Comparison of Wash-out Properties after Use of the Vital Dye Trypan Blue in the Form of an Ophthalmic Dye and Bound in a Sodium Hyaluronate by Raman Spectroscopy

In cataract surgery, the creation of the anterior capsulorhexis as one of the critical steps is of most importance for the surgical success. In challenging initial situations (e.g. in eyes with pseudoexfoliation syndrome, mature, brunescent cataract, juvenile cataract, corneal opacities, or in post-traumatic and postuveitic cases), vital dyes are used as a routine to increase the visibility and plasticity of the ocular structures in the anterior chamber. The range of applications of the vital dye trypan blue (TB) has expanded considerably in recent years due to its excellent staining properties.1 However, its use in ophthalmology as an effective and useful tool requires that the dye has no adverse effects on the cell structures of the eye. As two laboratory studies on cell cultures showed, the time of exposure to TB plays an important role in addition to concentration.2,3 The in vitro studies by Chang et al. with rabbit corneal endothelial cell cultures, and van Dooren et al.3 demonstrated no toxicity of TB with a maximum concentration of 0.4% after 1 minute in cell cultures of human corneal fibroplasts. A significant toxicity of a TB concentration of 0.01% or higher after exposure was observed. At 24-hour exposure, a TB concentration of 0.005% was found to be the threshold for a significant cytotoxicity index. In principle, it is important to note that trypan blue can be cytotoxic at a certain concentration. Monoazo, the most toxic of known impurities found in trypan blue dyes can be carcinogenic. However, the TB concentrations used in eye surgery do not have undesirable effects on the cell structures of the eye and are therefore generally considered safe.3,4 However, a case report showed a transient retinal toxic reaction in the form of transient visual field defect following the entry of TB into the vitreous body space.5 In modern intraocular procedures viscoelastic substances (OVDs, ophthalmic viscoelastic devices) are widely used. Since their introduction in the 1970s, they have been routinely used in cataract surgery and serve to protect sensitive eye structures from mechanical injuries or to create and maintain anatomical spaces such as the anterior chamber or the capsular bag. They increase safety during the procedure and can also shorten overall surgery time by improving visibility and simplifying some surgical steps for the surgeon.6 A shorter surgery time is associated with a lower degree of trauma and a lower risk of complications, and may ultimately be associated with faster recovery and a better final outcome and satisfaction for the patient. In addition, from an economic point of view, the time saving factor is particularly important for high-volume facilities. After the introduction of Healon® in 1979, sodium hyaluronate became the most widely used biopolymer for OVDs in intraocular surgery. Since then, the pharmacological, physiological, and clinical aspects of sodium hyaluronate for ophthalmic applications have been assessed in a large number of studies.7,8 Recently, a combination of a viscoelastic with the vital dye TB has been introduced (Pe-Ha-Blue®PLUS, Albomed, Schwarzenbruck, Germany) and has already been clinically investigated in a prospective case series of 52 eyes with pseudoexfoliation syndrome.6 In addition to a significantly shorter surgery time (due to fewer individual surgical steps) with cost- and safety-relevant advantages of Pe-Ha-Blue®PLUS compared to separate administration of OVD (POLY-HYL® 1. 6%; Polytech Domilens GmbH) and TB (Vision Blue®; DORC, Holland/Blue Color Caps®), the surgeon gains better control over whether the OVD is removed completely at the end of surgery by using the blue OVD. This should also reduce postoperative complications such as hypertension due to OVD residues remaining in the eye. The aim of the present in vitro study was to determine by Raman spectroscopy the amount of residue of the TB dye that remains on a slide during the routine application of two commercial products (TB dye Vision Blue® and Pe-Ha-Blue®PLUS). In Raman spectroscopy, the interaction of light and matter is used to investigate, for example, the properties of a material or to enable the microscopic examination of materials. Excited by monochromatic light, the sample emits scattered light with a specific frequency shift. The frequency shift (the so-called Raman shift) contain information about the vibrational states of the molecules and thus about the chemical composition and structure of the sample. This phenomenon was discovered by Sir C. V. Raman in the early 20th century. Since the beginning of the 20th century, the method, today mostly stimulated by a laser light source, is widely used in fields such as industry, chemistry, archaeology or for the qualitative and quantitative analysis of products in the pharmaceutical industry

Persistent and reversible solid iodine electrodeposition in nanoporous carbons

Aqueous iodine based electrochemical energy storage is considered a potential candidate to improve sustainability and performance of current battery and supercapacitor technology. It harnesses the redox activity of iodide, iodine, and polyiodide species in the confined geometry of nanoporous carbon electrodes. However, current descriptions of the electrochemical reaction mechanism to interconvert these species are elusive. Here we show that electrochemical oxidation of iodide in nanoporous carbons forms persistent solid iodine deposits. Confinement slows down dissolution into triiodide and pentaiodide, responsible for otherwise significant self-discharge via shuttling. The main tools for these insights are in situ Raman spectroscopy and in situ small and wide-angle X-ray scattering (in situ SAXS/WAXS). In situ Raman confirms the reversible formation of triiodide and pentaiodide. In situ SAXS/WAXS indicates remarkable amounts of solid iodine deposited in the carbon nanopores. Combined with stochastic modeling, in situ SAXS allows quantifying the solid iodine volume fraction and visualizing the iodine structure on 3D lattice models at the sub-nanometer scale. Based on the derived mechanism, we demonstrate strategies for improved iodine pore filling capacity and prevention of self-discharge, applicable to hybrid supercapacitors and batteries

Author Correction: Persistent and reversible solid iodine electrodeposition in nanoporous carbons

Correction to: Nature Communications https://doi.org/10.1038/s41467-020-18610-6, published online 24 September 2020

GREENET - An Early Stage Training Network in Enabling Technologies for Green Radio

International audienceIn this paper, we describe GREENET (an early stage training network in enabling technologies for green radio), which is a new project recently funded by the European Commission under the auspices of the 2010 Marie Curie People Programme. Through the recruitment and personalized training of 17 Early Stage Researchers (ESRs), in GREENET we are committed to the development of new disruptive technologies to address all aspects of energy efficiency in wireless networks, from the user devices to the core network infrastructure, along with the ways the devices and equipment interact with one another. Novel techniques at the physical, link, and network layers to reduce the energy consumption and carbon footprint of 4G devices will be investigated, such as Spatial Modulation (SM) for Multiple-Input-Multiple-Output (MIMO) systems, Cooperative Automatic Repeat reQuest (C-ARQ) protocols, and Network Coding (NC) for lossy networks. Furthermore, cooperation and cognition paradigms will be exploited as additional assets to improve the energy efficiency of wireless networks with the challenging but indispensable constraint of optimizing the system capacity without degrading the user's Quality-of-Service (QoS)

Immobilization of Polyiodide Redox Species in Porous Carbon for Battery-Like Electrodes in Eco-Friendly Hybrid Electrochemical Capacitors

Hybrid electrochemical capacitors have emerged as attractive energy storage option, which perfectly fill the gap between electric double-layer capacitors (EDLCs) and batteries, combining in one device the high power of the former and the high energy of the latter. We show that the charging characteristics of the positive carbon electrode are transformed to behave like a battery operating at nearly constant potential after it is polarized in aqueous iodide electrolyte (1 mol L−1 NaI). Thermogravimetric analysis of the positive carbon electrode confirms the decomposition of iodides trapped inside the carbon pores in a wide temperature range from 190 °C to 425 °C, while Raman spectra of the positive electrode show characteristic peaks of I3− and I5− at 110 and 160 cm−1, respectively. After entrapment of polyiodides in the carbon pores by polarization in 1 mol L−1 NaI, the positive electrode retains the battery-like behavior in another cell, where it is coupled with a carbon-based negative electrode in aqueous NaNO3 electrolyte without any redox species. This new cell (the iodide-ion capacitor) demonstrates the charging characteristics of a hybrid capacitor with capacitance values comparable to the one using 1 mol L−1 NaI. The constant capacitance profile of the new hybrid cell in aqueous NaNO3 for 5000 galvanostatic charge/discharge cycles at 0.5 A g−1 shows that iodide species are confined to the positive battery-like electrode exhibiting negligible potential decay during self-discharge tests, and their shuttling to the negative electrode is prevented in this system

Influence of environmentally affected hole-transport layers on spatial homogeneity and charge-transport dynamics of organic solar cells

After the efficiency of organic photovoltaic (OPV) cells achieved more than 10%, the control of stability and degradation mechanisms of solar cells became a prominent task. The improvement of device efficiency due to incorporation of a hole-transport layer (HTL) in bulk-heterojunction solar cells has been extensively reported. However, the most widely used HTL material, PEDOT:PSS is frequently suspected to be the dominating source for devices instability under environmental conditions. Thereby effects like photooxidation and electrode corrosion are often reported to shorten device lifetime. However, often in environmental device studies, the source of degradation, whether being from the HTL, the active layer or the metal cathode are rather difficult to distinguish, because the external diffusion of oxygen and water affects all components. In this study, different HTLs, namely prepared from traditional PEDOT:PSS and also two types of molybdenum trioxide (MoO3), are exposed to different environments such as oxygen, light or humidity, prior to device finalization under inert conditions. This allows investigating any effects within the HTL and from reactions at its interface to the indium-tin-oxide electrode or the active layer. The surface and bulk chemistry of the exposed HTL has been monitored and discussed in context to the observed device physics, dynamic charge transport and spatial performance homogeneity of the according OPV device. The results show that merely humidity-exposure of the HTL leads to decreased device performance for PEDOT:PSS, but also for one type of the tested MoO3. The losses are related to the amount of absorbed water in the HTL, inducing loss of active area in terms of interfacial contact. The device with PEDOT:PSS HTL after humid air exposure showed seriously decreased photocurrent by micro-delamination of swelling/shrinkage of the hygroscopic layer

Persistent and Reversible Solid Iodine Electrodeposition in Nanoporous Carbons

Aqueous iodine based electrochemical energy storage is considered a potential candidate to improve sustainability and performance of current battery and supercapacitor technology. It harnesses the redox activity of iodide, iodine and polyiodide species in the confined geometry of nanoporous carbon electrodes. However, current descriptions of the electrochemical reaction mechanism to interconvert these species are elusive. Here we show that in nanoporous carbons electrochemical oxidation of iodide forms persistent solid iodine deposits. Confinement slows down dissolution into triiodide and pentaiodide, responsible for otherwise significant self-discharge via shuttling. The main tools for these insights are in situ Raman spectroscopy and in situ small and wide angle X-ray scattering (in situ SAXS/WAXS). In-situ Raman confirms the reversible formation of triiodide and pentaiodide. In situ SAXS/WAXS indicates remarkable amounts of solid iodine deposited in the carbon nanopores. Combined with stochastic modelling, in situ SAXS allows quantifying the solid iodine volume fraction and visualizing the iodine structure on 3D lattice models at the sub-nanometer scale. Based on the derived mechanism we demonstrate strategies for improved iodine pore filling capacity and prevention of self-discharge, applicable to hybrid supercapacitors and batteries.<br /

Experimental identification of the impact of direct internal and external methane reforming on SOFC by detailed online monitoring and supporting measurements

Solid Oxide Fuel Cells (SOFCs) are able to use biogas or natural gas with its main compound methane as fuel but utilization of methane bears risks which can lead to early performance loss. Application of a suitable type of methane reforming as well as online monitoring tools and a holistic knowledge about possible degradation mechanisms can limit degradation rates. Here, we compare direct internal reforming and external methane reforming on a large planar SOFC with an active area of at different operating temperatures and methane flow rates. To do so, the measured temperature distribution, applied electrochemical impedance spectroscopy and its advanced tool distribution of relaxation times (DRT) as well as results from post mortem microscopic analysis are used. We observed that the ohmic resistance and high frequency peaks in the DRT spectra seem to be influenced not only by the average cell temperature but also by direct internal reforming (DIR) conditions. Furthermore, we observed that high temperature gradients induced by DIR could lead to or accelerate damages of the cells structure and the sealing. The results presented in this work are useful to control or manage safe SOFC operation with C containing fuels for real world SOFC applications

Influence of Environmentally Affected Hole-Transport Layers on Spatial Homogeneity and Charge-Transport Dynamics of Organic Solar Cells

After organic photovoltaic (OPV) cells achieved efficiency of more than 10%, the control of stability and degradation mechanisms of solar cells became a prominent task. The increase of device efficiency due to incorporation of a hole-transport layer (HTL) in bulk-heterojunction solar cells has been extensively reported. However, the most widely used HTL material, poly­(3,4-ethylenedioxythiophene):poly­(styrenesulfonate) (PEDOT:PSS), is frequently suspected to be the dominating source for device instability under environmental conditions. Thereby, effects like photooxidation and electrode corrosion are often reported to shorten device lifetime. However, often in environmental device studies, the source of degradation, whether being from the HTL, the active layer, or the metal cathode is rather difficult to distinguish because the external diffusion of oxygen and water affects all components. In this study, different HTLs, namely, those prepared from traditional PEDOT:PSS and also two types of molybdenum trioxide (MoO₃) are exposed to different environments, such as oxygen, light, or humidity, prior to device finalization under inert conditions. This allows investigating any effects within the HTL and from reactions at its interface to the indium tin oxide electrode or the active layer. The surface and bulk chemistry of the exposed HTL has been monitored and discussed in context to the observed device physics, dynamic charge transport, and spatial performance homogeneity of the corresponding OPV device. The results show that merely humidity exposure of the HTL leads to decreased device performance for PEDOT:PSS, but also for one type of the tested MoO₃. The losses are related to the amount of absorbed water in the HTL, inducing loss of active area in terms of interfacial contact. The device with PEDOT:PSS HTL after humid air exposure showed seriously decreased photocurrent by microdelamination of swelling/shrinkage of the hygroscopic layer. The colloidal MoO₃ with water-based precursor solution presents slight decay of solar cell performance, also here caused by swelling/shrinking reaction, but by a combination of in-plane particle contact and resistance scaling with particle expansion. However, the device with quasi-continuous and alcohol-based MoO₃ showed unharmed stable electrical performance