Solvent effects on the structure of N-methylpyrrole as studied by nmr in nematic solvents

The proton NMR spectra of N-methylpyrrole oriented in the nematic phases of liquid crystals with positive and negative diamagnetic anisotropies and their mixtures are reported. Geometrical parameters derived from the spectra at the critical point in the mixture of liquid crystals with positive and negative diamagnetic anisotropies, where macroscopic diamagnetic anisotropy vanishes, are similar to those obtained in the solvent with negative diamagnetic anisotropy. However, significant distortions in the molecular structure attributed to solvent effects have been observed in liquid crystals with positive diamagnetic anisotropy. The minimum energy conformation has one C---H of the methyl perpendicular to the ring.

Study of the structure and function of the sheath of tropically adapted bulls and risk factors for preputial eversion and preputial prolapse

Preputial prolapse is an obvious condition affecting bulls from many breeds. Unfortunately, the losses in production and welfare concerns associated with preputial prolapse can remain undetected for long periods of time in the extensive beef areas of northern Australia where the bulls are not inspected regularly. Thus, there is a critical need to identify the structural factors predisposing to preputial prolapse in young bulls so that they can be culled early. Despite there being no firm scientific evidence of an association between preputial eversion and preputial prolapse, it seems logical that the increased exposure of the sensitive prepuce as a consequence of preputial eversion may increase the risk of bulls developing preputial pathology, in particular preputial prolapse. This may be particularly relevant in Bos indicus bulls as they have a more pendulous sheath and thus eversion of the prepuce may be associated with a greater risk of injury to the prepuce compared to that in Bos taurus bulls. Further, studies of preputial eversion in Bos taurus bulls have concluded that there is an association between polledness and increased prevalence and severity (length of everted prepuce and duration of eversion) of preputial eversion due primarily to the absence or poor development of the caudal preputial muscles. No similar definitive work in Bos indicus bulls has been conducted and thus anatomical studies reported in this thesis were conducted to determine if a similar association occurred in Bos indicus bulls. A survey of a sample of large beef breeding herds in northern Australia found that preputial prolapse is a significant problem in Bos indicus and Bos indicus derived bulls and affected both young and older bulls. The importance of preputial prolapse confirmed the value of further research into the causes of this problem. A series of anatomical studies confirmed that preputial eversion in Bos indicus derived bulls was not more prevalent in polled bulls than horned bulls and was not associated with deficiency of the caudal preputial muscles as was established in Bos taurus bulls. An anatomical study of Bos indicus derived bulls with preputial prolapse found that preputial prolapse occurred in horned bulls of varying ages and these bulls did not have any evidence of deficiency in the caudal preputial muscles. However, preputial prolapse was observed in young polled bulls that had poorly developed or absent caudal preputial muscles. It was concluded that deficiency of the caudal preputial muscles in polled Bos indicus derived bulls may predispose to preputial prolapse at an early age, but no predisposing anatomical factors were found for horned Bos indicus derived bulls. In these studies, preputial eversion and preputial prolapse were found in horned Bos indicus derived bulls that did not have any preputial muscle deficiency and it was noted that preputial eversion was not related to the length of the prepuce. Further studies confirmed that preputial eversion was linearly and consistently associated with position of the glans penis within the sheath in Bos indicus derived bulls, and movement of the glans penis towards the preputial orifice consistently resulted in preputial eversion in these bulls. A method to objectively measure the relationship between movement of the glans penis within the sheath and preputial eversion was developed. Studies in humans have linked function of some abdominal muscles to function of the pelvic organs. This relationship was investigated in Bos indicus derived bulls to determine whether the function of specific abdominal muscles affected position of the penis in the sheath. Using the method developed to objectively measure the relationship between penis movement and preputial eversion, the abdominal muscles that potentially were associated with movement of the glans penis or preputial eversion were examined but no significant relationships were observed. In the anatomical study of Bos indicus derived bulls not affected with preputial prolapse a more pendulous sheath was associated with increased prevalence of preputial eversion. This relationship was confirmed for horned and polled bulls in the penis movement studies. Bos indicus derived bulls with more pendulous sheaths evert their prepuces more than bulls with less pendulous sheaths thus increasing the risk of damage to the prepuce either from the environment, other bulls, or from them inadvertently stepping on the everted prepuce when they get to their feet. Culling Bos indicus derived bulls with more pendulous sheaths should reduce the incidence of preputial eversion and possibly preputial prolapse. The anatomical study of Bos indicus derived bulls that did not have preputial prolapse demonstrates that there are herds of bulls where the polled bulls do not have any evidence of deficiency of the caudal preputial iv muscles. There is a need to develop a practical and cost effective test to identify polled Bos indicus bulls that have a deficiency in their caudal preputial muscles.

Theoretical studies on Beta-lactam antibiotics VI: Conformational analysis and structure-activity relationships of penicillin sulfoxides and cephalosporins

Conformational energy calculations were carried out on penicillin α-and Β-sulfoxides and δ2- and δ3-cephalosporins, in order to identify the structural features governing their biological activity. Results on penicillin Β-sulfoxide indicated that in its favoured conformation, the orientation of the aminoacyl group was different from the one required for biological activity. Penicillin α sulfoxide, like penicillin sulfide, favoured two conformations of nearly equal energies, but separated by a much higher energy barrier. The reduced activity of the sulfoxides despite the nonplanarity of their lactam peptide indicated that the orientations of the aminoacyl and carboxyl groups might also govern biological activity. δ3-cephalosporins favoured two conformations of nearly equal energies, whereas δ2-cephalosporins favoured only one conformation. The lactam peptide was moderately nonplanÄr in the former, but nearly planar in the latter. The differences in the.preferred orientations of the carboxyl group between penicillins and cephalosporins were correlated with the resistance of cephalosporins to penicillinases.

Development of cat's claw creeper leaf-tying moth Hypocosmia pyrochroma (Lepidoptera: Pyralidae) at different temperatures: Implications for establishment as a biological control agent in Australia and South Africa

The leaf-tying moth Hypocosmia pyrochroma Jones (Lepidoptera: Pyralidae), a native of sub tropical South America, has been introduced as a biological control agent for cat’s claw creeper, Dolichandra unguis-cati (L.) Lohman (Bignoniaceae), in Australia and South Africa. So far there has been no evidence of its field establishment in either country. A narrow temperature tolerance is a potential limiting factor for the establishment of weed biological control insects in novel habitats. In this study, we evaluated the effect of seven constant temperatures (12–40 °C) on the survival and development of H. pyrochroma in temperature-controlled cabinets. Temperatures between 20 and 30 °C were the most favorable for adult survival, oviposition, egg hatching, and larval and pupal development. Adult survival (12–40 °C) and egg development (15–35 °C) showed tolerance for wider temperature ranges than oviposition, and larval and pupal development, which were all negatively affected by both high (>30 °C) and low (<20 °C) temperatures. The degree-day (DD) requirement to complete a generation was estimated as 877 above a threshold temperature of 12 °C. Based on DD requirements and an obligatory winter diapause of pupae from mid-autumn to mid-spring, the potential number of generations (egg to adult) the leaf-tying moth can complete in a year in Australia or South Africa range from one to three. A climate-matching model predicted that the inland regions of both Australia and South Africa are less favorable for H. pyrochroma than the coastal areas. The study suggested that H. pyrochroma is more likely to establish in the coastal areas of Australia where most of the cat’s claw creeper infestations occur, than in South Africa where most of the cat’s claw creeper infestations are inland.

Structure and conformation of an anti-depressant drug, nitroxazepine hydrochloride monohydrate

CIsH20N3Oa+.C1-.H2 O, M r = 395, orthorhombic, Pn21a, a = 7.710 (4), b = 11.455 (3), c -- 21.199 (3)/k, Z = 4, V = 1872.4/k 3, D m = 1.38, D C = 1.403 g cm -3, F(000) = 832, g(Cu Kct) = 20.94 cm -l. Intensities for 1641 reflections were measured on a Nonius CAD-4 diffractometer; of these, 1470 were significant. The structure was solved by direct methods and refined to an R index of 0.045 using a blockdiagonal least-squares procedure. The angle between the least-squares planes through the benzene rings is 125.0 (5) ° and the side chain is folded similarly to one of the independent molecules of imipramine hydrochloride.

Structure of l-Diphenylmethyl-3-hydroxyazetidinium Chloride,* C 16 H lsN O+.CI -

M r=275.8, monoclinic, P21/a, a= 12.356 (5), b=9.054 (4), c= 14.043 (4) A, t= 100.34 (3) ° , V=1545.5A 3, Z=4, D,,,= 1.14, D x = 1.185 Mg m -3, p(Mo Ka, /l = 0.7107 ]k) = 2.77 mm -1, F(000) = 584.0, T= 293 K, R = 0.053 for 1088 reflections. The four-membered ring is buckled 13.0 ° (0= 167.0°). The azetidinium moiety is linked to the C1- ion through a hydrogen bond [O-H...C1 = 3.166 (5) A].

Tautomeric forms of hydroxycyclotriphosphazatrienes; X-ray crystal structure of N3P3Ph2(OMe)3OH

The prefered tautomer(s) of hydroxycyclotriphosphazatrienes and prototropic exchange in solution have been established by 31P n.m.r. spectroscopy, thus confirming predictions deduced from basicity calculations; the X-ray structure of N3P3Ph2(OMe)3OH shows that it exists as the hydrogen-bonded dimer of the oxophosphazadiene tautomer in which a proton is adjacent to the PPh2 group.

Structure, energetics and diffusion properties of isomers of trimethyl benzene in beta zeolite: Uptake and Monte Carlo simulation study

A Monte Carlo study along with experimental uptake measurements of 1,2,3-trimethyl benzene, 1,2,4-trimethyl benzene and 1,3,5-trimethyl benzene (TMB) in beta zeolite is reported. The TraPPE potential has been employed for hydrocarbon interaction and harmonic potential of Demontis for modeling framework of the zeolite. Structure, energetics and dynamics of TMB in zeolite beta from Monte Carlo runs reveal interesting information about the diameter, properties of these isomers on confinement. Of the three isomers, 135TMB is supposed to have the largest diameter. It is seen TraPPE with Demontis potential predicts a restricted motion of 135TMB in the channels of zeolite beta.Experimentally, 135TMB has the highest transport diffusivity whereas MID results suggest this has the lowest self diffusivity. (C) 2009 Elsevier Inc. Ail rights reserved.

Dynamics of dense sheared granular flows. Part 1. Structure and diffusion

Shear flows of inelastic spheres in three dimensions in the Volume fraction range 0.4-0.64 are analysed using event-driven simulations.Particle interactions are considered to be due to instantaneous binary collisions, and the collision model has a normal coefficient of restitution e(n) (negative of the ratio of the post- and pre-collisional relative velocities of the particles along the line joining the centres) and a tangential coefficient of restitution e(t) (negative of the ratio of post- and pre-collisional velocities perpendicular to the line Joining the centres). Here, we have considered both e(t) = +1 and e(t) = e(n) (rough particles) and e(t) =-1 (smooth particles), and the normal coefficient of restitution e(n) was varied in the range 0.6-0.98. Care was taken to avoid inelastic collapse and ensure there are no particle overlaps during the simulation. First, we studied the ordering in the system by examining the icosahedral order parameter Q(6) in three dimensions and the planar order parameter q(6) in the plane perpendicular to the gradient direction. It was found that for shear flows of sufficiently large size, the system Continues to be in the random state, with Q(6) and q(6) close to 0, even for volume fractions between phi = 0.5 and phi = 0.6; in contrast, for a system of elastic particles in the absence of shear, the system orders (crystallizes) at phi = 0.49. This indicates that the shear flow prevents ordering in a system of sufficiently large size. In a shear flow of inelastic particles, the strain rate and the temperature are related through the energy balance equation, and all time scales can be non-dimensionalized by the inverse of the strain rate. Therefore, the dynamics of the system are determined only by the volume fraction and the coefficients of restitution. The variation of the collision frequency with volume fraction and coefficient of estitution was examined. It was found, by plotting the inverse of the collision frequency as a function of volume fraction, that the collision frequency at constant strain rate diverges at a volume fraction phi(ad) (volume fraction for arrested dynamics) which is lower than the random close-packing Volume fraction 0.64 in the absence of shear. The volume fraction phi(ad) decreases as the coefficient of restitution is decreased from e(n) = 1; phi(ad) has a minimum of about 0.585 for coefficient of restitution e(n) in the range 0.6-0.8 for rough particles and is slightly larger for smooth particles. It is found that the dissipation rate and all components of the stress diverge proportional to the collision frequency in the close-packing limit. The qualitative behaviour of the increase in the stress and dissipation rate are well Captured by results derived from kinetic theory, but the quantitative agreement is lacking even if the collision frequency obtained from simulations is used to calculate the pair correlation function used In the theory.

Stock structure of the blue threadfin (Eleutheronema tetradactylum) across northern Australia derived from life-history characteristics

Life history characteristics were used to determine the stock structure of the polynemid Eleutheronema tetradactylum across northern Australia. Growth, estimated from back-calculated length-at-age from sagittal otoliths, and length at sex change were estimated from samples collected from 12 different locations across western, northern and eastern Australia between 2007 and 2009. Comparison of back-calculated length-at-age, growth and length at sex change between locations revealed significant variation in the life-history characteristics of E. tetradactylum across northern Australia, with significant differences detected in 43 of 45 location comparisons. Differences in otolith size relative to fish length also existed amongst locations. No differences in other morphometric relationships were detected. The results of this study provide evidence for a high degree of spatial population subdivision for E. tetradactylum across northern Australia, the finding of which has implications for E. tetradactylum fisheries throughout its range, and provides a biological basis for spatial management of the species in Australia. (C) 2012 Elsevier B.V. All rights reserved.

Interdiffusion and activation energy in Ti3Au phase with A15 crystal structure

The knowledge of diffusion parameters, such as integrated diffusion coefficient and the activation energy for diffusion is important to understand the growth rate of the product phase and the atomic mechanism of diffusion. These parameters are determined in Ti3Au phase with A15 crystal structure. The calculated diffusion parameters will help in validating the theoretical analysis on defect structure of the phase.

Origin of leaf rust adult plant resistance gene Rph20 in barley

Rph20 is the only reported, simply inherited gene conferring moderate to high levels of adult plant resistance (APR) to leaf rust (Puccinia hordei Otth) in barley (Hordeum vulgare L.). Key parental genotypes were examined to determine the origin of Rph20 in two-rowed barley. The Dutch cultivar 'Vada' (released in the 1950s) and parents, 'Hordeum laevigatum' and 'Gull' ('Gold'), along with the related cultivar 'Emir' (a derivative of 'Delta'), were assessed for APR to P. hordei in a disease screening nursery. The marker bPb-0837-PCR, co-located with Rph20 on the short arm of chromosome 5H (5HS), was used to screen genotypes for the resistance allele, Rph20.ai. Results from phenotypic assessment and DNA analysis confirmed that Rph20 originated from the landrace 'H. laevigatum' (i.e., Hordeum vulgare subsp. vulgare). Tracing back this gene through the pedigrees of two-rowed barley cultivars, indicated that Rph20 has contributed APR to P. hordei for more than 60 years. Although there have been no reports of an Rph20-virulent pathotype, the search for alternative sources of APR should continue to avoid widespread reliance upon a single resistance factor.

Reduced fungicide use on a new Australian peanut cultivar, highly resistant to the late leaf spot and rust pathogens

Rust (caused by Puccinia arachidis) and late leaf spot (LLS, caused by Mycosphaerella berkeleyi) can cause significant yield losses in Australian peanut crops. Until recently, all commercial peanut varieties were highly susceptible to these pathogens, but the new Australian cultivar Sutherland has significantly higher levels of resistance than the older cultivars. Field trials were conducted at two sites in Queensland to (a) confirm the improved resistance of cv. Sutherland over another commercial cultivar, Menzies, (b) study the effects of timing of first spray, spray interval and cultivar on disease severity and yield, and (c) develop a suitable fungicide management program for cv. Sutherland. In the 2006 and 2007 trials, rust and LLS developed slower and had lower final disease ratings and AUDPC values on unsprayed plots of cv. Sutherland than on cv. Menzies. The timing of the first spray is critical in managing both rust and late leaf spot, with the results demonstrating that the first fungicide spray on cv. Sutherland should be applied as soon as rust and LLS are first seen on cv. Menzies. In most trials spray intervals of 14 days or 21 days were suitable to effectively control rust and LLS. In years with low disease pressure, few, if any, fungicide applications will be needed to manage the diseases, but in other years up to four sprays may be necessary. © Australasian Plant Pathology Society Inc. 2012.

X-Ray Studies On Crystalline Complexes Involving Amino-Acids And Peptides .11. Peptide Aggregation And Water-Structure In The Crystals Of A Hydrated 1-1 Complex Between L-Histidyl-L-Serine And Glycyl-L-Glutamic Acid

The hexahydrate of a 1:1 complex between L-histidyl-L-serine and glycyl-L-glutamic acid crystallizes in space group P1 with a = 4.706(1), b= 8.578(2), c= 16.521(3) ÅA; α= 85.9(1), β= 89.7(1)°, = 77.4(1). The crystal structure, solved by direct methods, has been refined to an R value of 0.046 for 2150 observed reflections. The two peptide molecules in the structure have somewhat extended conformations. The unlike molecules aggregate into separate alternating layers. Each layer is stabilized by hydrogen bonded head-to-tail sequences as well as sequences of hydrogen bonds involving peptide groups. The arrangement of molecules in each layer is similar to one of the plausible idealized arrangements of L-alanyl-L-alanine worked out from simple geometrical considerations. Adjacent layers in the structure are held together by interactions involving side chains as well as water molecules. The water structure observed in the complex provides a good model, at atomic resolution, for that in protein crystals. An interesting feature of the crystal structure is the existence of two water channels in the interfaces between adjacent peptide layers.

Glycoalkaloid Content and Starch Structure in Solanum Species and Interspecific Somatic Potato Hybrids

When genome sections of wild Solanum species are bred into the cultivated potato (S. tuberosum L.) to obtain improved potato cultivars, the new cultivars must be evaluated for their beneficial and undesirable traits. Glycoalkaloids present in Solanum species are known for their toxic as well as for beneficial effects on mammals. On the other hand, glycoalkaloids in potato leaves provide natural protection against pests. Due to breeding, glycoalkaloid profile of the plant is affected. In addition, the starch properties in potato tubers can be affected as a result of breeding, because the crystalline properties are determined by the botanical source of the starch. Starch content and composition affect the texture of cooked and processed potatoes. In order to determine glycoalkaloid contents in Solanum species, simultaneous separation of glycoalkaloids and aglycones using reversed-phase high-performance liquid chromatography (HPLC) was developed. Clean-up of foliage samples was improved using a silica-based strong cation exchanger instead of octadecyl phases in solid-phase extraction. Glycoalkaloids alpha-solanine and alpha-chaconine were detected in potato tubers of cvs. Satu and Sini. The total glycoalkaloid concentration of non-peeled and immature tubers was at an acceptable level (under 20 mg/100 g of FW) in the cv. Satu, whereas concentration in cv. Sini was 23 mg/100 g FW. Solanum species (S. tuberosum, S. brevidens, S. acaule, and S. commersonii) and interspecific somatic hybrids (brd + tbr, acl + tbr, cmm + tbr) were analyzed for their glycoalkaloid contents using liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS). The concentrations in the tubers of the brd + tbr and acl + tbr hybrids remained under 20 mg/100 g FW. Glycoalkaloid concentration in the foliage of the Solanum species was between 110 mg and 890 mg/100 g FW. However, the concentration in the foliage of S. acaule was as low as 26 mg/100 g FW. The total concentrations of brd + tbr, acl + tbr, and cmm + tbr hybrid foliages were 88 mg, 180 mg, and 685 mg/100 g FW, respectively. Glycoalkaloids of both parental plants as well as new combinations of aglycones and saccharides were detected in somatic hybrids. The hybrids contained mainly spirosolanes, and glycoalkaloid structures having no 5,6-double bond in the aglycone. Based on these results, the glycoalkaloid profiles of the hybrids may represent a safer and more beneficial spectrum of glycoalkaloids than that found in currently cultivated varieties. Starch nanostructure of three different cultivars (Satu, Saturna, and Lady Rosetta), a wild species S. acaule, and interspecific somatic hybrids were examined by wide-angle and small-angle X-ray scattering (WAXS, SAXS). For the first time, the measurements were conducted on fresh potato tuber samples. Crystallinity of starch, average crystallite size, and lamellar distance were determined from the X-ray patterns. No differences in the starch nanostructure between the three different cultivars were detected. However, tuber immaturity was detected by X-ray scattering methods when large numbers of immature and mature samples were measured and the results were compared. The present study shows that no significant changes occurred in the nanostructures of starches resulting from hybridizations of potato cultivars.