Electronic spectroscopy of biomolecules in solution: fluorescein dianion in water

A combined and sequential Monte Carlo-quantum mechanics methodology is used to describe the electronic absorption spectrum of the fluorescein dianion in water. Different sets of 100 statistically relevant configurations composed of the solute and several solvent molecules are sampled from the Monte Carlo simulation for a posteriori quantum mechanical calculations of the spectra. In the largest case the configurations are composed of fluorescein and 90 explicit water molecules embedded in the electrostatic field of all remaining water molecules within a distance of 11.3 angstrom. These configurations include 305 atoms and 842 valence electrons, justifying the use of a semi-empirical approach. The electronic spectrum is then calculated using the INDO/CIS method. The solvatochromic shift of fluorescein in water, compared with in isolation, is calculated using the discrete and explicit solvent models. The use of electrostatically embedded explicit water molecules, in INDO/CIS calculations, gives a good description of the spectral shift of the fluorescein dianion in aqueous environment. The results are verified to converge both statistically and with respect to the number of explicit solvent molecules used.

Polarization and Spectral Shift of Benzophenone in Supercritical Water

Monte Carlo simulation and quantum mechanics calculations based on the INDO/CIS and TD-DFT methods were utilized to study the solvatochromic shift of benzophenone when changing the environment from normal water to supercritical (P = 340.2 atm and T = 673 K) condition. Solute polarization increases the dipole moment of benzophenone, compared to gas phase, by 88 and 35% in normal and supercritical conditions, giving the in-solvent dipole value of 5.8 and 4.2 D, respectively. The average number of solute-solvent hydrogen bonds was analyzed, and a large decrease of 2.3 in normal water to only 0.8 in the supercritical environment was found. By using these polarized models of benzophenone in the two different conditions of water, we performed MC simulations to generate statistically uncorrelated configurations of the solute surrounded by the solvent molecules and subsequent quantum mechanics calculations on these configurations. When changing from normal to supercritical water environment, INDO/CIS calculations explicitly considering all valence electrons of the 235 solvent water molecules resulted in a solvatochromic shift of 1425 cm(-1) for the most intense transition of benzophenone, that is, slightly underestimated in comparison with the experimentally inferred result of 1700 cm(-1). TD-B3LYP/6-311+G(2d,p) calculations on the same configurations but with benzophenone electrostatically embedded in the 320 water molecules resulted in a solvatochromic shift of 1715 cm(-1) for this transition, in very good agreement with the experimental result. When using the unpolarized model of the benzophenone, this calculated solvatochromic shift was only 640 cm(-1). Additional calculations were also made by using BHandHLYP/6-311+G(2d,p) to analyze the effect of the asymptotic decay of the exchange functional. This study indicates that, contrary to the general expectation, there is a sizable solute polarization even in the low-density regime of supercritical condition and that the inclusion of this polarization is important for a reliable description of the spectral shifts considered here.

Polarization and solvatochromic shift of ortho-betaine in water

Betaine dyes are known to show very large transition energy shifts in different solvents. The ortho-betaine molecule - a simple two-ring prototype of the E-T(30) Reichardt dye - has been investigated theoretically from a combined statistical and quantum mechanics approach. Using sequential Monte Carlo (MC) simulations and MP2/cc-pVDZ calculations the in-water dipole moment of ortho-betaine is obtained as 12.30 +/- 0.05 D. This result shows a considerable increase of 75% compared to the in-vacuum dipole moment. For comparison, the use of a polarizable continuum model using the same MP2/cc-pVDZ leads to an in-water dipole moment of 11.6 D, in good agreement. This large polarization is incorporated in the classical potential for another MC simulation to generate solute-solvent configurations and to obtain the contribution of the polarization effect in the solvatochromic shift. Using statistically uncorrelated configurations and supermolecular INDO/CIS calculations, including the solute and, explicitly, 230 solvent water molecules, the statistically converged calculated shift is obtained here as 6360 cm(-1), in good agreement with the experimental result of 7550 cm(-1). (c) 2007 Elsevier B.V. All rights reserved.

Coup Coup Land : A Comparative Study of the Coups of Fiji

A thesis presented on the political history of Fiji from cession to Britain in 1874 compares and analyses the country’s four political coups. A military coup occurred in 1987 by Lt. Col Sitiveni Rabuka. Six months later he staged a self-coup. In 2000 George Speight staged an armed civilian coup or putsch, and in 2006 Commodore Frank Bainimarama, head of Fiji’s military forces, overthrew the government of Laisenia Qarase. This paper is an internal comparison of the four coups of which the aim is to examine why coups occur in Fiji. The conclusion is that the level of influence of the country’s traditional paramount chiefs is a strong causal factor in events leading to the political overthrows. Issues such as ethnicity, constitutionalism, democracy, traditionalism, and modernity make the study of the Fiji coups complex. All of the major actors involved have been present or have been somehow linked to each coup. Questions of leadership arise as do issues regarding pluralism and multiculturalism. These issues are discussed in this paper. The end result is that if the question of traditional leadership is not addressed within a democratic framework then Fiji will continue to have coups.

Calescharidae, a new family for the Tertiary to Recent Genera Caleschara MacGillivray and Tretosina Canu and Bassler (Bryozoa: Cheilostomata)

A new family of Cheilostomata, the Calescharidae, is introduced for the genus Caleschara MacGillivray and its Recent Australian typespecies, C. denticulata(MacGillivray), which is redefined from type and other material. The Australian Tertiary genus Tretosina Canu & Bassler and its type species,T. arcifera Canu & Bassler, are closely related,and are also assigned to the Calescharidae. The history and significance of family attributions of both genera are outlined, and RecentC. denticulata from Australian and other localities is distinguished from the Late Tertiary Victorian species C. parva Maplestone. Caleschara lithconis, sp. nov., from the Late Eocene of Victoria is one of the earliest known species: its morphology closely resembles a Recent form from the Philippines, C. junctifera Canu & Bassler. Another Recent species, Caleschara minuta (Maplestone) from the GilbertIslands, is a senior synonym of three other Indo-Pacific species,C. levinseni Harmer, C. laxa Canu & Bassler and Floridinella arculifera Canu & Bassler, and resembles the European Paleocene C. squamosa. Three other related species are briefly discussed. Close relationships to other families are problematic and are discussed; divergence in the early history of the cheilostomes is inferred.

First fossil finds of some Australian Bryozoa (Cheilostomata)

The abundant fossil record of well-preserved Bryozoa in samples from the Tertiary of Victoria and South Australia includes some 'first fossil finds' which are recorded here. Several are of species known from the Recent of the Australian or Indo-West-Pacific regions, but some represent genera with a much wider temporal and geographical range. Of the 11 species illustrated, six are known, or may be inferred, to have inhabited 'sand fauna' environments. Specimens of one species are complete enough to allow its formal description as Chlidoniopsis inopina sp. nov.

Dimorphic brooding zooids in the genus Adeona Lamouroux from Australia (Bryozoa: Cheilostomata)

The genus Adeona is a characteristic and common part of the Australian shelf fauna, extending to the tropical Indo-West Pacific. The genus first appears in the fossil record of the Miocene of south-eastern Australia. Zooid dimorphism has been recognised initially from subtle differences in the external appearance, which have not been described previously. Detailed examination has shown enlarged brooding zooids with marked differences from autozooids in the internal structure of the peristomes and in the occurrence of a primary calcified orifice.

Ostracoda from Lee Point on Shoal Bay, Northern Australia: part 3, podocopina (cytheracea)

The littoral environments present in Shoal Bay, Northern Territory (Australia) show a high diversity of ostracods cytheráceos (51 genera and 97 species). Probably this diversity is due to three factors: (1) marine environments warm and well oxygenated leading to a high level of biological productivity, (2) shallow marine environments favorable for the accumulation of material conchífero post mortem, and (3) a location central in the way of dispersal on the continental shelf between the regions of the Pacific and Southeast Asia. A particular feature of this fauna Cytherscea is that some genres, such as Alocopocythere, can be traced back to the Cretaceous when it first appeared in the shallow waters of the Tethys. In this overlay component of the ancient ostracods are the dominant fauna in partnerships of the modern Indo / Pacific, such as gender Keiji. While the Cytheracea ostracods are the dominant groups, especially the Cypridacea marine Bairdiacea and Plstycopina, are well represented and are quite different (fide Whatley et al., 1995, 1996). We describe here a new genre, Paraxestoleberis, and 15 new species: Dentibyíhere multituberosa, Dampiercythere papillolineata, Neocyíheromorpha papilloporosa, Loxoconcha catasíeros, Semicyrherura gamma, Callistocyíhere cookei, Loxocorniculum koolpionyahensis, Keúia interim, K. profundosculpia, K. parademissa, Quasibradleya leepoiníensis, Actinocyíhereis gippsi, Henryhowella sinespinosa, Poníicocyíhereis spatulospinosa and Paraxestoleberis posteroacuminata. Due to the limited material obtained, 16 species are kept in open nomenclature: Bythoceratina sp. Corallicyíhere sp. Venericythere sp. Tanella sp. Loxocorniculum sp. 1 L. sp. 2, Gambiella sp. Javanella sp. Paradoxostoma sp. Neomonoceratina sp., Bradley (sl) sp. Echinocytbereis (sl) sp. Plaíycyíhereis? sp. Alocopocyíhere sp. Xestoleberis sp. and Paraxestoleberis sp. The remaining 66 species have been described previously in other areas.

The pursuit of muscularity among adolescent boys in Fiji and Tonga

The desire for muscularity is tied to Western views of the male gender role, which prescribe that men be strong, physically fit and athletically successful. Although, these ideals have been primarily studied among Western adolescent boys, there is emerging evidence that the same ideals are valued and promoted among males from the Pacific Islands. The aim of the present study was to examine body image concerns associated with muscularity and the reasons for these concerns among Fijian and Tongan adolescent boys. Semi-structured interviews were conducted with 24 Indigenous Fijian, 24 Indo-Fijian, and 24 Tongan boys aged between 13 and 20 years. A thematic analysis of boys’ narratives showed that the pursuit of muscularity was a dominant theme for many boys. Boys’ reasons for pursing muscularity included the attainment of strength and fitness, sporting performance, physical work, dominance, and health. These findings are examined in relation to previous research with Western adolescent boys.

"Sins of their fathers" : culturally at risk children and the colonial state in Asia

In contact with their foreign surroundings, European enclaves throughout imperial Asia and Africa formed new cultural communities. Nevertheless, over time as Cooper and Stoler (1997) have argued, such colonial communities became subject to the same bourgeois project as experienced in the metropolitan centres to which they remained connected. If, in terms of that project, metropolitan European society was deemed vulnerable from a brutish and unruly working class, these colonial outposts of Western society were even more vulnerable to what was deemed to be the more insidious dangers of miscegenation and cultural hybridity. Where nineteenth century educators typically suggested that working class children were “at risk” of not being able to benefit from, and simultaneously representing “a risk to”, the emerging opportunities of bourgeois capitalist society, this “risk” was accentuated in the colonies by the additional category of race. Focussing on the question of children of mixed parentage as a category of “children at risk”, this paper examines the way educationists and politicians responded to what was perceived as “civilisational decline” in four such communities - the Dutch East Indies, British India, (British) Australia and French Indo-China - to demonstrate the universality of these concerns in Imperial Asia.

Body image and body change strategies among adolescent males and females from Fiji, Tonga and Australia

The current study was designed to investigate the body image and body change strategies of adolescents from Fiji, Tonga and Australia. Participants were 628 Fijians, 463 Indo-Fijians, 598 Tongans and 535 European Australians. Adolescents completed measures of height, weight, body dissatisfaction, strategies to lose weight, increase weight and increase muscles. The results demonstrated that overweight adolescents were more dissatisfied with their bodies than those who were normal weight. Overweight Fijians and Tongans were more satisfied with their body than Indo-Fijian or Australian adolescents. Tongans, followed by Fijians and Indo-Fijians, were more likely to engage in strategies to lose weight, increase weight and increase muscles. These results are consistent with the focus in Fiji and Tonga on the value of the large body ideal, but may also reflect the recent focus on the attainment of a healthy body size.

Education and the colonial construction of whiteness

European imperialism spawned settlements of invasive white communities throughout Asia and Africa. Stoler and Cooper (1997: 27) argue these evolving colonial societies became subject to what amounts to an extended bourgeois project such that "we can not understand the construction of whiteness without exploring its class dimensions". If in terms of that project, nineteenth-century metropolitan society was deemed vulnerable to the ravages of a brutish and unruly working class, these white colonial outposts, whether constituted as settler colonies or colonies of exploitation, were even more vulnerable to the more insidious danger of miscegenation. Racial intermingling became simultaneously an issue of class and race. Imperialism therefore added a further dimension to the on-going detinition of "bourgeois-ness": the discourse of whiteness transforming a national discourse into a discourse on civilisation.

In focusing on education as the colonial authorities' response to what they perceived of as the danger of mixed parentage, this article develops a comparative framework that links coloniai settlements in Asia and Australia. It examines the discourse surrounding miscegenation, education and the "rising generation" in the late nineteenth and early twentieth centuries in the Dutch East Indies British India, French Indo China and (British) Australia. In so doing, I demonstrate the universality of a linked discourse of whiteness and class across Imperial Asia.

Mitochondrial DNA diversity of the Asian moon scallop, Amusium pleuronectes (Pectinidae), in Thailand

Sequence variation of the mitochondrial DNA 16S rRNA region of the Asian moon scallop, Amusium pleuronectes, was surveyed in seven populations along the coast of Thailand. A total of 16 unique haplotypes were detected among 174 individuals with a total 27 variable sites out of 534 bp sequenced. The mitochondrial haplotypes grouped into two distinct arrays (estimated to differ by about 2.62% to 2.99% nucleotide divergence) that characterized samples collected from the Gulf of Thailand versus the Andaman Sea. Low levels of intrapopulation variation were observed, while in contrast, significant divergence was observed between populations from the Gulf of Thailand and Andaman Sea. Results of AMOVA reveal a high F ST value (0.765) and showed that the majority of the total genetic variance (76.03%) occurred among groups (i.e., Andaman Sea and the Gulf of Thailand) and little among populations within the group (0.52%) and within populations (23.45%). The genetic differentiation between the populations recorded in the present study is similar to that observed in a variety of marine species in the Indo-Pacific. The implications of the findings for management of A. pleuronectes genetic resources in Thailand are discussed.

Phylogenetic relationships among nine scallop species (Bivalvia : Pectinidae) inferred from nucleotide sequences of one mitochondrial and three nuclear gene regions

Current knowledge of the evolutionary relationships among scallop species (Mollusca: Bivalvia: Pectinidae) in the Indo-Pacific region is rather scanty. To enhance the understanding of the relationships within this group, phylogenies of nine species of scallops with the majority from coastal regions of Thailand, were reconstructed by maximum parsimony, maximum likelihood, and Bayesian methods using sequences of the 16S rRNA of the mitochondrial genome, and a fragment containing the ITS1, 5.8S and ITS2 genes of the nuclear DNA. The trees that resulted from the three methods of analysis were topologically identical, however, gained different levels of support at some nodes. Nine species were clustered into two major clades, corresponding to two subfamilies (Pectininae and Chlamydinae) of the three currently recognized subfamilies within Pectinidae. Overall, the relationships reported herein are mostly in accordance with the previous molecular studies that used sequences of the mtDNA cytochrome oxidase subunit I, and the classification system based on microsculpture of shell features and morphological characteristics of juveniles. Levels of divergences were different among genes (i.e., the 5.8S gene showed the lowest levels of nucleotide divergence at all levels, whereas the 16S rRNA showed the highest level of variation within species, and ITS2 gene revealed the highest level of divergence at higher levels).