of individuals suffering adverse metabolic consequences. One of the impacts of globalization is to create environments that increase both diabetes and cardiovascular risk but further work is needed to elucidate other potential impacts. Research is also needed to develop effective approaches to reducing the frequency and health impact of the co-morbidities described here

How does iron interact with sporopollenin exine capsules? An X-ray absorption study including microfocus XANES and XRF imaging

Sporopollenin exine capsules (SECs) derived from plant spores and pollen grains have been proposed as adsorption, remediation and drug delivery agents. Despite many studies there is scant structural data available. This X-ray absorption investigation represents the first direct structural data on the interaction of metals with SECs and allows elucidation of their structure–property relationships. Fe K-edge XANES and EXAFS data have shown that the iron local environment in SECs (derived from Lycopodium clavatum) reacted with aqueous ferric chloride solutions is similar to that of ferrihydrite (FeOOH) and by implication ferritin. Fe Kα XRF micro-focus experiments show that there is a poor correlation between the iron distribution and the underlying SEC structure indicating that the SEC is coated in the FeOOH material. In contrast, the Fe Kα XRF micro-focus experiments on SECs reacted with aqueous ferrous chloride solutions show that there is a very high correlation between the iron distribution and the SEC structure, indicating a much more specific form of interaction of the iron with the SEC surface functional groups. Fe K-edge XANES and EXAFS data show that the FeII can be easily oxidised to give a structure similar to, but not identical to that in the FeIII case, and that even if anaerobic conditions are used there is still partial oxidation to FeIII

X-ray absorption study of platinum and palladium atoms in argon matrices: Evidence for platinum in a substitutional site and a short Pd–Ar interaction

The Pt L3-edge X-ray absorption spectrum of Pt atoms generated in a hollow cathode sputtering device and trapped in an Ar matrix yielded a PtAr distance of 3.78(4) Å with a coordination number of ca. 12 which confirms the evidence from electronic absorption spectroscopy that Pt atoms occupy a substitutional site in the Ar lattice. These data also yield a van der Waals radius for Pt atoms of 1.90 Å. The Pd K-edge X-ray absorption spectrum of sputtered Pd atoms trapped in an Ar matrix is radically different to that for Pt atoms. The analysis reveals a much shorter PdAr distance of 2.53(3) Å with a low coordination number close to 1, together with an “atomic” EXAFS like spectrum with no significant oscillations indicating the absence of any well defined nearest neighbours. On annealing to 25 K, the 2.53(3) Å interaction essentially disappears to leave the “atomic” spectrum. The featureless “atomic” spectrum is associated with Pd 1S0 atoms in an argon substitutional site, or other site such as a grain boundary with high disorder. The short PdAr distance of 2.53(3) Å is consistent with Pd atoms with a 1S0 atomic ground state in an interstitial octahedral site, the formation of a PdArn exciplex with a short PdAr distance, or the formation of a more formal palladium argon compound such as PdAr2. Although it is not possible to be definitive, the most likely carrier of the short PdAr distance is a PdArn exciplex. What is clear is that this work has identified a short PdAr interaction for the first time

Soft X-ray Photochemistry at the L₂,₃-edges in K₃[Fe(CN)₆], [Co(acac)₃] and [Cp₂Fe][BF₄]

Soft X-ray photoreduction has been observed in K3[Fe(CN)6], [Co(acac)3] and [Cp2Fe][BF4]

Searching for Monomeric Nickel Tetrafluoride: Unravelling Infrared Matrix Isolation Spectra of Higher Nickel Fluorides

Binary transition metal fluorides are textbook examples combining complex electronic features with most fundamental molecular structures. High‐valent nickel fluorides are among the strongest known fluorinating and oxidizing agents, but there is a lack of experimental structural and spectroscopic investigations on molecular NiF3 or NiF4. Apart from their demanding synthesis, also their quantum‐chemical description is difficult due to their open shell nature and low‐lying excited electronic states. Distorted tetrahedral NiF4 (D2d) and trigonal planar NiF3 (D3h) molecules were produced by thermal evaporation and laser ablation of nickel atoms in a fluorine/noble gas mixture and spectroscopically identified by a joint matrix‐isolation and quantum‐chemical study. Their vibrational band positions provide detailed insights into their molecular structures