The synthesis and evaluation of a molecularly imprinted polymer has been undertaken using an oxazine-based tryptophanamide transition state analogue (TSA) as template. An efficient route to the synthesis of oxazine-based TSAs for the reaction of pyridoxamine and indole-3-pyruvic acid has been established, with yields of up to 80%. NMR titration studies were performed to examine the interactions between the functional monomer, methacrylic acid and the template. Complexation of the template by functional monomer in the presence of crosslinker showed an apparent KD of 0.63-0.79 ± 0.04 M (293 K, acetonitrile-d3) based upon the chemical shift of the template amide protons. TSA-imprinted and non-imprinted reference polymers were synthesized by free radical polymerization in acetonitrile. Polymer monoliths were ground and fractionated into a 25-63 μm size range. Polymer-ligand recognition studies were conducted using the polymers as HPLC stationary phases. An imprinting factor (IF) of 2.93 was observed for the TSA, indicating the selectivity of the imprinted sites for the template. Studies using the D- and L-enantiomers of the phenylalaninamide analogue of the template showed enantioselectivity in the case of the imprinted polymer, α = 1.10, though not in the case of the non-imprinted reference polymer (1.00). Using UV-spectroscopy based polymer-ligand binding studies, a maximum theoretical capacity (Bmax) of 0.059 ± 0.004 mmol·g-1 was observed for the imprinted polymer. Conclusively, an imprinted polymer with binding sites selective for the TSA was successfully prepared and shall subsequently be studied with respect to its capacity to catalyse the transamination reaction between pyridoxamine and indole-3-pyruvic acid to yield pyridoxal and tryptophan.

Partitioning of poly(ethyleneglycol) (PEG) molecules in 2-D and 3-D systems is presented as a self-assembly approach for controlling non-specific adsorption of proteins at interfaces. Lateral restructuring of multi-component Langmuir monolayers to accommodate adsorbing proteins was investigated as a model 2-D system. Ferritin adsorption to monolayers containing cationic, nonionic, and PEG bearing phospholipids induced protein sized binding pockets surrounded by PEG rich regions. The number, size, and distribution of protein imprint sites were controlled by the molar ratios, miscibility, and lateral mobility of the lipids. The influence of PEG chain length on the ternary monolayer restructuring and protein distribution was also investigated using DSPE-PEGx (x= 7, 16, 22). Monolayer miscibility analysis demonstrated that longer PEG chains diminished the condensed phase formation for a fixed ratio of lipids. Thus, incorporation of longer PEG chains, intended to diminish protein adsorption outside of the imprint sites of cationic / non-ionic lipids, leads to dramatic changes in monolayer phase behavior and protein distribution in this 2-D system. The assembly of PEG-amphiphiles at elastomer surfaces and subsequent protein adsorption was investigated as a model 3-D system. Polydimethylsiloxane (PDMS) substrates were modified with block copolymers comprised of PEG and PDMS segments by two methods: (1) the block copolymer was mixed with PDMS during polymerization; (2) the block copolymer diffused into solvent swollen PDMS monoliths. Hydrophilic surfaces resulted for both approaches that, for 600 D block copolymer, exhibited up to 85% reduction in fibrinogen adsorption as compared to native PDMS. Higher MW block copolymers (up to 3000 D) resulted in less hydrophilic surfaces and greater protein adsorption, presumably due to diffusion limitations of copolymer in the PDMS monolith. All modified PDMS surfaces were dynamic and restructured when cycled between air and water. PDMS transparency also decreased with increase in block copolymer concentration for both methods, limiting this modification protocol for applications requiring high polymer transparency. The 2-D system presents a bottom-up approach, where adsorbing protein constructs the binding site, while the 3-D system presents a top down approach, where protein-binding elements may be introduced into the PEG-bearing polymer for fabrication of surfaces with controlled protein adsorption.

No description available.

The aim of this work was to investigate the effects of feather availability and imprinting to loose feathers in the litter on the incidence of feather pecking behaviour (FP), condition of the integument and fear reactions in two genotypes of laying hens. Hens that were deprived from loose feathers in the litter (feathers were collected 4 times/week) exhibited a significantly less rate of feather pecking, less number of severe FP and showed a better feather score in the laying period compared to the control groups (no feather treatment) in both Lohmann Tradition (LT) & Lohmann Silver (LS) genotypes. Addition of brown feathers to the floor in LT hens (feathers were added once/week) was associated with a reduction in feather pecking rate, the severe form of this behaviour and improved plumage and skin conditions. Contrary, the addition of white feathers to the floor in LS was associated with the highest rate of feather pecking, the highest severe form of this behaviour as well as the worst feather and skin conditions in the laying period compared to other groups of the same genotype. The LT birds in all feather treatments had a better feather cover than the LS birds. Hens that were imprinted to loose feathers in the litter in the rearing period exhibited a higher rate of FP, higher number of severe FP and showed the worst feather and skin conditions when feathers were collected from the floor during the laying period. Also, these hens reacted more fearful during the tonic immobility test. It is concluded that loose feathers may play a role in the development of feather pecking behaviour in laying hens. Large differences between genotypes were found in respect to the availability of loose feathers, feather pecking and plumage and integument condition. Imprinting of chicks to loose feathers from the floor may affect the incidence of feather pecking later on. Ziel dieser Arbeit war es, die Einflüsse des Federangebotes und der Prägung auf lose Federn in der Einstreu auf die Häufigkeit des Auftretens von Federpicken (FP), den Zustand des Integuments und die Furchtreaktionen an zwei Legehennengenotypen zu untersuchen. Hühnern beider untersuchter Genotypen (Lohmann Tradition (LT) und Lohmann Silber (LS)), denen die losen Federn 4 mal/ Woche aus der Einstreu abgesammelt wurden, zeigten eine geringere Federpickrate, eine geringere Anzahl der schweren Form des FP und eine bessere Gefiederbeschaffenheit in der Legeperiode verglichen mit der Kontrollgruppe (keine Federbehandlung). Das Hinzufügen brauner Federn zur Einstreu bewirkte bei LT Hennen eine Reduktion der FP-Rate, der schweren Form des Federpickens und verbesserte die Gefieder- und Hautbeschaffenheit. Dagegen führte das Hinzufügen weißer Federn in die Einstreu während der Legeperiode bei LS Hennen zur höchsten Federpickrate und Anzahl der schweren Form des Federpickens sowie zur schlechtesten Gefieder- und Hautbeschaffenheit im Vergleich zu anderen Gruppen des gleichen Genotyps. Hühner der LT Linie wiesen in allen Federbehandlungen eine bessere Befiederung als die LS Hühner auf. Hennen, die während der Aufzuchtsperiode auf lose Federn in der Einstreu geprägt wurden, zeigten nach Absammeln der Federn während der Legeperiode eine erhöhte FP-Rate mit einer erhöhten Anzahl der schweren Form des FP und die schlechteste Gefieder- und Hautbeschaffenheit. Außerdem reagierten diese Hühner ängstlicher während des Tests auf tonische Immobilität. Es kann geschlussfolgert werden, dass lose Federn in der Einstreu eine Rolle bei der Entwicklung des Federpickverhaltens von Legehennen spielen und dass Federpicken als Futtersuchverhalten interpretiert werden kann. Grosse Unterschiede zwischen den Genotypen bestanden hinsichtlich der Verfügbarkeit von losen Federn in der Einstreu, des Federpickens sowie der Gefieder- und Integumentbeschaffenheit. Eine Prägung der Junghennen auf lose Federn in der Einstreu könnte das Auftreten von Federpicken zu einem späteren Zeitpunkt beeinflussen.

No description available.

In recent years, the importance of sagebrush to shrub-steppe ecosystems and associated plant and animal species has been recognized. The historical removal of herbaceous species by excessive and uncontrolled livestock grazing on many of our sagebrush ecosystems has resulted in a stagnant state where dense, competitive stands of sagebrush prevent herbaceous species from recovering. Most early research on sagebrush control was directed toward eradication to increase herbaceous forage for livestock production, rather than sagebrush thinning to improve shrub vigor and understory production for wildlife habitat and community diversity. Mechanical treatments have the ability to retain shrub and herbaceous components, while improving diversity within degraded sagebrush communities. This study evaluated the effects of 6 mechanical treatments and revegetation of a Wyoming big sagebrush (Artemisia tridentata ssp. wyomingensis) community in northern Utah that were treated in the fall of 2001 and spring of 2002 (aerator only). Disking and imprinting killed 98% of the sagebrush and significantly (p < 0.05) lowered cover and density of sagebrush more than any other treatment. Disking and imprinting was the only mechanical treatment to reduce cover and density of residual understory species, but also to successfully establish seeded grasses. One-way Ely chaining, 1-way and 2-way pipe harrowing, and aerating in the fall and spring reduced sagebrush cover from greater than 20% to less than 5% and reduced density by about half. Two years after mechanical treatment surviving sagebrush had greater leader and seed stalk growth than untreated sagebrush. Choice of a mechanical treatment to increase and diversify the perennial herbaceous component and retain the shrub component of sagebrush communities depends on the amount of residual herbaceous species, as well as economics. Chaining is potentially most economical for diversifying communities with a residual herbaceous perennial component. It is uncertain whether successful revegetation from disking and imprinting was a result of significant reduction in sagebrush, residual perennial herbaceous species, or both. Response of sagebrush communities with a very limited perennial herbaceous understory needs to be tested to determine how much and what kind of mechanical reduction in sagebrush is needed for successful revegetation.

Unwanted uranium released in the aquatic environment from uranium mining and nuclear fuel industry has become a growing threat to human health and environment safety due to its radiological and chemical toxicity. Biosorbents from agro-industrial waste are the most preferred materials for the removal of uranium from the wastewater due to their good cost-to-performance ratio. Brewer’s spent grain (BSG), a widely produced by-product from the beer brewery industry, is an inexpensive and readily available feedstock for the production of uranium biosorbents. In the current work, the use of BSG as a promising starting feedstock for low-cost and efficient adsorbents with high adsorption capacity, fast kinetics, selectivity, and reusability, is investigated. Functionalization methods such as thermal treatment, chemical modification (oxidation), and polymer grafting were explored, and the selectivity was tuned using surface ion-imprinting technology. The adsorption performance of adsorbents prepared from BSG was tested under various conditions for practical application, and structure affinity principles were derived from the characterization, data modeling and experimental results (Fig. 1). In the first part of this work, BSG is successfully converted into altered BSG (ABSG), an effective biosorbent, by mild hydrothermal treatment approach (150 ℃, 16 h). Compared with the conventional hydrothermal carbonation method (up to 250 ℃), the current method is carried out at a significantly lower temperature without any additional activation process, which minimizes the energy consumption and environmental impact during the treatment. Maillard reaction plays an important role in increasing the adsorption capacity by forming various Maillard reaction products (methylglyoxal-derived hydroimidazolone-1 with the highest content) and melanoidins with a large number of functional groups. In addition, other pathways such as dehydration, decarboxylation, aromatization and oxidation also contribute to the increased adsorption capacity. Therefore, the content of carboxyl groups in ABSG increases up to 1.46 mmol/g with maximum adsorption capacities for La(Ⅲ), Eu(Ⅲ), Yb(Ⅲ) (pH = 5.7), and U(Ⅵ) (pH = 4.7) of 38, 68, 46 and 221 mg/g, respectively (estimated by the Langmuir model). Moreover, FT-IR spectra show that both O- and N-containing functional groups are involved in the adsorption of studied ions. The second part of this work demonstrates for the first time the successful oxidization of BSG using 85 wt% H3PO4 and NaNO2, increasing the carboxyl groups content from 0.15 mmol/g for BSG to 1.3 mmol/g for oxidized BSG (OBSG). OBSG exhibits fast adsorption kinetics in 1 h and an adsorption capacity for U(Ⅵ) of 297.3 mg/g (c0(U) = 900 mg/L, pH = 4.7), which is superior to other biosorbents reported in the literature. Possible adsorption mechanisms are based on ion-exchange between UO22+ and H+ released from carboxyl groups, and the complexation of UO22+ with the two oxygen atoms of carboxyl groups. For practical application, adsorption/desorption studies show that OBSG retains 60% of original adsorption capacity (167 mg/g) with a desorption ratio of 89% after 5 adsorption/desorption cycles. Evaluation of OBSG performance in simulated seawater (10.8 mg/g, c0(U) = 10 mg/L, 193 mg/L NaHCO3 and 25.6 g/L NaCl, pH0 = 7.7) indicates a potential usage at low concentration, high salinity, and in the presence of carbonate. In the third part of this work, brewer’s spent grain supported superabsorbent polymers (BSG-SAP) with various cross-linking density are prepared for the first time via one-pot swelling and graft polymerization of acrylic acid (AA) and acrylamide as low-cost and environmentally friendly adsorbents. A 7 wt% NaOH solution was used as a swelling agent for BSG and as a neutralization agent for AA without generating alkaline effluents. The use of BSG and graft polymerization can significantly increase the available hydroxyl, carboxyl and amide groups, resulting in a highly cross-linked and highly hydrophilic three-dimensional polymer network of BSG-SAP. The BSG-SAP (BSG-SAP-H) prepared with high cross-linking density exhibits better properties with exceptional adsorption capacity for U(VI) of 1465 mg/g (estimated by the Toth model) at pH0 = 4.6 within 45 min. It also shows good selectivity for U(VI) in the presence of several metal ions (V(V), K(I), Na(I), Mg(II), Zn(II), Co(II), Ni(II), and Cu(II)) with selectivity coefficients (SU) higher than 72%. In simulated seawater, BSG-SAP-H showed higher adsorption capacity (17.6 mg/g for c0(U) = 8 mg/L, pH0 = 8) compared to the currently reported adsorbents based on natural polymers. In the experiments with the fixed bed column (c0(U) = 30 mg/L), the uranyl ions could be concentrated up to 15 folders in U(VI)-spiked water and up to 13 folds in simulated seawater. Moreover, after four cycles, BSG-SAP-H was able to maintain 80% of adsorption capacity in U(VI)-spiked water (254.4 mg/g) and 90% in simulated seawater (37.4 mg/g). FT-IR and 13C solid-state NMR spectra show the function of amide groups for U(VI) adsorption, the bidentate binding structure between UO22+ and the carboxyl groups, and the cation exchange between Na+ in BSG-SAP and UO22+. The fourth part of this work describes a new strategy for the preparation of surface ion imprinted brewer’s spent grain (IIP-BSG) using binary functional monomers (2-hydroxyethyl methacrylate and diethyl vinylphosphonate) for selective removal of U(VI). A high monomer/template molar ratio of 500:1 is used to ensure high site accessibility and easy template removal. IIP-BSG exhibits a maximum U(VI) adsorption capacity of 165.7 mg/g (pH0 = 4.6, estimated by the Sips model), a high selectivity (SU > 80%) for U(VI) in the presence of an excess amount of Eu(III) (Eu/U molar ratio = 20), and good tolerance to salinity (47.4 mg/g for U(VI) at ionic strength = 1 mol/L and c0(U) = 0.5 mM = 120 mg/L). After 5 adsorption and desorption cycles, IIP-BSG retains 90% of its adsorption capacity (36.9 mg/g) and high selectivity (SU > 92%) in binary U(VI)/Eu(III) solution (c0 = 0.5 mM = 120 mg/L). In addition, FT-IR spectra show the electrostatic interaction and a coordination of uranyl ions by carboxyl and phosphoryl groups, the site energy distribution theory shows the predominant contribution of high-energy (specific) sites during selective adsorption, and the kinetic model shows that the internal mass transfer is the rate-determining step of U(VI) adsorption. In the last part of this work, the additional tests were performed for BSG and its derived adsorbents to evaluate their potential for practical application. BSG and most of its derived adsorbents retain 90% of their adsorption capacity after aging in water for 6 days, except for ABSG (60% decrease in adsorption capacity). IIP-BSG shows efficient separation of U(VI)/Ln(Ⅲ) (e.g. La(III), and Nd(III), Sm(III)) in weakly acidic nuclear wastewater (pH0 = 3.5) and U(VI) concentration in carbonate-rich-mine water (e.g. Schlema mine water, pH0 = 7.1) and tailings water (e.g. Helmsdorf tailings water, pH0 = 9.8), demonstrating a high potential for practical use. Selectivity of IIP-BSG is also given for acidic mine water (e.g. Königstein mine water, pH0 = 2.6). In addition, the unmodified BSG and BSG-SAP-H could effectively remove uranyl ions from acidic mine water with high selectivity. In particular, the cost efficiency and the availability of unmodified BSG make it of great interests for the remediation of uranium containing acidic mine water (Table 1).

The ‘extreme female brain’ (EFB) is derived from the empathising - systemising theory (E-S) which hypothesises that sex differences in cognition exist on a continuum, based on abilities in ‘empathising’ and ‘systemising’ (Baron-Cohen, 2003). The EFB profile; extreme empathising alongside deficient systemising, has received little attention in social cognitive neuroscience research, compared to the extreme male brain, which has advanced the knowledge of sex differences in the expression of autism. Currently, there is no solid evidence of a clinical pathology relating to the EFB nor a marker of cognition associated with a person’s ‘place’ on the E-S continuum. Here, an episodic memory paradigm with social and non-social conditions was given to participants along with measures of empathising and systemising. Scores on the social condition predicted where a person lies on the E-S continuum. The thesis then investigated the hypothesis that schizophrenia is expressed in the feminised profile (Badcock & Crepsi, 2006) and the presumption that empathising and systemising demonstrate a tradeoff. Elements of paranoia were associated with an empathising bias. However, a bias in systemising ability was associated with schizotypy along with a significant overlap in the expression of autistic traits and schizotypy. Therefore, schizophrenia as a whole is unlikely to be the pathology seen in the EFB, rather, the positive symptoms of schizophrenia. A trade-off between empathising and systemising was seen but only in participants over 36 years. These results have significant implications for assessment and treatment of neuropsychological disorders and provide more specific details on the potential EFB pathology. ii

No description available.

No description available.