Mediatizing the naked truth - a re-conceptualisation of the ideal beach body in contemporary media

This theoretical paper aims to deliver a new and enhanced definition of the ideal beach body based upon an extensive interdisciplinary literature review. It argues that the beach body theoretically comprises of two basic forms: (1) The real beach body as it appears on the beach and (2) the mediatized beach body, i.e. the one that prevails in the media

Differential Photoelectron Holography: A New Approach for Three-Dimensional Atomic Imaging

We propose differential holography as a method to overcome the long-standing forward-scattering problem in photoelectron holography and related techniques for the three-dimensional imaging of atoms. Atomic images reconstructed from experimental and theoretical Cu 3p holograms from Cu(001) demonstrate that this method suppresses strong forward-scattering effects so as to yield more accurate three-dimensional images of side- and back-scattering atoms.Comment: revtex, 4 pages, 2 figure

Iridium complexes of the conformationally rigid IBioxMe4Ligand : hydride complexes and dehydrogenation of cyclooctene

A method for accessing the formally 14 VE iridium(III) hydride fragment {Ir(IBioxMe4)2(H)2}+ (2), containing the conformationally rigid NHC ligand IBioxMe4, is reported. Hydrogenation of trans-[Ir(IBioxMe4)2(COE)Cl] (1) in the presence of excess Na[BArF4] leads to the formation of dimeric [{Ir(IBioxMe4)2(H)2}2Cl][BArF4] (3), which is structurally fluxional in solution and acts as a reservoir of monomeric 2 in the presence of excess halogen ion abstractor. Stable dihydride complexes trans-[Ir(IBioxMe4)2(2,2′-bipyridine)(H)2][BArF4] (4) and [Ir(IBioxMe4)3(H)2][BArF4] (5) were subsequently isolated through in situ trapping of 2 using 2,2′-bipyridine and IBioxMe4, respectively, and fully characterized. Using mixtures of 3 and Na[BArF4] as a latent source of 2, the reactive monomeric fragment’s reactivity was explored with excess ethylene and cyclooctene, and trans-[Ir(IBioxMe4)2(C2H4)2][BArF4] (6) and cis-[Ir(IBioxMe4)2(COD)][BArF4] (7) were isolated, respectively, through sacrificial hydrogenation of the alkenes. Complex 6 is notable for the adoption of a very unusual orthogonal arrangement of the trans-ethylene ligands in the solid state, which has been analyzed computationally using energy and charge decomposition (EDA-NOCV). The formation of 7 via transfer dehydrogenation of COE highlights the ability to partner IBioxMe4 with reactive metal centers capable of C–H bond activation, without intramolecular activation. Reaction of 7 with CO slowly formed trans-[Ir(IBioxMe4)2(CO)2][BArF4] (8), but the equivalent reaction with bis-ethylene 6 was an order of magnitude faster, quantifying the strong coordination of COD in 7

Primary and secondary care collaboration in clinical research

This is the final version. Available from the Royal College of Physicians via the DOI in this recordMore patients are seen in primary care than in any other part of the health system in the UK. Our NHS datasets are the envy of the world and provide us with huge opportunities to support our patients and populations. In this paper, we demonstrate the breadth of primary care research, recruitment and delivery options. We show how research can affect many different aspects of patient care and demonstrate, through the delivery and publication of game-changing research, the ability of recruitment in primary care to answer questions that are relevant to secondary care activity. Indeed, these complex and innovative study designs and their collaborative delivery across the multitude of diseases (acute and chronic) show the strength of primary care. Collaboration across boundaries, specialties and healthcare settings will provide increased opportunities for clinical research development and, most importantly, deliver the highest quality research to support our patients.National Institute for Health and Care Research (NIHR

Rhodium(I) and Iridium(I) complexes of the conformationally rigid IBioxMe4Ligand : computational and experimental studies of unusually tilted NHC coordination geometries

Computational methods have been used to analyze distorted coordination geometries in a coherent range of known and new rhodium(I) and iridium(I) complexes containing bioxazoline-based NHC ligands (IBiox). Such distortions are readily placed in context of the literature through measurement of the Cnt(NHC)–CNCN–M angle (ΘNHC; Cnt = ring centroid). On the basis of restricted potential energy calculations using cis-[M(IBioxMe4)(CO)2Cl] (M1; M = Rh, Ir), in-plane (yawing) tilting of the NHC was found to incur significantly steeper energetic penalties than orthogonal out-of-plane (pitching) movement, which is characterized by noticeably flat potential energy surfaces. Energy decomposition analysis (EDA) of the ground-state and pitched structures of M1 indicated only minor differences in bonding characteristics. In contrast, yawing of the NHC ligand is associated with a significant increase in Pauli repulsion (i.e., sterics) and reduction in M→NHC π back donation, but is counteracted by supplemental stabilizing bonding interactions only possible due to the closer proximity of the methyl substituents with the metal and ancillary ligands. Aided by this analysis, comparison with a range of carefully selected model systems and EDA, distorted coordination modes in trans-[M(IBioxMe4)2(COE)Cl] (M2; M = Rh, Ir) and [M(IBioxMe4)3]+ (M3; M = Rh, Ir) have been rationalized. Steric interactions were identified as the major contributing factor and are associated with a high degree of NHC pitching. In the case of Rh3, weak agostic interactions also contribute to the distortions, particularly with respect to NHC yawing, and are notable for increasing the bond dissociation energy of the distorted ligands. Supplementing the computational analysis, an analogue of the formally 14 VE Rh(I) species Rh3 bearing the cyclohexyl-functionalized IBiox6 ligand ([Rh(IBiox6)3]+, Rh3-Cy) was prepared and found to exhibit an exceptionally distorted NHC ligand (ΘNHC = 155.7(2)°) in the solid state

Feasibility tests of transmission x-ray photoelectron emission microscopy of wet samples

We performed feasibility tests of photoelectron emission spectromicroscopy of wet samples in the water window (285-532 eV) soft x-ray spectral region. Water was successfully confined in an ultrahigh vacuum compatible compartment with x-ray transparent sides. This water cell was placed in the MEPHISTO spectromicroscope in a transmission geometry, and complete x-ray absorption spectra of the water window region were acquired. We also show micrographs of test samples, mounted outside of the compartment, and imaged through the water. This technique can be used to study liquid chemistry and, at least to the micron level, the microstructure of wet samples. Possibilities include cells in water or buffer, proteins in solution, oils of tribological interest, liquid crystals, and other samples not presently accessible to the powerful x-ray photoelectron emission spectromicroscopy technique

Influence of Ring Contraction on the Electronic Structure of Nickel Tetrapyrrole Complexes: Corrole vs Porphyrin

The influence of the contracted corrole macrocycle, in comparison to the larger porphyrin macrocycle, on the electronic structure of nickel was studied with X-ray and ultraviolet photoelectron spectroscopy (XPS, UPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Synthesis and in situ characterization of the Ni complexes of octaethylporphyrin (NiOEP) and hexaethyldimethylcorrole (NiHEDMC) were performed in ultra-high vacuum. XPS and NEXAFS spectra reveal a +2 oxidation state and a low-spin d8 electron configuration of Ni in both complexes, despite the formal trianionic nature of the corrole ligand. UPS, in combination with density functional theory (DFT) calculations, support the electronic structure of a Ni(II) corrole with a π-radical character of the ligand. The NEXAFS spectra also reveal differences in the valence electronic structure, which are attributed to the size mismatch between the small Ni(II) center and the larger central cavity of NiOEP. Analysis of the gas-phase structures shows that the Ni−N bonds in NiOEP are 4%–6% longer than those in NiHEDMC, even when NiOEP adopts a ruffled conformation. The individual interactions that constitute the Ni−ligand bond are altogether stronger in the corrole complex, according to bonding analysis within the energy decomposition analysis and the natural orbitals for chemical valence theory (EDA-NOCV)