Complexes of Lanthanide Perchlorates with N-(2-Pyrimidyl)benzamide

New complexes of lanthanide perchlorates with N-(2-pyrimidyl)benzamide (BApymH) of the general formulae [Ln(BApymH)4](ClO4)3 (where Ln = La-Yb and Y) have been synthesised and characterised by chemical analysis, molar conductivity and physical methods such as infrared and electronic spectra in the visible region. Molar conductance and infrared data point to the ionic nature of the per-chlorate groups in the complexes. IR data unequivocally proves that the coordination of the ligand to the metal ion takes place in a bidentate fashion through the oxygen of the secondary amide and nitrogen of the pyrimidine ring. From a comparison of the visible electronic spectral shapes of the Nd3+ and Ho3+ complexes with those reported in the literature, an eight coordinate geometry around the metal ion has tentatively been assigned in all the complexes.

Migration of green turtles (Chelonia mydas) from Australasian feeding grounds inferred from genetic analyses

Coastal seagrass habitats in tropical and subtropical regions support aggregations of resident green turtles (Chelonia mydas) from several genetically distinct breeding populations. Migration of individuals to their respective dispersed breeding sites provides a complex pattern of migratory connectivity among nesting and feeding habitats of this species. An understanding of this pattern is important in regions where the persistence of populations is under threat from anthropogenic impacts. The present study uses mitochondrial DNA and mixed-stock analyses to assess the connectivity among seven feeding grounds across the north Australian coast and adjacent areas and 17 genetically distinct breeding populations from the Indo-Pacific region. It was hypothesised that large and geographically proximate breeding populations would dominate at nearby feeding grounds. As expected, each sampled feeding area appears to support multiple breeding populations, with two aggregations dominated by a local breeding population. Geographic distance between breeding and feeding habitat strongly influenced whether a breeding population contributed to a feeding ground (wi = 0.654); however, neither distance nor size of a breeding population was a good predictor of the extent of their contribution. The differential proportional contributions suggest the impact of anthropogenic mortality at feeding grounds should be assessed on a case-by-case basis.

Effect of constant temperature on the development of Sceliodes cordalis (Doubleday) (Lepidoptera: Crambidae) on eggplant.

Abstract Sceliodes cordalis, eggfruit caterpillar, is an important pest of eggplant in Australia but little information was available on its biology. This study was conducted to determine the effect of temperature on the development on eggplant of eggs, larvae and pupae. Insects were reared at five constant temperatures from 20.5°C to 30.5°C with a 12:12 L : D photoperiod and the thermal summation model was fitted to the developmental rate data. Developmental zeroes and thermal constants of 11.22°C and 61.32 day-degrees for eggs, 12.03°C and 179.60 day-degrees for larvae, and 14.43°C and 107.03 day-degrees for pupae were determined. Several larvae reared at 20.5°C entered diapause.

Axial heat conduction effects in natural convection along a vertical cylinder

MANY TRANSPORprTo cesses occur in nature and in industrial applications in which the transfer of heat is governed by the process of natural convection. Natural convection arises in fluids when the temperature changes cause density variations leading to buoyancy forces. An excellent review of natural convection flows has been given by Ede [I]. Recently, Minkowycz and Sparrow [2, 31, Cebeci [4], and Aziz and Na [S] have studied the steady, laminar, incompressible, natural convection flow over a vertical cylinder using a local nonsimilarity method, a finite-difference scheme, and an improved perturbation method, respectively. However, they did not take into account the effect ofaxial heat conduction for small Prandtl number. It is known that the axial heat conductioneffect becomesimportant for low-Prandtl-number fluids such as a liquid metal.

Gene-based pleiotropy across migraine with aura and migraine without aura patient groups

Introduction: It is unclear whether patients diagnosed according to International Classification of Headache Disorders criteria for migraine with aura (MA) and migraine without aura (MO) experience distinct disorders or whether their migraine subtypes are genetically related. Aim: Using a novel gene-based (statistical) approach, we aimed to identify individual genes and pathways associated both with MA and MO. Methods: Gene-based tests were performed using genome-wide association summary statistic results from the most recent International Headache Genetics Consortium study comparing 4505 MA cases with 34,813 controls and 4038 MO cases with 40,294 controls. After accounting for non-independence of gene-based test results, we examined the significance of the proportion of shared genes associated with MA and MO. Results: We found a significant overlap in genes associated with MA and MO. Of the total 1514 genes with a nominally significant gene-based p value (pgene-based ≤ 0.05) in the MA subgroup, 107 also produced pgene-based ≤ 0.05 in the MO subgroup. The proportion of overlapping genes is almost double the empirically derived null expectation, producing significant evidence of gene-based overlap (pleiotropy) (pbinomial-test = 1.5 × 10–4). Combining results across MA and MO, six genes produced genome-wide significant gene-based p values. Four of these genes (TRPM8, UFL1, FHL5 and LRP1) were located in close proximity to previously reported genome-wide significant SNPs for migraine, while two genes, TARBP2 and NPFF separated by just 259 bp on chromosome 12q13.13, represent a novel risk locus. The genes overlapping in both migraine types were enriched for functions related to inflammation, the cardiovascular system and connective tissue. Conclusions: Our results provide novel insight into the likely genes and biological mechanisms that underlie both MA and MO, and when combined with previous data, highlight the neuropeptide FF-amide peptide encoding gene (NPFF) as a novel candidate risk gene for both types of migraine.

Triplet-state Photophysics and Transient Photochemistry of Cyclic Enethiones A Laser Flash Photolysis Study

The triplets of four cyclic enethiones, including thiocoumarin, have been investigated by nanosecond laser flash photolysis. Data are presented for transient spectra and kinetics associated with triplets, quantum yields of intersystem crossing and singlet oxygen photosensitization. The quenching of the thiocoumarin triplet (A:, = 485 nm, E:,, = 8.8 x lo3 dm3 mol-' cm-'in benzene) by several olefins, amines and hydrogen donors occurs with rate constants of 107-5 x lo9 dm3 mol-' s-'; the lower limits of quantum yields ( c#+~) for the related photoreactions, estimated from ground-state depletion, are generally small (0.0-0.1 1 in benzene, except for good hydrogen donors, namely, p-methoxythiophenol and tri-n-butylstannane) . The radical anion of thiocoumarin (A,,, = 405-435 nm) is formed in two stages upon triplet quenching by triethylamine in acetonitrile; the fast component is the result of direct electron transfer to the triplet and the slower component is assigned to secondary photoreduction of the thione ground state by the a-aminoalkyl radical derived from the triethylamine radical-cation.

Structural studies of analgesics and their interactions. VII. Stereoisomerism and disorder in the structure of oxyphenbutazone monohydrate

Oxyphenbutazone, C19H20N203, a metabolite and perhaps the active form of phenylbutazone, is a widely used non-narcotic analgesic and anti-inflammatory pyrazolidinedione derivative. The monohydrate of the compound crystallizes in the triclinic space group Pi with two molecules in a unit cell of dimensions a -- 9.491 (4), b = 10.261 (5), c = 11.036 (3)A and ¢~ = 72.2 (1), fl = 64.3 (1), 7 = 73.0 (1) °. The structure was solved by direct methods and refined to an R value of 0.107 for 1498 observed reflections. The butyl group in the molecule is disordered. The hydroxyl group occupies two sites with unequal occupancies. On account of the asymmetry at the two N atoms and one of the C atoms in the central five-membered ring, the molecule can exist in eight isomeric states, of which four are sterically unfavourable. The disorder in the position of the hydroxyl group can be readily explained on the basis of the existence, with unequal abundances, of all four sterically favourable isomers.The bond lengths and angles in the molecule are similar to those in phenylbutazone. The crystal structure is stabilized by van der Waals interactions, and O-H... O hydrogen bonds involving the carbonyl and the hydroxyl groups as well as a water molecule.

Irreversible Thermal Denaturation Of Bovine Pancreatic Ribonuclease-A

The isolation and characterization of the products formed during the irreversible thermal denaturation of enzyme RNAase-A are described. RNAase-A, when maintained in aqueous solution at pH 7.0 and 70° for 2 h, gives soluble products which have been fractionated by gel filtration on Sephadex G-75 into four components. These components are designated RNAase-At1, RNAase-At2, RNAase-At3 and RNAase-At4 according to the order of their elution from Sephadex G-75. RNAase-At4 shows the same specific activity towards yeast RNA as native RNAase-A and is virtually indistinguishable from it by the physical methods employed. However, chromatography on CM-cellulose separates it into three components that show the same u.v. spectra and specific activity towards yeast RNA as native RNAase-A. RNAase-At1, RNAase-At2and RNAase-At3 are all structurally altered derivatives of RNAase-A and they exhibit low specific activity (5–10%) towards yeast RNA. In the presence of added S-protein, all these derivatives show greatly enhanced enzymic activity. RNAase-At1 and RNAase-At2 are polymers, covalently crosslinked by intermolecular disulfide bridges; whereas RNAase-At3 is a monomer. Physical studies such as 1H-n.m.r., sedimentation analysis, u.v. absorption spectra and CD spectra reveal that RNAase-At3 is a unfolded derivative of RNAase-A. However, it is seen to possess sufficient residual structure which gives rise to a low but easily detectable enzymic activity.

Fabrication and characterization of polyterpenol as an insulating layer and incorporated organic field effect transistor

A non-synthetic polymer material, polyterpenol, was fabricated using a dry polymerization process namely RF plasma polymerization from an environmentally friendly monomer and its surface, optical and electrical properties investigated. Polyterpenol films were found to be transparent over the visible wavelength range, with a smooth surface with an average roughness of less than 0.4 nm and hardness of 0.4 GPa. The dielectric constant of 3.4 for polyterpenol was higher than that of the conventional polymer materials used in the organic electronic devices. The non-synthetic polymer material was then implemented as a surface modification of the gate insulator in field effect transistor (OFET) and the properties of the device were examined. In comparison to the similar device without the polymer insulating layer, the polyterpenol based OFET device showed significant improvements. The addition of the polyterpenol interlayer in the OFET shifted the threshold voltage significantly; + 20 V to -3 V. The presence of trapped charge was not observed in the polyterpenol interlayer. This assisted in the improvement of effective mobility from 0.012 to 0.021 cm 2/Vs. The switching property of the polyterpenol based OFET was also improved; 107 compared to 104. The results showed that the non-synthetic polyterpenol polymer film is a promising candidate of insulators in electronic devices.

Effect of iodine doping on surface and optical properties of polyterpenol thin films

This study presents the effect of iodine doping on optical and surface properties of polyterpenol thin films deposited from non-synthetic precursor by means of plasma polymerisation. Spectroscopic ellipsometry studies showed iodine doping reduced the optical band gap from 2.82 eV to 1.50 eV for pristine and doped samples respectively. Higher levels of doping notably reduced the transparency of films, an issue if material is considered for applications that require high transparency. Contact angle studies demonstrated higher hydrophilicity for films deposited at increased doping levels, results confirmed by XPS Spectroscopy and FTIR. Doping had no significant effect on the surface profile or roughness of the film.

A study of a retention of antimicrobial activity by plasma polymerized terpinen-4-ol thin films

Terpinen-4-ol is the main constituent of Melaleuca alternifolia essential oil known for its biocidal and anti-inflammatory properties. The possibility of fabricating polymer thin films from terpinen-4-ol using radio frequency (RF) plasma polymerisation for the prevention of the growth of Pseudomonas aeruginosa was investigated, and the properties of the resultant films compared against their biologically active precursor. Films fabricated at 10 W prevented bacterial attachment and EPS secretion, whilst polyterpenol films deposited at 25 W demonstrated no biocidal activity against the pathogen.

Digitoitujen väri-infrailmakuvien numeerinen monikuvatulkinta metsäninventoinnissa

The use of remote sensing imagery as auxiliary data in forest inventory is based on the correlation between features extracted from the images and the ground truth. The bidirectional reflectance and radial displacement cause variation in image features located in different segments of the image but forest characteristics remaining the same. The variation has so far been diminished by different radiometric corrections. In this study the use of sun azimuth based converted image co-ordinates was examined to supplement auxiliary data extracted from digitised aerial photographs. The method was considered as an alternative for radiometric corrections. Additionally, the usefulness of multi-image interpretation of digitised aerial photographs in regression estimation of forest characteristics was studied. The state owned study area located in Leivonmäki, Central Finland and the study material consisted of five digitised and ortho-rectified colour-infrared (CIR) aerial photographs and field measurements of 388 plots, out of which 194 were relascope (Bitterlich) plots and 194 were concentric circular plots. Both the image data and the field measurements were from the year 1999. When examining the effect of the location of the image point on pixel values and texture features of Finnish forest plots in digitised CIR photographs the clearest differences were found between front-and back-lighted image halves. Inside the image half the differences between different blocks were clearly bigger on the front-lighted half than on the back-lighted half. The strength of the phenomenon varied by forest category. The differences between pixel values extracted from different image blocks were greatest in developed and mature stands and smallest in young stands. The differences between texture features were greatest in developing stands and smallest in young and mature stands. The logarithm of timber volume per hectare and the angular transformation of the proportion of broadleaved trees of the total volume were used as dependent variables in regression models. Five different converted image co-ordinates based trend surfaces were used in models in order to diminish the effect of the bidirectional reflectance. The reference model of total volume, in which the location of the image point had been ignored, resulted in RMSE of 1,268 calculated from test material. The best of the trend surfaces was the complete third order surface, which resulted in RMSE of 1,107. The reference model of the proportion of broadleaved trees resulted in RMSE of 0,4292 and the second order trend surface was the best, resulting in RMSE of 0,4270. The trend surface method is applicable, but it has to be applied by forest category and by variable. The usefulness of multi-image interpretation of digitised aerial photographs was studied by building comparable regression models using either the front-lighted image features, back-lighted image features or both. The two-image model turned out to be slightly better than the one-image models in total volume estimation. The best one-image model resulted in RMSE of 1,098 and the two-image model resulted in RMSE of 1,090. The homologous features did not improve the models of the proportion of broadleaved trees. The overall result gives motivation for further research of multi-image interpretation. The focus may be improving regression estimation and feature selection or examination of stratification used in two-phase sampling inventory techniques. Keywords: forest inventory, digitised aerial photograph, bidirectional reflectance, converted image co­ordinates, regression estimation, multi-image interpretation, pixel value, texture, trend surface

Separate and interacting effects within the catechol-O-methyltransferase (COMT) are associated with schizophrenia

Several lines of evidence have implicated the catechol-O-methyltransferase (COMT) gene as a candidate for schizophrenia (SZ) susceptibility, not only because it encodes a key dopamine catabolic enzyme but also because it maps to the velocardiofacial syndrome region of chromosome 22q11 which has long been associated with SZ predisposition. The interest in COMT as a candidate SZ risk factor has led to numerous case-control and family-based studies, with the majority placing emphasis on examining a functional Val/Met polymorphism within this enzyme. Unfortunately, these studies have continually produced conflicting results. To assess the genetic contribution of other COMT variants to SZ susceptibility, we investigated three single-nucleotide polymorphisms (SNPs) (rs737865, rs4633, rs165599) in addition to the Val/Met variant (rs4680) in a highly selected sample of Australian Caucasian families containing 107 patients with SZ. The Val/Met and rs4633 variants showed nominally significant associations with SZ (P<0.05), although neither of the individual SNPs remained significant after adjusting for multiple testing (most significant P=0.1174). However, haplotype analyses showed strong evidence of an association; the most significant being the three-marker haplotype rs737865-rs4680-rs165599 (global P=0.0022), which spans more than 26 kb. Importantly, conditional analyses indicated the presence of two separate and interacting effects within this haplotype, irrespective of gender. In addition, our results indicate the Val/Met polymorphism is not disease-causing and is simply in strong linkage disequilibrium with a causative effect, which interacts with another as yet unidentified variant approximately 20 kb away. These results may help explain the inconsistent results reported on the Val/Met polymorphism and have important implications for future investigations into the role of COMT in SZ susceptibility.