A new synthetic procedure for the preparation of pyridinium tetrafluoroborate and hexafluorosilicate

Pyridinium tetrafluoroborate (C5H5NHBF4) and pyridinium hexafluorosilicate [(C5H5NH)2SiF6] have been prepared in good yields and high purity by the reaction of pyridinium poly(hydrogen fluoride) with oxides and acids of boron and silicon respectively. The salts have been characterised by melting points, IR, 1H and 19F NMR spectroscopy and chemical analysis.

CIMMYT-selected derived synthetic bread wheats for rainfed environments: Yield evaluation in Mexico and Australia.

Synthetic backcrossed-derived bread wheats (SBWs) from CIMMYT were grown in the Northwest of Mexico at Centro de Investigaciones Agrícolas del Noroeste (CIANO) and sites across Australia during three seasons. During three consecutive years Australia received “shipments” of different SBWs from CIMMYT for evaluation. A different set of lines was evaluated each season, as new materials became available from the CIMMYT crop enhancement program. These consisted of approximately 100 advanced lines (F7) per year. SBWs had been top and backcrossed to CIMMYT cultivars in the first two shipments and to Australian wheat cultivars in the third one. At CIANO, the SBWs were trialled under receding soil moisture conditions. We evaluated both the performance of each line across all environments and the genotype-by-environment interaction using an analysis that fits a multiplicative mixed model, adjusted for spatial field trends. Data were organised in three groups of multienvironment trials (MET) containing germplasm from shipment 1 (METShip1), 2 (METShip2), and 3 (METShip3), respectively. Large components of variance for the genotype × environment interaction were found for each MET analysis, due to the diversity of environments included and the limited replication over years (only in METShip2, lines were tested over 2 years). The average percentage of genetic variance explained by the factor analytic models with two factors was 50.3% for METShip1, 46.7% for METShip2, and 48.7% for METShip3. Yield comparison focused only on lines that were present in all locations within a METShip, or “core” SBWs. A number of core SBWs, crossed to both Australian and CIMMYT backgrounds, outperformed the local benchmark checks at sites from the northern end of the Australian wheat belt, with reduced success at more southern locations. In general, lines that succeeded in the north were different from those in the south. The moderate positive genetic correlation between CIANO and locations in the northern wheat growing region likely reflects similarities in average temperature during flowering, high evaporative demand, and a short flowering interval. We are currently studying attributes of this germplasm that may contribute to adaptation, with the aim of improving the selection process in both Mexico and Australia.

Synthetic peptides as chemoattractants for bull spermatozoa structure activity correlations

The ability of various synthetic peptide analogs of. Formyl-Met-Leu-Phe to induce chemotaxis in bull sperm is compared using an inverted capillary assay. The formyl group is essential for chemotactic activity and corresponding t-butyloxycarbonyl tripeptides are inactive. Sequence analogs, Formyl-Met-Phe-Leu, Formyl-Leu-Met-Phe and Formyl-Leu-Phe-Met are active. Replacement of Met and Leu by Pro does not diminish activity. Formyl-Met-Leu-Phe-NH2 is active suggesting that electrostatic interactions involving the carboxyl group may be unimportant in receptor interactions. The studies establish the importance of an amino terminal formyl group and a sequence of at least three hydrophobic residues, for inducing sperm chemotaxis.

Crop and environmental attributes underpinning genotype by environment interaction in synthetic-derived bread wheat evaluated in Mexico and Australia

Synthetic backcrossed-derived bread wheats (SBWs) from CIMMYT were grown in the north-west of Mexico (CIANO) and sites across Australia during 3 seasons. A different set of lines was evaluated each season, as new materials became available from the CIMMYT crop enhancement program. Previously, we have evaluated both the performance of genotypes across environments and the genotype x environment interaction (G x E). The objective of this study was to interpret the G x E for yield in terms of crop attributes measured at individual sites and to identify the potential environmental drivers of this interaction. Groups of SBWs with consistent yield performance were identified, often comprising closely related lines. However, contrasting performance was also relatively common among sister lines or between a recurrent parent and its SBWs. Early flowering was a common feature among lines with broad adaptation and/or high yield in the northern Australian wheatbelt, while yields in the southern region did not show any association with the maturity type. Lines with high yields in the southern and northern regions had cooler canopies during flowering and early grain filling. Among the SBWs with Australian genetic backgrounds, lines best adapted to CIANO were tall (>100 cm), with a slightly higher ground cover. These lines also displayed a higher concentration of water-soluble carbohydrates in the stem at flowering, which was negatively correlated with stem number per unit area when evaluated in southern Australia (Horsham). Possible reasons for these patterns are discussed. Selection for yield at CIANO did not specifically identify the lines best adapted to northern Australia, although they were not the most poorly adapted either. In addition, groups of lines with specific adaptation to the south would not have been selected by choosing the highest yielding lines at CIANO. These findings suggest that selection at CIMMYT for Australian environments may be improved by either trait based selection or yield data combined with trait information. Flowering date, canopy temperature around flowering, tiller density, and water-soluble carbohydrate concentration in the stem at flowering seem likely candidates.

Novel Self-Supported Natural and Synthetic Polymer Membranes for Air Humidification

Novel self-supported natural and synthetic polymer membranes of chitosan-hydroxy ethyl Cellulose-montmorillonite (CS-HEC-MMT) and polyvinyl alcohol (PVA)-polystyrene sulfonic acid (PSSA) are prepared by solution casting method followed by crosslinking. These membranes are employed for air humidification at varying temperatures between 30 degrees C and 70 degrees C and their performances are compared with commercial Nafion membranes. High hater fluxes with desired humidified-air output have been achieved for CS-HEC-MMT and PVA-PSSA hybrid membranes at air-flow rates of 1-10 slpm. Variation in the air/water mixing ratio, dew point, and relative humidity that ultimately results in desired water flux With respect to air-flow rates are also quantified for all the membranes. Water flux values for CS-HEC-MMT are less than those for Nafion (R) and PVA-PSSA membranes, but the operational Stability of CS-HEC-MMT membrane is higher than PVA-PSSA and comparable with Nafion (R) both of which can operate up to 70 degrees C at repetitive cycles of humidification.

Mapping quantitative trait loci for resistance to Pratylenchus thornei from synthetic hexaploid wheat in the International Triticeae Mapping Initiative (ITMI) population

Root-lesion nematode (Pratylenchus thornei) is a serious pathogen of wheat in many countries. The International Triticeae Mapping Initiative (ITMI) population of recombinant inbred lines (RILs) was assessed for resistance to P. thornei to determine the chromosome locations of the resistance genes. The ITMI population is derived from a cross between the resistant synthetic hexaploid wheat W-7984 and a susceptible bread wheat cultivar Opata 85. Two years of phenotypic data for resistance to P. thornei were obtained in replicated glasshouse trials. Quantitative trait locus (QTL) analysis was performed using available segregation and map data for 114 RILs. A QTL on chromosome 6DS showed consistent effects for reduced nematode numbers (partial resistance) across years and accounted for 11% and 23% of the phenotypic variation. A second QTL for P. thornei resistance on chromosome 2BS accounted for an additional 19% and 5%. Restriction fragment length polymorphism (RFLP) and simple sequence repeat (SSR) markers associated with the QTLs are physically located in regions rich in major genes at the distal ends of the short chromosome arms of 6D and 2B. SSR markers with potential for marker-assisted selection of P. thornei resistance effective in different genetic backgrounds have been identified.

Synthetic studies towards the phloroglucin natural product hyperforin: construction of the fully prenylated bicyclic core

An approach towards the highly functionalized bicyclo[3.3.1]nonan-9-one core of the complex PPAP-based natural product hyperforin, with the full complement of prenyl substituents in required stereo-disposition, is delineated.

Identification of a mutation in the para-sodium channel gene of the cattle tick Rhipicephalus (Boophilus) microplus associated with resistance to synthetic pyrethroid acaricides

Resistance against synthetic pyrethroid (SP) products for the control of cattle ticks in Australia was detected in the field in 1984, within a very short time of commercial introduction. We have identified a mutation in the domain II S4-5 linker of the para-sodium channel that is associated with resistance to SPs in the cattle tick Rhipicephalus (Boophilus) microplus from Australia. The cytosine to adenine mutation at position 190 in the R. microplus sequence AF134216, results in an amino acid substitution from leucine in the susceptible strain to isoleucine in the resistant strain. A similar mutation has been shown to confer SP resistance in the whitefly, Bemisia tabaci, but has not been described previously in ticks. A diagnostic quantitative PCR assay has been developed using allele-specific Taqman® minor groove-binding (MGB) probes. Using the assay to screen field and laboratory populations of ticks showed that homozygote allelic frequencies correlated highly with the survival percentage at the discriminating concentration of cypermethrin.

Resistance to root-lesion nematodes (Pratylenchus thornei and P-neglectus) in synthetic hexaploid wheats and their durum and Aegilops tauschii parents.

Root-lesion nematodes (Pratylenchus thornei Sher and Allen and P. neglectus (Rensch) Filipijev and Schuurmans Stekhoven) cause substantial yield loss to wheat crops in the northern grain region of Australia. Resistance to P. thornei for use in wheat breeding programs was sought among synthetic hexaploid wheats (2n= 6x = 42, AABBDD) produced through hybridisations of Triticum turgidum L. subsp. durum (Desf.) Husn (2n= 4x = 28, AABB) with Aegilops tauschii Coss. (2n= 2x = 14, DD). Resistance was determined for the synthetic hexaploid wheats and their durum and Ae. tauschii parents from the numbers of nematodes in the roots of plants grown for 16 weeks in pots of pasteurised soil inoculated with P. thornei. Fifty-nine (32%) of 186 accessions of synthetic hexaploid wheats had lower numbers of nematodes than Gatcher Selection 50a (GS50a), a partially resistant bread wheat. Greater frequencies of partial resistance were present in the durum parents (72% of 39 lines having lower nematode numbers than GS50a) and in the Ae. tauschii parents (55% of 53 lines). The 59 synthetic hexaploids were re-tested in a second experiment along with their parents. In a third experiment, 11 resistant synthetic hexaploid wheats and their F-1 hybrids with Janz, a susceptible bread wheat, were tested and the F(1)s were found to give nematode counts intermediate between the respective two parents. Synthetic hexaploid wheats with higher levels of resistance resulted from hybridisations where both the durum and Ae. tauschii parents were partially resistant, rather than where only one parent was partially resistant. These results suggest that resistance to P. thornei in synthetic hexaploid wheats is polygenic, with resistances located both in the D genome from Ae. tauschii and in the A and/or B genomes from durum. Five synthetic hexaploid wheats were selected for further study on the basis of (1) a high level of resistance to P. thornei of the synthetic hexaploid wheats and of both their durum and Ae. tauschii parents, (2) being representative of both Australian and CIMMYT (International Maize and Wheat Improvement Centre) durums, and (3) being representative of the morphological subspecies and varieties of Ae. tauschii. These 5 synthetic hexaploid wheats were also shown to be resistant to P. neglectus, whereas GS50a and 2 P. thornei-resistant derivatives were quite susceptible. Results of P. thornei resistance of F(1)s and F(2)s from a half diallel of these 5 synthetic hexaploid wheats, GS50a, and Janz from another study indicate polygenic additive resistance and better general combining ability for the synthetic hexaploid wheats than for GS50a. Published molecular marker studies on a doubled haploid population between the synthetic hexaploid wheat with best general combining ability (CPI133872) and Janz have shown quantitative trait loci for resistance located in all 3 genomes. Synthetic hexaploid wheats offer a convenient way of introgressing new resistances to P. thornei and P. neglectus from both durum and Ae. tauschii into commercial bread wheats.

Cyclononitols: a flexible synthetic approach towards nine-membered carbasugar analogues

A novel, concise, stereocontrolled approach to nine-membered carbasugar analogues (cyclononitols) from a bicyclo[4.3.1]deca-2,4-dien-10-one scaffold, harbouring a `locked' cyclononane ring and latent functionalities, is described.

Development of a synthetic plant volatile-based attracticide for female noctuid moths. I. Potential sources of volatiles attractive to Helicoverpa armigera (Hubner) (Lepidoptera: Noctuidae).

This paper is the first of a series which will describe the development of a synthetic plant volatile-based attracticide for noctuid moths. It discusses potential sources of volatiles attractive to the cotton bollworm, Helicoverpa armigera (Hubner), and an approach to the combination of these volatiles in synthetic blends. We screened a number of known host and non-host (for larval development) plants for attractiveness to unmated male and female moths of this species, using a two-choice olfactometer system. Out of 38 plants tested, 33 were significantly attractive to both sexes. There was a strong correlation between attractiveness of plants to males and females. The Australian natives, Angophora floribunda and several Eucalyptus species were the most attractive plants. These plants have not been recorded either as larval or oviposition hosts of Helicoverpa spp., suggesting that attraction in the olfactometer might have been as nectar foraging rather than as oviposition sources. To identify potential compounds that might be useful in developing moth attractants, especially for females, collections of volatiles were made from plants that were attractive to moths in the olfactometer. Green leaf volatiles, floral volatiles, aromatic compounds, monoterpenes and sesquiterpenes were found. We propose an approach to developing synthetic attractants, here termed 'super-blending', in which compounds from all these classes, which are in common between attractive plants, might be combined in blends which do not mimic any particular attractive plant.

The effect of foliar sprays of the synthetic auxin 3-5-6 TPA, on fruit drop, fruit size and seed development in three lychee (Litchi chinensis) cultivars: Tai So, Fay Zee Sui and Kwai Mai Pink.

Fruit drop in lychee can cause major yield losses in Australia, the severity varying with cultivar and season. Research in China, South Africa and Israel has demonstrated the potential for synthetic auxins used as foliar sprays to reduce fruit drop in lychee. Trials were initiated in Australia to test the efficacy of the synthetic auxin, 3-5-6 Trichloro-2-phridyl-oxyacetic acid (3-5-6 TPA) at 50 ppm on the cultivars Tai So, Fay Zee Sui and Kwai Mai Pink. Results indicate that in most cases the TPA reduced natural fruit drop however the size of the fruit at the time of application affects the response and the ideal application time varies with cultivar; approximately 13 mm fruit length in 'Kwai Mai Pink', 20 mm in 'Fay Zee Sui' and 27 mm in 'Tai So'. If applied too early in 'Tai So', it caused an increase in fruit drop. The TPA was most effective when natural fruit drop was high, reducing fruit drop from 74.7 to 34.9% in 'Kwai Mai Pink' and least effective when natural fruit drop was low. An increase in the percentage of fruit with poorly developed (chicken tongue) seed and slightly larger fruit size was also observed in treated trees.

Daphnane- and Tigliane-Type Diterpenoid Esters and Orthoesters from Pimelea elongata.

Investigation of Pimelea elongata ("Lakebed Pimelea") afforded 18 tigliane- and daphnane-type diterpenes (1-18). Eight of these were new compounds: four (1-3, 5) tigliane esters and four (7, 8, 10, 11) daphnane orthoesters. The 10 known compounds were 12-O-decanoylphorbol-13-acetate (4), P. simplex subtoxin B (6), wikstroelide E (9), pimelotides A and B (12, 13), gnidiglaucin (14), simplexin (15), huratoxin (16), kirkinine D (17), and 12-beta-acetoxyhuratoxin (18). The structures and relative configurations of the new compounds were determined by ID and 2D NMR spectroscopic studies in combination with MS analyses.

A novel approach to structure—flammability correlation in polyphosphate esters

The relationship between the structure and flammability of a number of polyphosphate esters has been examined. The conventional correlation of char residue with limiting oxygen index was found to be unproductive in these polymers, giving insight into the importance of gas-phase reactions in addition to condensed-phase reactions in determining their flammability. A novel approach was sought in understanding the structure-flammability relationships of these polymers relating thermal stability, phosphorus content and limiting oxygen index. An empirical relationship has been derived amongst these three parameters.

High-density lipoprotein 17beta-estradiol fatty acyl esters and phytoestrogens : Impact on reverse cholesterol transport and women's cardiovascular health

Reverse cholesterol transport (RCT) is an important function of high-density lipoproteins (HDL) in the protection of atherosclerosis. RCT is the process by which HDL stimulates cholesterol removal from peripheral cells and transports it to the liver for excretion. Premenopausal women have a reduced risk for atherosclerosis compared to age-matched men and there exists a positive correlation for serum 17β-estradiol (E2) and HDL levels in premenopausal women supporting the role of E2 in atherosclerosis prevention. In premenopausal women, E2 associates with HDL as E2 fatty acyl esters. Discovery of the cellular targets, metabolism, and assessment of the macrophage cholesterol efflux potential of these HDL-associated E2 fatty acyl esters were the major objectives of this thesis (study I, III, and IV). Soy phytoestrogens, which are related to E2 in both structure and function, have been proposed to be protective against atherosclerosis but the evidence to support these claims is conflicting. Therefore, another objective of this thesis was to assess the ability of serum from postmenopausal women, treated with isoflavone supplements (compared to placebo), to promote macrophage cholesterol efflux (study II). The scope of this thesis was to cover the roles that HDL-associated E2 fatty acyl esters have in the cellular aspects of RCT and to determine if soy isoflavones can also influence RCT mechanisms. SR-BI was a pivotal cellular receptor, responsible for hepatic and macrophage uptake and macrophage cholesterol efflux potential of HDL-associated E2 fatty acyl esters. Functional SR-BI was also critical for proper LCAT esterification activity which could impact HDL-associated E2 fatty acyl ester assembly and its function. In hepatic cells, LDL receptors also contributed to HDL-associated E2 fatty acyl esters uptake and in macrophage cells, estrogen receptors (ERs) were necessary for both HDL-associated E2 ester-specific uptake and cholesterol efflux potential. HDL-containing E2 fatty acyl esters (E2-FAE) stimulated enhanced cholesterol efflux compared to male HDL (which are deficient in E2) demonstrating the importance of the E2 ester in this process. To support this, premenopausal female HDL, which naturally contains E2, showed greater macrophage cholesterol efflux compared to males. Additionally, hepatic and macrophage cells hydrolyzed the HDL-associated E2 fatty acyl ester into unesterified E2. This could have important biological ramifications because E2, not the esterified form, has potent cellular effects which may influence RCT mechanisms. Lastly, soy isoflavone supplementation in postmenopausal women did not modulate ABCA1-specific macrophage cholesterol efflux but did increase production of plasma pre-β HDL levels, a subclass of HDL. Therefore, the impact of isoflavones on RCT and cardiovascular health needs to be further investigated. Taken as a whole, HDL-associated E2 fatty acyl esters from premenopausal women and soy phytoestrogen treatment in postmenopausal women may be important factors that increase the efficiency of RCT through cellular lipoprotein-related processes and may have direct implications on the cardiovascular health of women.