Influence of pH on the phototransformation process of PhotogemA (R)

PhotogemA (R) is a hematoporphyrin derivative that has been used as a photosensitizer in experimental and clinical Photodynamic Therapy (PDT) in Brazil. Photosensitizers are degraded under illumination. This process, usually called photobleaching, can be monitored by decreasing in fluorescence intensities and includes the following photoprocesses: photodegradation, phototransformation, and photorelocalization. Photobleaching of hematoporphyrin-type sensitizers during illumination in aqueous solution is related not only to photodegradation but is also followed by the formation of photoproducts with a new fluorescence band at around 640-650 nm and with increased light absorption in the red spectral region at 640 nm. In this study, the influence of pH on the phototransformation process was investigated. PhotogemA (R) solutions, 40 mu g/ml, were irradiated at 514 nm with intensity of 100 mW/cm(2) for 20 min with different pH environments. The controls were performed with the samples in the absence of light. The PhotogemA (R) photodegradation is dependent on the pH. The behavior of photodegradation and photoproducts formation (monitored at 640 nm) is distinct and depends on the photosensitizer concentration. The processes of degradation and photoproducts formation were monitored with Photogemin the concentration of 40 mu g/mL since that demonstrated the best visualization of both processes. While below pH 5 the photodegradation occurred, there was no detectable presence of photoproducts. The increase of pH led to increase of photoproducts formation rate with photodegradation reaching the highest value at pH 10. The increase of photoproducts formation and instability of PhotogemA (R) from pH 6 to pH 10 are in agreement with the desired properties of an ideal photosensitizer since there are significant differences in pH between normal (7.0 < pH < 8.6) and tumor (5.8 < pH < 7.9) tissues. It is important to know the effect of pH in the process of phototransformation (degradation and photoproduct formation) of the molecule since low pH values promotes increase in the proportion of aggregates species in solution and high pH values promotes increase in the proportion of monomeric species. There must be an ideal pH interval which favors the phototransformation process that is correlated with the singlet oxygen formation responsible by the photodynamic effect. These differences in pH between normal and tumor cells can explain the presence of photosensitizers in target tumor cells, making PDT a selective therapy.

Influence of pre-heat treatment and different light-curing units on Vickers hardness of a microhybrid composite resin

The aim of this study was to evaluate the hardness of a dental composite resin submitted to temperature changes before photo-activation with two light-curing unite (LCUs). Five samples (4 mm in diameter and 2 mm in thickness) for each group were made with pre-cure temperatures of 37, 54, and 60A degrees C. The samples were photo-activated with a conventional quartz-tungsten-halogen (QTH) and blue LED LCUs during 40 s. The hardness Vickers test (VHN) was performed on the top and bottom surfaces of the samples. According to the interaction between light-curing unit and different pre-heating temperatures of composite resin, only the light-curing unit provided influences on the mean values of initial Vickers hardness. The light-curing unit based on blue LED showed hardness mean values more homogeneous between the top and bottom surfaces. The hardness mean values were not statistically significant difference for the pre-cure temperature used. According to these results, the pre-heating of the composite resin provide no influence on Vickers hardness mean values, however the blue LED showed a cure more homogeneous than QTH LCU.

Influence of ceria addition on thermal properties and local structure of bismuth germanate glasses

Bismuth germanate glasses are interesting materials due to their physical properties and their unique structural characteristics caused by the coordination changes of bismuth and germanium atoms. Glasses of the bismuth germanate system were prepared by melting/molding method and were investigated concerning their thermal and structural properties. The structural analysis of the samples was carried out by micro-Raman and Fourier transform infrared spectroscopes. It was observed that the glass structure is formed basically by GeO(4) tetrahedral units also having the formation of the GeO(6) octahedral units. BiO(2) was considered a network former by observing the presence of octahedral BiO(6) and pyramidal BiO(3) groups in the local structure of the samples. An absorption band observed at 1103 cm(-1) in the IR spectrum of the undoped glass was attributed to the Bi-O-Ge and/or Bi-O-Bi linkage vibration. The said band shifted to lower wavenumbers after the CeO(2) addition thus reflecting changes in the glass network. Cerium oxide was an efficient oxidant agent to prevent the darkening of the glasses which was probably associated to the reduction of Bi ions. However, CeO(2) was incorporated as a local network modifier in the glass structure even at concentrations of 0.2 mol%. (C) 2010 Elsevier B.V. All rights reserved.

Influence of light guide tip used in the photo-activation on degree of conversion and hardness of one nanofilled dental composite

The aim of this study was to evaluate the degree of conversion and hardness of a dental composite resin Filtek (TM) Z-350 (3M ESPE, Dental Products St. Paul, MN) photo-activated for 20 s of irradiation time with two different light guide tips, metal and polymer, coupled on blue LED Ultraled LCU (Dabi Atlante, SP, Brazil). With the metal light tip, power density was of 352 and with the polymer was of 456 mW/cm(2), respectively. Five samples (4 mm in diameter and 2mm in thickness-ISO 4049), were made for each Group evaluated. The measurements for DC (%) were made in a Nexus-470 FT-IR, Thermo Nicolet, E.U.A. Spectroscopy (FTIR). Spectra for both uncured and cured samples were analyzed using an accessory of reflectance diffuse. The measurements were recorded in absorbance operating under the following conditions: 32 scans, 4 cm(-1) resolution, 300-4000 cm(-1) wavelength. The percentage of unreacted carbon double bonds (% C=C) was determined from the ratio of absorbance intensities of aliphatic C=C (peak at 1637 cm(-1)) against internal standard before and after curing of the sample: aromatic C-C (peak at 1610 cm(-1)). The Vickers hardness measurements (top and bottom surfaces) were performed in a universal testing machine (Buehler MMT-3 digital microhardness tester Lake Bluff, Illinois USA). A 50 gf load was used and the indenter with a dwell time of 30 s. The data were submitted to the test t Student at significance level of 5%. The mean values of degree of conversion for the polymer and metal light guide tip no were statistically different (p = 0.8389). The hardness mean values were no statistically significant different among the light guide tips (p = 0.6244), however, there was difference between top and bottom surfaces (p < 0.001). The results show that so much the polymer light tip as the metal light tip can be used for the photo-activation, probably for the low quality of the light guide tip metal.

Influence of chromium concentration on the optical-electronic properties of ruby microstructures

Films of amorphous aluminium nitride (AlN) were prepared by conventional radio frequency sputtering of an Al + Cr target in a plasma of pure nitrogen. The Cr-to-Al relative area determines the Cr content, which remained in the similar to 0-3.5 at% concentration range in this study. Film deposition was followed by thermal annealing of the samples up to 1050 degrees C in an atmosphere of oxygen and by spectroscopic characterization through energy dispersive x-ray spectrometry, photoluminescence and optical transmission measurements. According to the experimental results, the optical-electronic properties of the Cr-containing AlN films are highly influenced by both the Cr concentration and the temperature of the thermal treatments. In fact, thermal annealing at 1050 degrees C induces the development of structures that, because of their typical size and distinctive spectral characteristics, were designated by ruby microstructures (RbMSs). These RbMSs are surrounded by a N-rich environment in which Cr(3+) ions exhibit luminescent features not present in other Cr(3+)-containing systems such as ruby, emerald or alexandrite. The light emissions shown by the RbMSs and surroundings were investigated according to the Cr concentration and temperature of measurement, allowing the identification of several Cr(3+)-related luminescent lines. The main characteristics of these luminescent lines and corresponding excitation-recombination processes are presented and discussed in view of a detailed spectroscopic analysis.

Spectroscopic investigations of OH- influence on near-infrared fluorescence quenching of Yb3+/Tm3+ co-doped sodium-metaphosphate glasses

Energy transfer processes were studied in two sets of Yb3+ and Tm3+ co-doped sodium-metaphosphate glasses, prepared in air and nitrogen atmospheres. Using Forster, Dexter, and Miyakawa theoretical models, the energy transfer parameters were calculated. The main ion-ion energy transfer processes analyzed were energy migration among Yb3+ ions, cross-relaxations between Yb3+ and Tm3+ ions, and interactions with OH- radicals. The results indicated that Yb -> Tm energy transfer favors 1.8 mu m emissions, and there is no evidence of concentration quenching up to 2% Tm2O3 doping. As expected, samples prepared in nitrogen atmosphere present higher fluorescence quantum efficiency than those prepared in air, and this feature is specially noted in the near-infrared region, where the interaction with the OH- radicals is more pronounced. (c) 2007 Published by Elsevier B.V.

Influence of neodymium ions on photocatalytic activity of TiO(2) synthesized by sol-gel and precipitation methods

Titanium dioxide with and without the addition of neodymium ions was prepared using sol-gel and precipitation methods. The resulting catalysts were characterized by thermal analysis, X-ray diffraction and BET specific surface area. Neodymium addition exerted a remarkable influence on the phase transition temperature and the surface properties of the TiO(2) matrix. TiO(2) samples synthesized by precipitation exhibit an exothermic event related from the amorphous to anatase phase transition at 510 degrees C, whereas in Nd-doped TiO(2) this transition occurred at 527 degrees C. A similar effect was observed in samples obtained using sol-gel method. The photocatalytic reactivity of the catalysts was evaluated by photodegradation of Remazol Black B (RB) under ultraviolet irradiation. Nd-doped TiO(2) showed enhanced photodegradation ability compared to undoped TiO(2) samples, independent of the method of synthesis. In samples obtained by sol-gel, RB decoloration was enhanced by 16% for TiO(2) doped with 0.5% neodymium ions. (C) 2010 Elsevier B.V. All rights reserved.

Methane conversion reactions on Ni catalysts promoted with Rh: Influence of support

Ni catalysts supported on gamma-Al(2)O(3) and Mg(Al)O were prepared with and without Rh as a promoter and tested in the reforming of methane in the presence of excess methane, simulating a model biogas. The effects of adding synthetic air on the methane conversion and the formation of carbon were assessed. The catalysts were characterized by X-ray spectroscopy (EDS), surface area (BET), X-ray diffraction (XRD), Temperature-programmed reduction (TPR), X-ray absorption near-edge structure (XANES) and XPD. The results showed that in catalysts without Rh, the Ni interacts strongly with the supports, showing high reduction temperatures in TPR tests. The addition of Rh increased the amount of reducible Ni and facilitated the reduction of the species interacting strongly with the support. In the catalytic tests, the samples promoted with Rh suffered higher carbon deposition. The in situ XPD suggested that on the support gamma-Al(2)O(3), the presence of Rh probably led to a segregation of Ni species with time on stream, leading to carbon deposition. On the support MgAlO, the presence of Rh improved the dispersion of Ni, by reducing the Ni(0) crystallite size, suggesting that in this case the carbon deposition was due to a favoring of CH(4) decomposition by Rh. (C) 2011 Elsevier B.V. All rights reserved.

The influence of sex, age, and race experience on pacing profiles during the 90 km Vasaloppet ski race

The purpose of this study was to investigate pacing-profile differences during the 90 km Vasaloppet ski race related to the categories of sex, age, and race experience. Skiing times from eight sections (S1 to S8) were analyzed. For each of the three categories, 400 pairs of skiers were matched to have a finish time within 60 seconds, the same start group, and an assignment to the same group for the other two categories. Paired-samples Student’s t-tests were used to investigate sectional pacing-profile differences between the subgroups. Results showed that males skied faster in S2 (P=0.0042), S3 (P=0.0049), S4 (P=0.010), and S1–S4 (P<0.001), whereas females skied faster in S6 (P<0.001), S7 (P<0.001), S8 (P=0.0088), and S5–S8 (P<0.001). For the age category, old subjects (40 to 59 years) skied faster than young subjects (19 to 39 years) in S3 (P=0.0029), and for the other sections, there were no differences. Experienced subjects (≥4 Vasaloppet ski race completions) skied faster in S1 (P<0.001) and S1–S4 (P=0.0054); inexperienced skiers (<4 Vasaloppet ski race completions) had a shorter mean skiing time in S5–S8 (P=0.0063). In conclusion, females had a more even pacing profile than that of males with the same finish time, start group, age, and race experience. No clear age-related pacing-profile difference was identified for the matched subgroups. Moreover, experienced skiers skied faster in the first half whereas inexperienced skiers had higher skiing speeds during the second half of the race.

Individual differences in children's suggestibility : a comparison between intellectually disabled and mainstream samples

This study examined whether age, gender, intelligence, communication ability and shyness predict intellectually disabled children’s susceptibility to an interviewer’s misleading suggestions. Further, the study examined whether the relative influence of these factors differs between intellectually disabled and mainstream samples. Participants included 75 children with mild and borderline intellectual disabilities (aged 77–158 months) and 83 mainstream children (aged 68–152 months). All children were individually administered the Yield and Shift subscales of the Gudjonsson Suggestibility Scale (Form 2) as well as standardised measures of IQ, shyness and communication ability. For the intellectually disabled children, multiple regression analyses revealed that age, IQ and communication inversely predicted Yield suggestibility, however, none of the factors predicted Shift suggestibility. For the mainstream children, age made a significant independent contribution to both Yield and Shift suggestibility, while IQ was a significant predictor of Shift suggestibility. When comparing the relative impact of these factors across the samples, age had a significantly greater impact on mainstream (compared with intellectually disabled) children’s Shift suggestibility, while IQ had a significantly greater influence on intellectually disabled (compared with mainstream) children’s Yield scores. These findings highlight the limited generalisability of previous findings involving mainstream children’s suggestibility to intellectually disabled samples.

The influence of solute carbon in cold-rolled steels on shear band formation and recrystallization texture

Two experiments were conducted to clarify the roles of grain size, solute carbon and strain in determining the recrystallization textures of cold-rolled and annealed steels. In the first experiment, samples of coarse-grained low-carbon (LC) and interstitial-free (IF) steels were cold-rolled to a 75% reduction in thickness. One sample from each steel was polished and cold-rolled an additional 5%, while the remaining samples were annealed for various times at 650°C. In the second experiment, three samples from a commercial LC steel sheet were rolled 70% at 300°C. Two of the samples were given a further rolling reduction of 5% of the original thickness, with one of the samples being given this additional reduction at 300°C and the other at room temperature. Goss recrystallization textures are strengthened by coarse initial grain sizes, the presence of solute carbon and rolling at a temperature where dynamic strain ageing occurs, but are weakened by additional rolling beyond a reduction of 70%, especially when this extra rolling is conducted at a temperature where dynamic strain ageing does not occur. Characterization of key features of the deformed and recrystallized steels using optical microscopy, scanning electron microscopy (SEM) and electron back-scatter diffraction (EBSD) supports a rationale for these effects based on the repeated activation and deactivation of shear bands and the influence of solute carbon and dynamic strain ageing on the operating life of the bands and the accumulation of strain within them.

Influence of grain size on the compressive deformation of wrought Mg-3A1-1Zn

The influence of the grain size on the flow stress of extruded Mg–3Al–1Zn tested in compression is examined. Samples with grain sizes varying between 3 and 23 μm were prepared by altering the extrusion conditions. Compression testing of the extruded bar was carried out at temperatures between ambient and 200 °C. Twinning dominated the deformation at lower temperatures but this gave way to slip dominated flow when the temperature was raised. For tests carried out at intermediate temperatures, a similar transition was observed when the grain size was reduced. The transition was accompanied by a change in flow curve shape and Hall–Petch slope. The peak stresses achieved when twinning dominated the deformation were up to 100 MPa greater than those seen when slip dominated the flow. Critical grain sizes marking the twinning–slip transition were identified and these are described in terms of the deformation conditions.

Marketing research performance and strategy

Purpose - To investigate whether strategic orientation affects the evaluation of specific market research projects in for-profit firms.
Design/methodology/approach - A small-scale follow-up survey was conducted, building on qualitative and quantitative research among a sample of the top-1,000 marketing managers in Australia. The study used an existing market research evaluation tool, the USER scale and items generated from the qualitative research, to investigate the firm's most recent market research project.
Findings - Four market research performance factors were identified - market research as a knowledge enhancing (KE) function, the internal political use of market research, the misuse of market research and the generation of market understanding. The Miles and Snow strategy types were related to these factors, with Prospector types more likely to use market research rationally and less likely to use it for internal political purposes. Tactical projects were more likely to be misused than were those with a strategic orientation. Prospectors were far less likely and analysers far more likely to misuse tactical research projects. Prospectors were more often satisfied with the performance of their most recent market research. The Porter typology was less successful in predicting market research performance.
Research limitations/implications - The study was based on a small sample of market research projects in Australian for-profit firms. Future studies need to study these phenomena more intensively using ethnographic methods and more extensively using larger multi-country samples.
Practical implications - Market research suppliers should learn the nature of their client's strategic intent to improve their effectiveness. Defender firms should carefully monitor the use of market research, especially that of a tactical nature, which may be wasted or misused.
Originality/value - Contributes to an understanding of how strategic orientation relates to the ways market research information is used within the firm.

The influence of twinning on the hot working flow stress and microstructural evolution of magnesium alloy AZ31

The microstructural evolution during compression (at 350°C and a strain rate of 0.01s-1) was examined for magnesium alloy AZ31 received in the "as-cast" condition. It was revealed that at low strains, many twins are produced and dynamically recrystallized (DRX) grains form as a necklace along pre-existing grain boundaries. At higher strains, DRX stagnates, most likely due to the accommodation of deformation in the DRX fraction of the material. It was also observed that twin boundaries act as sites for the nucleation of DRX grains. The analysis was repeated for samples pre-compressed to a strain of 0.15 at room temperature prior to the hot deformation step. The idea of these additional tests was to increase the degree of twinning and therefore the density of sites for the nucleation of DRX. It was found that statically recrystallized (SRX) grains developed at the twins during heating to the test temperature. When these samples were deformed, the peak flow stress was reduced by approximately 20% and the development of DRX was enhanced. This can be attributed to the accelerated nucleation of DRX in the refined SRX structure.

The influence of reduced flow during a drought on patterns of variation in macroinvertebrate assemblages across a spatial hierarchy in two lowland rivers

1. With the aim of determining whether patterns of variation in macroinvertebrate assemblage composition across the hierarchy of spatial units in two lowland rivers changed during a supra-seasonal drought (1997–2000), patterns during a reduced flow season (1999–2000) were compared with those during two preceding higher flow seasons (1997–98 and 1998–99) using samples from the Glenelg and Wimmera Rivers, two lowland regulated rivers in western Victoria, Australia.

2. We hypothesised that (i) differences between reaches would increase during the reduced flow season owing to decreased hydrological connectivity, (ii) differences between the habitats would decrease because the cessation of flow in run habitats should cause them to become more similar to pool habitats and (iii) differences between microhabitats would also decrease because of reduced scour of inorganic substrata and large woody debris.

3. During each season, macroinvertebrates were sampled from three microhabitats (sand/silt substratum, large woody debris and macrophytes) that were hierarchically nested within a run or pool habitat and within one of three reaches within each river. A range of physico-chemical variables was also sampled.

4. Analysis of similarity showed that assemblage composition in both rivers during the higher flow seasons differed more among microhabitats than other spatial units. However, during the reduced flow season, assemblage composition in the Wimmera River differed most among reaches. This change in pattern was associated with the combined effects of decreased flow and longitudinal increases in salinity. In contrast, the fauna of the Glenelg River appeared to be resistant to the effects of the reduced flow season, owing to limited decline in water quality despite lower river discharge.

5. As salinisation and poor water quality in the Wimmera River result from human activities in the catchment, these results support the idea that human impacts on rivers can change macroinvertebrate scaling patterns and exacerbate the effects of drought beyond the tolerance of many riverine macroinvertebrates.