Photochemical, thermal and spectroscopic studies of metal carbonyl complexes

Flash photolysis of CpMn(C0)3, CbFe(C0)3 and ArCr(C0)3 in alkane solvents, resulted m the immediate formation of the solvent substituted dicarbonyl species. The reactivity of these species were investigated by uv/vis flash photolysis studies and in the case of CpMn(C0)3 by tnr flash photolysis. The rate constants for the reaction of theses species with a variety of nucleophiles were determined and the thermodynamic parameters associated with these reactions were measured. The chelation reactions of chromium carbonyl complexes, containing multidentate ligands, were investigated by uv/vis and ir spectroscopy. These chelation reaction were seen to proceed via bridging intermediates, even in those cases where the initial complex was coordinated in a monodentate fashion. The crystal structures of a number of chromium and tungsten complexes were determined and correlated with their spectroscopic features

Aquadi-u-chloro-bis(diethylenetriamine)dicopper(11) dichloride: A redetermination at 180 K

The structure of the title compound, [Cu2Cl2(C4H13N3)2(H2O)]Cl2, at 180 K is described in space group P21/n with a unit-cell volume twice that reported previously for the structure at 293 K [Willett (2001[Willett, R. D. (2001). Acta Cryst. E57, m605-m606.]). Acta Cryst. E57, m605-m606]. In the smaller unit cell, in space group P21/m, the complex has imposed mirror symmetry and unusually elongated displacement ellipsoids. At 180 K, refinement in the larger unit cell with no imposed symmetry resolves this issue. With room-temperature data collected from the same crystal, however, refinement using the larger unit cell gives no significant improvement, and the previously reported structure is considered to be most appropriate

Non-trivial solution chemistry between amido-pyridylcalix[4]arenes and some metal salts

Mercury ion complexation reactions were carried out between 3 and various mercury(II) salts. 1H NMR studies showed that the role of solvent, the anion chosen and the initial reaction conditions were critical and that the formation of a “simple” mercury(II) complex was non-trivial. The mercury(II) ion can cause either (i) the formation of an ion-pair system, which have a characteristic doubling of all signals in the 1H NMR spectrum, (ii) a cleavage reaction to occur resulting in the reformation of the calix[4]arene diester compound 2, but only when the reaction is heated and (iii) “simple” mercury binding to the pyridine rings when the binding studies are carried out using NMR titration techniques. The electrochemistry results, on the same systems, show that the initial reaction involves the removal of the phenoxide protons followed by the resulting catalysis of the mercury species. This proton removal is not observed in the NMR spectra of any of the mercury reactions. It was also found that 3 could bind silver and zinc salts and was not selective for mercury(II) as was previously described

Copper(11) complex of a tridentate N-Donor ligand with unexpected Cu-H interaction

The new pyridineâamine ligand, meophdpa (bis(dipyridylmethyl)-4-methoxyaniline) was synthesised and reacted with copper(II) perchlorate. The X-ray crystal structure of the resulting complex revealed a monomeric copper(II) site, with the copper bound to the three ligand nitrogens in a relatively unusual meridional fashion, as well as a chloride and a water molecule. The sixth coordination site was, unexpectedly, occupied by a phenyl ring hydrogen atom. Graphical abstract A new pyridineâamine ligand has been prepared and its reaction with copper perchlorate characterised. An interesting phenyl-HâCu interaction was observed

Anti-Hypochlorite and Catalytic Activity of Commercially Available Moringa oleifera Diet Supplement

Aiming at the assessment of the pro-health, and especially anti-hypochlorite properties of Moringa oleifera species a representative, commercially available Moringaoleifera dietary supplement was used as a substrate for the preparation of aqueous Moringa extract. The anti-hypochlorite activity of the extract was assessed using the hypochlorite-specific coumarin-based fluorescence turn-off sensor, namely 7-diethylamino-coumarin-3-carboxylic acid (7-DCCA). This compound was synthesized via the Knoevenagel condensation of 4-diethylamino-2-hydroxybenzaldehyde with Meldrum’sacidandtheMoringaextractwasemployedasamediumandcatalyst. Moreover,thetotal phenoliccontent(TPC)aswellasthereactiveoxygenspecies(ROS)–scavengingabilityoftheaqueous Moringa extract were determined. The results obtained demonstrated the applicability of Moringa extract as an anti-hypochlorite agent. Additionally, the satisfactory yield of the 7-DCCA obtained suggests the usefulness of the extract as a catalyst and the reaction medium. The antioxidative potentialoftheextractwasnotablylowerthanthatofthestandard(TROLOX).DeterminationofTPC in 100 g of the dry weight (DW) of studied material revealed a high number of polyphones present

Emergentist Marxism : a materialistic application of realism in the social sciences

This thesis will be concerned with articulating and defending a form of realist social theory entitled "emergentist Marxism". As such its principal objective is less to investigate or review the voluminous literature on "social realism" and more to show the ways in which Marxian social theory can be legitimately "constructed" as a specific "materialistic" application of ontological and methodological realism in the human sciences. The significance of this research is that it functions simultaneously as a contribution to the social science component of Roy Bhaskar's philosophical realism and as a Marxist commentary upon and perhaps intervention against it. The latter is less certain, however, because Bhaskar's depth realism appears to be consistent with the form of anti-reductive materialism defended here. "Realism" or "emergentism" refers to an ontological position denoting a stratified social world of irreducible levels, of which persons, practices and structures are the most fundamental, all of which are efficacious by virtue of the properties and powers which pertain to each of them. "Materialism" denotes the ontological position that the material structures of social systems vertically explain social and cultural structures without "explaining them away". Thus "emergentist Marxism" is an anti-reductive socio-historical ontological materialism and attendant dialectical realist method. Translated into practical social research, it is applied concretely here to the task of theorising the interface between the properties and powers which pertain to human agents and those which pertain to social structures in shaping the constitution and dynamics of social systems

A Sense of Trust: Somatic Spiritual Practices as a Path to Wholeness in Spiritually Integrated Trauma Care

A traumatic event holds the power to rupture one’s world, generating lingering effects on embodied existence. Research has demonstrated that overwhelmingly stressful events often call into question deeply held values and beliefs and that spiritual struggles “tend to be partially responsible for the distress experienced (Pomerleau et al., 2020, pp. 456–457). Similarly, research with veterans has demonstrated that religious and spiritual struggles mediate the relationship between a potentially morally injurious event and both anxiety and PTSD (Evans et al., 2018), often intensifying trauma and moral injury symptoms as well as opening a pathway for spiritual integration and growth (Pargament & Exline, 2022). In this dissertation, I focus on the role of intrinsically meaningful somatic spiritual practices in helping trauma survivors reclaim embodied trust, lament loss, and seek wholeness. I use an interreligious approach, based on a revised correlational method from practical theology (Bennett et al., 2018; Marshall, 2004; Miller-McLemore, 2010). This approach brings lived experiences of intrinsically meaningful somatic spiritual practices into dialogue with interdisciplinary research, scholarship, and clinical approaches to propose a spiritually oriented trauma care praxis. Existential–phenomenological therapies—notably, gestalt therapy and Eugene Gendlin’s focusing-oriented therapy—as well as interoception research support my argument that embodiment is an important integrative process that can occur in four stages. After summarizing the somatic impact of moral injury and trauma, I highlight three evidence-based somatic therapies for trauma integration that utilize interoception. I argue for the incorporation of relational trust and cocreativity in trauma care by utilizing (a) developmental psychologist Edward Tronick’s (2007; Tronick & Beeghly, 2011) mutual regulation model, (b) the dialogically derived cocreativity of field theory, (c) polyvagal theory regarding socially enhanced alert ease, and (d) Heart Rate Variability (HRV) research on coherence and synchrony. I propose a spiritually oriented, interreligious, trauma care praxis for cocreating intrinsically meaningful somatic spiritual practices that enable an abiding sense of trust. Such trust facilitates lament and spiritual wholeness in survivors of trauma and moral injury. An extended case study illustrates this praxis. The end goal is to help mental health and spiritual care practitioners develop competencies for spiritually oriented trauma care that integrate research and relational mystery by exploring somatic spiritual practices as a path to wholeness

Wide-and narrow-rim functionalised calix[4]arenes: synthesis and characterisation

Functionalisation of calix[4]arene at both the wide and narrow rims leads to the formation of compounds containing bipyridyl, via an amide linkage, at the wide rim and having either a butyl chain, a benzyl group or an alkyl ester functionality at the narrow rim. All compounds were characterised using 1H and 13C NMR spectroscopies. Initial binding studies with Ru(bipy)2Cl2 are reported. Graphical abstract Functionalisation of calix[4]arene was carried out such that metal complexation could occur at both the wide and narrow rims, a rare occurrence in calixarene chemistry