Synthesis and electrochemical properties of mesoporous nickel oxide

Mesoporous Ni(OH)(2) is synthesized using sodium dodecyl sulfate as a template and urea as a hydrolysis-controlling agent. Mesoporous NiO with a centralized pore-size distribution is obtained by calcining Ni(OH)(2) at different temperatures. The BET specific surface area reaches 477.7 m(2) g(-1) for NiO calcined at 250 degreesC. Structure characterizations indicate a good mesoporous structure for the nickel oxide samples. Cyclic voltammetry shows the NiO to have good capacitive behaviour due to its unique mesoporous structure when using a large amount of NiO to fabricate the electrode. Compared with NiO prepared by dip-coating and cathodic precipitation methods, mesoporous NiO with a controlled pore structure can be used in much larger amounts to fabricate electrodes and still maintain a high specific capacitance and good capacitive behaviour. (C) 2004 Elsevier B.V. All rights reserved.

Characterisation of xerogels derived from sucrose templated sol-gel synthesis

This work presents the results of the nanostructural characterisation of the effect of sucrose as a template added to a sol derived from a tetraethoxysilane acid catalysed process. By increasing the sucrose template ratio, N-2 adsorption isotherms showed that the xerogel samples changed from a micropore to a mesopore nanostructure as evidenced by the formation of hysteresis at 0.5 partial pressure. In turn, this led to a direct increase in surface areas, pore volumes and average pore sizes. Sucrose has two molecular components of the same molecular weight: D-fructose and D-glucose. D-fructose resulted in the formation of higher pore volumes and pore sizes, while D-glucose formed higher surface area xerogels. Depending of the template ratio employed in the xerogel synthesis, average pore radius ranged from 8.8 to 26 Angstrom, while surface areas increased by over two fold up to 750 m(2) . g(-1). However, pore volumes increased by as much as six fold, from 0.15 to almost 1 cm(3) . g(-1).

Novel natriuretic peptides from the venom of the inland taipan (Oxyuranus microlepidotus): isolation, chemical and biological characterisation

Three natriuretic-like peptides (TNP-a, TNP-b, and TNP-c) were isolated from the venom of Oxyuranus microlepidotus (inland taipan) and were also present in the venoms of Oxyuranus scutellatus canni (New Guinea taipan) and Oxyuranus scutellatus scutellatus (coastal taipan). They were isolated by HPLC, characterised by mass spectrometry and Edman analysis, and consist of 35-39 amino acid residues. These molecules differ from ANP/BNP through replacement of invariant residues within the 17-membered ring structure and by inclusion of proline residues in the C-terminal tail. TNP-c was equipotent to ANP in specific GC-A assays or aortic ring assays whereas TNP-a and TNP-b were either inactive (GC-A over-expressing cells and endothelium-denuded aortic rings) or weakly active (endothelium-in tact aortic rings). TNP-a and TNP-b were also unable to competitively inhibit the binding of TNP-c in endothelium-denuded aortae (GC-A) or endothelium-in tact aortae (NPR-C). Thus, these naturally occurring isoforms provide a new platform for further investigation of structure-function relationships of natriuretic peptides. (C) 2004 Elsevier Inc. All rights reserved.

Proton conductivity of mesoporous sol-gel zirconium phosphates for fuel cell applications

Zirconium phosphate has been extensively studied as a proton conductor for proton exchange membrane (PEM) fuel cell applications. Here we report the synthesis of mesoporous, templated sol-gel zirconium phosphate for use in PEM applications in an effort to determine its suitability for use as a surface functionalised, solid acid proton conductor in the future. Mesoporous zirconium phosphates were synthesised using an acid-base pair mechanism with surface areas between 78 and 177 m(2) g(-1) and controlled pore sizes in the range of 2-4 nm. TEM characterisation confirmed the presence of a wormhole like pore structure. The conductivity of such materials was up to 4.1 x 10(-6) S cm(-1) at 22degreesC and 84% relative humidity (RH), while humidity reduction resulted in a conductivity decrease by more than an order of magnitude. High temperature testing on the samples confirmed their dependence on hydration for proton conduction and low hydroscopic nature. It was concluded that while the conductivity of these materials is low compared to Nafion, they may be a good candidate as a surface functionalised solid acid proton conductor due to their high surface area, porous structure and inherent ability to conduct protons.

Synthesis and characterization of mesoporous nickel oxide and its application to electrochemical capacitor

Mesoporous Ni(OH)(2) was synthesized using cationic surfactant as template and urea as hydrolysis-controlling agent. Mesoporous NiO with centralized pore size distribution was obtained by calcining Ni(OH)(2) at different temperatures. The BET specific surface area reaches 477.7 m(2).g(-1) for NiO calcined at 523 K. Structure characterizations indicate the polycrystalline pore wall of mesoporous nickel oxide. The pore-formation mechanism is also deduced to be quasi-reverse micelle mechanism. Cyclic voltammetry shows the good capacitive behavior of these NiO samples due to its unique mesoporous structure when using large amount of NiO to fabricate electrode. Compared with NiO prepared by dip-coating and cathodic precipitation methods, this mesoporous NiO with controlled pore structure can be used in much larger amount to fabricate the electrode and still maintains high specific capacitance and good capacitive behavior.

Patched1 functions as a gatekeeper by promoting cell cycle progression

Mutations in the Hedgehog receptor, Patched 1 (Ptch1), have been linked to both familial and sporadic forms of basal cell carcinoma (BCC), leading to the hypothesis that loss of Ptch1 function is sufficient for tumor progression. By combining conditional knockout technology with the inducible activity of the Keratin6 promoter, we provide in vivo evidence that loss of Ptch1 function from the basal cell population of mouse skin is sufficient to induce rapid skin tumor formation, reminiscent of human BCC. Elimination of Ptch1 does not promote the nuclear translocation of beta-catenin and does not induce ectopic activation or expression of Notch pathway constituents. In the absence of Ptch1, however, a large proportion of basal cells exhibit nuclear accumulation of the cell cycle regulators cyclin D1 and B1. Collectively, our data suggest that Ptch1 likely functions as a tumor suppressor by inhibiting G(1)-S phase and G(2)-M phase cell cycle progression, and the rapid onset of tumor progression clearly indicates Ptch1 functions as a gatekeeper. In addition, we note the high frequency and rapid onset of tumors in this mouse model makes it an ideal system for testing therapeutic strategies, such as Patched pathway inhibitors.

The absolute structural requirement for a proline in the P3 '-position of Bowman-Birk protease inhibitors is surmounted in the minimized SFTI-1 scaffold

SFTI-1 is a small cyclic peptide from sunflower seeds that is one of the most potent trypsin inhibitors of any naturally occurring peptide and is related to the Bowman-Birk family of inhibitors (BBIs). BBIs are involved in the defense mechanisms of plants and also have potential as cancer chemopreventive agents. At only 14 amino acids in size, SFTI-1 is thought to be a highly optimized scaffold of the BBI active site region, and thus it is of interest to examine its important structural and functional features. In this study, a suite of 12 alanine mutants of SFTI-1 has been synthesized, and their structures and activities have been determined. SFTI-1 incorporates a binding loop that is clasped together with a disulfide bond and a secondary peptide loop making up the circular backbone. We show here that the secondary loop stabilizes the binding loop to the consequences of sequence variations. In particular, full-length BBIs have a conserved cis-proline that has been shown previously to be required for well defined structure and potent activity, but we show here that the SFTI-1 scaffold can accommodate mutation of this residue and still have a well defined native-like conformation and nanomolar activity in inhibiting trypsin. Among the Ala mutants, the most significant structural perturbation occurred when Asp(14) was mutated, and it appears that this residue is important in stabilizing the trans peptide bond preceding Pro(13) and is thus a key residue in maintaining the highly constrained structure of SFTI-1. This aspartic acid residue is thought to be involved in the cyclization mechanism associated with excision of SFTI-1 from its 58-amino acid precursor. Overall, this mutational analysis of SFTI-1 clearly defines the optimized nature of the SFTI-1 scaffold and demonstrates the importance of the secondary loop in maintaining the active conformation of the binding loop.

Preparation and electrochemical properties of the layered material of LixVyO2 (x=0.86 and y=0.8)

Layered lithium-vanadium oxide with a composition of LixVyO2 (x = 0.86 and y = 0.8) was prepared by the hydrothermal reaction of V2O3 with LiOH center dot H2O at 180 degrees C. This material corresponds to a layered rhombohedral structure related to alpha-NaFeO2 in which the vanadium ions are disordered in alternate layers of octahedral 3a (0, 0, 0) and 3b (0, 0, 1/2) sites. The electrochemical properties of this Li0.86V0.8O2 material were investigated and compared with those of the layered Li0.96VO2 made by the conventional solid-state reaction. It was found that the electrochemical capacity and reversibility of the Li0.86V0.8O2 material are significantly improved compared to those of the Li0.96VO2 material; the reversible specific capacities of the Li/Li0.86V0.8O2 and Li/Li0.96VO2 systems are similar to 100 and similar to 50 mAh g(-1), respectively, under the current densities of 7.14 mA g(-1) over 20 charge-discharge cycles with a potential window of 1.50-4.50 V. Such a reversibility results from the structural stability of Li0.86V0.8O2, whereas the increase in the reversible specific capacity can be qualitatively interpreted in terms of the presence of vanadium vacancies in the structure. (c) 2005 The Electrochemical Society.

Characterization of titanium phosphate as electrolytes in fuel cells

Titanium phosphate is currently a promising material for proton exchange membrane fuel cells applications (PEMFC) allowing for operation at high temperature conditions. In this work, titanium phosphate was synthesized from tetra iso-propoxide (TTIP) and orthophosphoric acid (H3PO4) in different ratios by a sol gel method. High BET surface areas of 271 m(2).g(-1) were obtained for equimolar Ti:P samples whilst reduced surface areas were observed by varying the molar ratio either way. Highest proton conductivity of 5.4 x 10(-2) S.cm(-1) was measured at 20 degrees C and 93% relative humidity (RH). However, no correlation was observed between surface area and proton conductivity. High proton conductivity was directly attributed to hydrogen bonding in P-OH groups and the water molecules retained in the sample structure. The proton conductivity increased with relative humidity, indicating that the Grotthuss mechanism governed proton transport. Further, sample Ti/P with 1:9 molar ratio showed proton conductivity in the order of 10(-1) S.cm(-1) (5% RH) and similar to 1.6x10(-2) S.cm(-1) (anhydrous condition) at 200 degrees C. These proton conductivities were mainly attributed to excess acid locked into the functionalized TiP structure, thus forming ionisable protons.

On the modelling of wave breaking and set-up on coral reefs

An extended refraction-diffraction equation [Massel, S.R., 1993. Extended refraction-diffraction equation for surface waves. Coastal Eng. 19, 97-126] has been applied to predict wave transformation and breaking as well as wave-induced set-up on two-dimensional reef profiles of various shapes. A free empirical coefficient alpha in a formula for the average rate of energy dissipation [epsilon(b)] = (alpha rho g omega/8 pi)(root gh/C)(H-3/h) in the modified periodic bore model was found to be a function of the dimensionless parameter F-c0 = (g(1.25)H(0)(0.5)T(2.5))/h(r)(1.75), proposed by Gourlay [Gourlayl M.R., 1994. Wave transformation on a coral reef. Coastal Eng. 23, 17-42]. The applicability of the developed model has been demonstrated for reefs of various shapes subjected to various incident wave conditions. Assuming proposed relationships of the coefficient alpha and F-c0, the model provides results on wave height attenuation and set-up elevation which compare well with experimental data. (C) 2000 Elsevier Science B.V. All rights reserved.

Rapid depletion of mutant eukaryotic initiation factor 5A at restrictive temperature reveals connections to actin cytoskeleton and cell cycle progression

Eukaryotic initiation factor 5A (eIF5A) is the only protein in nature that contains hypusine, an unusual amino acid derived from the modification of lysine by spermidine. Two genes, TIF51A and TIF51B, encode eIF5A in the yeast Saccharomyces cerevisiae. In an effort to understand the structure-function relationship of eIF5A, we have generated yeast mutants by introducing plasmid-borne tif51A into a double null strain where both TIF51A and TIF51B have been disrupted. One of the mutants, tsL102A strain (tif51A L102A tif51aDelta tif51bDelta) exhibits a strong temperature-sensitive growth phenotype. At the restrictive temperature, tsL102A strain also exhibits a cell shape change, a lack of volume change in response to temperature increase and becomes more sensitive to ethanol, a hallmark of defects in the PKC/WSC cell wall integrity pathway. In addition, a striking change in actin dynamics and a complete cell cycle arrest at G1 phase occur in tsL102A cells at restrictive temperature. The temperature-sensitivity of tsL102A strain is due to a rapid loss of mutant eIF5A with the half-life reduced from 6 h at permissive temperature to 20 min at restrictive temperature. Phenylmethyl sulfonylfluoride (PMSF), an irreversible inhibitor of serine protease, inhibited the degradation of mutant eIF5A and suppressed the temperature-sensitive growth arrest. Sorbitol, an osmotic stabilizer that complement defects in PKC/WSC pathways, stabilizes the mutant eIF5A and suppresses all the observed temperature-sensitive phenotypes.

The use of site-directed mutagenesis to study GPCRs

G protein coupled receptors (GPCRs) are highly flexible and dynamic proteins, which are able to interact with diverse ligands, effectors, and regulatory proteins. Site-directed mutagenesis (SDM) is a powerful tool for providing insight into how these proteins actually work, both in its own right and when used in conjunction with information provided by other techniques such as crystallography or molecular modelling. Mutagenesis has been used to identify and characterise a myriad of functionally important residues, motifs and domains within the GPCR architecture, and to identify aspects of similarity and differences between the major families of GPCRs. This chapter presents the necessary information for undertaking informative SDM of these proteins. Whilst this is relevant to protein structure/function studies in -general, specific pitfalls and protocols suited to investigating GPCRs in particular will be highlighted.

The antimicrobial action of pseudin-2

The amphibian antimicrobial peptide pseudin-2 is a peptide derived from the skin of the South-American frog Pseudis paradoxa (Olson et al., 2001). This peptide possesses tremendous potential as a therapeutic lead since it has been shown to possess both antimicrobial as well insulin-releasing properties (Olson et al., 2001; Abdel-Wahab et al., 2008). This study aimed to develop pseudin-2’s potential by understanding and improving its properties as an antimicrobial agent. The structure-function relationships of pseudin-2 were explored using a combination of in-vitro and in-silico techniques, with an aim to predict how the structure of the peptide may be altered in order to improve its efficacy. A library of pseudin-2 mutants was generated by randomizing codons at positions 10, 14 and 18 of a synthetic gene, using NNK saturation mutagenesis. Analysis of these novel peptides broadly confirmed, in line with literature precedent, that anti-microbial activity increases with increased positive charge. Specifically, 2 positively-charged residues at positions 10 and 14 and a hydrophobic at position 18 are preferred. However, substitution at position 14 with some polar, non-charged residues also created peptides with antimicrobial activity. Interestingly, the pseudin-2 analogue [10-E, 14-Q, 18-L] which is identical to pseudin-2, except that the residues at positions 10 and 14 are switched, showed no anti-microbial activity at all. Molecular dynamics simulations of pseudin-2 showed that the peptide possesses two equilibrium structures in a membrane environment: a linear and a kinked a-helix which both embed into the membrane at an angle. Biophysical characterization using circular dichroism spectroscopy confirmed that the peptide is helical within the membrane environment whilst linear dichroism established that the peptide has no defined orientation within the membrane. Collectively, these data indicate that Pseudin-2 exerts its antimicrobial activity via the carpet model.

Enhanced selective aerobic alcohol oxidation through nanoengineered catalyst supports

The selective conversion of alcohols to their carbonyl derivatives is a critical step towards a sustainable chemical industry. Heterogeneous Pd catalysts represent some of the most active systems known, even so further studies into the active species and role of support are required. Through controlling support mesostructure, using non-interconnected SBA-15 and interlinked SBA-16 and KIT-6, we have evaluated the role of pore architecture on supported Pd nanoparticles and their subsequent activity for liquid phase aerobic allylic alcohol selective oxidation.[1,2] These synthesised silica supports exhibit high surface areas (>800 m2g-1), and similar mesopore diameters (3.5 to 5 nm), but differ in their pore connectivity and arrangement; p6mm (SBA-15), I3mm (SBA-16) and I3ad (KIT-6). When evaluated alongside commercial non-mesoporous silica (200 m2 g-1) they promote enhanced Pd dispersion with interpenetrating assemblies providing further elevation. Macropore introduction into SBA-15, producing a hierarchical macro-mesoporous silica (MM-SBA-15), allows control over mesopore length and accessibility which escalates Pd distribution to levels akin to KIT-6 and SBA-16. Controlling dispersion, and likewise nanoparticle size, is thus facilitated through the choice of support and additionally Pd loading, with cluster sizes spanning 3.2 to 0.8 nm. X-ray spectroscopies indicate nanoparticles are PdO terminated with the oxide content a function of dispersion. Kinetic studies allude to surface PdO being the active site responsible, with a constant TOF observed, independent of loading and support. This confirms activity is governed by PdO density, whilst also overruling internal mass diffusion constraints. MM-SBA-15 facilitates superior activity and TOFs for long chain acyclic terpene alcohols due to reduced internal mass transport constraints.

Preparation of a microporous silicon oximide gel from the reaction of tris(dimethylamino)silylamine with formamide and its pyrolytic conversion into a silicon oxynitride based glass

A high-surface-area silicon oximide-based gel [SiOC(H)=NSi]m[Si2N-C(H)=O]n[SiN(H)-C(H)=O]p[SiOC(H)=NH]q[SiNH]r[SiNH2]s[SiNMe2]t was prepared via a formamide-based aminolysis of tris(dimethylamino)silylamine, (Me2N)3SiNH2. The structure of the gel and the mechanism of formation are elucidated. Pyrolysis of the gel at 1000 °C under N2 flow gave an amorphous microporous oxynitride-based glass with a BET surface area of 195 m2 g−1. © The Royal Society of Chemistry 2005.