Electron- Spin-Resonance studies of phase transitions in double propionates

Detailed ESR investigations of Mn2+ substituting for Ca2+ in Ca2Sr(C2H5COO)6, (DSP) and Ca2Pb(C2H5COO)6, (DLP) and Ca2Ba(C2H5COO)6, (DBP), in single crystals and powders, over the temperature range from 300°C to -180°C have been carried out to study the successive phase transitions in these compounds. Spectra have been analyzed in terms of axial spin Hamiltonians and the temperature dependences of the parameters studied. Across the I-II transition, new physically and chemically inequivalent sites appear indicating the disappearance of the diad axes on which the propionate groups are located, bringing out the connection between the motional states of the propionate groups and the occurrence of ferroelectricity. The II-III transition also causes chemically inequivalent sites to develop, indicating that the transitions may not be isomorphous as believed previously. Similarities and dissimilarities of the ESR spectra of DLP, DSP and DBP are discussed in relation to the phase transitions.

Preparation and properties of nickel(II) complex dyes

The preparation and properties of five new dyes derived from nickel(I1) ions and aromatic azo derivatives of ethylenebls(P-ketoesters) are reported.

Structure-thermal behaviour studies on the salicylato complex of cobalt

The salicylato complex of cobalt was synthesized and its structure established to be [Co(sal)2] · 4 H2O, where, sal =, from elemental analysis, IR spectroscopy, magnetic susceptibility, cryoscopy and conductivity. The X-ray diffractogram of the complex has been given. Thermal decomposition has been studied in air by thermogravimetry (TG), differential thermal analysis and differential scanning calorimetry. TG shows three main steps of decomposition. The intermediates formed at various stages were collected and analysed. From the TG results and chemical analysis of the intermediates, a mechanism has been proposed for the thermal decomposition of the complex, leading to the oxide formation in the final stage.

The role of tillage, fertiliser and forage species in sustaining dairying based on crops in southern Queensland 2. Double-crop and summer sole-crop systems.

Dairy farms located in the subtropical cereal belt of Australia rely on winter and summer cereal crops, rather than pastures, for their forage base. Crops are mostly established in tilled seedbeds and the system is vulnerable to fertility decline and water erosion, particularly over summer fallows. Field studies were conducted over 5 years on contrasting soil types, a Vertosol and Sodosol, in the 650-mm annual-rainfall zone to evaluate the benefits of a modified cropping program on forage productivity and the soil-resource base. Growing forage sorghum as a double-crop with oats increased total mean annual production over that of winter sole-crop systems by 40% and 100% on the Vertosol and Sodosol sites respectively. However, mean annual winter crop yield was halved and overall forage quality was lower. Ninety per cent of the variation in winter crop yield was attributable to fallow and in-crop rainfall. Replacing forage sorghum with the annual legume lablab reduced fertiliser nitrogen (N) requirements and increased forage N concentration, but reduced overall annual yield. Compared with sole-cropped oats, double-cropping reduced the risk of erosion by extending the duration of soil water deficits and increasing the time ground was under plant cover. When grown as a sole-crop, well fertilised forage sorghum achieved a mean annual cumulative yield of 9.64 and 6.05 t DM/ha on the Vertosol and Sodosol, respectively, being about twice that of sole-cropped oats. Forage sorghum established using zero-tillage practices and fertilised at 175 kg N/ha. crop achieved a significantly higher yield and forage N concentration than did the industry-standard forage sorghum (conventional tillage and 55 kg N/ha. crop) on the Vertosol but not on the Sodosol. On the Vertosol, mean annual yield increased from 5.65 to 9.64 t DM/ha (33 kg DM/kg N fertiliser applied above the base rate); the difference in the response between the two sites was attributed to soil type and fertiliser history. Changing both tillage practices and N-fertiliser rate had no affect on fallow water-storage efficiency but did improve fallow ground cover. When forage sorghum, grown as a sole crop, was replaced with lablab in 3 of the 5 years, overall forage N concentration increased significantly, and on the Vertosol, yield and soil nitrate-N reserves also increased significantly relative to industry-standard sorghum. All forage systems maintained or increased the concentration of soil nitrate-N (0-1.2-m soil layer) over the course of the study. Relative to sole-crop oats, alternative forage systems were generally beneficial to the concentration of surface-soil (0-0.1 m) organic carbon and systems that included sorghum showed most promise for increasing soil organic carbon concentration. We conclude that an emphasis on double-or summer sole-cropping rather than winter sole-cropping will advantage both farm productivity and the soil-resource base.

Complex permittivity measurements of RF plasma polymerized polyterpenol organic thin films employing split post dielectric resonator

In the fields of organic electronics and biotechnology, applications for organic polymer thin films fabricated using low-temperature non-equilibrium plasma techniques are gaining significant attention because of the physical and chemical stability of thin films and the low cost of production. Polymer thin films were fabricated from non-synthetic terpinen-4-ol using radiofrequency polymerization (13.56 MHz) on low loss dielectric substrates and their permittivity properties were ascertained to determine potential applications for these organic films. Real and imaginary parts of permittivity as a function of frequency were measured using the variable angle spectroscopic ellipsometer. The real part of permittivity (k) was found to be between 2.34 and 2.65 in the wavelength region of 400–1100 nm, indicating a potential low-k material. These permittivity values were confirmed at microwave frequencies. Dielectric properties of polyterpenol films were measured by means of split post dielectric resonators (SPDRs) operating at frequencies of 10 GHz and 20 GHz. Permittivity increased for samples deposited at higher RF energy – from 2.65 (25 W) to 2.83 (75 W) measured by a 20-GHz SPDR and from 2.32 (25 W) to 2.53 (100 W) obtained using a 10-GHz SPDR. The error in permittivity measurement was predominantly attributed to the uncertainty in film thickness measurement.

Investigation of interfacial charging and discharging in double-layer pentacene-based metal-insulator-metal device with polyterpenol blocking layer using electric field induced second harmonic generation

Time-resolved electric field induced second harmonic generation technique was used to probe the carrier transients within double-layer pentacene-based MIM devices. Polyterpenol thin films fabricated from non-synthetic environmentally sustainable source were used as a blocking layer to assist in visualisation of single-species carrier transportation during charging and discharging under different bias conditions. Results demonstrated that carrier transients were comprised of charging on electrodes, followed by carrier injection and charging of the interface. Polyterpenol was demonstrated to be a sound blocking material and can therefore be effectively used for probing of double-layer devices using EFISHG.

Stem cankers on sunflower (Helianthus annuus) in Australia reveal a complex of pathogenic Diaporthe (Phomopsis) species.

The identification of Diaporthe (anamorph Phomopsis) species associated with stem canker of sunflower (Helianthus annuus) in Australia was studied using morphology, DNA sequence analysis and pathology. Phylogenetic analysis revealed three clades that did not correspond with known taxa, and these are believed to represent novel species. Diaporthe gulyae sp. nov. is described for isolates that caused a severe stem canker, specifically pale brown to dark brown, irregularly shaped lesions centred at the stem nodes with pith deterioration and mid-stem lodging. This pathogenicity of D. gulyae was confirmed by satisfying Koch's Postulates. These symptoms are almost identical to those of sunflower stem canker caused by D. helianthi that can cause yield reductions of up to 40% in Europe and the USA, although it has not been found in Australia. We show that there has been broad misapplication of the name D. helianthi to many isolates of Diaporthe ( Phomopsis) found causing, or associated with, stem cankers on sunflower. In GenBank, a number of isolates had been identified as D. helianthi, which were accommodated in several clades by molecular phylogenetic analysis. Two less damaging species, D. kochmanii sp. nov. and D. kongii sp. nov., are also described from cankers on sunflower in Australia.

Visualization of enantiomers using natural abundant 13C-filtered single and double quantum selective refocusing experiments: Application to small chiral molecules

The routine use of proton NMR for the visualization of enantiomers, aligned in the chiral liquid crystal solvent poly-γ-benzyl-l-glutamate (PBLG), is restricted due to severe loss of resolution arising from large number of pair wise interaction of nuclear spins. In the present study, we have designed two experimental techniques for their visualization utilizing the natural abundance 13C edited selective refocusing of single quantum (CH-SERF) and double quantum (CH-DQSERF) coherences. The methods achieve chiral discrimination and aid in the simultaneous determination of homonuclear couplings between active and passive spins and heteronuclear couplings between the excited protons and the participating 13C spin. The CH-SERF also overcomes the problem of overlap of central transitions of the methyl selective refocusing (SERF) experiment resulting in better chiral discrimination. Theoretical description of the evolution of magnetization in both the sequences has been discussed using polarization operator formalism.

Interaction of Metal Ions with 2'-Deoxyribonucleotides. Crystal and Molecular Structure of a Cobalt(l1) Complex with 2'-Deoxyinosine 5'-Monophosphate

The crystal structure of the cobalt( 11) complex with 2'-deoxyinosine 5'-monophosphate (5'- dlMP), [Co(5'-dlMP) (H,0),]-2H20, has been analysed by X-ray diffraction. The complex crystallizes in the space group P2,2,2, with a = 6.877(3), b = 10.904(2), c = 25.421 (6) A, and Z = 4. The structure was solved by the heavy-atom method and refined to an R value of 0.043 using 1 776 unique reflections. The cobalt ion binds only to the 6-oxopurine base of the nucleotide at the N(7) position, the octahedral co-ordination of the metal being completed by five water oxygens. The phosphate oxygens are involved in hydrogen bonding with the co-ordinated water molecules. The structure is closely similar to that of the corresponding ribonucleotide complex. The nucleotide has the energetically preferred conformation: an anti base, a C(3') -endo sugar pucker, and a gauche-gauche conformation about the C(4')-C( 5') bond. The significance of sugar puckering in the monomeric complexes of general formula [ M (5'-nucleotide) (H20),] is explained in terms of the structural requirements for metal-water-phosphate bridging interactions.

Complex carbohydrates: 1. Conformational studies on some oligosaccharides related to N-glycosyl proteins which interact with concanavalin A

Empirical potential energy calculations have been carried out to determine the preferred conformations of some oligosaccharides having the trimannosidic core structure (Man3GlcNAc2) and which interact with concanavalin A. In the minimum energy conformations for the trimannosidic core the mannose residue on the Man α(1–6) arm comes close to one of the N-acetylglucosamine residues of the core. The addition of N-acetylglucosamine residues to the terminal mannose residues does not alter the preferred conformation of the trimannosidic core although it alters the relative preference of some of the higher energy conformations. The minimum energy conformation broadly agrees with available X-ray data. The presence of a bisecting N-acetylglucosamine residue on the middle mannose does not push the trimannosidic core to any new conformation but it does alter the relative preference for a particular conformation.

Complex carbohydrates: 2. The modes of binding of complex carbohydrates to concanavalin A - a computer modelling approach

The probable modes of binding of some complex carbohydrates, which have the trimannosidic core structure (Man3GlcNAc2), to concanavalin A (Con A) have been determined using a computer modelling technique. These studies show that Con a can bind to the terminal mannose residues of the trimannosidic core structure and to the internal mannosyl as well as to the terminal N-acetylglucosamine residues of the N-acetylglucosamine substituted trimannosidic core structure. The oligosaccharide with terminal mannose residues can bind in its minimum energy conformers, whereas the oligosaccharide with internal mannosyl and terminal N-acetylglucosamine residues can bind only in higher energy conformers. In addition the former oligosaccharide forms more hydrogen bonds with Con A than the latter. These results suggest that, for these oligosaccharides, the terminal mannose residue has a much higher probability of reaching the binding site than either the internal mannosyl or the terminal N-acetylglucosamine residues. The substitution of a bisecting N-acetylglucosamine residue on these oligosaccharides, affects significantly the accessibility of the residues which bind to Con A and thereby reduces their binding affinity. It thus seems that the binding affinity of an oligosaccharide to Con A depends not only on the number of sugar residues which possess free 3-, 4- and 6-hydroxyl groups but also on the accessibility of these sugar residues to Con A. This study also reveals that the sugar binding site of Con A is small and that the interactions between Con A and carbohydrates are extended slightly beyond the single sugar residue that is placed in the binding site.

The importance of modelling heterogeneity in complex disease: application to NIMH Schizophrenia Genetics Initiative data

As for other complex diseases, linkage analyses of schizophrenia (SZ) have produced evidence for numerous chromosomal regions, with inconsistent results reported across studies. The presence of locus heterogeneity appears likely and may reduce the power of linkage analyses if homogeneity is assumed. In addition, when multiple heterogeneous datasets are pooled, inter-sample variation in the proportion of linked families (alpha) may diminish the power of the pooled sample to detect susceptibility loci, in spite of the larger sample size obtained. We compare the significance of linkage findings obtained using allele-sharing LOD scores (LOD(exp))-which assume homogeneity-and heterogeneity LOD scores (HLOD) in European American and African American NIMH SZ families. We also pool these two samples and evaluate the relative power of the LOD(exp) and two different heterogeneity statistics. One of these (HLOD-P) estimates the heterogeneity parameter alpha only in aggregate data, while the second (HLOD-S) determines alpha separately for each sample. In separate and combined data, we show consistently improved performance of HLOD scores over LOD(exp). Notably, genome-wide significant evidence for linkage is obtained at chromosome 10p in the European American sample using a recessive HLOD score. When the two samples are combined, linkage at the 10p locus also achieves genome-wide significance under HLOD-S, but not HLOD-P. Using HLOD-S, improved evidence for linkage was also obtained for a previously reported region on chromosome 15q. In linkage analyses of complex disease, power may be maximised by routinely modelling locus heterogeneity within individual datasets, even when multiple datasets are combined to form larger samples.

From spent Mg/Al layered double hydroxide to porous carbon materials

Adsorption has been considered as an efficient method for the treatment of dye effluents, but properdisposal of the spent adsorbents is still a challenge. This work attempts to provide a facile methodto reutilize the spent Mg/Al layered double hydroxide (Mg/Al-LDH) after the adsorption of orange II(OII). Herein, the spent hybrid was carbonized under the protection of nitrogen, and then washedwith acid to obtain porous carbon materials. Thermogravimetric analysis results suggested that thecarbonization could be well achieved above 600◦C, as mass loss of the spent hybrid gradually stabilized. Therefore, the carbonization process was carried out at 600, 800, and 1000 ◦C, respectively. Scanning electron microscope showed that the obtained carbon materials possessed a crooked flaky morphology. Nitrogen adsorption–desorption results showed that the carbon materials had large BET surface area and pore volume, e.g., 1426 m2/g and 1.67 cm3/g for the sample carbonized at 800 ◦C. Moreover, the pore structure and surface chemistry compositions were tunable, as they were sensitive to the temperature. Toluene adsorption results demonstrated that the carbon materials had high efficiency in toluene removal. This work provided a facile approach for synthesizing porous carbon materials using spent Mg/Al-LDH.

ESR studies of phase transitions in double propionates

Detailed ESR investigations of Mn2+ substituting for Ca2+ in Ca2Sr(C2H5COO)6 (DSP), Ca2Pb(C2H5COO)6 (DLP) and Ca2Ba(C2H5COO)6 (DBP), in single crystals and powders, over the temperature range from 200°C to -180°C have been carried out to study the successive phase transitions in these compounds. (DSP: [Tetragonal] ← 8.5°C → [tetragonal, ferroelectric] [tetragonal] ← -169°C → [monoclinic, ferroelectric]; DLP : [tetragonal] ← 60°C → [tetragonal, ferroelectric] ← -71.5°C → [monoclinic, ferroelectric]; [Cubic] ← -6°C → [orthorhombic] ← -75°C → [?]). Spectra have been analysed in terms of axial spin Hamiltonians and the temperature dependences of the parameters studied. In DSP and DLP across the I ↔ II transition, new physically and chemically inequivalent sites appear indicating the disappearance of the diad axes on which the propionate groups are located, bringing out the connection between the motional states of the propionate groups and the occurence of ferroelectricity. The II ↔ III transition also causes chemically inequivalent sites to develop, indicating that the transitions may not be isomorphous as believed previously. In DBP, the -6°C transition leads to (i) a doubling of both physically and chemically inequivalent sites (ii) a small (150 G at -6°C to 170 G at -8°C), but abrupt change in the magnitude of the zero-field splitting tensor D, and (iii) displacements of the orientations of the D tensors. Results are interpreted in terms of alternate rotations of the oxygen octahedra, showing participation of the carboxyl oxygens in the transition. No drastic changes in the parameters occur across the -75°C transition consistent with its second order nature. Similarities and dissimilarities of the ESR spectra of the three compounds in relation to the phase transitions, are discussed.

The Colletotrichum boninense species complex

Although only recently described, Colletotrichum boninense is well established in literature as an anthracnose pathogen or endophyte of a diverse range of host plants worldwide. It is especially prominent on members of Amaryllidaceae, Orchidaceae, Proteaceae and Solanaceae. Reports from literature and preliminary studies using ITS sequence data indicated that C. boninense represents a species complex. A multilocus molecular phylogenetic analysis (ITS, ACT, TUB2, CHS-1, GAPDH, HIS3, CAL) of 86 strains previously identified as C. boninense and other related strains revealed 18 clades. These clades are recognised here as separate species, including C. boninense s. str., C. hippeastri, C. karstii and 12 previously undescribed species, C. annellatum, C. beeveri, C. brassicicola, C. brasiliense, C. colombiense, C. constrictum, C. cymbidiicola, C. dacrycarpi, C. novae-zelandiae, C. oncidii, C. parsonsiae and C. torulosum. Seven of the new species are only known from New Zealand, perhaps reflecting a sampling bias. The new combination C. phyllanthi was made, and C. dracaenae Petch was epitypified and the name replaced with C. petchii. Typical for species of the C. boninense species complex are the conidiogenous cells with rather prominent periclinal thickening that also sometimes extend to form a new conidiogenous locus or annellations as well as conidia that have a prominent basal scar. Many species in the C. boninense complex form teleomorphs in culture. TAXONOMIC NOVELTIES: New combination - Colletotrichum phyllanthi (H. Surendranath Pai) Damm, P.F. Cannon & Crous. Name replacement - C. petchii Damm, P.F. Cannon & Crous. New species - C. annellatum Damm, P.F. Cannon & Crous, C. beeveri Damm, P.F. Cannon, Crous, P.R. Johnst. & B. Weir, C. brassicicola Damm, P.F. Cannon & Crous, C. brasiliense Damm, P.F. Cannon, Crous & Massola, C. colombiense Damm, P.F. Cannon, Crous, C. constrictum Damm, P.F. Cannon, Crous, P.R. Johnst. & B. Weir, C. cymbidiicola Damm, P.F. Cannon, Crous, P.R. Johnst. & B. Weir, C. dacrycarpi Damm, P.F. Cannon, Crous, P.R. Johnst. & B. Weir, C. novae-zelandiae Damm, P.F. Cannon, Crous, P.R. Johnst. & B. Weir, C. oncidii Damm, P.F. Cannon & Crous, C. parsonsiae Damm, P.F. Cannon, Crous, P.R. Johnst. & B. Weir, C. torulosum Damm, P.F. Cannon, Crous, P.R. Johnst. & B. Weir. Typifications: Epitypifications - C. dracaenae Petch.