Isoindigo dye incorporated copolymers with naphthalene and anthracene: promising materials for stable organic field effect transistors

In this paper, we report the design and synthesis of isoindigo based low band gap polymer semiconductors, poly{N,N′-(2-octyldodecyl)-isoindigo-alt- naphthalene} (PISD-NAP) and poly{N,N′-(2-octyldodecyl)-isoindigo-alt- anthracene} (PISD-ANT). A series of donor-acceptor (D-A) copolymers can be prepared where donor and acceptor conjugated blocks can be attached alternately using organometallic coupling. In these polymers, an isoindigo dye acceptor moiety has been attached alternately with naphthalene and anthracene donor comonomer blocks by Suzuki coupling. PISD-NAP and PISD-ANT exhibit excellent solution processibility and good film-forming properties. Gel permeation chromatography exhibits a higher molecular mass with lower polydispersity. UV-vis-NIR absorption of these polymers exhibits a wide absorption band ranging from 300 nm to 800 nm, indicating the low band gap nature of the polymers. Optical band gaps calculated from the solid state absorption cutoff value for PISD-NAP and PISD-ANT are around 1.80 eV and 1.75 eV, respectively. Highest occupied molecular orbital (HOMO) values calculated respectively for PISD-NAP and PISD-ANT thin films on glass substrate by photoelectron spectroscopy in air (PESA) are 5.66 eV and 5.53 eV, indicative of the good stability of these materials in organic electronic device applications. These polymers exhibit p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices in ambient conditions. The highest hole mobility of 0.013 cm2 V-1 s-1 is achieved in top contact and bottom-gate OTFT devices for PISD-ANT, whereas polymer PISD-NAP exhibited a hole mobility of 0.004 cm2 V -1 s-1. When these polymer semiconductors were used as a donor and PC71BM as an acceptor in OPV devices, the highest power conversion efficiency (PCE) of 1.13% is obtained for the PISD-ANT polymer.

Updates in inducible transgene expression using viral vectors : from transient to stable expression

The prospect of economically producing useful biologics in plants has greatly increased with the advent of viral vectors. The ability of viral vectors to amplify transgene expression has seen them develop into robust transient platforms for the high-level, rapid production of recombinant proteins. To adapt these systems to stably transformed plants, new ways of deconstructing the virus machinery and linking its expression and replication to chemically controlled promoters have been developed. The more advanced of these stable, inducible hyper-expression vectors provide both activated and amplified heterologous transgene expression. Such systems could be deployed in broad acre crops and provide a pathway to fully exploit the advantages of plants as a platform for the manufacture of a wide spectrum of products.

High order unconditionally stable difference schemes for the Riesz space-fractional telegraph equation

In this paper, a class of unconditionally stable difference schemes based on the Pad´e approximation is presented for the Riesz space-fractional telegraph equation. Firstly, we introduce a new variable to transform the original dfferential equation to an equivalent differential equation system. Then, we apply a second order fractional central difference scheme to discretise the Riesz space-fractional operator. Finally, we use (1, 1), (2, 2) and (3, 3) Pad´e approximations to give a fully discrete difference scheme for the resulting linear system of ordinary differential equations. Matrix analysis is used to show the unconditional stability of the proposed algorithms. Two examples with known exact solutions are chosen to assess the proposed difference schemes. Numerical results demonstrate that these schemes provide accurate and efficient methods for solving a space-fractional hyperbolic equation.

An investigation of the effect of some stable nitroxide antioxidants in prostate cancer cells

The risk of prostate cancer and disease progression may potentially be increased by oxidative stress. This project examined the stability of nitroxide antioxidants and their effects on cell growth, survival and gene regulation in prostate cancer cells. The novel nitroxide, CTMIO, synthesised here at QUT, was found to have minimal toxicity and modulated the expression of a subset of oxidative stress and antioxidant-related genes distinct from those regulated by a related derivative. This study has provided a step forward in our understanding of the mechanism of action of nitroxides within cells.

Stable organic photovoltaics using Ag thin film anodes

The interaction at the interface between a metal electrode and photoactive polymer is crucial for overall performance and stability of organic photovoltaics (OPVs). In this article, we report a comparative study of the stability of thin film Ag and indium tin oxide (ITO) as electrodes when used in conjunction with an interfacial PEDOT:PSS layer for P3HT:PCBM blend OPV devices. XPS measurements were taken for Ag and ITO/PEDOT:PSS layered samples with different exposure times to ambient conditions (∼25 °C, ∼50% relative humidity) to investigate the migration of Ag and In into the PEDOT:PSS layer. The change in efficiency of OPVs with a longer exposure time and degree of migration is explained by the analysis of XPS results. We propose the mechanism behind the interactions occurring at the interfaces. The efficiency of the ITO electrode OPVs continuously decreased to below 10% of the initial efficiency. However, the Ag devices displayed a slower degradation and maintained 50% of the initial efficiency for the same period of time.

Phase Equilibria in the System $Al_{2}O_{3}-CaO-CoO$ and Gibbs Energy of Formation of $Ca_{3}CoAl_{4}O_{10}$

The floating-zone method with different growth ambiences has been used to selectively obtain hexagonal or orthorhombic DyMnO3 single crystals. The crystals were characterized by x-ray powder diffraction of ground specimens and a structure refinement as well as electron diffraction. We report magnetic susceptibility, magnetization and specific heat studies of this multiferroic compound in both the hexagonal and the orthorhombic structure. The hexagonal DyMnO3 shows magnetic ordering of Mn3+ (S = 2) spins on a triangular Mn lattice at T-N(Mn) = 57 K characterized by a cusp in the specific heat. This transition is not apparent in the magnetic susceptibility due to the frustration on the Mn triangular lattice and the dominating paramagnetic susceptibility of the Dy3+ (S = 9/2) spins. At T-N(Dy) = 3 K, a partial antiferromagnetic order of Dy moments has been observed. In comparison, the magnetic data for orthorhombic DyMnO3 display three transitions. The data broadly agree with results from earlier neutron diffraction experiments, which allows for the following assignment: a transition from an incommensurate antiferromagnetic ordering of Mn3+ spins at T-N(Mn) = 39 K, a lock-in transition at Tlock-in = 16 K and a second antiferromagnetic transition at T-N(Dy) = 5 K due to the ordering of Dy moments. Both the hexagonal and the orthorhombic crystals show magnetic anisotropy and complex magnetic properties due to 4f-4f and 4f-3d couplings.

Expression of the extracellular domain of the human heat-stable enterotoxin receptor in Escherichia coli and generation of neutralizing antibodies

The entire extracellular domain of the human heat-stable enterotoxin (ST) receptor as well as a truncated N-terminal domain were cloned as glutathione S-transferase fusion proteins and expressed in Escherichia coli. The recombinant fusion proteins were purified from both the cytosol and the inclusion body fractions by selective detergent extraction followed by glutathione-agarose affinity chromatography. The purified protein, corresponding to the entire extracellular domain, bound the stable toxin peptide with an affinity comparable to that of the native receptor characterized from the human colonic T84 cell line. No binding was observed with the N-terminal truncated fragment of the receptor under similar conditions, Polyclonal antibodies were raised to the entire extracellular domain fusion protein as well as the truncated extracellular domain fusion protein, and the antibodies were purified by affinity chromatography. Addition of the purified antibodies to T84 cells inhibited ST binding and abolished ST-mediated cGMP production, indicating that critical epitopes involved in ligand interaction are present in the N-terminal fragment of the receptor, Purified antibodies recognized a single protein of M(r) 160,000 Da on Western blotting with T84 membranes, corresponding to a size of the native glycosylated receptor in T84 cells. These studies are the first report of the expression, purification, and characterization of any member of the guanylyl cyclase family of receptors in E. coli and show that binding of the toxin to the extracellular domain of the receptor is possible in the absence of any posttranslational modifications such as glycosylation. The recombinant fusion proteins as well as the antibodies that we have generated could serve as useful tools in the identification of critical residues of the extracellular domain involved in ligand interaction.

Activities in the $FeTiO_{3}-NiTiO_{3}$ Solid Solution from Alloy-Oxide Equilibria at 1273 K

Nine tie-lines between Fe-Ni alloys and FeTiO3-NiTiO3 solid solutions were determined at 1273 K. Samples were equilibrated in evacuated quartz ampoules for periods up to 10 days. Compositions of the alloy and oxide phases at equilibrium were determined by energy-dispersive x-ray spectroscopy. X-ray powder diffraction was used to confirm the results. Attainment of equilibrium was verified by the conventional tie-line rotation technique and by thermodynamic analysis of the results. The tie-lines are skewed toward the FeTiO3 corner. From the tie-line data and activities in the Fe-Ni alloy phase available in the literature, activities of FeTiO3 and NiTiO3 in the ilmenite solid solution were derived using the modified Gibbs-Duhem technique of Jacob and Jeffes [K.T. Jacob and J.H.E. Jeffes, An Improved Method for Calculating Activities from Distribution Equilibria, High Temp. High Press., 1972, 4, p 177-182]. The components of the oxide solid solution exhibit moderate positive deviations from Raoult's law. Within experimental error, excess Gibbs energy of mixing for the FeTiO3-NiTiO3 solid solution at 1273 K is a symmetric function of composition and can be represented as: Delta G(E) = 8590 (+/- 200) X-FeTiO3 X-NiTiO3 J/mol Full spectrum of tie-lines and oxygen potentials for the three-phase equilibrium involving Fe-Ni alloys, FeTiO3-NiTiO3 solid solutions, and TiO2 at 1273 K were computed using results obtained in this study and data available in the literature.

Self-Assembled Pd(II) Metallocycles Using an Ambidentate Donor and the Study of Square-Triangle Equilibria

The self-assembly reaction of a cis-blocked 90° square planar metal acceptor with a symmetrical linear flexible linker is expected to yield a [4 + 4] self-assembled square, a [3 + 3] assembled triangle, or a mixture of these.However, if the ligand is a nonsymmetrical ambidentate, it is expected to form a complex mixture comprising several linkage isomeric squares and triangles as a result of different connectivities of the ambidentate linker. We report instead that the reaction of a 90° acceptor cis-(dppf)Pd(OTf)2 [where dppf ) 1,1′-bis(diphenylphosphino)- ferrocene] with an equimolar amount of the ambidentate unsymmetrical ligand Na-isonicotinate unexpectedly yields a mixture of symmetrical triangles and squares in the solution. An analogous reaction using cis-(tmen)Pd(NO3)2 instead of cis-(dppf)Pd(OTf)2 also produced a mixture of symmetrical triangles and squares in the solution. In both cases the square was isolated as the sole product in the solid state, which was characterized by a single crystal structure analysis. The equilibrium between the triangle and the square in the solution is governed by the enthalpic and entropic contributions. The former parameter favors the formation of the square due to less strain in the structure whereas the latter one favors the formation of triangles due to the formation of more triangles from the same number of starting linkers. The effects of temperature and concentration on the equilibria have been studied by NMR techniques. This represents the first report on the study of square-triangle equilibria obtained using a nonsymmetric ambidentate linker. Detail NMR spectroscopy along with the ESI-mass spectrometry unambiguously identified the components in the mixture while the X-ray structure analysis determined the solid-state structure.

Phase transformations and metastable phase equilibria in Al-Ge alloy

In this paper the results of a detailed investigation on the metastable phase relations in undercooled as well as rapidly solidified Al---Ge alloys containing 2–50 at.% Ge are reported. Data obtained on the structure and morphology of phases enable us to arrive at the phase relations and transformation processes occurring in undercooled and rapidly quenched melts of this system. These results are explained with the help of a metastable phase diagram consisting of a peritectic and eutectic reaction involving metastable phases.

Spin-state equilibria in the LCoO3 system from 59Co NMR

Spin-state equilibria in the whole set of LCoO3 (where L stands for a rare-earth metal or Y) have been investigated with the use of 59Co NMR as a probe for the polycrystalline samples (except Ce) in the temperature interval 110-550 K and frequency range 3- 11.6 MHz. Besides confirming the coexistence of the high-spin—low-spin state in this temperature range, a quadrupolar interaction of ∼0.1 -0.5 MHz has been detected for the first time from 59Co NMR. The NMR line shape is found to depend strongly on the relative magnitude of the magnetic and quadrupolar interactions present. Analysis of the powder pattern reveals two basically different types of transferred hyperfine interaction between the lighter and heavier members of the rare-earth series. The first three members of the lighter rare-earth metals La, Pr (rhombohedral), and Nd (tetragonal), exhibit second-order quadrupolar interaction with a zero-asymmetry parameter at lower temperatures. Above a critical temperature TS (dependent on the size of the rare-earth ion), the quadrupolar interaction becomes temperature dependent and eventually gives rise to a first-order interaction thus indicating a possible second-order phase change. Sm and Eu (orthorhombic) exhibit also a second-order quadrupolar interaction with a nonzero asymmetry parameter ((η∼0.47)) at 300 K, while the orthorhombic second-half members (Dy,..., Lu and Y) exhibit first-order quadrupolar interaction at all temperatures. Normal paramagnetic behavior, i.e., a linear variation of Kiso with T-1, has been observed in the heavier rare-earth cobaltites (Er,..., Lu and Y), whereas an anomalous variation has been observed in (La,..., Nd)CoO3. Thus, Kiso increases with increasing temperature in PrCoO3 and NdCoO3. These observations corroborate the model of the spin-state equilibria in LCoO3 originally proposed by Raccah and Goodenough. A high-spin—low-spin ratio, r=1, can be stabilized in the perovskite structure by a cooperative displacement of the oxygen atoms from the high-spin towards the low-spin cation. Where this ordering into high- and low-spin sublattices occurs at r=1, one can anticipate equivalent displacement of all near-neighbor oxygen atoms towards a low-spin cobalt ion. Thus the heavier LCoO3 exhibits a small temperature-independent first-order quadrupolar interaction. Where r<1, the high- and low-spin states are disordered, giving rise to a temperature-dependent second-order quadrupolar interaction with an anomalous Kiso for the lighter LCoO3.

59Co NMR studies of the spin-state equilibria in rare-earth cobaltites

Hyperfine interaction parameters reveal differences in the nature of spin-state equilibria in the lighter and heavier rare-earth cobaltites; the crystal-field parameter is lower in the lighter cobaltites. Temperature variation of the quadrupolar coupling constant is also more marked in the lighter rare-earth cobaltites, with NdCoO3 showing evidence for a structural phase transition.

Development of a stable isotope index to assess decadal-scale vegetation change and application to woodlands of the Burdekin catchment, Australia

Forty-four study sites were established in remnant woodland in the Burdekin River catchment in tropical north-east Queensland, Australia, to assess recent (decadal) vegetation change. The aim of this study was further to evaluate whether wide-scale vegetation 'thickening' (proliferation of woody plants in formerly more open woodlands) had occurred during the last century, coinciding with significant changes in land management. Soil samples from several depth intervals were size separated into different soil organic carbon (SOC) fractions, which differed from one another by chemical composition and turnover times. Tropical (C4) grasses dominate in the Burdekin catchment, and thus δ13C analyses of SOC fractions with different turnover times can be used to assess whether the relative proportion of trees (C3) and grasses (C4) had changed over time. However, a method was required to permit standardized assessment of the δ13C data for the individual sites within the 13 Mha catchment, which varied in soil and vegetation characteristics. Thus, an index was developed using data from three detailed study sites and global literature to standardize individual isotopic data from different soil depths and SOC fractions to reflect only the changed proportion of trees (C3) to grasses (C3) over decadal timescales. When applied to the 44 individual sites distributed throughout the Burdekin catchment, 64% of the sites were shown to have experienced decadal vegetation thickening, while 29% had remained stable and the remaining 7% had thinned. Thus, the development of this index enabled regional scale assessment and comparison of decadal vegetation patterns without having to rely on prior knowledge of vegetation changes or aerial photography.

Improved Approach for Analyzing Bromophenols in Seafood Using Stable Isotope Dilution Analysis in Combination with SPME

An analytical method for the measurement of five naturally occurring bromophenols of sensory relevance in seafood (barramundi and prawns) is presented. The method combines simultaneous distillation−extraction followed by alkaline back extraction of a hexane extract and subsequent acetylation of the bromophenols. Analysis of the bromophenol acetates was accomplished by headspace solid phase microextraction and gas chromatography−mass spectrometry using selected ion monitoring. The addition of 13C6 bromophenol stable isotope internal standards for each of the five congeners studied permitted the accurate quantitation of 2-bromophenol, 4-bromophenol, 2,6-dibromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol down to a limit of quantification of 0.05 ng/g of fish flesh. The method indicated acceptable precision and repeatability and excellent linearity over the typical concentration range of these compounds in seafood (0.5−50 ng/g). The analytical method was applied to determine the concentration of bromophenols in a range of farmed and wild barramundi and prawns and was also used to monitor bromophenol uptake in a pilot feeding trial.