On the relationship between dissociation and disordered eating

This thesis investigated the psychological processes that underlie the relationship between dissociation and disordered eating. Although previous theories have emphasized that dissociation undermines behavioural self-control and, in turn, contributes to disordered eating, present findings indicate that dissociation may also influence disordered eating via disturbances to one's sense of identity.

The enhancement of lithium ion dissociation in polyelectrolyte gels on the addition of ceramic nano-fillers

Nano-particle oxide fillers including TiO₂, SiO₂ and Al₂O₃ have previously been shown to have a significant affect on the properties of both polymer and polymer gel electrolytes. In some cases, conductivity increases of one order of magnitude have been reported in crystalline PEO–base complexes. In this work, we report the effects of TiO₂ and SiO₂ on a poly(Li-AMPS)-based gel polyelectrolyte. Impedance spectroscopy and pfg-NMR spectroscopy indicates an increase in the number of available charge carriers with the addition of filler. An ideal amount of ceramic filler has been identified, with additional filler only saturating the system and reducing the conductivity below that of the pristine polyelectrolyte system. SEM micrographs suggest a model whereby the filler interacts readily with the sulfonate group; the surface area of the filler being an important factor.

The additive effect of zwitterion and nano-particles on ion dissociation in polyelectrolytes

To realise the battery potential of gel polyelectrolytes greater ion dissociation, ultimately leading to higher conductivities, must be achieved. Higher conductivities will result through increasing the ion-dissociating properties of the gel polyelectrolyte. The poor degree of ion dissociation arises as the active ion tends to remain in close proximity to the backbone charge. Nano-particle inorganic oxides, and zwitterionic compounds have been shown to act as dissociation enhancers in certain polyelectrolyte systems. In an attempt to further increase ion dissociation the addition of both TiO₂ nano-particles and a zwitterionic compound based on 1-butylimidazolium-3-N-(butanesulphonate) were added to the gel polyelectrolyte system poly (Li-2-acrylamido-2-methyl-1-propane sulphonate-co-N,N′-dimethylacrylamide), poly(Li-AMPS-co-DMAA) to determine if a synergistic effect occurs. Two different solvents were used to determine the breadth of applicability of the additive effect. The use of both dissociators resulted in the maximum ionic conductivity being achieved at lower nano-particle concentrations when compared to an identical system without zwitterion.

Enhancement of ion dissociation in polyelectrolyte gels

High conductivity in single ion conducting polymer electrolytes is still the ultimate aim for many electrochemical devices such as secondary lithium batteries. Achieving effective ion dissociation in these cases remains a challenge since the active ion tends to remain in close proximity to the backbone charge as a result of a low degree of ion dissociation. A unique aspect of this dissociation problem in polyelectrolytes is the repulsion between the backbone charges created by dissociation. One way of enhancing ion dissociation in polyelectrolyte systems is to use copolymers in which only a fraction (<20%) of the mer units are charged and where the comonomer is itself chosen to be polar and preferably to be compatible with potential solvents. We have also found that certain dissociation enhancers based on ionic liquids or boroxine ring compounds can lead to high ionic conductivity. In the cases where an ionic liquid is used as the solvent in a polyelectrolyte gel, the viscosity of the ionic liquid and its hydrophilicity are critical to achieving high conductivity. Compounds based on the dicyanamide anion appear to be very effective ionic solvents; polyelectrolyte gels incorporating such ionic liquids exhibit conductivities as high as 10⁻² S/cm at room temperature. In the case of boroxine ring dissociation enhancers, gels based on poly(lithium-2-acrylamido-2-methyl-1-propanesulfonate) and ethylene carbonate produce conductivities approaching 10⁻³ S/cm. This paper will discuss these approaches for achieving higher conductivity in polyelectrolyte materials and suggest future directions to ensure single ion transport.

On the components of the dielectric constants of ionic liquids : ionic polarization?

According to dielectric spectroscopy measurements, ionic liquids (ILs) have rather modest dielectric constants that reflect contributions from distortion and electronic polarization caused by the molecular polarizability as well as the orientation polarization caused by the permanent dipole moment of the ions. To understand the relative importance of these various contributions, the electronic polarizabilities of 27 routinely used ionic liquid ions of different symmetry and size were calculated using ab initio-based methods such as HF and MP2. Using the Clausius–Mossotti equation, these polarizabilities were then used to obtain the electronic polarization contribution (ε_op) to the dielectric constants of six ionic liquids, [C₂mim][BF₄], [C₂mpyr][N(CN)₂], [C₂mim][CF₃SO₃], [EtNH₃][NO₃], [C₂mim][NTf₂] and [C₂mim][EtSO₄]. Theoretical ε_op values were compared to experimental refractive indices of these ionic liquids as well as to those of traditional molecular solvents such as water, tetrahydrofuran (THF), dimethylsulfoxide (DMSO) and formamide. The dipole moments of the ions were also calculated, and from these it is shown that the molecular reorientation component of the dielectric constants of the ionic liquids consisting of ions with small or negligible dipole moments is quite small. Thus it is concluded that a contribution from a form of “ionic polarization” must be present.

Boroxine ring compounds as dissociation enhancers in gel polyelectrolytes

In order to combine the advantages of both traditional gel electrolytes and polyelectrolytes, a novel polyelectrolyte which incorporates a boroxine ring-containing anion-trapping agent has been explored. Poly(lithium 2-acrylamido-2-methyl-1-propanesulfonate) (PAMPSLi), ethylene carbonate (EC) and tri(methoxyethoxyethoxyethoxy)boroxine (TME₃Bx) were combined to prepare various gel systems. The thermal properties and conductivities of these gels have been investigated. A conductivity of 10^−3.6 S cm⁻¹ at 20 °C has been achieved in a gel polyelectrolyte system with a molar ratio of [EC]:[TME3Bx]:[Li⁺]=24:1.7:1. Temperature-dependent NMR measurements indicated that a significant interaction exists between the boroxine ring and the polyelectrolyte.

Determining binding constants from 1H NMR titration data using global and local methods : a case study using [n]polynorbornane-based anion hosts

From data generated using 1H NMR titrations, different methodologies to calculate binding constants are compared. The ‘local’ analysis method that uses only a single isotherm (only one H-bond donor) is compared against the ‘global’ method (that includes many or all H-bond donors). The results indicate that for simple systems both methods are suitable, however, the global approach consistently provides a K a value with uncertainties up to 30% smaller. For more complex binding, the global analysis method gives much more robust results than the local methods. This study also highlights the need to explore several different modes when data do not fit well to a simple 1:1 complexation model and illustrates the need for better methods to estimate uncertainties in supramolecular binding experiments.

The role of anxiety and dissociation in young Australian gamblers

The aim of the present study was to examine predictors of 'escape style' problem gambling among young Australian gamblers. Anxiety and dissociation are considered to be predictors of 'escape style' gambling behaviour although this assessment has neglected consideration of different modes of gambling. This study builds on existing research, to examine the role of anxiety and dissociation in the gambling habits of young Australian male and female gamblers. One hundred and forty-two participants aged between 18 and 35 years self-selected and completed an online questionnaire. The hypothesis that gamblers would have similar levels of dissociation and anxiety despite different modes of gambling was supported. The hypothesis that anxiety and dissociation would both together and uniquely predict problem gambling behaviour across a range of gambling modalities was supported. Further, the hypothesis that there would be an interaction effect between anxiety and dissociation such that their presence together would predict a higher degree of problem gambling behaviour was supported. Results suggest that anxiety and dissociation play an important role in 'escape style' gambling and that strategies to combat problem gambling may benefit from research targeting anxiety and attempting to rechannel dissociative behaviour into healthier pursuits.

Dissociation between the circulating renin-angiotensin system and angiotensin II receptors in central losartan-induced hypertension

Losartan, an AT1 angiotensin II (ANG II) receptor non-peptide antagonist, induces an increase in mean arterial pressure (MAP) when injected intracerebroventricularly (icv) into rats. The present study investigated possible effector mechanisms of the increase in MAP induced by icv losartan in unanesthetized rats. Male Holtzman rats (280-300 g, N = 6/group) with a cannula implanted into the anterior ventral third ventricle received an icv injection of losartan (90 µg/2 µl) that induced a typical peak pressor response within 5 min. In one group of animals, this response to icv losartan was completely reduced from 18 ± 1 to 4 ± 2 mmHg by intravenous (iv) injection of losartan (2.5-10 mg/kg), and in another group, it was partially reduced from 18 ± 3 to 11 ± 2 mmHg by iv prazosin (0.1-1.0 mg/kg), an alpha1-adrenergic antagonist (P<0.05). Captopril (10 mg/kg), a converting enzyme inhibitor, injected iv in a third group inhibited the pressor response to icv losartan from 24 ± 3 to 7 ± 2 mmHg (P<0.05). Propranolol (10 mg/kg), a ß-adrenoceptor antagonist, injected iv in a fourth group did not alter the pressor response to icv losartan. Plasma renin activity and serum angiotensin-converting enzyme activity were not altered by icv losartan in other animals. The results suggest that the pressor effect of icv losartan depends on angiotensinergic and alpha1-adrenoceptor activation, but not on increased circulating ANG II.

Advantages of using nested collision induced dissociation/post-source decay with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry: sequencing of novel peptides from wasp venom

We have examined the applicability of the 'nested' collision induced dissociation/post-source decay (CID/PSD) method to the sequencing of novel peptides from solitary wasps which have neurotoxic venom for paralyzing other insects. The CID/PSD spectrum of a ladder peptide derived from an exopeptidase digest was compared with that of the intact peptide. The mass peaks observed only in the CID/PSD spectrum of a ladder peptide were extracted as C-terminal fragment ions. Assignment of C-terminal fragment ions enabled calculation of N-terminal fragment masses, leading to differentiation between N-terminal fragment ions and internal fragment ions. This methodology allowed rapid and sensitive identification by removing ambiguity in the assignment of the fragment ions, and proved useful for sequencing unknown peptides, in particular those available as natural products with a limited supply. Copyright (C) 2000 John Wiley & Sons, Ltd.