The effect of pH on the photonic efficiency of the destruction of methyl orange under controlled periodic illumination with UV-LED sources

The nature of photon interaction and reaction pH can have significant impacts on semiconductor photocatalysis. This paper describes the effect of pH on the photonic efficiency of photocatalytic reactions in the aqueous phase using TiO2 catalysts. The reactor was irradiated using periodic illumination with UV-LEDs through control of the illumination duty cycle (γ) through a series of light and dark times (Ton/Toff). Photonic efficiencies for methyl orange degradation were found to be comparable at high γ irrespective of pH. At lower γ, pH effects on photonic efficiency were very distinct across acidic, neutral and alkaline pH indicating an effect of complementary parameters. The results suggest photonic efficiency is greatest as illumination time, Ton approaches interfacial electron-transfer characteristic time which is within the range of this study or charge-carrier lifetimes upon extrapolation and also when electrostatic attraction between surface-trapped holes, {TiIVOH}ads+ and substrate molecules is strongest.

Controlled periodic illumination in semiconductor photocatalysis

Controlled periodic illumination is a hypothesis postulated in the early 1990s for enhancing the efficiency of semiconductor photocatalytic reactions. This technique has been proposed to improve photocatalytic efficiency by the nature of photon introduction alone. Before its application in semiconductor photocatalysis, controlled periodic illumination had been investigated in other fields including photosynthesis. This paper presents a detailed review of the state of the art research undertaken on the application of controlled periodic illumination in semiconductor photocatalysis. The review briefly introduces semiconductor photocatalysis, and then presents a detailed explanation of this technique, its importance to photocatalytic efficiency, an overview of previous results of its application in significant studies and present knowledge. Results from previous as well as some of the most recent studies indicate potential applications of controlled periodic illumination in areas other than just the improvement of the efficiency of the photocatalytic process.

Effect of controlled periodic-based illumination on the photonic efficiency of photocatalytic degradation of methyl orange

The use of controlled periodic illumination with UV LEDs for enhancing photonic efficiency of photocatalytic decomposition processes in water has been investigated using methyl orange as a model compound. The impact of the length of light and dark time periods (T _ON/T _OFF times) on photodegradation and photonic efficiency using a UV LED-illuminated photoreactor has been studied. The results have shown an inverse dependency of the photonic efficiency on duty cycle and a very little effect on T _ON or T _OFF time periods, indicating no effect of rate-limiting steps through mass diffusion or adsorption/desorption in the reaction. For this reactor, the photonic efficiency under controlled periodic illumination (CPI) matches to that of continuous illumination, for the same average UV light intensities. Furthermore, under CPI conditions, the photonic efficiency is inversely related to the average UV light intensity in the reactor, in the millisecond time regime. This is the first study that has investigated the effect of controlled periodic illumination using ultra band gap UV LED light sources in the photocatalytic destruction of dye compounds using titanium dioxide. The results not only enhance the understanding of the effect of periodic illumination on photocatalytic processes but also provide a greater insight to the potential of these light sources in photocatalytic reactions. 

Mathematical modelling of quantum yield enhancements of methyl orange photooxidation in aqueous TiO2 suspensions under controlled periodic UV LED illumination

Quantum yields of the photocatalytic degradation of methyl orange under controlled periodic illumination (CPI) have been modelled using existing models. A modified Langmuir-Hinshelwood (L-H) rate equation was used to predict the degradation reaction rates of methyl orange at various duty cycles and a simple photocatalytic model was applied in modelling quantum yield enhancement of the photocatalytic process due to the CPI effect. A good agreement between the modelled and experimental data was observed for quantum yield modelling. The modified L-H model, however, did not accurately predict the photocatalytic decomposition of the dye under periodic illumination.

The post-illumination pupil response of melanopsin expressing intrinsically photosensitive retinal ganglion cells in diabetes

Purpose: This study investigates the clinical utility of the melanopsin expressing intrinsically photosensitive retinal ganglion cell (ipRGC) controlled post-illumination pupil response (PIPR) as a novel technique for documenting inner retinal function in patients with Type II diabetes without diabetic retinopathy. Methods: The post-illumination pupil response (PIPR) was measured in seven patients with Type II diabetes, normal retinal nerve fiber thickness and no diabetic retinopathy. A 488 nm and 610 nm, 7.15º diameter stimulus was presented in Maxwellian view to the right eye and the left consensual pupil light reflex was recorded. Results: The group data for the blue PIPR (488 nm) identified a trend of reduced ipRGC function in patients with diabetes with no retinopathy. The transient pupil constriction was lower on average in the diabetic group. The relationship between duration of diabetes and the blue PIPR amplitude was linear, suggesting that ipRGC function decreases with increasing diabetes duration. Conclusion: This is the first report to show that the ipRGC controlled post-illumination pupil response may have clinical applications as a non-invasive technique for determining progression of inner neuroretinal changes in patients with diabetes before they are ophthalmoscopically or anatomically evident. The lower transient pupil constriction amplitude indicates that outer retinal photoreceptor inputs to the pupil light reflex may also be affected in diabetes.

Periodic window arising in the parameter space of an impact oscillator

In the bi-dimensional parameter space of an impact-pair system, shrimp-shaped periodic windows are embedded in chaotic regions. We show that a weak periodic forcing generates new periodic windows near the unperturbed one with its shape and periodicity. Thus, the new periodic windows are parameter range extensions for which the controlled periodic oscillations substitute the chaotic oscillations. We identify periodic and chaotic attractors by their largest Lyapunov exponents. (C) 2010 Elsevier B.V. All rights reserved.

The circadian response of intrinsically photosensitive retinal ganglion cells

Intrinsically photosensitive retinal ganglion cells (ipRGC) signal environmental light level to the central circadian clock and contribute to the pupil light reflex. It is unknown if ipRGC activity is subject to extrinsic (central) or intrinsic (retinal) network-mediated circadian modulation during light entrainment and phase shifting. Eleven younger persons (18–30 years) with no ophthalmological, medical or sleep disorders participated. The activity of the inner (ipRGC) and outer retina (cone photoreceptors) was assessed hourly using the pupil light reflex during a 24 h period of constant environmental illumination (10 lux). Exogenous circadian cues of activity, sleep, posture, caffeine, ambient temperature, caloric intake and ambient illumination were controlled. Dim-light melatonin onset (DLMO) was determined from salivary melatonin assay at hourly intervals, and participant melatonin onset values were set to 14 h to adjust clock time to circadian time. Here we demonstrate in humans that the ipRGC controlled post-illumination pupil response has a circadian rhythm independent of external light cues. This circadian variation precedes melatonin onset and the minimum ipRGC driven pupil response occurs post melatonin onset. Outer retinal photoreceptor contributions to the inner retinal ipRGC driven post-illumination pupil response also show circadian variation whereas direct outer retinal cone inputs to the pupil light reflex do not, indicating that intrinsically photosensitive (melanopsin) retinal ganglion cells mediate this circadian variation.

Anomalous shift of the beating nodes in illumination-controlled In1-xGaxAs/In1-yAlyAs two-dimensional electron gases with strong spin-orbit interaction

The beating patterns in the Shubnikov-de Haas oscillatory magnetoresistance originating from zero-field spin splitting of two-dimensional electron gases (2DEGs) in In0.52Al0.48As/InxGa1-xAs/In0.52Al0.48As quantum wells with silicon delta doped on the upper barrier layer have been investigated by means of magnetotransport measurements before and after illumination. Contrary to the expectation, after each illumination, the beating nodes induced by the zero-field spin-splitting effect shift to lower and lower magnetic field due to the decrease in the zero-field spin-splitting energy of the 2DEGs. The anomalous phenomenon of the shift of the beating nodes and the decrease in spin-orbit coupling constants after illumination cannot be explained by utilizing the previous linear Rashba model. It is suggested that the decrease in the zero-field spin-splitting energy and the spin-orbit coupling constant arise from the nonlinear Rashba spin splitting.

Intrinsically photosensitive melanopsin retinal ganglion cell contributions to the post-illumination pupil response and circadian rhythm

Intrinsically photosensitive retinal ganglion cells (ipRGCs) in the eye transmit the environmental light level, projecting to the suprachiasmatic nucleus (SCN) (Berson, Dunn & Takao, 2002; Hattar, Liao, Takao, Berson & Yau, 2002), the location of the circadian biological clock, and the olivary pretectal nucleus (OPN) of the pretectum, the start of the pupil reflex pathway (Hattar, Liao, Takao, Berson & Yau, 2002; Dacey, Liao, Peterson, Robinson, Smith, Pokorny, Yau & Gamlin, 2005). The SCN synchronizes the circadian rhythm, a cycle of biological processes coordinated to the solar day, and drives the sleep/wake cycle by controlling the release of melatonin from the pineal gland (Claustrat, Brun & Chazot, 2005). Encoded photic input from ipRGCs to the OPN also contributes to the pupil light reflex (PLR), the constriction and recovery of the pupil in response to light. IpRGCs control the post-illumination component of the PLR, the partial pupil constriction maintained for > 30 sec after a stimulus offset (Gamlin, McDougal, Pokorny, Smith, Yau & Dacey, 2007; Kankipati, Girkin & Gamlin, 2010; Markwell, Feigl & Zele, 2010). It is unknown if intrinsic ipRGC and cone-mediated inputs to ipRGCs show circadian variation in their photon-counting activity under constant illumination. If ipRGCs demonstrate circadian variation of the pupil response under constant illumination in vivo, when in vitro ipRGC activity does not (Weng, Wong & Berson, 2009), this would support central control of the ipRGC circadian activity. A preliminary experiment was conducted to determine the spectral sensitivity of the ipRGC post-illumination pupil response under the experimental conditions, confirming the successful isolation of the ipRGC response (Gamlin, et al., 2007) for the circadian experiment. In this main experiment, we demonstrate that ipRGC photon-counting activity has a circadian rhythm under constant experimental conditions, while direct rod and cone contributions to the PLR do not. Intrinsic ipRGC contributions to the post-illumination pupil response decreased 2:46 h prior to melatonin onset for our group model, with the peak ipRGC attenuation occurring 1:25 h after melatonin onset. Our results suggest a centrally controlled evening decrease in ipRGC activity, independent of environmental light, which is temporally synchronized (demonstrates a temporal phase-advanced relationship) to the SCN mediated release of melatonin. In the future the ipRGC post-illumination pupil response could be developed as a fast, non-invasive measure of circadian rhythm. This study establishes a basis for future investigation of cortical feedback mechanisms that modulate ipRGC activity.

Temporal dynamics of rod and cone photoreceptor interactions under mesopic illumination

Purpose: Photoreceptor interactions reduce the temporal bandwidth of the visual system under mesopic illumination. The dynamics of these interactions are not clear. This study investigated cone-cone and rod-cone interactions when the rod (R) and three cone (L, M, S) photoreceptor classes contribute to vision via shared post-receptoral pathways. Methods: A four-primary photostimulator independently controlled photoreceptor activity in human observers. To determine the temporal dynamics of receptoral (L, S, R) and post-receptoral (LMS, LMSR, +L-M) pathways (5 Td, 7° eccentricity) in Experiment 1, ON-pathway sensitivity was assayed with an incremental probe (25ms) presented relative to onset of an incremental sawtooth conditioning pulse (1000ms). To define the post-receptoral pathways mediating the rod stimulus, Experiment 2 matched the color appearance of increased rod activation (30% contrast, 25-1000ms; constant cone excitation) with cone stimuli (variable L+M, L/L+M, S/L+M; constant rod excitation). Results: Cone-cone interactions with luminance stimuli (LMS, LMSR, L-cone) reduced Weber contrast sensitivity by 13% and the time course of adaptation was 23.7±1ms (μ±SE). With chromatic stimuli (+L-M, S), cone pathway sensitivity was also reduced and recovery was slower (+L-M 8%, 2.9±0.1ms; S 38%, 1.5±0.3ms). Threshold patterns at ON-conditioning pulse onset were monophasic for luminance and biphasic for chromatic stimuli. Rod-rod interactions increased sensitivity(19%) with a recovery time of 0.7±0.2ms. Compared to cone-cone interactions, rod-cone interactions with luminance stimuli reduced sensitivity to a lesser degree (5%) with faster recovery (42.9±0.7ms). Rod-cone interactions were absent with chromatic stimuli. Experiment 2 showed that rod activation generated luminance (L+M) signals at all durations, and chromatic signals (L/L+M, S/L+M) for durations >75ms. Conclusions: Temporal dynamics of cone-cone interactions are consistent with contrast sensitivity loss in the MC pathway for luminance stimuli and chromatically opponent responses in the PC and KC pathway with chromatic stimuli. Rod-cone interactions limit contrast sensitivity loss during dynamic illumination changes and increase the speed of mesopic light adaptation. The change in relative weighting of the temporal rod signal within the major post-receptoral pathways modifies the sensitivity and dynamics of photoreceptor interactions.

Melanopsin mediated post-illumination pupil response in early age-related macular degeneration

Purpose To determine whether melanopsin expressing intrinsically photosensitive Retinal Ganglion Cell (ipRGC) inputs to the pupil light reflex (PLR) are affected in early age-related macular degeneration (AMD). Methods The PLR was measured in 40 participants (20 early AMD and 20 age-matched controls) using a custom-built Maxwellian-view pupillometer. Sinusoidal stimuli (0.5 Hz, 11.9 s duration, 35.6° diameter) were presented to the study eye and the consensual pupil response was measured for stimuli with high melanopsin excitation (464nm; blue) and with low melanopsin excitation (638 nm; red) that biased activation to the outer retina. Two melanopsin PLR metrics were quantified: the Phase Amplitude Percentage (PAP) during the sinusoidal stimulus presentation and the Post-Illumination Pupil Response (PIPR). The PLR during stimulus presentation was analyzed using latency to constriction, transient pupil response and maximum pupil constriction metrics. Diagnostic accuracy was evaluated using receiver operating characteristic (ROC) curves. Results The blue PIPR was significantly less sustained in the early AMD group (p<0.001). The red PIPR was not significantly different between groups (p>0.05). The PAP and blue stimulus constriction amplitude were significantly lower in the early AMD group (p < 0.05). There was no significant difference between groups in the latency or transient amplitude for both stimuli (p>0.05). ROC analysis showed excellent diagnostic accuracy for the blue PIPR metrics (AUC>0.9). Conclusions This is the initial report that the melanopsin controlled PIPR is dysfunctional in early AMD. The non-invasive, objective measurement of the ipRGC controlled PIPR has excellent diagnostic accuracy for early AMD.

Nonlinear measures of heart rate time series: influence of posture and controlled breathing

In this study, we investigated measures of nonlinear dynamics and chaos theory in regards to heart rate variability in 27 normal control subjects in supine and standing postures, and 14 subjects in spontaneous and controlled breathing conditions. We examined minimum embedding dimension (MED), largest Lyapunov exponent (LLE) and measures of nonlinearity (NL) of heart rate time series. MED quantifies the system's complexity, LLE predictability and NL, a measure of deviation from linear processes. There was a significant decrease in complexity (P<0.00001), a decrease in predictability (P<0.00001) and an increase in nonlinearity (P=0.00001) during the change from supine to standing posture. Decrease in MED, and increases in NL score and LLE in standing posture appear to be partly due to an increase in sympathetic activity of the autonomous nervous system in standing posture. An improvement in predictability during controlled breathing appears to be due to the introduction of a periodic component. (C) 2000 published by Elsevier Science B.V.

Regimes of spray formation in gas-centered swirl coaxial atomizers

Spray formation in ambient atmosphere from gas-centered swirl coaxial atomizers is described by carrying out experiments in a spray test facility. The atomizer discharges a circular air jet and an axisymmetric swirling water sheet from its coaxially arranged inner and outer orifices. A high-speed digital imaging system along with a backlight illumination arrangement is employed to record the details of liquid sheet breakup and spray development. Spray regimes exhibiting different sheet breakup mechanisms are identified and their characteristic features presented. The identified spray regimes are wave-assisted sheet breakup, perforated sheet breakup, segmented sheet breakup, and pulsation spray regime. In the regime of wave-assisted sheet breakup, the sheet breakup shows features similar to the breakup of two-dimensional planar air-blasted liquid sheets. At high air-to-liquid momentum ratios, the interaction process between the axisymmetric swirling liquid sheet and the circular air jet develops spray processes which are more specific to the atomizer studied here. The spray exhibits a periodic ejection of liquid masses whose features are dominantly controlled by the central air jet.

Controlled synthesis of TiO2 nanoparticles and nanospheres using a microwave assisted approach for their application in dye-sensitized solar cells

Rapid and facile synthesis of similar to 7 nm and similar to 100-400 nm nano-structures of anatase titania is achieved by exploiting the chemical nature of solvents through a microwave based approach. After using these nanostructures as a photoanode in dye-sensitized solar cells, a modest yet appreciable efficiency of 6.5% was achieved under the illumination of AM 1.5 G one sun (100 mW cm(-2)).