Conformational dynamics of thyroid hormones by variable temperature nuclear magnetic resonance: The role of side chain rotations and cisoid/transoid interconversions

H-1 NMR spectra of the thyroid hormone thyroxine recorded at low temperature and high field show splitting into two peaks of the resonance due to the H2,6 protons of the inner (tyrosyl) ring. A single resonance is observed in 600 MHz spectra at temperatures above 185 K. An analysis of the line shape as a function of temperature shows that the coalescence phenomenon is due to an exchange process with a barrier of 37 kJ mol(-1). This is identical to the barrier for coalescence of the H2',6' protons of the outer (phenolic) ring reported previously for the thyroid hormones and their analogues. It is proposed that the separate peaks at low temperature are due to resonances for H2,6 in cisoid and transoid conformers which are populated in approximately equal populations. These two peaks are averaged resonances for the individual H2 and H6 protons. Conversion of cisoid to transoid forms can occur via rotation of either the alanyl side chain or the outer ring, from one face of the inner ring to the other. It is proposed that the latter process is the one responsible for the observed coalescence phenomenon. The barrier to rotation of the alanyl side chain is greater than or equal to 37 kJ mol(-1), which is significantly larger than has previously been reported for Csp(2)-Csp(3) bonds in other Ph-CH2-X systems. The recent crystal structure of a hormone agonist bound to the ligand-binding domain of the rat thyroid hormone receptor (Wagner et al. Nature 1995, 378, 690-697) shows the transoid form to be the bound conformation. The significant energy barrier to cisoid/transoid interconversion determined in the current study combined with the tight fit of the hormone to its receptor suggests that interconversion between the forms cannot occur at the receptor site but that selection for the preferred bound form occurs from the 50% population of the transoid form in solution.

Stiffly accurate Runge-Kutta methods for stiff stochastic differential equations

In this paper we discuss implicit methods based on stiffly accurate Runge-Kutta methods and splitting techniques for solving Stratonovich stochastic differential equations (SDEs). Two splitting techniques: the balanced splitting technique and the deterministic splitting technique, are used in this paper. We construct a two-stage implicit Runge-Kutta method with strong order 1.0 which is corrected twice and no update is needed. The stability properties and numerical results show that this approach is suitable for solving stiff SDEs. (C) 2001 Elsevier Science B.V. All rights reserved.

A servicing strategy for items sold under warranty

When repairable items sold under warranty fail, the rectification action taken by the manufacturer can be either a repair or a replacement, In this paper a new repair-replacement strategy is proposed for the manufacturer when the items are sold with a non-renewing free replacement warranty policy. The strategy involves splitting the warranty period into two intervals where only repairs are carried out, separated by a third interval with at most one replacement.

Experimental infections of pigs with Japanese encephalitis virus and closely related Australian flaviviruses

The flavivirus Japanese encephalitis (JE) virus has recently emerged in the Australasian region. To investigate the involvement of infections with related enzootic flaviviruses, namely Murray Valley encephalitis (MVE) virus and Kunjin (KUN) virus, on immunity of pigs to JE virus and to provide a basis for interpretation of serologic data, experimental infections were conducted with combinations of these viruses. Antibody responses to primary and secondary infections were evaluated using panels of monoclonal antibody-based blocking enzyme-link-ed immuno-sorbent assays and microtiter scrum neutralization tests (mSNTs). Identification of the primary infecting virus was possible only using the mSNTs. Following challenge, unequivocal diagnosis was impossible due to variation in immune responses between animals and broadened and/or anamnestic responses. Viremia for JE virus was readily detected in pigs following primary infection, but was not detected following prior exposure to MVE or KUN viruses. Boosted levels of existing cross-neutralizing antibodies to JE virus suggested a role for this response in suppressing JE viremia.

Depositional environments for strata cored in CRP-3 (Cape Roberts Project), Victoria Land Basin, Antarctica: palaeoglaciological and palaeoclimatological inferences

Cape Roberts Project drill core 3 (CRP-3) was obtained from Roberts ridge, a sea-floor high located at 77°S, 12 km offshore from Cape Roberts in western McMurdo Sound, Antarctica. The recovered core is about 939 m long and comprises strata dated as being early Oligocene (possibly latest Eocene) in age, resting unconformably on ∼ 116 m of basement rocks consisting of Palaeozoic Beacon Supergroup sediments. The core includes ten facies commonly occuring in five major associations that are repeated in particular sequences throughout the core and which are interpreted as representing different depositional environments through time. Depositional systems inferred to be represented in the succession include: outer shelf, inner shelf, nearshore to shoreface each under iceberg influence, deltaic and/or grounding-line fan, and ice proximal-ice marginal-subglacial (mass flow/rainout diamictite/subglacial till) singly or in combination. The record is taken to represent the initial talus/alluvial fan setting of a glaciated rift margin adjacent to the block-uplifted Transantarctic Mountains. Development of a deltaic succession upcore was probably associated with the formation of palaeo-Mackay valley with temperate glaciers in its headwaters. At that stage glaciation was intense enough to support glaciers ending in the sea elsewhere along the coast, but a local glacier was fluctuating down to the sea by the time the youngest part of CRP-3 was being deposited. Changes in palaeoenvironmental interpretations in this youngest part of the core are used to estimate relative glacial proximity to the drillsite through time. These inferred glacial fluctuations are compared with the global δ18O and Mg/Ca curves to evaluate the potential of glacial fluctuations on Antarctica for influencing these records of global change. Although the comparisons are tentative at present, the records do have similarities, but there are also some differences that require further evaluation.

Quaternary continental weathering geochronology by laser-heating Ar-40/Ar-39 analysis of supergene cryptomelane

Incremental laser-heating analyses of supergene cryptomelane clusters extracted from three distinct weathering profiles from the Mary Valley region, southeast Queensland, Australia, yield reproducible and well-defined plateau ages ranging from 346 +/- 15 to 291 +/- 14 ka (2 a). Precipitation of supergene cryptomelane in this period implies that relative humid climate prevailed in southeast Queensland from 340 to 290 ha, a result consistent with oxygen isotope analyses of marine sediments from Ocean Drilling Program Site 820 and with regional pollen and spore records. These results, the first report on the precise Ar-40/Ar-39 dating of Quaternary supergene cryptomelane, indicate that Ar-40/Ar-39 analysis of pedogenic minerals provides a reliable geochronometer for the study of Quaternary surficial processes useful in the study of soil formation rates, continental paleoclimates, and archaeological sites devoid of datable volcanic minerals.

An ESR study on gamma-irradiated poly(vinyl alcohol)

The formation of radicals in poly(vinyl alcohol), PVA, powder irradiated at 77 K by gamma -rays and the transformations of these radicals during photolysis with visible wavelengths and on thermal annealing have been studied. After irradiation a four-line ESR spectrum was observed. It was assigned to a triplet of the C-alpha-radical (38%), with a splitting of 3.27 mT, superimposed on a doublet (62%) with a splitting of 2.7 mT. The doublet appears to be composed of two radicals, one of which is photo-bleachable (58%) and the other which is not photo-bleachable (42%). This suggests that the latter radical is a neutral radical. The photo-bleachable component of the doublet has been assigned to a carbonyl anion radical. but the second doublet due to a neutral radical is unassigned. The total G-value for formation of radicals at 77 K was found to be 2.41 +/- 0.03. Upon illumination with visible light, the anion radicals were removed and the doublet components or the spectrum diminished in intensity, while the three-line spectrum of the C-alpha-radical became more clearly visible. This transition was due to the photo-detachment of electrons from traps which were proposed to be located on carbonyl groups in the polymer resulting from incomplete hydrolysis of the vinyl acetate. The photo-decay of the anion radicals could be satisfactorily described by a two-stage process. The first stage comprised the decay of approximately 80% of the anion radicals present, while the second stage was associated with the decay of the remaining 20%. Subsequent thermal annealing of a photolysed sample to 290 K led to a change in the shape of the spectrum to form a more clearly defined triplet, As the doublet of the neutral radical decays on thermal annealing between 150 and 250K, the C-alpha-radical is formed. (C) 2001 Elsevier Science Ltd. All rights reserved.

Effect of quantum interference on a three-level atom driven by two laser fields

We study the effect of quantum interference on the population distribution and absorptive properties of a V-type three-level atom driven by two lasers of unequal intensities and different angular frequencies. Three coupling configurations of the lasers to the atom are analysed: (a) both lasers coupled to the same atomic transition, (b) each laser coupled to different atomic transition and (c) each laser coupled to both atomic transitions. Dressed stales for the three coupling configurations are identified, and the population distribution and absorptive properties of the weaker field are interpreted in terms of transition dipole moments and transition frequencies among these dressed states. In particular, we find that in the first two cases there is no population inversion between the bare atomic states, but the population can be trapped in a superposition of the dressed states induced by quantum interference and the stronger held. We show that the trapping of the population, which results from the cancellation of transition dipole moments, does not prevent the weaker field to be coupled to the cancelled (dark) transitions. As a result, the weaker field can be strongly amplified on transparent transitions. In the case of each laser coupled to both atomic transitions the population can be trapped in a linear superposition of the excited bare atomic states leaving the ground state unpopulated in the steady state. Moreover, we find that the absorption rate of the weaker field depends on the detuning of the strong field from the atomic resonances and the splitting between the atomic excited states. When the strong held is resonant to one of the atomic transitions a quasi-trapping effect appears in one of the dressed states. In the quasi-trapping situation all the transition dipole moments are different from zero, which allows the weaker field to be amplified on the inverted transitions. When the strong field is tuned halfway between the atomic excited states, the population is completely trapped in one of the dressed states and no amplification is found for the weaker field.

Isolation of arboviruses from mosquitoes (Diptera : Culicidae) collected from the Gulf Plains region of northwest Queensland, Australia

As part of investigations into Japanese encephalitis (JE) virus and related flaviviruses in northern Australia, 153,529 mosquitoes were collected and processed for virus isolation from the Gulf Plains region of northwest Queensland. Collections front within 30 km of each of the townships of Croydon, Normanton and Karumba yielded 3,087 (2.0%), 66,009 (43.0%), and 84,433 (55.0%) mosquitoes, respectively, from which 16 viruses were isolated. Four isolates of Murray Valley encephalitis (MVE), two of Kunjin (KUN), three of Ross River (1111), and one of Sindbis (SIN) viruses were obtained from Culex sitiens subgroup mosquitoes. Molecular identification of the mosquito species composition of these virus positive pools revealed that most isolates were from pools containing mainly Culex annulirostris Skuse and low numbers of Cidex palpalis (Taylor). Only three pools, one each of MVE, KUN, and RR, were from mosquitoes identified exclusively as Cx. annulirostris. Other viruses isolated include one Edge Hill Virus from Ochlerotatus normanensis (Taylor), an isolate of SIN from Anopheles meraukensis Venhuis, two isolates of RR from Anopheles amictus Edwards, and single isolates of RR from Anopheles bancroftii Giles and Aedes lineatopennis (Ludlow). The isolate of RR from Ae. lineatopennis was the first reported from this species. The public health implications of these isolations in the Gulf Plains region are discussed briefly.

Magnetic-field-induced superconductivity in layered organic molecular crystals with localized magnetic moments

l-(BETS)2FeCl4 undergoes transitions from an antiferromagnetic insulator to a metal and then to a superconductor as a magnetic field is increased. We use a Hubbard-Kondo model to clarify the role of the Fe31 magnetic ions in these phase transitions. In the high-field regime, the magnetic field acting on the electron spins is compensated by the exchange field He due to the magnetic ions. We show how He can be extracted from the observed splitting of the Shubnikov–de Haas frequencies. We predict the field range for field-induced superconductivity in other materials.

The radiation chemistry of ultem at 77 K as revealed by ESR spectroscopy

Radical formation in ultem following gamma-radiolysis has been reassessed, and the G(R*) values at different temperatures have been determined by ESR spectroscopy. The radical assignment and radical reactivity have been re-examined by photobleaching and thermal annealing studies. Photobleachable radical anions were found to comprise approximate to40% of the total number of radicals formed on radiolysis at 77 K. Spectral subtraction methods, ESR spectral simulations, measurement of g-values and the hyperfine splitting constants were used to identify the other radical intermediates. The principal chain scission radicals are formed due to scission of the main-chain at (i) the ether linkage, (ii) the isopropylidene group and (iii) the imide ring in the main chain. The side chain methyl groups of the isopropylidine units also lose hydrogen to form methylene radicals. The five-line spectrum observed to decay in the temperature range 370-430 K, which has not been assigned previously, has been identified as being characteristic of a di-substituted benzyl radical. (C) 2002 Elsevier Science Ltd. All rights reserved.

Diversity in the Monogenea and Digenea: does lifestyle matter?

If the cestodes are excluded, then the parasitic platyhelminths of fishes divide neatly into the external and monoxenous Monogenea and the internal and heteroxenous Digenea. Both groups have apparently had long associations of coevolution, host switching and adaptation with fishes and have become highly successful in their respective habitats. Current estimates of species richness for the two groups suggest that they may be remarkably similar. Here we consider the nature of the diversity of the Monogenea. and Digenea of fishes in terms of richness of species and higher taxa to determine what processes may be responsible for observed differences. The Monogenea includes at least two super-genera (Dactylogyrus and Gyrodactylus) each of which has hundreds of species, no comparable genera are found in the Digenea. Possible reasons for this difference include the higher host specificity of monogeneans and their shorter generation Lime. If allowance is made for the vagaries of taxonomic 'lumping' and 'splitting', then there are probably comparable numbers of families of monogeneans and digeneans in fishes. However, the nature of the families differ profoundly. Richness in higher taxa (families) in the Digenea is explicable in terms of processes that appear to have been unimportant in the Monogenea. Readily identifiable sources of diversity in the Digenea are: recolonisation of fishes by taxa that arose in association with tetrapods; adoption of new sites within hosts; adoption of new diets and feeding mechanisms; adaptations relating to the exploitation of ecologically similar groups of fishes and second intermediate hosts; and adaptations relating to the exploitation of phylogenetic lineages of molluscs. In contrast, most higher- level monogenean diversity (other than that associated with the subclasses) relates principally to morphological specialisation for attachment by the haptor. (C) 2002 Australian Society for Parasitology Inc. Published by Elsevier Science Ltd. All rights reserved.

Observations of foehn onset in the Southern Alps, New Zealand

Local scale windfield and air mass characteristics during the onset of two foehn wind events in an alpine hydro-catchment are presented. Grounding of the topographically modified foehn was found to be dependent on daytime surface heating and topographic channelling of flow. The foehn front was observed to advance down-valley until the valley widened significantly. The foehn wind appeared to decouple from the surface downstream of the accelerated flow associated with the valley constriction. and to be lifted above local thermally generated circulations including a lake breeze. Towards evening. the foehn front retreated up valley in response to reduced surface heating and the intrusion into the study area of a deep and cool air mass associated with a regional scale mountain-plain circulation. Differences in the local windfield observed during both case study events reflect the importance of different thermal and dynamic forcings on airflow in complex terrain. These are the result of variation in surface energy exchanges, channelling and blocking of airflow. Observations presented here have both theoretical and applied implications with regard to forecasting foehn onset, wind hazard management, recreational activities and air quality management in alpine settings.

Analysis of the wind field and heat budget in an alpine lake basin during summertime fair weather conditions

Observational data collected in the Lake Tekapo hydro catchment of the Southern Alps in New Zealand are used to analyse the wind and temperature fields in the alpine lake basin during summertime fair weather conditions. Measurements from surface stations, pilot balloon and tethersonde soundings, Doppler sodar and an instrumented light aircraft provide evidence of multi-scale interacting wind systems, ranging from microscale slope winds to mesoscale coast-to-basin flows. Thermal forcing of the winds occurred due to differential heating as a consequence of orography and heterogeneous surface features, which is quantified by heat budget and pressure field analysis. The daytime vertical temperature structure was characterised by distinct layering. Features of particular interest are the formation of thermal internal boundary layers due to the lake-land discontinuity and the development of elevated mixed layers. The latter were generated by advective heating from the basin and valley sidewalls by slope winds and by a superimposed valley wind blowing from the basin over Lake Tekapo and up the tributary Godley Valley. Daytime heating in the basin and its tributary valleys caused the development of a strong horizontal temperature gradient between the basin atmosphere and that over the surrounding landscape, and hence the development of a mesoscale heat low over the basin. After noon, air from outside the basin started flowing over mountain saddles into the basin causing cooling in the lowest layers, whereas at ridge top height the horizontal air temperature gradient between inside and outside the basin continued to increase. In the early evening, a more massive intrusion of cold air caused rapid cooling and a transition to a rather uniform slightly stable stratification up to about 2000 m agl. The onset time of this rapid cooling varied about 1-2 h between observation sites and was probably triggered by the decay of up-slope winds inside the basin, which previously countered the intrusion of air over the surrounding ridges. The intrusion of air from outside the basin continued until about mid-night, when a northerly mountain wind from the Godley Valley became dominant. The results illustrate the extreme complexity that can be caused by the operation of thermal forcing processes at a wide range of spatial scales.