Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

Rapid word learning by 15-month-olds under tightly-controlled conditions

Infants (12 to 17 months) were taught 2 novel words for 2 images of novel objects, by pairing isolated auditory labels with to-be-associated images. Comprehension was tested using a preferential looking task in which the infant was presented with both images together with an isolated auditory label. The auditory label usually, but not always, matched one of the images. Infants looked preferentially at images that matched the auditory stimulus. The experiment controlled within-subjects for both side bias and preference for previously named items. Infants showed learning after 12 presentations of the new words. Evidence is presented that, in certain circumstances, the duration of longest look at a target may be a more robust measure of target preference than overall looking time. The experiment provides support for previous demonstrations of rapid word learning by pre-vocabulary spurt children, and offers some methodological improvements to the preferential looking task.

Random number generation as an index of controlled processing

Random number generation (RNG) is a functionally complex process that is highly controlled and therefore dependent on Baddeley's central executive. This study addresses this issue by investigating whether key predictions from this framework are compatible with empirical data. In Experiment 1, the effect of increasing task demands by increasing the rate of the paced generation was comprehensively examined. As expected, faster rates affected performance negatively because central resources were increasingly depleted. Next, the effects of participants' exposure were manipulated in Experiment 2 by providing increasing amounts of practice on the task. There was no improvement over 10 practice trials, suggesting that the high level of strategic control required by the task was constant and not amenable to any automatization gain with repeated exposure. Together, the results demonstrate that RNG performance is a highly controlled and demanding process sensitive to additional demands on central resources (Experiment 1) and is unaffected by repeated performance or practice (Experiment 2). These features render the easily administered RNG task an ideal and robust index of executive function that is highly suitable for repeated clinical use.

Operator performance evaluation of controlled depth of field in a stereographically displayed virtual environment

Retinal blurring resulting from the human eye's depth of focus has been shown to assist visual perception. Infinite focal depth within stereoscopically displayed virtual environments may cause undesirable effects, for instance, objects positioned at a distance in front of or behind the observer's fixation point will be perceived in sharp focus with large disparities thereby causing diplopia. Although published research on incorporation of synthetically generated Depth of Field (DoF) suggests that this might act as an enhancement to perceived image quality, no quantitative testimonies of perceptional performance gains exist. This may be due to the difficulty of dynamic generation of synthetic DoF where focal distance is actively linked to fixation distance. In this paper, such a system is described. A desktop stereographic display is used to project a virtual scene in which synthetically generated DoF is actively controlled from vergence-derived distance. A performance evaluation experiment on this system which involved subjects carrying out observations in a spatially complex virtual environment was undertaken. The virtual environment consisted of components interconnected by pipes on a distractive background. The subject was tasked with making an observation based on the connectivity of the components. The effects of focal depth variation in static and actively controlled focal distance conditions were investigated. The results and analysis are presented which show that performance gains may be achieved by addition of synthetic DoF. The merits of the application of synthetic DoF are discussed.

The Aqua-Planet Experiment (APE): CONTROL SST Simulation

Climate simulations by 16 atmospheric general circulation models (AGCMs) are compared on an aqua-planet, a water-covered Earth with prescribed sea surface temperature varying only in latitude. The idealised configuration is designed to expose differences in the circulation simulated by different models. Basic features of the aqua-planet climate are characterised by comparison with Earth. The models display a wide range of behaviour. The balanced component of the tropospheric mean flow, and mid-latitude eddy covariances subject to budget constraints, vary relatively little among the models. In contrast, differences in damping in the dynamical core strongly influence transient eddy amplitudes. Historical uncertainty in modelled lower stratospheric temperatures persists in APE. Aspects of the circulation generated more directly by interactions between the resolved fluid dynamics and parameterized moist processes vary greatly. The tropical Hadley circulation forms either a single or double inter-tropical convergence zone (ITCZ) at the equator, with large variations in mean precipitation. The equatorial wave spectrum shows a wide range of precipitation intensity and propagation characteristics. Kelvin mode-like eastward propagation with remarkably constant phase speed dominates in most models. Westward propagation, less dispersive than the equatorial Rossby modes, dominates in a few models or occurs within an eastward propagating envelope in others. The mean structure of the ITCZ is related to precipitation variability, consistent with previous studies. The aqua-planet global energy balance is unknown but the models produce a surprisingly large range of top of atmosphere global net flux, dominated by differences in shortwave reflection by clouds. A number of newly developed models, not optimised for Earth climate, contribute to this. Possible reasons for differences in the optimised models are discussed. The aqua-planet configuration is intended as one component of an experimental hierarchy used to evaluate AGCMs. This comparison does suggest that the range of model behaviour could be better understood and reduced in conjunction with Earth climate simulations. Controlled experimentation is required to explore individual model behaviour and investigate convergence of the aqua-planet climate with increasing resolution.

A simple and versatile 2-dimensional platform to study plant germination and growth under controlled humidity

We describe a simple, inexpensive, but remarkably versatile and controlled growth environment for the observation of plant germination and seedling root growth on a flat, horizontal surface over periods of weeks. The setup provides to each plant a controlled humidity (between 56% and 91% RH), and contact with both nutrients and atmosphere. The flat and horizontal geometry of the surface supporting the roots eliminates the gravitropic bias on their development and facilitates the imaging of the entire root system. Experiments can be setup under sterile conditions and then transferred to a non-sterile environment. The system can be assembled in 1-2 minutes, costs approximately 8.78$ per plant, is almost entirely reusable (0.43$ per experiment in disposables), and is easily scalable to a variety of plants. We demonstrate the performance of the system by germinating, growing, and imaging Wheat (Triticum aestivum), Corn (Zea mays), and Wisconsin Fast Plants (Brassica rapa). Germination rates were close to those expected for optimal conditions.

A scale-model room as a practical teaching experiment

A practical experiment is described which was used to help university students increase their understanding of the effect of construction methods and window design on passive solar heating and electrical heating. A number of one tenth scale model rooms were constructed by students and sited out-of-doors in the late autumn. The models were fabricated to mimic available commercial construction techniques with careful consideration being given to window size and placement for solar access. Each model had a thermostatically controlled electric heating element. The temperatures and electricity use of the models were recorded using data-loggers over a two week period. The performances of the models based on energy consumption and internal temperature were compared with each other and with predictions based upon thermal mass and R-values. Examples of questions used by students to facilitate this process are included. The effect of scaling on thermal properties was analysed using Buckingham’s p-theorem.

Controlled field studies on soil aquifer treatment in a constructed coastal sandfill

A controlled artificial recharge experiment was conducted to investigate the effect of soil aquifer treatment during percolation of secondary and tertiary (ultrafiltered) treated wastewater through the shallow vadoze zone of a newly constructed coastal sandfill. The sandfill is a reclaimed land constructed from marine sand dredged from the seabed. To obtain 1-D flow, a stainless steel column was driven to a depth of 2.5 m, penetrating the phreatic surface. Wastewater was percolated through the column under fully-saturated and unsaturated conditions. Infiltration rates, dissolved organic carbon (DOC) and ultra-violet absorption (UVA) were monitored. The wastewaters were recharged at similar infiltration rates of approximately 5.5 m/day and 3.5 m/day under fully-saturated and unsaturated conditions, respectively. In both cases, clogging occurred 40 days after the start of recharge, under saturated conditions. For secondary treated wastewater, DOC concentration (mg/l) reduced by 28% and 13% under unsaturated and saturated conditions, respectively. The corresponding UVA reduction was 19.4% and 14.1%. Similar reductions in DOC were observed for the tertiary treated wastewater; however, the reduction in UVA was higher; 28% and 22% under unsaturated and saturated conditions, respectively. On an mass removal (mg/m(2) DOC) basis, DOC reduction appeared to be more significant under unsaturated conditions. This is attributed to the presence of interstitial oxygen.

RAFT controlled synthesis of graphene/polymer hydrogel with enhanced mechanical property for pH-controlled drug release

A pH-sensitive, mechanically strong and thermally stable graphene/poly (acrylic acid) (graphene/PAA) hydrogel was prepared via reversible addition fragmentation transfer (RAFT) polymerizations in the presence of a cross-linking agent. The RAFT agent was covalently coupled onto graphene basal planes via an esterification reaction, with benzoic acid functionalities pre-attached on graphene with its aryl diazonium salt precursor. AFM and SEM analysis revealed the successful preparation of single layered graphene sheets and graphene/polymer hydrogels with pH controlled porous structures. Attenuated total reflection infrared (ATR-IR) and thermogravimetric analyzer (TGA) verified the successful stepwise preparation of graphene/PAA hydrogel. This graphene/PAA hydrogel was pH-sensitive and more mechanically elastic than the PAA hydrogel prepared without graphene. The pH sensitivity of the hydrogel was further utilized for controlled drug release. Doxorubicin was chosen as a model drug and loaded into the hydrogels. The drug loading and release experiment indicated that this hydrogel can be used to efficiently control drug release in the intestine environment (pH = 7.4), better than release in a more acidic environment.© 2013 Elsevier Ltd. All rights reserved.

Rent-sharing in Brazil: using trade liberalization as a natural experiment

This paper examines the extent of rent-sharing in Brazil, between 1988 and 1995, combining two different data sets: annual industrial surveys (pIA) and annual household surveys (PNADs). The aim is to use the trade liberalization policies that took place in Brazil in the early 1990s as a "natural experiment" to examine the impact ofproduct market rents on wages. We first estimate inter-industry wage differentials in Brazil, using the household surveys, afier controlling for various observable workers' characteristics. In a reduced form fixed effects equation, these controlled inter-industry differentials are seen to depend on the industries' rate of effective tariff. We also find that LSDV estimates of the effect of value-added per worker (computed using the industrial surveys) on the wage differentials are positive, but somewhat small. However, we find that instrumenting the valued-added with the effective tariffs more than doubles the estimated rent-sharing coefficient. The paper concludes that rent-sharing is prevalent in the Brazilian manufacturing sector, and this mechanism transferred part of the productivity gains due to trade liberalization to manufacturing workers in the form ofhigher (controlled) wage premium.

Equine tendonitis therapy using mesenchymal stem cells and platelet concentrates: A randomized controlled trial

Introduction. Tendon injury is a major cause of lameness and decreased performance in athletic equines. Various therapies for tendonitis have been described; however, none of these therapies results in complete tissue regeneration, and the injury recurrence rate is high even after long recovery periods involving rest and physiotherapy. Methods. A lesion was induced with collagenase gel in the superficial digital flexor tendon in the center portion of the metacarpal region of eight equines of mixed breed. After two weeks, the lesions of the animals in the treated and control groups were treated through the intralesional administration of mesenchymal stem cells derived from adipose tissue (adMSCs) suspended in platelet concentrate (PC) and with phosphate buffered saline (PBS), respectively. Serial ultrasound analyses were performed every two weeks. After 16 weeks of therapy, a biopsy was performed for histopathological, immunohistochemical and gene expression (type I collagen (COL1A1), type III collagen (COL3A1), tenascin-C (TNC), tenomodulin (TNMD), and scleraxis (SCX)) analyses. Results: Differences in the ultrasound and histopathological analyses were observed between the groups. Improved results were reported in the group treated with adMSCs suspended in PC. There was no difference in the gene expression levels observed after the different treatments. The main results observed from the histopathological evaluation of the treated group were as follows: a prevention of the progression of the lesion, a greater organization of collagen fibers, and a decreased inflammatory infiltrate. A lack of progression of the lesion area and its percentage was observed in the ultrasound image, and increased blood flow was measured by Power Doppler. Conclusions: The use of adMSCs combined with PC for the therapy of experimentally induced tendonitis prevented the progression of the tendon lesion, as observed in the ultrasound examination, and resulted in a greater organization and decreased inflammation, as observed in the histopathological evaluation. These data demonstrate the therapeutic potential of this therapy for the treatment of equine tendonitis. © 2013 Carvalho et al.; licensee BioMed Central Ltd.

A computer-controlled color vision test for children based on the Cambridge Colour Test

The present study aimed at providing conditions for the assessment of color discrimination in children using a modified version of the Cambridge Colour Test (CCT, Cambridge Research Systems Ltd., Rochester, UK). Since the task of indicating the gap of the Landolt C used in that test proved counterintuitive and/or difficult for young children to understand, we changed the target Stimulus to a patch of color approximately the size of the Landolt C gap (about 7 degrees Of Visual angle at 50 cm from the monitor). The modifications were performed for the CCT Trivector test which measures color discrimination for the protan, deutan and tritan confusion lines. Experiment I Sought to evaluate the correspondence between the CCT and the child-friendly adaptation with adult subjects (n = 29) with normal color vision. Results showed good agreement between the two test versions. Experiment 2 tested the child-friendly software with children 2 to 7 years old (n = 25) using operant training techniques for establishing and maintaining the subjects` performance. Color discrimination thresholds were progressively lower as age increased within the age range tested (2 to 30 years old), and the data-including those obtained for children-fell within the range of thresholds previously obtained for adults with the CCT. The protan and deutan thresholds were consistently lower than tritan thresholds, a pattern repeatedly observed in adults tested with the CCT. The results demonstrate that the test is fit for assessment of color discrimination in young children and may be a useful tool for the establishment of color vision thresholds during development.

Assessing the efficiency of a pharmacokinetic-based algorithm for target-controlled infusion of ketamine in ponies

The objective of this study was to assess a pharmacokinetic algorithm to predict ketamine plasma concentration and drive a target-controlled infusion (TCI) in ponies. Firstly, the algorithm was used to simulate the course of ketamine enantiomers plasma concentrations after the administration of an intravenous bolus in six ponies based on individual pharmacokinetic parameters obtained from a previous experiment. Using the same pharmacokinetic parameters, a TCI of S-ketamine was then performed over 120 min to maintain a concentration of 1 microg/mL in plasma. The actual plasma concentrations of S-ketamine were measured from arterial samples using capillary electrophoresis. The performance of the simulation for the administration of a single bolus was very good. During the TCI, the S-ketamine plasma concentrations were maintained within the limit of acceptance (wobble and divergence <20%) at a median of 79% (IQR, 71-90) of the peak concentration reached after the initial bolus. However, in three ponies the steady concentrations were significantly higher than targeted. It is hypothesized that an inaccurate estimation of the volume of the central compartment is partly responsible for that difference. The algorithm allowed good predictions for the single bolus administration and an appropriate maintenance of constant plasma concentrations.

Quantification of gold nanoparticle cell uptake under controlled biological conditions and adequate resolution

Aim: We examined cellular uptake mechanisms of fluorescently labeled polymer-coated gold nanoparticles (NPs) under different biological conditions by two quantitative, microscopic approaches. Materials & methods: Uptake mechanisms were evaluated using endocytotic inhibitors that were tested for specificity and cytotoxicity. Cellular uptake of gold NPs was analyzed either by laser scanning microscopy or transmission electron microscopy, and quantified by means of stereology using cells from the same experiment. Results: Optimal inhibitor conditions were only achieved with chlorpromazine (clathrin-mediated endocytosis) and methyl-β-cyclodextrin (caveolin-mediated endocytosis). A significant methyl-β-cyclodextrin-mediated inhibition (63-69%) and chlorpromazine-mediated increase (43-98%) of intracellular NPs was demonstrated with both imaging techniques, suggesting a predominant uptake via caveolin-medicated endocytois. Transmission electron microscopy imaging revealed more than 95% of NPs localized in intracellular vesicles and approximately 150-times more NP events/cell were detected than by laser scanning microscopy. Conclusion: We emphasize the importance of studying NP-cell interactions under controlled experimental conditions and at adequate microscopic resolution in combination with stereology. Original submitted 10 July 2012; Revised submitted 23 January 2013.