Crystal Structure of the VV Dimer [V2O2(μ-O)(dmpp)2(OCH3)2] and Its Equilibrium with the VV Trimer [V3O3(μ-O)3(dmpp)3(H2O)](H2O)2 in Methanol/Water Solutions

The behaviour of the cyclic trimeric VV complex [V3O3(μ-O)3(dmpp)3(H2O)](H2O)2, V3L3, (L = Hdmpp = 3-hydroxy-1,2-dimethyl-4-pyridinone) was studied in methanol and methanol/water solutions by using 51V and 1D- and 2D 1H NMR spectroscopy. Red crystals, isolated from a highly concentrated methanol solution of the trimeric complex, were analysed by X-ray crystallography. The solid-state structure of the compound showed the presence of a new dinuclear VV cluster and allowed for its formulation as a [V2O2(μ-O)(dmpp)2(OCH3)2] complex, V2Y2L2 (Y = OCH3). This complex crystallises in the monoclinic system: P21/c, a = 8.4573(11) Å, b = 15.034(2) Å and c = 15.849(2) Å, β = 105.300(2)°, V = 1943,7(4) Å3, Z = 2, and R1(wR2) = 0.0492(0.1706). The trimer V3L3 complex dissolved in a dry methanol solution fully decomposes, as shown by the 51V NMR signals at -388, -450 and -551 ppm, which are assigned to a monomer complex [VO(OMe)(dmpp)2] (VYL2), the dimer V2Y2L2 and the monomethyl ester of monovanadate, V1Y (V1 = monovanadate; Y = OCH3), respectively. In methanol/water solutions, a new 51V NMR signal appears at delta = -492 ppm, which is assigned to the [VO2(dmpp)(H2O)2] (VL) complex. When the percentage of water in the mixture increases, the relative intensities of the V2Y2L2 and V1Y signals decrease sharply, and a broad signal at -488 ppm appears, corresponding to the original VV trimer complex, which is the only species present in 94 % water. A temperature-dependent 1H NMR study of a CD3OD solution of V3L3 confirmed the presence, at room temperature, of the dinuclear V2L2 complex and the VL2 species. At temperatures below 0 °C down to -50 °C, the appearance of new signals reflects the presence of isomers for the V2Y2L2 and VYL2 species with different stabilities and symmetries. 2D 1H homonuclear NMR exchange experiments (EXSY) allowed us to establish the isomeric equilibria that take place in solution, and indicates intramolecular exchange between the two ligands of the major isomer of VYL2 and intermolecular exchange between the major and minor isomers of species of different nuclearity, V2Y2L2 and VYL2. However, no evidence was found for intermolecular exchange between the major isomers and between the minor isomers of species of different nuclearity or between isomers of species of the same nuclearity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006

Trends in seasonal influenza vaccine uptake during pregnancy in Western Australia: Implications for midwives

Background: Antenatal influenza vaccination is an important public health intervention for preventing serious illness in mothers and newborns, yet uptake remains low. Aim: To evaluate trends in seasonal influenza vaccine coverage and identify determinants for vaccination among pregnant women in Western Australia. Methods: We conducted an annual telephone survey in a random sample of post-partum women who delivered a baby in Western Australia between 2012 and 2014. Women were asked whether influenza vaccination was recommended and/or received during their most recent pregnancy; women were also asked why or why they were not immunised. Findings: Between 2012 and 2014, influenza vaccine coverage increased from 22.9% to 41.4%. Women who reported receiving the majority of their antenatal care from a private obstetrician were significantly more likely to have influenza vaccination recommended to them than those receiving the majority of their care from a public antenatal hospital or general practitioner (p \u3c 0.001). In 2014, the most common reason women reported for accepting influenza vaccination was to protect the baby (92.8%) and the most common reason for being unimmunised was lack of a healthcare provider recommendation (48.5%). Discussion: Antenatal influenza vaccination uptake is increasing, but coverage remains below 50%. A recommendation from the principal care provider is an important predictor of maternal influenza vaccination. Conclusion: Antenatal care providers, including midwives, have a key role in providing appropriate information and evidence-based recommendations to pregnant women to ensure they are making informed decisions. Consistent recommendations from antenatal care providers are critical to improving influenza vaccine coverage in pregnant women

Abstracts from the NIHR INVOLVE Conference 2017

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A unique association between cognitive inhibition and pain sensitivity in healthy participants.

Contains fulltext : 90741.pdf (publisher's version ) (Closed access)The experience of pain constitutes a complex phenomenon that is determined by and reflects the interplay of many factors, including cognitive functions. Little is known, however, about the precise role of executive functions in pain sensitivity. Importantly, these functions may be directly related to the ability to control pain. The present study evaluated the relationship between pain sensitivity and executive functions in a sample of healthy volunteers. Pain sensitivity was assessed with the cold pressor test. The immersion time, here defined as the time until substantial pain was reported, was measured. Additional pain intensity and pain unpleasantness ratings were obtained as an indication of pain experience. The results revealed a unique association between cognitive inhibition (i.e. the Stroop interference score), but not other executive functions, and immersion time, pain intensity, and pain unpleasantness. Specifically, better cognitive inhibition was related to a reduction in pain sensitivity as evident by an increased immersion time and decreased pain intensity and pain unpleasantness ratings. As such, cognitive inhibition may be an important determinant of pain sensitivity