Formation and characterisation of ordered porous vanadium oxide inverse opal materials for Li-ion batteries

This thesis presents several routes towards achieving artificial opal templates by colloidal self-assembly of polystyrene (PS) or poly(methyl methacrylate) (PMMA) spheres and the use of these template for the fabrication of V2O5 inverse opals as cathode materials for lithium ion battery applications. First, through the manipulation of different experimental factors, several methods of affecting or directing opal growth towards realizing different structures, improving order and/or achieving faster formation on a variety of substrates are presented. The addition of the surfactant sodium dodecyl sulphate (SDS) at a concentration above the critical micelle concentration for SDS to a 5 wt% solution of PMMA spheres before dip-coating is presented as a method of achieving ordered 2D PhC monolayers on hydrophobic Au-coated silicon substrates at fast and slow rates of withdrawal. The effect that the degree of hydrophilicity of glass substrates has on the ordering of PMMA spheres is next investigated for a slow rate of withdrawal under noise agitation. Heating of the colloidal solution is also presented as a means of affecting order and thickness of opal deposits formed using fast rate dip coating. E-beam patterned substrates are shown as a means of altering the thermodynamically favoured FCC ordering of polystyrene spheres (PS) when dip coated at slow rate. Facile routes toward the synthesis of ordered V2O5 inverse opals are presented with direct infiltration of polymer sphere templates using liquid precursor. The use of different opal templates, both 2D and 3D partially ordered templates, is compared and the composition and arrangement of the subsequent IO structures post infiltration and calcination for various procedures is characterised. V2O5 IOs are also synthesised by electrodeposition from an aqueous VOSO4 solution at constant voltage. Electrochemical characterisation of these structures as cathode material for Li-ion batteries is assessed in a half cell arrangement for samples deposited on stainless steel foil substrates. Improved rate capabilities are demonstrated for these materials over bulk V2O5, with the improvement attributed to the shorter Li ion diffusion distances and increased electrolyte infiltration provided by the IO structure.

3D vanadium oxide inverse opal growth by electrodeposition

Three-dimensional vanadium pentoxide (V2O5) material architectures in the form of inverse opals (IOs) were fabricated using a simple electrodeposition process into artificial opal templates on stainless steel foil using an aqueous solution of VOSO4.χH2O with added ethanol. The direct deposition of V2O5 IOs was compared with V2O5 planar electrodeposition and confirms a similar progressive nucleation and growth mechanism. An in-depth examination of the chemical and morphological nature of the IO material was performed using X-ray crystallography, X-ray photoelectron spectroscopy, Raman scattering and scanning/transmission electron microscopy. Electrodeposition is demonstrated to be a function of the interstitial void fraction of the artificial opal and ionic diffusivity that leads to high quality, phase pure V2O5 inverse opals is not adversely affected by diffusion pathway tortuosity. Methods to alleviate electrodeposited overlayer formation on the artificial opal templates for the fabrication of the porous 3D structures are also demonstrated. Such a 3D material is ideally suited as a cathode for lithium ion batteries, electrochromic devices, sensors and for applications requiring high surface area electrochemically active metal oxides.

The s-process nucleosynthesis

Theoretical as well as observational aspects of the s-process nucleosynthesis are reviewed. The classical site-independent s-process model as well as the s-process in massive stars are shortly described. A special attention is paid to the nucleosynthesis taking place in AGB stars and the extra-mixing invoked to explain the production of neutrons in the C-rich layers during the interpulse. We also discuss the nucleosynthesis found in hot AGB stars for which the s-process during the interpulse phase is inhibited, but the one resulting from the large temperatures in the thermal pulse is boosted. We comment on the uncertainties affecting our understanding of the physical mechanisms responsible for a successful s-process. Finally, various types of spectroscopic observations of s-process elements are discussed. © 2005 International Astronomical Union.

Convenient synthetic routes to bidentate and monodentate 2-, 3- and 4-pyridyl phosphines: potentially useful ligands for water-soluble complex catalysts

The monodentate and bidentate pyridyl phosphines, PR3 and R2P(CH2)2PR2, where R=3- or 4-pyridyl can be prepared in high yields by treatment of butyllithium/TMEDA/3- or 4-bromopyridine with PCl3 or Cl2P(CH2)2PCl2 at low temperature. 1,2-Bis(di-2-pyridylphosphino)ethane is conveniently synthesised by an alternative route involving reaction of 1,2-dibromoethane with lithium di-2-pyridylphosphide.

Tailoring the morphology of WO₃films with substitutional cation doping: Effect on the photoelectrochemical properties

With the aim of improving the performance and extending the range of applications of mesoporous WO₃films, which were initially developed for the photoelectrochemical oxidation of water, we investigated the effect of a number of dopants (lithium, silicon, ruthenium, molybdenum and tin) upon the transparency, crystallinity, porosity and conductivity of the modified films. Tin, molybdenum and silicon were shown to improve the electrochromic behaviour of the layers whereas ruthenium enhanced considerably the electronic conductivity of the WO₃films. Interestingly, most of the dopants also affected the film morphology and the size of WO₃nanocrystals. X-ray photoelectron spectra revealed absence of significant segregation of doping elements within the film. Raman analyses confirmed that the monoclinic structure of WO₃films does not change upon substitutional cation doping; thus, the crystallinity of WO₃films is maintained.

Ion-Atom/Argon - Calculation of ionization cross sections by fast ion impact for neutral target atoms ranging from hydrogen to argon

A FORTRAN 90 program is presented which calculates the total cross sections, and the electron energy spectra of the singly and doubly differential cross sections for the single target ionization of neutral atoms ranging from hydrogen up to and including argon. The code is applicable for the case of both high and low Z projectile impact in fast ion-atom collisions. The theoretical models provided for the program user are based on two quantum mechanical approximations which have proved to be very successful in the study of ionization in ion-atom collisions. These are the continuum-distorted-wave (CDW) and continuum-distorted-wave eikonal-initial-state (CDW-EIS) approximations. The codes presented here extend previously published. codes for single ionization of. target hydrogen [Crothers and McCartney, Comput. Phys. Commun. 72 (1992) 288], target helium [Nesbitt, O'Rourke and Crothers, Comput. Phys. Commun. 114 (1998) 385] and target atoms ranging from lithium to neon [O'Rourke, McSherry and Crothers, Comput. Phys. Commun. 131 (2000) 129]. Cross sections for all of these target atoms may be obtained as limiting cases from the present code. Title of program: ARGON Catalogue identifier: ADSE Program summary URL: http://cpc.cs.qub.ac.uk/cpc/summaries/ADSE Program obtainable from: CPC Program Library Queen's University of Belfast, N. Ireland Licensing provisions: none Computer for which the program is designed and others on which it is operable: Computers: Four by 200 MHz Pro Pentium Linux server, DEC Alpha 21164; Four by 400 MHz Pentium 2 Xeon 450 Linux server, IBM SP2 and SUN Enterprise 3500 Installations: Queen's University, Belfast Operating systems under which the program has been tested: Red-hat Linux 5.2, Digital UNIX Version 4.0d, AIX, Solaris SunOS 5.7 Compilers: PGI workstations, DEC CAMPUS Programming language used: FORTRAN 90 with MPI directives No. of bits in a word: 64, except on Linux servers 32 Number of processors used: any number Has the code been vectorized or parallelized? Parallelized using MPI No. of bytes in distributed program, including test data, etc.: 32 189 Distribution format: tar gzip file Keywords: Single ionization, cross sections, continuum-distorted-wave model, continuum- distorted-wave eikonal-initial-state model, target atoms, wave treatment Nature of physical problem: The code calculates total, and differential cross sections for the single ionization of target atoms ranging from hydrogen up to and including argon by both light and heavy ion impact. Method of solution: ARGON allows the user to calculate the cross sections using either the CDW or CDW-EIS [J. Phys. B 16 (1983) 3229] models within the wave treatment. Restrictions on the complexity of the program: Both the CDW and CDW-EIS models are two-state perturbative approximations. Typical running time: Times vary according to input data and number of processors. For one processor the test input data for double differential cross sections (40 points) took less than one second, whereas the test input for total cross sections (20 points) took 32 minutes. Unusual features of the program: none (C) 2003 Elsevier B.V All rights reserved.

Sulfur-tolerant NOx storage traps: an infrared and thermodynamic study of the reactions of alkali and alkaline-earth metal sulfates

The sulfur tolerance of a barium-containing NOx storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 degreesC. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NOx storage capacity to give sulfur-tolerant NOx traps.

On the nature of the silver phases of Ag/Al2O3 catalysts for reactions involving nitric oxide

The nature of the silver phases of Ag/Al2O3 catalysts (prepared by silver nitrate impregnation followed by calcination) was investigated by X-ray diffractograms (XRD), transmission electron microscopy (TEM) and UV-VIS analyses and related to the activity of the corresponding materials for the oxidation of NO to NO2. The UV-VIS spectrum of the 1.2 wt.% Ag/Al2O3 exhibited essentially one band associated with Ag+ species and the NO2 yields measured over this material were negligible. A 10 wt.% Ag/Al2O3 material showed the presence of oxidic species of silver (as isolated Ag+ cations and silver aluminate), but the UV-VIS data also revealed the presence of some metallic silver. The activity for the NO oxidation to NO2 of this sample was moderate. The same 10% sample either reduced in H-2 or used for the C3H6-selective catalytic reduction (SCR) of NO showed a significantly larger proportion of silver metallic phases and these samples displayed a high activity for the formation of NO2. These data show that the structure and nature of the silver phases of Ag/Al2O3 catalysts can markedly change under reaction feed containing only a fraction of reducing agent (i.e. 500 ppm of propene) in net oxidizing conditions (2.5% O-2). The low activity for N-2 formation during the C3H6-SCR of NO (reported in an earlier study) over the high loading sample can. therefore, he related to the presence of metallic silver. which is yet a good catalyst for NO oxidation to NO2. The reverse observations apply for the oxide species observed over the low loading sample, which is a good SCR catalyst but do not oxidize NO to NO2. (C) 2002 Elsevier Science B.V. All rights reserved.

Transesterification of vegetable oils on basic large mesoporous alumina supported alkaline fluorides-Evidences of the nature of the active site and catalytic performances

KF, LiF and CsF/A(2)O(3) catalysts with different loadings from 1 to 20 wt% were prepared using aqueous solutions of the alkaline fluoride compounds by wet impregnation of basic mesoporous MSU-type alumina. The catalysts were activated under At at 400 degrees C for 2 h and monitored by in situ XRD measurements. The catalysts were also characterized using several techniques: N-2 adsorption/desorption isotherms at -196 degrees C, FTIR, DR-UV-vis, CO2-TPD, XRD, Al-27 CP/MAS NMR. These characterizations led to the conclusion that the deposition of alkaline fluorides on the alumina surface generates fluoroaluminates and aluminate species. The process is definitivated at 400 degrees C. The fluorine in these structures is less basic than in the parent fluorides, but the oxygen becomes more basic. The catalysts were tested for the transesterification of fatty esters under different experimental conditions using conventional heating, microwave and Ultrasound irradiation. Recycling experiments showed that these catalysts are stable for a limited number of cycles. (C) 2009 Elsevier Inc. All rights reserved.

WASP-14b: 7.3 M-J transiting planet in an eccentric orbit

We report the discovery of a 7.3 M-J exoplanet WASP-14b, one of the most massive transiting exoplanets observed to date. The planet orbits the 10th-magnitude F5V star USNO-B1 11118-0262485 with a period of 2.243 752 d and orbital eccentricity e = 0.09. A simultaneous fit of the transit light curve and radial velocity measurements yields a planetary mass of 7.3 +/- 0.5 M-J and a radius of 1.28 +/- 0.08 R-J. This leads to a mean density of about 4.6 g cm(-3) making it the densest transiting exoplanets yet found at an orbital period less than 3 d. We estimate this system to be at a distance of 160 +/- 20 pc. Spectral analysis of the host star reveals a temperature of 6475 +/- 100 K, log g = 4.07 cm s(-2) and v sin i = 4.9 +/- 1.0 km s(-1), and also a high lithium abundance, log N(Li) = 2.84 +/- 0.05. The stellar density, effective temperature and rotation rate suggest an age for the system of about 0.5-1.0 Gyr.

Li-6 in the atmosphere of GJ 117 revisited

Detection of Li-6 has been shown for energetic solar events, one chromospherically active binary, and several dwarf halo stars. We had previously found a Li-6/Li-7 = 0.03 +/- 0.01 for active K dwarf GJ 117 using VLT UVES observations. Here we present high signal-to-noise (> 1000) high spectral resolution observations taken with the McDonald Observatory's 2.7 m and echelle spectrometer of GJ 117. We have used the solar spectrum and template stars to eliminate possible blends, such as Ti I, in the Li-6 spectral region. Our new analysis, using an updated PHOENIX model atmosphere, finds Li-6/Li-7 = 0.05 +/- 0.02. In addition, bisector analysis showed no significant red asymmetries that would affect the lithium line profile. No changes above the statistical uncertainties are found between the VLT and McDonald data. The amount of Li-6 derived for GJ 117 is consistent with creation in spallation reactions on the stellar surface, but we caution that uncertainties in the continuum level may cause additional uncertainty in the Li-6 fraction.

Synthesis of the alkaloids hopromine, hoprominol and hopromalinol, using transamidation methods.

Synthesis of the unsym. Homalium alkaloids hopromine (I, R = H, R1 = pentyl), hoprominol (I, R = OH, R1 = pentyl) and hopramalinol (I, R = OH, R1 = Ph), in diastereoisomeric mixt. form, is reported. The component eight-membered azalactams are first prepd. N-(3-halogenopropyl)-4-pentyl- and 4-heptylazetidin-2-ones are aminated and ring expanded in liq. ammonia to give, after reductive methylation, the corresponding 4-alkyl-5-methyl-1,5-diazacyclooctan-2-ones. Synthesis of the 4-(2-hydroxyheptyl)-5-methyl-1,5-diazacyclooctan-2-one required for hoprominol and hopromalinol is carried out via 4-allyl ?-lactam ring expansion to the eight-membered 4-allylazalactam, followed by methylation, epoxidn. and epoxide opening with lithium dibutylcuprate. A similar epoxidn.-cuprate sequence was carried out on the epoxypropyl ?-lactam, as its N-tert-butyldimethylsilyl deriv., and led to a convenient copper-catalyzed N- to O-migration of the protection; this migration is examd. Alkylation gave O-tert-butyldimethylsilyl-protected N-(3-chloropropyl)-4-(2-hydroxyheptyl)azetidin-2-one which could be aminated and transamidated in excellent yield, to give, after methylation, a superior sequence to the required eight-membered hydroxy azalactam. Although satisfactory for attachment of the first azalactam unit, a dibromobutane coupling system proved unreactive for the second. Couplings with unmethylated, methylated, and benzyloxycabronyl-protected azalactams were examd. using (E)-1,4-dibromobutene and (Z)-1,4-dichlorobutene as the bridging unit. Employing the latter, coupling the first N-methylated azalactam with potassium bis(trimethylsilyl)amide as the base, and then the second with bis(trimethylsilyl)amide-sodium hydride as the base system, provided a satisfactory synthetic outcome. Hydrogenation under acidic conditions gave the unsym. structures hopromine, hoprominol and hopromalinol, as well as the more simple and sym. alkaloid, homaline.

MML 53: a new low-mass, pre-main sequence eclipsing binary in the Upper Centaurus-Lupus region discovered by SuperWASP

We announce the discovery of a new low-mass, pre-main sequence eclipsing binary, MML 53. Previous observations of MML 53 found it to be a pre-main sequence spectroscopic multiple associated with the 15-22 Myr Upper Centaurus-Lupus cluster. We identify the object as an eclipsing binary for the first time through the analysis of multiple seasons of time series photometry from the SuperWASP transiting planet survey. Re-analysis of a single archive spectrum shows MML 53 to be a spatially unresolved triple system of young stars which all exhibit significant lithium absorption. Two of the components comprise an eclipsing binary with period, P = 2.097891(6) ± 0.000005 and mass ratio, q ~ 0.8. Here, we present the analysis of the discovery data.

New ruthenium(II) complexes of functionalized monoanionic aryldiamine N,C,N'-terdentate ligands: Syntheses of [Ru-II{2,6-(Me(2)NCH(2))(2)-4-R-C6H2}(terpy)]Cl+(-); X-ray structure of a dimeric organolithium compound,[Li{2,6-(Me(2)NCH(2))(2)-4-Ph-C6H2}](2)

The new anionic functionalized aryldiamine ligands [2,6-(Me(2)NCH(2))(2)-4-R-C6H2](-) (R = Me(3)SiC=C, C6H5, Me(3)Si), formally derived from [2,6-(Me(2)NCH(2))(2)C6H3](-), have been prepared as their lithium compounds. The compound [Li{2,6-(Me(2)NCH(2))(2)-4-Ph-C6H2}](2) crystallizes in the monoclinic space group C2/c (no. 15) with a = 13.1225(5), b = 13.5844(7), c = 15.9859(12) Angstrom, beta = 105.329(5)degrees, V = 3264.0(3)Angstrom(3), Z = 4. The structure refinement converged to R(1) = 0.0374 for 2037 observed reflections [F-o>4 sigma(F-o)] and wR(2) = 0.0922 for 2560 unique data. The organolithium compounds have been used in transmetalation reactions to give the corresponding functionalized organoruthenium(II) complexes [Ru-II{2,6-(Me(2)NCH(2))(2)-4-R-C6H2}(terpy)]Cl-+(-) (terpy = 2,2';6',2 ''-terpyridine). The Ru-II species with R = HC = C has also been synthesized.

PTEN regulates colorectal epithelial apoptosis through Cdc42 signalling.

BACKGROUND:
Phosphatase and tensin homologue deleted on chromosome 10 (PTEN) regulation of the Rho-like GTPase Cdc42 has a central role in epithelial polarised growth, but effects of this molecular network on apoptosis remain unclear.

METHODS:
To investigate the role of Cdc42 in PTEN-dependent cell death, we used flow cytometry, in vitro pull-down assays, poly(ADP ribose) polymerase (PARP) cleavage and other immunoblots in isogenic PTEN-expressing and -deficient colorectal cells (HCT116PTEN(+/+), HCT116PTEN(-/-), Caco2 and Caco2 ShPTEN cells) after transfection or treatment strategies.

RESULTS:
The PTEN knockout or suppression by short hairpin RNA or small interfering RNA (siRNA) inhibited Cdc42 activity, PARP cleavage and/or apoptosis in flow cytometry assays. Transfection of cells with wild-type or constitutively active Cdc42 enhanced PARP cleavage, whereas siRNA silencing of Cdc42 inhibited PARP cleavage and/or apoptosis. Pharmacological upregulation of PTEN by sodium butyrate (NaBt) treatment enhanced Cdc42 activity, PARP cleavage and apoptosis, whereas Cdc42 siRNA suppressed NaBt-induced PARP cleavage. Cdc42-dependent signals can suppress glycogen synthase kinase-ß (GSK3ß) activity. Pharmacological inhibition of GSK3ß by lithium chloride treatment mimicked effects of Cdc42 in promotion of PARP cleavage and/or apoptosis.

CONCLUSION:
Phosphatase and tensin homologue deleted on chromosome 10 may influence apoptosis in colorectal epithelium through Cdc42 signalling, thus providing a regulatory framework for both polarised growth and programmed cell death.