Nature of ``Disorder'' in the Ordered Double Perovskite Sr2FeMoO6

The degree of B/B alternate cation order is known to heavily influence the magnetic properties of A2BB O6 double perovskites although the nature of such disorder has never been critically studied. Our detailed x-ray absorption fine structure studies in conjunction with synchrotron radiation x-ray diffraction experiments on polycrystalline Sr2FeMoO6 samples with various degrees of disorder reveal that a very high degree of short range order is preserved even in samples with highly reduced long range chemical order. Based on these experimental results and with the help of detailed structural simulations, we are able to model the nature of the disorder in this important class of materials and discuss the consequent implications on its physical properties.

Sensing Shape Recovery Using Conductivity Noise in Thin Films of NiTi Shape Memory Alloys

Low frequency fluctuations in the electrical resistivity, or noise, have been used as a sensitive tool to probe into the temperature driven martensite transition in dc magnetron sputtered thin films of nickel titanium shape-memory alloys. Even in the equilibrium or static case, the noise magnitude was more than nine orders of magnitude larger than conventional metallic thin films and had a characteristic dependence on temperature. We observe that the noise while the temperature is being ramped is far larger as compared to the equilibrium noise indicating the sensitivity of electrical resistivity to the nucleation and propagation of domains during the shape recovery. Further, the higher order statistics suggests the existence of long range correlations during the transition. This new characterization is based on the kinetics of disorder in the system and separate from existing techniques and can be integrated to many device applications of shape memory alloys for in-situ shape recovery sensing.

Observation of reentrant spin glass behavior in LaCo0.5Ni0.5O3

The magnetic and transport properties of LaCo0.5Ni0.5O3 have been studied. The dc magnetization and the ac susceptibility studies suggest the presence of a magnetic-phase transition from a ferromagnetic (FM) to a spin glass phase at a low temperature. This type of reentrant spin-glass (RSG) behavior attached to a long-range ordered ferromagnet is observed in this system. A magnetoresistance of ~10% is observed at 5 K which is unsaturated up to 11 Tesla suggests the presence of antiferromagnetic (AFM) interactions. It is likely that the competition between such AFM interactions with FM interactions yield an RSG phase.

Proton NMR studies of dihalogenated phenyl benzamides: two-dimensional higher quantum methodologies

The scalar coupled proton NMR spectra of many organic molecules possessing more than one phenyl ring are generally complex due to degeneracy of transitions arising from the closely resonating protons, in addition to several short- and long- range couplings experienced by each proton. Analogous situations are generally encountered in derivatives of halogenated benzanilides. Extraction of information from such spectra is challenging and demands the differentiation of spectrum pertaining to each phenyl ring and the simplification of their spectral complexity. The present study employs the blend of independent spin system filtering and the spin-state selective detection of single quantum (SO) transitions by the two-dimensional multiple quantum (MQ) methodology in achieving this goal. The precise values of the scalar couplings of very small magnitudes have been derived by double quantum resolved experiments. The experiments also provide the relative signs of heteronuclear couplings. Studies on four isomers of dilhalogenated benzanilides are reported in this work.

Critical-point Properties of Liquids and the Born-Green Theory

Recent work of Jones et al. giving the long-range behaviour of the pair correlation function is used to confirm that the critical ratio Pc/nckBTc = 1/2 in the Born-Green theory. This deviates from experimental results on simple insulating liquids by more than the predictions of the van der Waals equation of state. A brief discussion of conditions for thermodynamic consistency, which the Born-Green theory violates, is then given. Finally, the approach of the Ornstein-Zernike correlation function to its critical point behaviour is discussed within the Born-Green theory.

Precise Values of the "C Component Vicinal Coupling Constants for Calculating Side-Chain Conformations in Amino Acids

From consideration of 'H-lH vicinal coupling constants and '"G'H long-range coupling constants in a series of amino acid derivatives, the precise values of uC component vicinal coupling constants have been calculated for the three minimum energy staggered rotamers for the C(or)H-C(P)H, side-chains of amino acids.

Self Assembly and Electronic Structure of ZnO Nanocrystals

In this paper, we report the synthesis and self assembly of various sizes of ZnO nanocrystals. While the crystal structure and the quantum confinement of nanocrystals were mainly characterized using XRD and UV absorption spectra, the self assembly and long range ordering were studied using scanning tunneling microscopy after spin casting the nanocrystal film on the highly oriented pyrolytic graphite surface. We observe self assembly of these nanocrystals over large areas making them ideal candidates for various potential applications. Further, the electronic structure of the individual dots is obtained from the current-voltage characteristics of the dots using scanning tunneling spectroscopy and compared with the density of states obtained from the tight binding calculations. We observe an excellent agreement with the experimentally obtained local density of states and the theoretically calculated density of states.

Valence states and magnetic properties of LaNi1-xMnxO3 (for 0≤x≤0.2 and x=0.5)

Single-phase LaNi1-xMnxO3 samples in the compositional range 0long-range magnetic coupling occurs via solvent electrons in a narrow conduction band. The conductivity changes from that of a narrow-band metal for x<0.01 to that more characteristic of diffusive motion for x>0.05, but any motional enthalpy appears to remain small ( Delta Hm approximately=0). The x=0.1 sample exhibits ferrimagnetic spin glass behaviour below 40K, and the ferromagnetic interactions increase with manganese concentration. The oxide with x=0.50 is ferromagnetic with a well defined Curie temperature.

Integrated pest management in cotton: exploiting behaviour-modifying (semiochemical) compounds for managing cotton pests

We review here research on semiochemicals for cotton pest management carried out in successive Cotton Co-operative Research Centres from 1998 to 2012. Australian cotton is now dominated by transgenic (Bt) varieties, which provide a strong platform for integrated pest management of key pests such as Helicoverpa spp., but new technologies are required to manage the development of resistance in Helicoverpa spp. to transgenic cotton and the problems posed by emerging and secondary pests, especially sucking insects. A long-range attractant for Helicoverpa moths, based on plant volatiles, has been commercialised as Magnet®. The product has substantial area-wide impacts on moth populations, and only limited effects on beneficial insects. Potential roles are being investigated for this product in resistance management of Helicoverpa spp. on transgenic cotton. Short-range, non-volatile compounds on organ surfaces of plants that do not support development of Helicoverpa spp. have been identified; these compounds deter feeding or oviposition, or are toxic to insect pests. One such product, Sero X®, is effective on Helicoverpa spp. and sucking pests such as whiteflies (Bemisia tabaci), green mirids (Creontiades dilutus), and other hemipteran insects, and is in the advanced stages of commercialisation.

Aspects and Applications of Pulse Sequence Design for Solution-State Nuclear Magnetic Resonance Spectroscopy

NMR spectroscopy enables the study of biomolecules from peptides and carbohydrates to proteins at atomic resolution. The technique uniquely allows for structure determination of molecules in solution-state. It also gives insights into dynamics and intermolecular interactions important for determining biological function. Detailed molecular information is entangled in the nuclear spin states. The information can be extracted by pulse sequences designed to measure the desired molecular parameters. Advancement of pulse sequence methodology therefore plays a key role in the development of biomolecular NMR spectroscopy. A range of novel pulse sequences for solution-state NMR spectroscopy are presented in this thesis. The pulse sequences are described in relation to the molecular information they provide. The pulse sequence experiments represent several advances in NMR spectroscopy with particular emphasis on applications for proteins. Some of the novel methods are focusing on methyl-containing amino acids which are pivotal for structure determination. Methyl-specific assignment schemes are introduced for increasing the size range of 13C,15N labeled proteins amenable to structure determination without resolving to more elaborate labeling schemes. Furthermore, cost-effective means are presented for monitoring amide and methyl correlations simultaneously. Residual dipolar couplings can be applied for structure refinement as well as for studying dynamics. Accurate methods for measuring residual dipolar couplings in small proteins are devised along with special techniques applicable when proteins require high pH or high temperature solvent conditions. Finally, a new technique is demonstrated to diminish strong-coupling induced artifacts in HMBC, a routine experiment for establishing long-range correlations in unlabeled molecules. The presented experiments facilitate structural studies of biomolecules by NMR spectroscopy.

Chemical and source characterisation of size-segregated urban air particulate matter

Recent epidemiological studies have shown a consistent association of the mass concentration of urban air thoracic (PM10) and fine (PM2.5) particles with mortality and morbidity among cardiorespiratory patients. However, the chemical characteristics of different particulate size ranges and the biological mechanisms responsible for these adverse health effects are not well known. The principal aims of this thesis were to validate a high volume cascade impactor (HVCI) for the collection of particulate matter for physicochemical and toxicological studies, and to make an in-depth chemical and source characterisation of samples collected during different pollution situations. The particulate samples were collected with the HVCI, virtual impactors and a Berner low pressure impactor in six European cities: Helsinki, Duisburg, Prague, Amsterdam, Barcelona and Athens. The samples were analysed for particle mass, common ions, total and water-soluble elements as well as elemental and organic carbon. Laboratory calibration and field comparisons indicated that the HVCI can provide a unique large capacity, high efficiency sampling of size-segregated aerosol particles. The cutoff sizes of the recommended HVCI configuration were 2.4, 0.9 and 0.2 μm. The HVCI mass concentrations were in a good agreement with the reference methods, but the chemical composition of especially the fine particulate samples showed some differences. This implies that the chemical characterization of the exposure variable in toxicological studies needs to be done from the same HVCI samples as used in cell and animal studies. The data from parallel, low volume reference samplers provide valuable additional information for chemical mass closure and source assessment. The major components of PM2.5 in the virtual impactor samples were carbonaceous compounds, secondary inorganic ions and sea salt, whereas those of coarse particles (PM2.5-10) were soil-derived compounds, carbonaceous compounds, sea salt and nitrate. The major and minor components together accounted for 77-106% and 77-96% of the gravimetrically-measured masses of fine and coarse particles, respectively. Relatively large differences between sampling campaigns were observed in the organic carbon content of the PM2.5 samples as well as the mineral composition of the PM2.5-10 samples. A source assessment based on chemical tracers suggested clear differences in the dominant sources (e.g. traffic, residential heating with solid fuels, metal industry plants, regional or long-range transport) between the sampling campaigns. In summary, the field campaigns exhibited different profiles with regard to particulate sources, size distribution and chemical composition, thus, providing a highly useful setup for toxicological studies on the size-segregated HVCI samples.

Dilute Solution Properties of Methyl Methacrylate/Acrylonitrile Random Copolymers, 2a)

The Stockmayer-Fixman relation was used to evaluate the short range and long range interaction parameters for methyl methacrylate/acrylonitrile copolymers of 0,566 and 0,657 mole fraction of monomeric units of acrylonitrile in the solvents acetonitrile, 2-butanone, dimethyl formamide, and y-butyrolactone, at different temperatures (30, 45, and 60 “C). The values of KO were found to be lower than those of the parent homopolymers, and their values depend on both solvent and temperature. Even negative Ko-values were obtained, in cases in which the Mark Houwink exponent a is nearly unity. The values of the polymer-solvent interaction parameter, x, , are high and close to 0,5, indicating that these solvents are not good. The values of the excess interaction parameter, xAB, are negative and are not affected by temperature. The large extension of these copolymer chains, as exhibited by a and a;-values, can be understood in terms of unusual short range interactions only. Similar results were obtained for some cellulose derivatives.

Resistivity noise in crystalline magnetic nanowires and its implications to domain formation and kinetics

We have investigated the time-dependent fluctuations in electrical resistance, or noise, in high quality crystalline magnetic nanowires within nanoporous templates. The noise increases exponentially with increasing temperature and magnetic field, and has been analyzed in terms of domain wall depinning within the Neel-Brown framework. The frequency-dependence of noise also indicates a crossover from nondiffusive kinetics to long-range diffusion at higher temperatures, as well as a strong collective depinning, which need to be considered when implementing these nanowires in magnetoelectronic devices.

Intermolecular interactions in the formation of aromatic hydrocarbon dimers

Both short-range and long-range intermolecular interaction energies between two aromatic hydrocarbon molecules, both in their ground state, separated by a range of interplanar distances of 3 ∼ 4 Aring, are estimated using the standard perturbation theory. The results show that aromatic hydrocarbons can form weak sandwich dimers with larger separation between them than is normally believed in their excimers. The non-sandwich form of dimer in which the long in-plane axes of the monomers are parallel and their short in-plane axes inclined, represents an unstable orientation because this form can pass to the perfect sandwich form without an energy barrier.

Monte Carlo simulation of Ising chains showing several phase transitions

A Monte Carlo simulation of Ising chains with competing short-range and infiniterange interactions has been carried out. Results show that whenever the system does not enter a metastable state, variation of temperature brings about phase transitions in the Ising chain. These phase transitions, except for two sets of interaction strengths, are generally of higher order and involve changes in the long-range order while the short-range order remains unaffected.