Reproducibility of retinal thickness measurements in healthy subjects using spectralis optical coherence tomography

PURPOSE: To test the reproducibility of retinal thickness measurements in healthy volunteers of a new Frequency-domain optical coherence tomography (OCT) device (Spectralis OCT; Heidelberg Engineering, Heidelberg, Germany). DESIGN: Prospective, observational study. METHODS: Forty-one eyes of 41 healthy subjects were included into the study. Intraobserver reproducibility was tested with 20 x 15 degree raster scans consisting of 37 high-resolution line scans that were repeated three times by one examiner (M.N.M.). Mean retinal thickness was calculated for nine areas corresponding to the Early Treatment Diabetic Retinopathy Study (ETDRS) areas. Coefficients of variation (COV) were calculated. RESULTS: Retinal thickness measurements were highly reproducible for all ETDRS areas. Mean total retinal thickness was 342 +/- 15 microm. Mean foveal thickness was 286 +/- 17 microm. COVs ranged from 0.38% to 0.86%. Lowest COV was found for the temporal outer ETDRS area (area 7; COV, 0.38%). Highest COV was found for the temporal inner ETDRS area (area 3; COV, 0.86%). Mean difference between measurement 1 and 2, measurement 1 and 3, and measurement 2 and 3 for all ETDRS areas was 1.01 microm, 0.98 microm, and 0.99 microm, respectively. CONCLUSION: Spectralis OCT retinal thickness measurements in healthy volunteers showed excellent intraobserver reproducibility with virtually identical results between retinal thickness measurements performed by one operator.

Automatic assessment of time-resolved OCT images for selective retina therapy

Purpose In recent years, selective retina laser treatment (SRT), a sub-threshold therapy method, avoids widespread damage to all retinal layers by targeting only a few. While these methods facilitate faster healing, their lack of visual feedback during treatment represents a considerable shortcoming as induced lesions remain invisible with conventional imaging and make clinical use challenging. To overcome this, we present a new strategy to provide location-specific and contact-free automatic feedback of SRT laser applications. Methods We leverage time-resolved optical coherence tomography (OCT) to provide informative feedback to clinicians on outcomes of location-specific treatment. By coupling an OCT system to SRT treatment laser, we visualize structural changes in the retinal layers as they occur via time-resolved depth images. We then propose a novel strategy for automatic assessment of such time-resolved OCT images. To achieve this, we introduce novel image features for this task that when combined with standard machine learning classifiers yield excellent treatment outcome classification capabilities. Results Our approach was evaluated on both ex vivo porcine eyes and human patients in a clinical setting, yielding performances above 95 % accuracy for predicting patient treatment outcomes. In addition, we show that accurate outcomes for human patients can be estimated even when our method is trained using only ex vivo porcine data. Conclusion The proposed technique presents a much needed strategy toward noninvasive, safe, reliable, and repeatable SRT applications. These results are encouraging for the broader use of new treatment options for neovascularization-based retinal pathologies.

Error control on spectral data of four-wave mixing based on a-SiC technology

In this paper we exploit the nonlinear property of the SiC multilayer devices to design an optical processor for error detection that enables reliable delivery of spectral data of four-wave mixing over unreliable communication channels. The SiC optical processor is realized by using double pin/pin a-SiC:H photodetector with front and back biased optical gating elements. Visible pulsed signals are transmitted together at different bit sequences. The combined optical signal is analyzed. Data show that the background acts as selector that picks one or more states by splitting portions of the input multi optical signals across the front and back photodiodes. Boolean operations such as EXOR and three bit addition are demonstrated optically, showing that when one or all of the inputs are present, the system will behave as an XOR gate representing the SUM. When two or three inputs are on, the system acts as AND gate indicating the present of the CARRY bit. Additional parity logic operations are performed using four incoming pulsed communication channels that are transmitted and checked for errors together. As a simple example of this approach, we describe an all-optical processor for error detection and then provide an experimental demonstration of this idea. (C) 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fine structure in the time of flight distribution of C2 in laser produced plasma from graphite

Time resolved optical emission spectroscopy is employed to study the expansion dynamics of C2 species in a graphite plasma produced during the Nd : YAG ablation. At low laser fluences a single peak distribution with low kinetic energy is observed. At higher fluences a twin peak distribution is found. It has been noted that these double peak time of flight distribution splits into a triple peak structure at distances >_ 17mm from the target surface. The reason for the occurrence of multiple peak is due to different formation mechanisms of C2 species

Emission characteristics and dynamics of C2 from laser produced graphite plasma

The emission features of laser ablated graphite plume generated in a helium ambient atmosphere have been investigated with time and space resolved plasma diagnostic technique. Time resolved optical emission spectroscopy is employed to reveal the velocity distribution of different species ejected during ablation. At lower values of laser fluences only a slowly propagating component of C2 is seen. At high fluences emission from C2 shows a twin peak distribution in time. The formation of an emission peak with diminished time delay giving an energetic peak at higher laser fluences is attributed to many body recombination. It is also observed that these double peaks get modified into triple peak time of flight distribution at distances greater than 16 mm from the target. The occurrence of multiple peaks in the C2 emission is mainly due to the delays caused from the different formation mechanism of C2 species. The velocity distribution of the faster peak exhibits an oscillating character with distance from the target surface.

Elucidating capacitance and resistance terms in confined electroactive molecular layers

Electrochemical analyses on confined electroactive molecular layers, herein exemplified with electroactive self-assembled monolayers, sample current contributions that are significantly influenced by additional nonfaradaic and uncompensated resistance effects that, though unresolved, can strongly distort redox analysis. Prior work has shown that impedance-derived capacitance spectroscopy approaches can cleanly resolve all contributions generated at such films, including those which are related to the layer dipolar/electrostatic relaxation characteristics. We show herein that, in isolating the faradaic and nonfaradaic contributions present within an improved equivalent circuit description of such interfaces, it is possible to accurately simulate subsequently observed cyclic voltammograms (that is, generated current versus potential patterns map accurately onto frequency domain measurements). Not only does this enable a frequency-resolved quantification of all components present, and in so doing, a full validation of the equivalent circuit model utilized, but also facilitates the generation of background subtracted cyclic voltammograms remarkably free from all but faradaic contributions. © 2012 American Chemical Society.

Elucidating Redox-Level Dispersion and Local Dielectric Effects within Electroactive Molecular Films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Label-free Capacitive Diagnostics: Exploiting Local Redox Probe State Occupancy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

lmmittance electroanalysis in diagnostics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aerosol profiling with lidar in the Amazon Basin during the wet and dry season

For the first time, multiwavelength polarization Raman lidar observations of optical and microphysical particle properties over the Amazon Basin are presented. The fully automated advanced Raman lidar was deployed 60 km north of Manaus, Brazil (2.5 degrees S, 60 degrees W) in the Amazon rain forest from January to November 2008. The measurements thus cover both the wet season (Dec-June) and the dry or burning season (July-Nov). Two cases studies of young and aged smoke plumes are discussed in terms of spectrally resolved optical properties (355, 532, and 1064 nm) and further lidar products such as particle effective radius and single-scattering albedo. These measurement examples confirm that biomass burning aerosols show a broad spectrum of optical, microphysical, and chemical properties. The statistical analysis of the entire measurement period revealed strong differences between the pristine wet and the polluted dry season. African smoke and dust advection frequently interrupt the pristine phases during the wet season. Compared to pristine wet season conditions, the particle scattering coefficients in the lowermost 2 km of the atmosphere were found to be enhanced, on average, by a factor of 4 during periods of African aerosol intrusion and by a factor of 6 during the dry (burning) season. Under pristine conditions, the particle extinction coefficients and optical depth for 532 nm wavelength were frequently as low as 10-30 Mm(-1) and <0.05, respectively. During the dry season, biomass burning smoke plumes reached to 3-5 km height and caused a mean optical depth at 532 nm of 0.26. On average during that season, particle extinction coefficients (532 nm) were of the order of 100 Mm(-1) in the main pollution layer (up to 2 km height). Angstrom exponents were mainly between 1.0 and 1.5, and the majority of the observed lidar ratios were between 50-80 sr.

The coupling between electron transfer and Protein/Solvent Dynamics in Photosynthetic Reaction Centers: Spectroscopic Studies in Amorphous Matrices

We investigated at the molecular level protein/solvent interactions and their relevance in protein function through the use of amorphous matrices at room temperature. As a model protein, we used the bacterial photosynthetic reaction center (RC) of Rhodobacter sphaeroides, a pigment protein complex which catalyzes the light-induced charge separation initiating the conversion of solar into chemical energy. The thermal fluctuations of the RC and its dielectric conformational relaxation following photoexcitation have been probed by analyzing the recombination kinetics of the primary charge-separated (P+QA-) state, using time resolved optical and EPR spectroscopies. We have shown that the RC dynamics coupled to this electron transfer process can be progressively inhibited at room temperature by decreasing the water content of RC films or of RC-trehalose glassy matrices. Extensive dehydration of the amorphous matrices inhibits RC relaxation and interconversion among conformational substates to an extent comparable to that attained at cryogenic temperatures in water-glycerol samples. An isopiestic method has been developed to finely tune the hydration level of the system. We have combined FTIR spectral analysis of the combination and association bands of residual water with differential light-minus-dark FTIR and high-field EPR spectroscopy to gain information on thermodynamics of water sorption, and on structure/dynamics of the residual water molecules, of protein residues and of RC cofactors. The following main conclusions were reached: (i) the RC dynamics is slaved to that of the hydration shell; (ii) in dehydrated trehalose glasses inhibition of protein dynamics is most likely mediated by residual water molecules simultaneously bound to protein residues and sugar molecules at the protein-matrix interface; (iii) the local environment of cofactors is not involved in the conformational dynamics which stabilizes the P+QA-; (iv) this conformational relaxation appears to be rather delocalized over several aminoacidic residues as well as water molecules weakly hydrogen-bonded to the RC.

Charge generation and recombination in hybrid organic,inorganic solar cells

This thesis deals with the investigation of exciton and charge dynamics in hybrid solar cells by time-resolved optical spectroscopy. Quasi-steady-state and transient absorption spectroscopy, as well as time-resolved photoluminescence spectroscopy, were employed to study charge generation and recombination in solid-state organic dye-sensitized solar cells, where the commonly used liquid electrolyte is replaced by an organic solid hole transporter, namely 2,2′7,7′-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9′-spirobifluorene (spiro-MeOTAD), and polymer-metal oxide bulk heterojunction solar cells, where the commonly used fullerene acceptor [6,6]-phenyl C61 butyric acid methyl ester (PCBM) is replaced by zinc oxide (ZnO) nanoparticles. By correlating the spectroscopic results with the photovoltaic performance, efficiency-limiting processes and processes leading to photocurrent generation in the investigated systems are revealed. rnIt is shown that the charge generation from several all-organic donor-π-bridge-acceptor dyes, specifically perylene monoimide derivatives, employed in solid-state dye-sensitized solar cells, is strongly dependent on the presence of a commonly used additive lithium bis(trifluoromethanesulphonyl)imide salt (Li-TFSI) at the interface. rnMoreover, it is shown that charges can not only be generated by electron injection from the excited dye into the TiO2 acceptor and subsequent regeneration of the dye cation by the hole transporter, but also by an alternative mechanism, called preceding hole transfer (or reductive quenching). Here, the excited dye is first reduced by the hole transporter and the thereby formed anion subsequently injects an electron into the titania. This additional charge generation process, which is only possible for solid hole transporters, helps to overcome injection problems. rnHowever, a severe disadvantage of solid-state dye-sensitized solar cells is re-vealed by monitoring the transient Stark effect on dye molecules at the inter-face induced by the electric field between electrons and holes. The attraction between the negative image charge present in TiO2, which is induced by the positive charge carrier in the hole transporter due to the dielectric contrast between the organic spiro-MeOTAD and inorganic titania, is sufficient to at-tract the hole back to the interface, thereby increasing recombination and suppressing the extraction of free charges.rnBy investigating the effect of different dye structures and physical properties on charge generation and recombination, design rules and guidelines for the further advancement of solid-state dye-sensitized solar cells are proposed.rnFinally, a spectroscopic study on polymer:ZnO bulk heterojunction hybrid solar cells, employing different surfactants attached to the metal oxide nanoparticles, was performed to understand the effect of surfactants upon photovoltaic behavior. By applying a parallel pool analysis on the transient absorption data, it is shown that suppressing fast recombination while simultaneously maintaining the exciton splitting efficiency by the right choice of surfactants leads to better photovoltaic performances. Suppressing the fast recombination completely, whilst maintaining the exciton splitting, could lead to a doubling of the power conversion efficiency of this type of solar cell.

A photophysical study of excited state dynamics in donor-acceptor copolymer photovoltaic blends

This thesis deals with the investigation of charge generation and recombination processes in three different polymer:fullerene photovoltaic blends by means of ultrafast time-resolved optical spectroscopy. The first donor polymer, namely poly[N-11"-henicosanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT), is a mid-bandgap polymer, the other two materials are the low-bandgap donor polymers poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole) (PCPDTBT) and poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (PSBTBT). Despite their broader absorption, the low-bandgap polymers do not show enhanced photovoltaic efficiencies compared to the mid-bandgap system.rnrnTransient absorption spectroscopy revealed that energetic disorder plays an important role in the photophysics of PCDTBT, and that in a blend with PCBM geminate losses are small. The photophysics of the low-bandgap system PCPDTBT were strongly altered by adding a high boiling point cosolvent to the polymer:fullerene blend due to a partial demixing of the materials. We observed an increase in device performance together with a reduction of geminate recombination upon addition of the cosolvent. By applying model-free multi-variate curve resolution to the spectroscopic data, we found that fast non-geminate recombination due to polymer triplet state formation is a limiting loss channel in the low-bandgap material system PCPDTBT, whereas in PSBTBT triplet formation has a smaller impact on device performance, and thus higher efficiencies are obtained.rn

Excited-state dynamics in donor-acceptor systems for energy conversion

In dieser Arbeit werden die Dynamiken angeregter Zustände in Donor-Akzeptorsystemen für Energieumwandlungsprozesse mit ultraschneller zeitaufgelöster optischer Spektroskopie behandelt. Der Hauptteil dieser Arbeit legt den Fokus auf die Erforschung der Photophysik organischer Solarzellen, deren aktive Schichten aus diketopyrrolopyrrole (DPP) basierten Polymeren mit kleiner Bandlücke als Elektronendonatoren und Fullerenen als Elektronenakzeptoren bestehen. rnEin zweiter Teil widmet sich der Erforschung von künstlichen primären Photosynthesereaktionszentren, basierend auf Porphyrinen, Quinonen und Ferrocenen, die jeweils als Lichtsammeleinheit, Elektronenakzeptor beziehungsweise als Elektronendonatoren eingesetzt werden, um langlebige ladungsgetrennte Zustände zu erzeugen.rnrnZeitaufgelöste Photolumineszenzspektroskopie und transiente Absorptionsspektroskopie haben gezeigt, dass Singulettexzitonenlebenszeiten in den Polymeren PTDPP-TT und PFDPP-TT Polymeren kurz sind (< 20 ps) und dass in Mischungen der Polymere mit PC71BM geminale Rekombination von gebundenen Ladungstransferzuständen ein Hauptverlustkanal ist. Zudem wurde in beiden Systemen schnelle nichtgeminale Rekombination freier Ladungen zu Triplettzuständen auf dem Polymer beobachtet. Für das Donor-Akzeptor System PDPP5T:PC71BM wurde nachgewiesen, dass die Zugabe eines Lösungsmittels mit hohem Siedepunkt, und zwar ortho-Dichlorbenzol, die Morphologie der aktiven Schicht stark beeinflusst und die Solarzelleneffizienz verbessert. Der Grund hierfür ist, dass die Donator- und Akzeptormaterialien besser durchmischt sind und sich Perkolationswege zu den Elektroden ausgebildet haben, was zu einer verbesserten Ladungsträgergeneration und Extraktion führt. Schnelle Bildung des Triplettzustands wurde in beiden PDPP5T:PC71BM Systemen beobachtet, da der Triplettzustand des Polymers über Laungstransferzustände mit Triplettcharakter populiert werden kann. "Multivariate curve resolution" (MCR) Analyse hat eine starke Intensitätsabhängigkeit gezeigt, was auf nichtgeminale Ladungsträgerrekombination in den Triplettzustand hinweist.rnrnIn den künstlichen primären Photosynthesereaktionszentren hat transiente Absorptionsspektroskopie bestätigt, dass photoinduzierter Ladungstransfer in Quinon-Porphyrin (Q-P) und Porphyrin-Ferrocen (P-Fc) Diaden sowie in Quinon-Porphyrin-Ferrocen (Q-P-Fc) Triaden effizient ist. Es wurde jedoch auch gezeigt, dass in den P-Fc unf Q-P-Fc Systemen die ladungsgetrennten Zustände in den Triplettzustand der jeweiligen Porphyrine rekombinieren. Der ladungsgetrennte Zustand konnte in der Q-P Diade durch Zugabe einer Lewissäure signifikant stabilisiert werden.

Dynamic directed interictal connectivity in left and right temporal lobe epilepsy.

OBJECTIVE There is increasing evidence that epileptic activity involves widespread brain networks rather than single sources and that these networks contribute to interictal brain dysfunction. We investigated the fast-varying behavior of epileptic networks during interictal spikes in right and left temporal lobe epilepsy (RTLE and LTLE) at a whole-brain scale using directed connectivity. METHODS In 16 patients, 8 with LTLE and 8 with RTLE, we estimated the electrical source activity in 82 cortical regions of interest (ROIs) using high-density electroencephalography (EEG), individual head models, and a distributed linear inverse solution. A multivariate, time-varying, and frequency-resolved Granger-causal modeling (weighted Partial Directed Coherence) was applied to the source signal of all ROIs. A nonparametric statistical test assessed differences between spike and baseline epochs. Connectivity results between RTLE and LTLE were compared between RTLE and LTLE and with neuropsychological impairments. RESULTS Ipsilateral anterior temporal structures were identified as key drivers for both groups, concordant with the epileptogenic zone estimated invasively. We observed an increase in outflow from the key driver already before the spike. There were also important temporal and extratemporal ipsilateral drivers in both conditions, and contralateral only in RTLE. A different network pattern between LTLE and RTLE was found: in RTLE there was a much more prominent ipsilateral to contralateral pattern than in LTLE. Half of the RTLE patients but none of the LTLE patients had neuropsychological deficits consistent with contralateral temporal lobe dysfunction, suggesting a relationship between connectivity changes and cognitive deficits. SIGNIFICANCE The different patterns of time-varying connectivity in LTLE and RTLE suggest that they are not symmetrical entities, in line with our neuropsychological results. The highest outflow region was concordant with invasive validation of the epileptogenic zone. This enhanced characterization of dynamic connectivity patterns could better explain cognitive deficits and help the management of epilepsy surgery candidates.