Motional Averaging of Electric Field Gradients. Temperature Dependence of Nqr in Sodium Chlorate and Copper Chlorate

Es wird die Temperaturabhiingigkeit der CI35-Kernquadrupolresonanz in Natriumchlorat und Kupferchlorat im Temperature von 77 bis 300 °K untersucht. Es wird gezeigt, daß die Annahmen, die in der Theorie von Bayer gemacht werden, fur Chlorate gelten. Die Frequenz der Torsionsschwingungen der ClO3-Gruppe wird folglich mit dieser Theorie berechnet. Der berechnete Wert der Torsionsfrequenz stimmt gut mit vorhandenen Werten der Ramanspektroskopie überein.

Development of Sample Pretreatment and Liquid Chromatographic Techniques for Antioxidative Compounds

In this study, novel methodologies for the determination of antioxidative compounds in herbs and beverages were developed. Antioxidants are compounds that can reduce, delay or inhibit oxidative events. They are a part of the human defense system and are obtained through the diet. Antioxidants are naturally present in several types of foods, e.g. in fruits, beverages, vegetables and herbs. Antioxidants can also be added to foods during manufacturing to suppress lipid oxidation and formation of free radicals under conditions of cooking or storage and to reduce the concentration of free radicals in vivo after food ingestion. There is growing interest in natural antioxidants, and effective compounds have already been identified from antioxidant classes such as carotenoids, essential oils, flavonoids and phenolic acids. The wide variety of sample matrices and analytes presents quite a challenge for the development of analytical techniques. Growing demands have been placed on sample pretreatment. In this study, three novel extraction techniques, namely supercritical fluid extraction (SFE), pressurised hot water extraction (PHWE) and dynamic sonication-assisted extraction (DSAE) were studied. SFE was used for the extraction of lycopene from tomato skins and PHWE was used in the extraction of phenolic compounds from sage. DSAE was applied to the extraction of phenolic acids from Lamiaceae herbs. In the development of extraction methodologies, the main parameters of the extraction were studied and the recoveries were compared to those achieved by conventional extraction techniques. In addition, the stability of lycopene was also followed under different storage conditions. For the separation of the antioxidative compounds in the extracts, liquid chromatographic methods (LC) were utilised. Two novel LC techniques, namely ultra performance liquid chromatography (UPLC) and comprehensive two-dimensional liquid chromatography (LCxLC) were studied and compared with conventional high performance liquid chromatography (HPLC) for the separation of antioxidants in beverages and Lamiaceae herbs. In LCxLC, the selection of LC mode, column dimensions and flow rates were studied and optimised to obtain efficient separation of the target compounds. In addition, the separation powers of HPLC, UPLC, HPLCxHPLC and HPLCxUPLC were compared. To exploit the benefits of an integrated system, in which sample preparation and final separation are performed in a closed unit, dynamic sonication-assisted extraction was coupled on-line to a liquid chromatograph via a solid-phase trap. The increased sensitivity was utilised in the extraction of phenolic acids from Lamiaceae herbs. The results were compared to those of achieved by the LCxLC system.

Oral medication delivery in impaired swallowing: Thickening liquid medications for safe swallowing alters dissolution characteristics

Acetaminophen (paracetamol) is available in a wide range of oral formulations designed to meet the needs of the population across the age-spectrum, but for people with impaired swallowing, i.e. dysphagia, both solid and liquid medications can be difficult to swallow without modification. The effect of a commercial polysaccharide thickener, designed to be added to fluids to promote safe swallowing by dysphagic patients, on rheology and acetaminophen dissolution was tested using crushed immediate-release tablets in water, effervescent tablets in water, elixir and suspension. The inclusion of the thickener, comprised of xanthan gum and maltodextrin, had a considerable impact on dissolution; acetaminophen release from modified medications reached 12-50% in 30 minutes, which did not reflect the pharmacopeia specification for immediate release preparations. Flow curves reflect the high zero-shear viscosity and the apparent yield stress of the thickened products. The weak gel nature, in combination with high G’ values compared to G” (viscoelasticity) and high apparent yield stress, impact drug release. The restriction on drug release from these formulations is not influenced by the theoretical state of the drug (dissolved or dispersed), and the approach typically used in clinical practice (mixing crushed tablets into pre-prepared thickened fluid) cannot be improved by altering the order of incorporation or mixing method.

Re-examination of one-point methods of liquid limit determination

This Paper deals with the analysis of liquid limit of soils, an inferential parameter of universal acceptance. It has been undertaken primarily to re-examine one-point methods of determination of liquid limit water contents. It has been shown by basic characteristics of soils and associated physico-chemical factors that critical shear strengths at liquid limit water contents arise out of force field equilibrium and are independent of soil type. This leads to the formation of a scientific base for liquid limit determination by one-point methods, which hitherto was formulated purely on statistical analysis of data. Available methods (Norman, 1959; Karlsson, 1961; Clayton & Jukes, 1978) of one-point liquid limit determination have been critically re-examined. A simple one-point cone penetrometer method of computing liquid limit has been suggested and compared with other methods. Experimental data of Sherwood & Ryley (1970) have been employed for comparison of different cone penetration methods. Results indicate that, apart from mere statistical considerations, one-point methods have a strong scientific base on the uniqueness of modified flow line irrespective of soil type. Normalized flow line is obtained by normalization of water contents by liquid limit values thereby nullifying the effects of surface areas and associated physico-chemical factors that are otherwise reflected in different responses at macrolevel.Cet article traite de l'analyse de la limite de liquidité des sols, paramètre déductif universellement accepté. Cette analyse a été entreprise en premier lieu pour ré-examiner les méthodes à un point destinées à la détermination de la teneur en eau à la limite de liquidité. Il a été démontré par les caractéristiques fondamentales de sols et par des facteurs physico-chimiques associés que les résistances critiques à la rupture au cisaillement pour des teneurs en eau à la limite de liquidité résultent de l'équilibre des champs de forces et sont indépendantes du type de sol concerné. On peut donc constituer une base scientifique pour la détermination de la limite de liquidité par des méthodes à un point lesquelles, jusqu'alors, n'avaient été formulées que sur la base d'une analyse statistique des données. Les méthodes dont on dispose (Norman, 1959; Karlsson, 1961; Clayton & Jukes, 1978) pour la détermination de la limite de liquidité à un point font l'objet d'un ré-examen critique. Une simple méthode d'analyse à un point à l'aide d'un pénétromètre à cône pour le calcul de la limite de liquidité a été suggérée et comparée à d'autres méthodes. Les données expérimentales de Sherwood & Ryley (1970) ont été utilisées en vue de comparer différentes méthodes de pénétration par cône. En plus de considérations d'ordre purement statistque, les résultats montrent que les méthodes de détermination à un point constituent une base scientifique solide en raison du caractère unique de la ligne de courant modifiée, quel que soit le type de sol La ligne de courant normalisée est obtenue par la normalisation de la teneur en eau en faisant appel à des valeurs de limite de liquidité pour, de cette manière, annuler les effets des surfaces et des facteurs physico-chimiques associés qui sans cela se manifesteraient dans les différentes réponses au niveau macro.

The insecticidal spider toxin SFI1 is a knottin peptide that blocks the pore of insect voltage-gated sodium channels via a large β-hairpin loop

Spider venoms contain a plethora of insecticidal peptides that act on neuronal ion channels and receptors. Because of their high specificity, potency and stability, these peptides have attracted much attention as potential environmentally friendly insecticides. Although many insecticidal spider venom peptides have been isolated, the molecular target, mode of action and structure of only a small minority have been explored. Sf1a, a 46-residue peptide isolated from the venom of the tube-web spider Segesteria florentina, is insecticidal to a wide range of insects, but nontoxic to vertebrates. In order to investigate its structure and mode of action, we developed an efficient bacterial expression system for the production of Sf1a. We determined a high-resolution solution structure of Sf1a using multidimensional 3D/4D NMR spectroscopy. This revealed that Sf1a is a knottin peptide with an unusually large β-hairpin loop that accounts for a third of the peptide length. This loop is delimited by a fourth disulfide bond that is not commonly found in knottin peptides. We showed, through mutagenesis, that this large loop is functionally critical for insecticidal activity. Sf1a was further shown to be a selective inhibitor of insect voltage-gated sodium channels, consistent with its 'depressant' paralytic phenotype in insects. However, in contrast to the majority of spider-derived sodium channel toxins that function as gating modifiers via interaction with one or more of the voltage-sensor domains, Sf1a appears to act as a pore blocker.

Line tension of a two dimensional gas-liquid interface

In two dimensional (2D) gas-liquid systems, the reported simulation values of line tension are known to disagree with the existing theoretical estimates. We find that while the simulation erred in truncating the range of the interaction potential, and as a result grossly underestimated the actual value, the earlier theoretical calculation was also limited by several approximations. When both the simulation and the theory are improved, we find that the estimate of line tension is in better agreement with each other. The small value of surface tension suggests increased influence of noncircular clusters in 2D gas-liquid nucleation, as indeed observed in a recent simulation.

Viscoelastic Properties of Nanocrystalline Films of Semiconducting Chalcogenides at Liquid/Liquid Interface

The interfacial shear rheological properties of a continuous single-crystalline film of CuS and a 3D particulate gel of CdS nanoparticles (3−5 nm in diameter) formed at toluene−water interfaces have been studied. The ultrathin films (50 nm in thickness) are formed in situ in the shear cell through a reaction at the toluene−water interface between a metal−organic compound in the organic layer and an appropriate reagent for sulfidation in the aqueous layer. Linear viscoelastic spectra of the nanofilms reveal solid-like rheological behavior with the storage modulus higher than the loss modulus over the range of angular frequencies probed. Large strain amplitude sweep measurements on the CdS nanofilms formed at different reactant concentrations suggest that they form a weakly flocculated gel. Under steady shear, the films exhibit a yield stress, followed by a steady shear thinning at high shear rates. The viscoelastic and flow behavior of these films that are in common with those of many 3D “soft” materials like gels, foams, and concentrated colloidal suspensions can be described by the “soft” glassy rheology model.

Amide-catalysed isomerisation of 5,6-dihydroisoquinolines: a novel synthesis of 1,2-dihydroisoquinolines

Knoevenagel condensation of 2-acylcyclohexanones or 2-ethoxycarbonylcyclohexanone with either cyanoacetamide or malononitrile followed by silver salt alkylation gave the 5,6,7,8-tetrahydroisoquinolines (3a–i). Chromic acid oxidation of the 5,6,7,8-tetrahydroisoquinolines (3a–i) to the corresponding tetralones (4a–i) followed by sodium borohydride reduction and p-toluenesulphonic acid-catalysed dehydration of the resulting alcohols (5a–i) gave the 5,6-dihydroisoquinolines (6a–i). Reaction of 5,6-dihydroisoquinolines (6a–g) with potassium amide in liquid ammonia gave a mixture of the 1,3-dihydroisoquinolines (7a–g) and the isoquinolines (8a–g). The C-1 unsubstituted 1,2-dihydroisoquinoline (7c) was found to be very unstable. In the case of the 5,6-dihydroisoquinolines (6h and 6i), reaction of potassium amide in liquid ammonia resulted in a mixture of 1-aminoisoquinoline (9) and the isoquinolines (8h and 8i). All the above compounds have been characterised by spectral data. A probable pathway for the formation of the 1,2-dihydroisoquinolines (7a–g) and the isoquinolines (8a–i) is suggested.

Similarities in Different Experiments of Erosion Caused by Cavitation and Liquid Impingement

Correlations of erosion resistances of materials tested in different equipment are reported. Analysis of the authors' data from rotating disk and venturi equipment indicates that there exists a good correlation between the erosion resistances of materials tested at different intensities. The study indicates that time effects on erosion are important in correlations of this type. The erosion resistances of materials tested in two different devices exhibit good correlations indicating a quantitative similarity between different forms of erosion. The investigations also show that the prediction of erosion resistances of materials in a field device may be made with the data from a laboratory device which may not fully reproduce the flow conditions in the field. These conclusions are also checked with data reported from other laboratories.

Non-target species interaction with sodium fluoroacetate (1080) meat bait for controlling feral pigs (Sus scrofa)

Fresh meat baits containing sodium fluoroacetate (1080) are widely used for controlling feral pigs in Queensland, but there is a potential poisoning risk to non-target species. This study investigated the non-target species interactions with meat bait by comparing the time until first approach, investigation, sample and consumption, and whether dying bait green would reduce interactions. A trial assessing species interactions with undyed bait was completed at Culgoa Floodplain National Park, Queensland. Meat baits were monitored for 79 consecutive days with camera traps. Of 40 baits, 100% were approached, 35% investigated (moved) and 25% sampled, and 25% consumed. Monitors approached (P < 0.05) and investigated (P < 0.05) the bait more rapidly than pigs or birds, but the median time until first sampling was not significantly different (P > 0.05), and did not consume any entire bait. A trial was conducted at Whetstone State Forest, southern Queensland, with green-dyed and undyed baits monitored for eight consecutive days with cameras. Of 60 baits, 92% were approached and also investigated by one or more non-target species. Most (85%) were sampled and 57% were consumed, with monitors having slightly more interaction with undyed baits than with green-dyed baits. Mean time until first approach and sample differed significantly between species groups (P = 0.038 and 0.007 respectively) with birds approaching sooner (P < 0.05) and monitors sampling later (P < 0.05) than other (unknown) species (P > 0.05). Undyed bait was sampled earlier (mean 2.19 days) than green-dyed bait (2.7 days) (P = 0.003). Data from the two trials demonstrate that many non-target species regularly visit and sample baits. The use of green-dyed baits may help reduce non-target uptake, but testing is required to determine the effect on attractiveness to feral pigs. Further research is recommended to quantify the benefits of potential strategies to reduce the non-target uptake of meat baits to help improve the availability of bait to feral pigs.

The elastic constants of isomorphous sodium bromate and sodium chlorate from 77 to 350 K

The elastic constants of NaBrO3 and NaClO3 are evaluated from ultrasonic velocity measurements using pulse superposition techniques. The values of C11, C12 and C44 for NaBrO3 at 298°K are 5.578, 1.705, 1.510 (x 1010 N/m2) and for NaClO3 the values are 4.897, 1.389, 1.174. The values at 77°K are respectively 6.35, 1.98 and 1.65 for NaBrO3 and 6.15, 2.16 and 1.32 for NaClO3.