Association of polymorphisms in the hepatocyte growth factor gene promoter with keratoconus

Purpose. Keratoconus is a progressive disorder of the cornea that can lead to severe visual impairment or blindness. Although several genomic regions have been linked to rare familial forms of keratoconus, no genes have yet been definitively identified for common forms of the disease. Methods. Two genome-wide association scans were undertaken in parallel. The first used pooled DNA from an Australian cohort, followed by typing of top-ranked single-nucleotide polymorphisms (SNPs) in individual DNA samples. The second was conducted in individually genotyped patients, and controls from the USA. Tag SNPs around the hepatocyte growth factor (HGF) gene were typed in three additional replication cohorts. Serum levels of HGF protein in normal individuals were assessed with ELISA and correlated with genotype. Results. The only SNP observed to be associated in both the pooled discovery and primary replication cohort was rs1014091, located upstream of the HGF gene. The nearby SNP rs3735520 was found to be associated in the individually typed discovery cohort (P = 6.1 × 10 ). Genotyping of tag SNPs around HGF revealed association at rs3735520 and rs17501108/rs1014091 in four of the five cohorts. Meta-analysis of all five datasets together yielded suggestive P values for rs3735520 (P = 9.9 × 10 ) and rs17501108 (P = 9.9 × 10 ). In addition, SNP rs3735520 was found to be associated with serum HGF level in normal individuals (P = 0.036). Conclusions. Taken together, these results implicate genetic variation at the HGF locus with keratoconus susceptibility. © 2011 The Association for Research in Vision and Ophthalmology, Inc.

Determination of the molar extinction coefficient for the ferric reducing/antioxidant power assay

The FRAP reagent contains 2,4,6-tris(2-pyridyl)-s-triazine, which forms a blue-violet complex ion in the presence of ferrous ions. Although the FRAP (ferric reducing/antioxidant power) assay is popular and has been in use for many years, the correct molar extinction coefficient of this complex ion under FRAP assay conditions has never been published, casting doubt on the validity of previous calibrations. A previously reported value of 19.800 is an underestimate. We determined that the molar extinction coefficient was 21,140. The value of the molar extinction coefficient was also shown to depend on the type of assay and was found to be 22,230 under iron assay conditions, in good agreement with published data. Redox titration indicated that the ferrous sulfate heptahydrate calibrator recommended by Benzie and Strain, the FRAP assay inventors, is prone to efflorescence and, therefore, is unreliable. Ferrous ammonium sulfate hexahydrate in dilute sulfuric acid was a more stable alternative. Few authors publish their calibration data, and this makes comparative analyses impossible. A critical examination of the limited number of examples of calibration data in the published literature reveals only that Benzie and Strain obtained a satisfactory calibration using their method. (C) 2011 Elsevier Inc. All rights reserved.

Characterisation of Genome-Wide PLZF/RARA Target Genes

The PLZF/RARA fusion protein generated by the t(11;17)(q23;q21) translocation in acute promyelocytic leukaemia (APL) is believed to act as an oncogenic transcriptional regulator recruiting epigenetic factors to genes important for its transforming potential. However, molecular mechanisms associated with PLZF/RARA-dependent leukaemogenesis still remain unclear. We searched for specific PLZF/RARA target genes by ChIP-on-chip in the haematopoietic cell line U937 conditionally expressing PLZF/RARA. By comparing bound regions found in U937 cells expressing endogenous PLZF with PLZF/RARA-induced U937 cells, we isolated specific PLZF/RARA target gene promoters. We next analysed gene expression profiles of our identified target genes in PLZF/RARA APL patients and analysed DNA sequences and epigenetic modification at PLZF/RARA binding sites. We identify 413 specific PLZF/RARA target genes including a number encoding transcription factors involved in the regulation of haematopoiesis. Among these genes, 22 were significantly down regulated in primary PLZF/RARA APL cells. In addition, repressed PLZF/RARA target genes were associated with increased levels of H3K27me3 and decreased levels of H3K9K14ac. Finally, sequence analysis of PLZF/RARA bound sequences reveals the presence of both consensus and degenerated RAREs as well as enrichment for tissue-specific transcription factor motifs, highlighting the complexity of targeting fusion protein to chromatin. Our study suggests that PLZF/RARA directly targets genes important for haematopoietic development and supports the notion that PLZF/RARA acts mainly as an epigenetic regulator of its direct target genes.

Thin-film oxygen sensors using a luminescent polynuclear gold(I) complex

Robust thin-film oxygen sensors were fabricated by encapsulating a lipophilic, polynuclear gold(I) complex, bis{m-(bis(diphenylphosphino)octadecylamine-P,P')}dichlorodigold(I), in oxygen permeable polystyrene and ormosil matrices. Strong phosphorescence, which was quenched by gaseous and dissolved oxygen, was observed from both matrices. The polystyrene encapsulated dye exhibited downward-turning Stern-Volmer plots which were well fitted by a two-site model. The ormosil trapped complex showed linear Stern-Volmer plots for dissolved oxygen quenching but was downward turning for gaseous oxygen. No leaching was observed when the ormosil based sensors were immersed in flowing water over an 8 h period. Both films exhibited fully reversible response and recovery to changing oxygen concentration with rapid response times. (C) 2011 Elsevier B.V. All rights reserved.

UV-activated photocatalyst films and inks for cleaning tarnished metals

A simple UV-activated, TiO2-based film or ink for removing thin oxide or sulfide layers from metal surfaces by reductive photocatalysis is described.

Effect of glass substrate and deposition technique on the properties of sol gel TiO2 thin films

Na+ ions have a detrimental effect on the photocatalytic activity of thin sot gel films deposited on soda lime glass due to their diffusion into the film during the calcination process. Given that the content of sodium in glass substrate might be the crucial parameter in determining the activity of a photocatalyst, the aim of the present work was the comparison of the photoinduced properties of a thin TiO2 film prepared on three different glass substrates namely on quartz (Q) glass, borosilicate (BS) glass and soda lime (SL) glass which have different sodium content. The prepared layers were characterised by X-ray diffraction and UV-vis spectroscopy. The diffusion of Na+ from the substrate into the layers was determined by Glow Discharge Atomic Emission Spectroscopy. The photocatalytic activities of the films were assessed using two model pollutant test systems (resazurin/resorufin ink and stearic acid film), which appeared to correlate reasonably well. It was observed that TiO2 layer on SL glass has a brookite crystalline structure while the TiO2 layer on BS and Q glass has an anatase crystalline structure. On the other hand, the photodegradation of the model dye on TiO2 films deposited on Q and BS glass is about an order higher than on SL glass. The low sodium content of BS glass makes it the most suitable substrate for the deposition of photoactive sol gel TiO2 films. (C) 2011 Elsevier B.V. All rights reserved.

Novel photocatalyst-based colourimetric indicator for oxygen: Use of a platinum catalyst for controlling response times

The preparation and characterisation of a novel, UV-activated, solvent-based, colourimetric indicator for oxygen is described, comprising a redox dye (methylene blue, MB), semiconductor photocatalyst (Pt-TiO2), and a sacrificial electron donor (SED = glycerol), all dispersed/dissolved in a polymer medium (sulfonated polystyrene. SPS). Upon exposure to UVA light, the Pt-TiO2/MB/glycerol/SPS oxygen indicator is readily photobleached as the MB is converted into its oxygen-sensitive, leuco form, LMB. In contrast to its non-platinised TiO2 counterpart (TiO2/MB/glycerol/SPS oxygen indicator), the recovery of the original colour is faster (ca. 1.5 days cf. 5 days at 21 degrees C). This is due to the catalytic action of the 0.38 wt% platinum loaded onto the semiconductor photocatalyst. TiO2, on the oxidation of the photogenerated LMB by ambient O-2. Furthermore, by increasing the level of platinum loading, recovery times can be decreased further; e.g. a Pt-TiO2/MB/glycerol/SPS oxygen indicator with platinum level of 1.52 wt% recovers fully within 12 h. A study of the kinetics of recovery as a function of film thickness revealed the recovery step is not controlled by the diffusion of O-2 through the film, but instead dependent upon the slow rate of oxidation of LMB to MB by O-2 in the low dielectric polymer encapsulation medium. Other work showed this recovery is only moderately dependant upon temperatures above -10 degrees C and very sensitive to relative humidity above 30% RH. Potential uses of this UV light activated indicator are discussed briefly. (C) 2011 Elsevier B.V. All rights reserved.

An investigation into the effect of thickness of titanium dioxide and gold-silver nanoparticle titanium dioxide composite thin-films on photocatalytic activity and photo-induced oxygen production in a sacrificial system

Thin films of titanium dioxide and titanium dioxide with incorporated gold and silver nanoparticles were deposited onto glass microscope slides, steel and titanium foil coupons by two sol-gel dip-coating methods. The film's photocatalytic activity and ability to evolve oxygen in a sacrificial solution were assessed. It was found that photocatalytic activity increased with film thickness (from 50 to 500 nm thick samples) for the photocatalytic degradation of methylene blue in solution and resazurin redox dye in an intelligent ink dye deposited on the surface. Contrastingly, an optimum film thickness of similar to 200 nm for both composite and pure films of titanium dioxide was found for water oxidation, using persulfate (S2O82-) as a sacrificial electron acceptor. The nanoparticle composite films showed significantly higher activity in oxygen evolution studies compared with plain TiO2 films.

Novel photocatalyst-based colourimetric indicator for oxygen

The preparation and characterisation of a novel, UV-activated solvent-based, colourimetric indicator for O-2 is described, comprising a redox dye (methylene blue, MB), semiconductor photocatalyst (TiO2), and a sacrificial electron donor (SED), all dispersed/dissolved in a polymer medium (sulfonated polystyrene, SPS). Upon exposure, the indicator is readily photobleached as the MB is converted into its oxygen-sensitive, leuco form, LMB. Unlike its water-based counterpart, the recovery of the original colour is very slow (ca. 5 days cf. 6 min), probably due to the largely hydrophobic nature of the polymer encapsulation medium. The kinetics of film photobleaching appear to fit very well, in terms of: irradiance, [TiO2] and [MB], to the usual Langmuir-Hinshelwood type equation associated with a photocatalytic process. The glycerol appears not only to function as a SED, but also a plasticizer and medium for dye dissolution. The kinetics of colour recovery of the photobleached film appear directly dependent upon the ambient level of O-2 but shows a more complex dependence upon the relative humidity, RH. The photobleached film does not recover any of its colour over a 24 h period if the RH

A novel 'fizziness' indicator

A novel colourimetric 'fizziness' indicator is described which changes colour depending on the headspace pressure of carbon dioxide above a carbonated liquid.

Photocatalytic evolution of hydrogen and oxygen from ceramic wafers of commercial titanias

Several commercial titania photocatalyst powders were formed into thin (ca. 350 mu m), 25 mm diameter ceramic wafers, sputter deposited with Pt on one side. The activities of each of the ceramic wafers were tested for hydrogen and oxygen evolution from aqueous sacrificial systems. The commercial sample PC50 (Millennium Chemicals, UK) yielded reproducible ceramic wafers with high activity for water photoreduction. Many of the ceramic wafers displayed low water photo-oxidation activities; however, these were greatly increased with addition of a NiO co-catalyst. In a selected case, hydrogen evolution activity was compared between a PC50 wafer and an identical weight of platinised PC50 powder suspension. (C) 2010 Elsevier B.V. All rights reserved.

Adsorption and photocatalytic bleaching of acid orange 7 on P25 titania

The observed adsorption of acid orange 7, AO7(-), on P25 titania over a range of pH values (pH 2-8) gives a good fit to data generated using a charge distribution, multisite complexation, i.e. CD-MUSIC, model, modified for aggregated dye adsorption. For this system the model predicts that both the apparent dark Langmuir adsorption constant. K-L, and the number of adsorption sites, n(o), increase with decreasing pH, and are negligible above pH 6. At pH 2 the CD-MUSIC model predicts the fraction of singly co-ordinated sites occupied by the dye,f(AO7), is ca. 32% under the in situ monitoring experimental conditions used in this work to study the photocatalytic bleaching of AO7(-) under UV light illumination ([TiO2] = 20 mgdm(-3); [AO7(-)](total) = 4.86 x 10(-5) M). Although AO7(-) adsorption on P25 titania is insignificant above pH 6 and increases almost linearly and markedly below this pH, the measured initial rate of bleaching of AO7(-), photocatalysed by titania using UV appears to only increase modestly (

NMR analysis of Nile Blue (C I Basic Blue 12) and Thionine (C I 52000) in solution

The dyes Nile Blue (C I Basic Blue 12) and Thionine (C I 52000) were examined in both ionic and neutral forms in different solvents using NMR and UV-visible spectroscopy to firmly establish the structures of the molecules and to assess the nature and extent of their aggregation H-1 and C-13 NMR assignments and chemical shift data were used together with nuclear Overhauser effect information to propose a self-assembly structure These data were supplemented with variable temperature dilution and diffusion-based experimental results using H-1 NMR spectroscopy thereby enabling extended aggregate structures to be assessed in terms of the relative strength of self-association and the extent to which extended aggregates could form (C) 2010 Elsevier Ltd All rights reserved