Measurement of molecular orientation in thermotropic liquid crystalline polymers

Procedures for obtaining molecular orientational parameters from wide angle X-ray scattering patterns of samples of thermotropic liquid crystalline polymers are presented. The methods described are applied to an extrusion-aligned sample of a random copolyester of poly(ethylene terephthalate) (PET) and p-acetoxybenzoic acid. Values of the orientational parameters are obtained from both the interchain and intrachain maxima in the scattering pattern. The differences in the values so derived suggest some level of local rotational correlation

The determination of molecular orientation in uniaxially compressed PMMA by X-ray scattering

A procedure is presented for obtaining full molecular orientation information from wide angle X-ray scattering patterns of deformed non-crystalline polymers. The method is based on the analysis of experimental and calculated scattering patterns into their spherical harmonics. The results obtained for PMMA are compared with values predicted by the pseudo affine and affine deformation schemes.

A two-dimensional X-ray scattering system for in-situ time-resolving studies of polymer structures subjected to controlled deformations

A two-dimensional X-ray scattering system developed around a CCD-based area detector is presented, both in terms of hardware employed and software designed and developed. An essential feature is the integration of hardware and software, detection and sample environment control which enables time-resolving in-situ wide-angle X-ray scattering measurements of global structural and orientational parameters of polymeric systems subjected to a variety of controlled external fields. The development and operation of a number of rheometers purpose-built for the application of such fields are described. Examples of the use of this system in monitoring degrees of shear-induced orientation in liquid-crystalline systems and crystallization of linear polymers subsequent to shear flow are presented.

WAXS studies of global molecular orientation induced in nematic liquid crystals by simple shear flow

Global molecular orientation function coefficients for the nematic liquid crystal 4-cyano 4'-nn -pentylbiphenyl (5CB) in shear flow are presented, being extracted from 2-dimensional Wide-Angle X-ray Scattering data. A linear increase in orientation parameter P2 is observed with a logarithmic increase in shear rate. It is proposed that this arises from an increased number of LC directors aligning to the shear axis. Upon cessation of shear flow, the anisotropy is seen to relax away completely, over a time scale which is inversely proportional to the previously applied shear rate.

Quantitative analysis of mannitol polymorphs: X-ray powder diffractometry—exploring preferred orientation effects

Mannitol is a polymorphic pharmaceutical excipient, which commonly exists in three forms: alpha, beta and delta. Each polymorph has a needle-like morphology, which can give preferred orientation effects when analysed by X-ray powder diffractometry (XRPD) thus providing difficulties for quantitative XRPD assessments. The occurrence of preferred orientation may be demonstrated by sample rotation and the consequent effects on X-ray data can be minimised by reducing the particle size. Using two particle size ranges (less than 125 and 125–500�microns), binary mixtures of beta and delta mannitol were prepared and the delta component was quantified. Samples were assayed in either a static or rotating sampling accessory. Rotation and reducing the particle size range to less than�125 microns halved the limits of detection and quantitation to 1 and 3.6%, respectively. Numerous potential sources of assay errors were investigated; sample packing and mixing errors contributed the greatest source of variation. However, the rotation of samples for both particle size ranges reduced the majority of assay errors examined. This study shows that coupling sample rotation with a particle size reduction minimises preferred orientation effects on assay accuracy, allowing discrimination of two very similar polymorphs at around the 1% level

Adult attachment orientation and implicit behavioral mimicry

We investigated whether adult attachment orientation predicted the extent to which individuals engaged in implicit behavioral mimicry of a confederate presented by video. Results demonstrated that following an attachment threat prime: (1) those low in attachment anxiety and high in attachment avoidance showed less mimicry of face-rubbing gestures than individuals low in both attachment avoidance and attachment anxiety; (2) those high in attachment anxiety and low in attachment avoidance showed less mimicry of face-rubbing gestures than individuals low in both attachment avoidance and attachment anxiety. Importantly, attachment orientation did not predict baseline levels of face-rubbing gesturing; demonstrating that attachment orientation had an effect on mimicry rather than overall behavior expression. Attachment anxiety was positively related to attraction to the confederate such that those higher in attachment anxiety rated the confederate as more attractive. The findings are discussed with reference to both the mimicry and attachment literatures.

Addressee orientation in political speeches: tracing the dialogical 'other' in argumentative monologue

This article suggests that the addressees as the dialogical ‘other’ loom large in monological political speeches. However, political speeches are produced under conditions of addressee heterogeneity, i.e. the speakers do not actually know who they will be talking to. It will be argued that the addressees are nevertheless a crucial element in speakers’ context models, that speakers orientate towards imagined addressees and that certain aspects – what possible addressees may do, think or believe and that they are a part of an imagined community – are particularly relevant from the speakers’ point of view. An analysis of addressee orientation in political speeches aims at reconstructing speakers’ conceptualisations of possible addressees. The analysis reveals patterns of addressee orientation which suggest that the addressees are framed in terms of presumed nearness (i.e. agreement) or distance (i.e. disagreement) to the speakers. Both presumed agreement and disagreement will be discussed in terms of how the speakers aim to impose their default perspectives on the addressees. The analysis is based on examples from a substantial corpus of German chancellors’ political speeches from 1951-2001.

Preferred orientation in an angled intercalation site of a chloro-substituted lambda- [Ru(TAP)2(dppz)]2+ complex bound to d(TCGGCGCCGA)2

The crystal structure of the ruthenium DNA ‘light-switch’ complex -[Ru(TAP)2(11-Cl-dppz)]2+ (TAP = tetraazaphenanthrene, dppz = dipyrido[3,2-a':2',3'-c]phenazine)) bound to the oligonucleotide duplex d(TCGGCGCCGA)2 is reported. The synthesis of the racemic ruthenium complex is described for the first time, and the racemate was used in this study. The crystal structure, at atomic resolution (1.0 Å), shows one ligand as a wedge in the minor groove, resulting in the 51 kinking of the double helix, as with the parent lambda-[Ru(TAP)2(dppz)]2+. Each complex binds to one duplex by intercalation of the dppz ligand and also by semi-intercalation of one of the orthogonal TAP ligands into a second symmetrically equivalent duplex. The 11-Cl substituent binds with the major component (66%) oriented with the 11-chloro substituent on the purine side of the terminal step of the duplex.

Associating spontaneous with evoked activity in a neural mass model of cat visual cortex

Spontaneous activity of the brain at rest frequently has been considered a mere backdrop to the salient activity evoked by external stimuli or tasks. However, the resting state of the brain consumes most of its energy budget, which suggests a far more important role. An intriguing hint comes from experimental observations of spontaneous activity patterns, which closely resemble those evoked by visual stimulation with oriented gratings, except that cortex appeared to cycle between different orientation maps. Moreover, patterns similar to those evoked by the behaviorally most relevant horizontal and vertical orientations occurred more often than those corresponding to oblique angles. We hypothesize that this kind of spontaneous activity develops at least to some degree autonomously, providing a dynamical reservoir of cortical states, which are then associated with visual stimuli through learning. To test this hypothesis, we use a biologically inspired neural mass model to simulate a patch of cat visual cortex. Spontaneous transitions between orientation states were induced by modest modifications of the neural connectivity, establishing a stable heteroclinic channel. Significantly, the experimentally observed greater frequency of states representing the behaviorally important horizontal and vertical orientations emerged spontaneously from these simulations. We then applied bar-shaped inputs to the model cortex and used Hebbian learning rules to modify the corresponding synaptic strengths. After unsupervised learning, different bar inputs reliably and exclusively evoked their associated orientation state; whereas in the absence of input, the model cortex resumed its spontaneous cycling. We conclude that the experimentally observed similarities between spontaneous and evoked activity in visual cortex can be explained as the outcome of a learning process that associates external stimuli with a preexisting reservoir of autonomous neural activity states. Our findings hence demonstrate how cortical connectivity can link the maintenance of spontaneous activity in the brain mechanistically to its core cognitive functions.

Review of the formulation of present‐generation stratospheric chemistry‐climate models and associated external forcings

The goal of the Chemistry‐Climate Model Validation (CCMVal) activity is to improve understanding of chemistry‐climate models (CCMs) through process‐oriented evaluation and to provide reliable projections of stratospheric ozone and its impact on climate. An appreciation of the details of model formulations is essential for understanding how models respond to the changing external forcings of greenhouse gases and ozonedepleting substances, and hence for understanding the ozone and climate forecasts produced by the models participating in this activity. Here we introduce and review the models used for the second round (CCMVal‐2) of this intercomparison, regarding the implementation of chemical, transport, radiative, and dynamical processes in these models. In particular, we review the advantages and problems associated with approaches used to model processes of relevance to stratospheric dynamics and chemistry. Furthermore, we state the definitions of the reference simulations performed, and describe the forcing data used in these simulations. We identify some developments in chemistry‐climate modeling that make models more physically based or more comprehensive, including the introduction of an interactive ocean, online photolysis, troposphere‐stratosphere chemistry, and non‐orographic gravity‐wave deposition as linked to tropospheric convection. The relatively new developments indicate that stratospheric CCM modeling is becoming more consistent with our physically based understanding of the atmosphere.

Satanic Mills? An illustration of Victorian external environmental accounting

The paper evaluates a Victorian environmental account of the pollution of the River Wandle. This account was produced during a period of social and environmental crisis, when there were no significant industrial environmental regulations. This problematising external environmental account provides valuable insights into the historical development of social and environmental accounting. Our analysis located this account within an institutional reform programme to create systems of governance to mitigate the damage arising from unfettered industrial growth. We argue that problematising external environmental accounting has a longer tradition than previously recognised in the literature and predates corporate social and environmental reporting.

Effect of disease-selective predation on prey infected by contact and external sources

We propose and analyze a simple mathematical model for susceptible prey (S)–infected prey (I)–predator (P) interaction, where the susceptible prey population (S) is infected directly from external sources as well as through contact with infected class (I) and the predator completely avoids consuming the infected prey. The model is analyzed to obtain different thresholds of the key parameters under which the system exhibits stability around the biologically feasible equilibria. Through numerical simulations we display the effects of external infection and the infection through contact on the system dynamics in the absence as well as in the presence of the predator. We compare the system dynamics when infection occurs only through contact, with that when it occurs through contact and external sources. Our analysis demonstrates that under a disease-selective predation, stability and oscillations of the system is determined by two key parameters: the external infection rate and the force of infection through contact. Due to the introduction of external infection, the predator and the prey population show limit-cycle oscillations over a range parametric values. We suggest that while predicting the dynamics of such an eco-epidemiological system, the modes of infection and the infection rates might be carefully investigated.