Both hemoglobin and hemin cause damage to retinal pigment epithelium through the iron ion accumulation.

Subretinal hemorrhages result in poor vision and visual field defects. During hemorrhage, several potentially toxic substances are released from iron-based hemoglobin and hemin, inducing cellular damage, the detailed mechanisms of which remain unknown. We examined the effects of excess intracellular iron on retinal pigment epithelial (RPE) cells. A Fe2+ probe, SiRhoNox-1 was used to investigate Fe2+ accumulation after treatment with hemoglobin or hemin in the human RPE cell line ARPE-19. We also evaluated the production of reactive oxygen species (ROS) and lipid peroxidation. Furthermore, the protective effect of-an iron chelator, 2,2'-bipyridyl (BP), and ferrostatin-1 (Fer-1) on the cell damage, was evaluated. Fe2+ accumulation increased in the hemoglobin- or hemin-treated groups, as well as intracellular ROS production and lipid peroxidation. In contrast, BP treatment suppressed RPE cell death, ROS production, and lipid peroxidation. Pretreatment with Fer-1 ameliorated cell death in a concentration-dependent manner and suppressed ROS production and lipid peroxidation. Taken together, these findings indicate that hemoglobin and hemin, as well as subretinal hemorrhage, may induce RPE cell damage and visual dysfunction via intracellular iron accumulation.

An Aqueous Redox Flow Battery Using CO2 as an Active Material with a Homogeneous Ir Catalyst.

For the application of CO2 as an energy storage material, a H2 storage system has been proposed based on the interconversion of CO2 and formic acid (or formate). However, energy losses are inevitable in the conversion of electrical energy to H2 as chemical energy (≈70 % electrical efficiency) and H2 to electrical energy (≈40 % electrical efficiency). To overcome these significant energy losses, we developed a system based on the interconversion of CO2 and formate for the direct storage and generation of electricity. In this paper, we report an aqueous redox flow battery system using homogeneous Ir catalysts with CO2 -formate redox pair. The system exhibited a maximum discharge capacity of 10.5 mAh (1.5 Ah L-1 ), capacity decay of 0.2 % per cycle, and total turnover number of 2550 after 50 cycles. During charging-discharging, in situ fluorescence X-ray absorption fine structure spectroscopy based on an online setup indicated that the active species was in a high valence state of IrIV .

Structural and Functional Change in Albino Rat Retina Induced by Various Visible Light Wavelengths.

The effects of visible light, from short to long wavelengths, on the retina were investigated functionally and histologically. The left eyes of Sprague-Dawley albino rats (6-weeks old, n = 6 for each wavelength) were exposed to seven narrow-band wavelengths (central wavelengths, 421, 441, 459, 501, 541, 581, and 615 nm) with bandwidths of 16 to 29 nm (half bandwidth, ±8-14.5 nm) using a xenon lamp source with bandpass filters at the retinal radiant exposures of 340 and 680 J/cm2. The right unexposed eyes served as controls. Seven days after exposure, flash electroretinograms (ERGs) were recorded, and the outer nuclear layer (ONL) thickness was measured. Compared to the unexposed eyes, significant reductions in the a- and b-wave ERG amplitudes were seen in eyes exposed to 460-nm or shorter wavelengths of light. The ONL thickness near the optic nerve head also tended to decrease with exposure to shorter wavelengths. The decreased ERG amplitudes and ONL thicknesses were most prominent in eyes exposed to 420-nm light at both radiant exposures. When the wavelengths were the same, the higher the amount of radiant exposure and the stronger the damage. Compared to the unexposed eyes, the a- and b-waves did not decrease significantly in eyes exposed to 500-nm or longer wavelength light. The results indicate that the retinal damage induced by visible light observed in albino rats depends on the wavelength and energy level of the exposed light.

Carteolol hydrochloride reduces visible light-induced retinal damage in vivo and BSO/glutamate-induced oxidative stress in vitro.

The purpose of this study was to determine whether carteolol eye drops, a ß-adrenoceptor antagonist used as an intraocular hypotensive agent, has protective effects against the light-induced oxidative stress in retina. Dark-adapted pigmented rats were pre-treated with topical carteolol ophthalmic solution or saline and then exposed to visible light. The effects on electroretinogram (ERG), morphology, oxidative stress, and expression of mRNAs in the retinas were determined. The l-buthionine-(S,R)-sulfoximine (BSO)/glutamate-induced oxidative stress in 661 W cells, a murine photoreceptor cell line, was evaluated by cell death assays, production of reactive oxygen species (ROS), and activation of caspase. In vivo studies showed that exposure to light caused a decrease in the amplitudes of ERGs and the outer nuclear layer (ONL) thickness and an increase of the 8-hydroxy-2'-deoxyguanosine (8-OHdG)-positive cells in the ONL. These changes were significantly reduced by pre-treatment with carteolol. Carteolol also significantly up-regulated the mRNA levels of thioredoxin 1 and glutathione peroxidase 1 compared to saline-treated group. Moreover, carteolol and timolol, another ß-adrenoceptor antagonist, significantly inhibited BSO/glutamate-induced cell death and reduced caspase-3/7 activity and ROS production in vitro. Therefore, carteolol could protect retina from light-induced damage with multiple effects such as enhancing the antioxidative potential and decreasing the intracellular ROS production.

Estimations of Retinal Blue-Light Irradiance Values and Melatonin Suppression Indices Through Clear and Yellow-Tinted Intraocular Lenses.

Spectral transmittance values in the wavelength range of 300 to 800 nanometers were measured using a spectrophotometer for 18 intraocular lenses (IOLs) including clear (ZCB00) and yellow-tinted (ZCB00V, both from AMO Japan) IOLs with three different lens powers. Also measured were the blue-light irradiance (BLI) values, which might reflect retinal damage caused by sunlight, and the melatonin suppression indices (MSIs), which might reflect the nonvisual photoreception function, through these IOLs. The BLIs (in mWcm-2) calculated were 7.62, 7.50, and 7.46 for the +10-diopter (D), +20-D, and +30-D ZCB00 IOLs, respectively; 4.10, 3.92, and 4.00 for the +10-D, +20-D, and +30-D ZCB00V IOLs, respectively; 5.76 for phakic eyes; and 15.00 for aphakic eyes. The MSIs (in mWcm-2sr-1) calculated were 1.18, 1.19, and 1.18 for the +10-D, +20-D, and +30-D ZCB00 IOLs, respectively; 0.98, 0.94, and 0.95 for the +10-D, +20-D, and +30-D ZCB00V IOLs, respectively; 1.03 for phakic eyes; and 1.21 for aphakic eyes. The data from the six clear IOLs (SA60AT, Alcon Japan; VA-60BBR, Hoya; AU6 K, Kowa, N4-18B, Nidek; X-60, Santen; KS-3Ai, Staar Japan) and seven yellow-tinted IOLs (SN60AT; YA-60BBR, Hoya; AU6N, Kowa; N4-18YG, Nidek; NX-60, Santen; KS-AiN, Staar Japan; XY-1, Hoya) reported previously also were discussed. Compared to aphakic eyes, ZCB00 and ZCB00V IOLs reduce the BLI values by 49-50% and 73-74%, respectively; and currently available ultraviolet-blocking clear and yellow-tinted IOLs reduce the BLI values by 43-82%, respectively. Yellow-tinted IOLs absorb more circadian rhythm-associated light than clear IOLs. Although the data presented in this study cannot be applied directly to IOL implanted in patients, the balance between photoprotection and photoreception must be considered when using IOLs in a clinical setting.

Axonal protection by thioredoxin-1 with inhibition of interleukin-1ß in TNF-induced optic nerve degeneration.

Interleukin (IL)-1ß, a proinflammatory cytokine, is a key mediator in several acute and chronic neurological diseases. Thioredoxin-1 (TRX1) acts as an antioxidant and plays a protective role in certain neurons. We examined whether exogenous TRX1 exerts axonal protection and affects IL-1ß levels in tumor necrosis factor (TNF)-induced optic nerve degeneration in rats. Immunoblot analysis showed that IL-1ß was upregulated in the optic nerve after intravitreal injection of TNF. Treatment with recombinant human (rh) TRX1 exerted substantial protective effects against TNF-induced axonal loss. The increase in the IL-1ß level in the optic nerve was abolished by rhTRX1. Treatment with rhTRX1 also significantly inhibited increased glial fibrillary acidic protein (GFAP) levels induced by TNF. Immunohistochemical analysis showed substantial colocalization of IL-1ß and GFAP in the optic nerve after TNF injection. These results suggest that IL-1ß is upregulated in astrocytes in the optic nerve after TNF injection and that exogenous rhTRX1 exerts axonal protection with an inhibitory effect on IL-1ß.

A case report of progressive obstruction of Ex-PRESS miniature glaucoma shunt after transient flat anterior chamber and treatment using Nd:YAG laser.

BACKGROUND: We report a case of Ex-PRESS miniature glaucoma shunt obstruction resulting from progressive iris synechial formation after transient anterior chamber shallowing. CASE PRESENTATION: A 68-year-old woman with pseudoexfoliation glaucoma in her right eye underwent filtration surgery with implantation of the Ex-PPESS shunt (model P-50, Alcon Japan, Tokyo, Japan) in combination with intra-surgical 0.04% mitomycin C use. After the anterior chamber injection of viscoelastic material and 100% sulfur hexafluoride gas for treatment of early postoperative over filtration, the intraocular pressure (IOP) was controlled between 9 and 12 mmHg. On postoperative day 121, gonioscopy showed that synechial formation around the shunt obstructed the axial port leaving the relief port opened. On postoperative day 274, the intraocular pressure increased to 40 mmHg and synechiae obstructed both the axial and relief ports. Dispersion of iris tissue by neodymium:yttrium-aluminium-garnet (Nd:YAG) laser (2 mJ, one shot to each port) opened both ports and immediately lowered the IOP, leaving peripheral anterior synechiae around the shunt. Up to postoperative day 400, the IOP was controlled between 13 and 15 mmHg, and the cystic bleb was maintained. CONCLUSION: The synechiae formed gradually extends around the shunt's shaft and can result in later external obstruction of the relief port. The current case requires further follow-up since synechiae remaining around the shaft can cause future obstruction. We emphasize the fact that, if the iris synechiae to the shunt once formed, it can progress and obstruct the shunt ports later.

Ab initio studies on the proton dissociation and infrared spectra of sulfonated poly(ether ether ketone) (SPEEK) membranes.

SPEEK is known to possess high proton conductivity at high water content, being comparable with other popular membranes used in fuel cells, such as Nafion and sulfonated polyethersulfone (SPES). However, much less is known about its fundamental properties, including the status of proton dissociation and spectral features. In this work, the properties of two model molecules of SPEEK, M1 (20 atoms), M2 (50 atoms) and their hydrated systems, M1 + nH2O and M2 + nH2O (n = 1-9), have been investigated using static electronic structure calculations and the ab initio molecular dynamics (MD) method. Optimized structures for all of the systems and the trajectories of M1 + nH2O (n = 3-6) at finite temperatures have been computed using density functional theory at the B3LYP level of theory. Proton dissociation has been discussed in detail, especially for n = 3 and n = 4. In addition, the infrared spectra of SPEEK and its hydrated systems have been studied using a combination of theory and experiment. The characteristic bands of SPEEK and the surrounding water clusters have been assigned with emphasis on their relationship with the degree of proton dissociation. We have found that the hydronium ion stretching modes, which appear in the 2000-3000 cm(-1) region in static electronic structure calculations, are not observed experimentally. This discrepancy is explained by the stationary structure and the temperature effect.

Effect of age and other factors on macular pigment optical density measured with resonance Raman spectroscopy.

BACKGROUND: Macular pigment is a defense system against phototoxic damage of the retina by visible light. It is still under debate whether or not macular pigment optical density (MPOD) levels decline with age, because the age effect varied depending on the technique used to measure MPOD levels. Resonance Raman spectroscopy (RRS) is an objective method to measure MPOD, and studies using RRS showed a drastic age-related decline of MPOD levels; however, since RRS measurements are influenced by cataracts, it has been argued that the age-related decline of RRS measurements is an artifact from lens changes in aged subjects. In the present study, MPOD levels were measured with RRS in pseudophakic eyes, and the effects of age and other factors on MPOD levels were investigated. METHODS: The subjects included 144 patients with no fundus disorders who received cataract surgery with untinted intraocular lens implantation. MPOD levels were measured in 144 eyes using integral RRS 1 day post surgery. Factors potentially associated with MPOD levels such as age, gender, smoking habits, body mass index, diabetes, glaucoma, axial length, pupil diameter, spherical equivalent refractive error, and foveal thickness were examined by multiple regression analysis. RESULTS: The macular pigment RRS levels ranged from 776 to 11,815 Raman counts, with an average level of 4,375 ± 1,917 (standard deviation [SD]) Raman counts. Multiple regression analysis revealed that age and axial length were significantly correlated with low MPOD values (regression coefficient of -59 for age and -404 for axial length, respectively). No significant correlations were observed for other factors. CONCLUSIONS: After removing the potentially confounding effect of age-related lens yellowing on the RRS measurements, age remained a significant patient parameter for lowered MPOD levels. MPOD levels were found to decline by more than 10 % each decade. Axial length was also a negative predictor of MPOD levels. Since the present study included only patients aged 50 years and older, the effects of age and other factors on MPOD levels for younger subjects remain unknown.

Construction and characterization of molecular nonwoven fabrics consisting of cross-linked poly(γ-methyl-L-glutamate).

Molecular nonwoven fabrics in the form of ultrathin layer-by-layer (LbL) helical polymer films with covalent cross-linking were assembled on substrates by an alternate ester-amide exchange reaction between poly(γ-methyl L-glutamate) (PMLG) and cross-linking agent ethylene diamine or 4,4'-diamino azobenzene. The regular growth of helical monolayers without excessive adsorption and the formation of amide bonds were confirmed by ultraviolet-visible (UV-vis) spectrophotometry, quartz crystal microbalance (QCM), ellipsometry, and infrared reflection-absorption spectroscopy (IR-RAS) measurements. Nanostructures with high uniformity and ultrathin films with few defects formed by helical rod segments of PMLG were characterized by atomic force microscopy (AFM) and Kelvin probe force microscopy (KFM).

Effect of interface on surface morphology and proton conduction of polymer electrolyte thin films.

To understand the relationship between surface morphology and proton conduction of polymer electrolyte thin films, perfluorinated ionomer Nafion® thin films were prepared on different substrates such as glassy carbon (GC), hydrophilic-GC (H-GC), and platinum (Pt) as models for the ionomer film within a catalyst layer. Atomic force microscopy coupled with an electrochemical (e-AFM) technique revealed that proton conduction decreased with film thickness; an abrupt decrease in proton conductance was observed when the film thickness was less than ca. 10 nm on GC substrates in addition to a significant change in surface morphology. Furthermore, thin films prepared on H-GC substrates with UV-ozone treatment exhibited higher proton conduction than those on untreated GC substrates. However, Pt substrates exhibited proton conduction comparable to that of GCs for films thicker than 20 nm; a decrease in proton conduction was observed at ∼5 nm thick film but was still much higher than for carbon substrates. These results indicate that the number of active proton-conductive pathways and/or the connectivity of the proton path network changed with film thickness. The surface morphology of thinner films was significantly affected by the film/substrate interface and was fundamentally different from that of the bulk thick membrane.

Electrochemistry in bicontinuous microemulsions derived from two immiscible electrolyte solutions for a membrane-free redox flow battery.

HYPOTHESES: Bicontinuous microemulsions (BMEs) have attracted attention as unique heterogeneous mixture for electrochemistry. An interface between two immiscible electrolyte solutions (ITIES) is an electrochemical system that straddles the interface between a saline and an organic solvent with a lipophilic electrolyte. Although most BMEs have been reported with nonpolar oils, such as toluene and fatty acids, it should be possible to construct a sponge-like three-dimensionally expanded ITIES comprising a BME phase. EXPERIMENTS: Dichloromethane (DCM)-water microemulsions stabilized by a surfactant were investigated in terms of the concentrations of co-surfactants and hydrophilic/lipophilic salts. A Winsor III microemulsion three-layer system, consisting of an upper saline phase, a middle BME phase, and a lower DCM phase, was prepared, and electrochemistry was conducted in each phase. FINDINGS: We found the conditions for ITIES-BME phases. Regardless of where the three electrodes were placed in the macroscopically heterogeneous three-layer system, electrochemistry was possible, as in a homogeneous electrolyte solution. This indicates that the anodic and cathodic reactions can be divided into two immiscible solution phases. A redox flow battery comprising a three-layer system with a BME as the middle phase was demonstrated, paving the way for applications such as electrolysis synthesis and secondary batteries.

Redox Reaction in Ti-Mn Redox Flow Battery Studied by X-ray Absorption Spectroscopy.

We performed X-ray absorption studies for the electrolytes of a Ti-Mn redox flow battery (RFB) to understand the redox reaction of the Ti/Mn ions and formation of precipitates in charged catholyte, because suppression of the disproportionation reaction is a key to improve the cyclability of Ti-Mn RFB and enhance the energy density. Hard X-ray absorption spectroscopy with a high transmittance and soft X-ray absorption spectroscopy to directly observe the 3d orbitals were complementarily employed. Moreover, the Ti/Mn 3d electronic structure for each precipitate and solution in the charged catholyte was investigated by using scanning transmission X-ray microscopy: the valence of Mn in the precipitate is mostly attributed to 4+, and the solution includes only Mn2+ . This charge disproportionation reaction should occur after the Mn ions in the catholyte should be oxidized from Mn2+ to Mn3+ by charge.

Vibrational analysis of side chain model compounds of perfluorinated alkyl sulfonic Acid ionomers.

Perfluorinated sulfonic acid ionomers have been extensively studied in particular for application to polymer electrolyte fuel cells as they show high proton conductivity at relatively low humidity. While vibrational spectroscopic methods have been successfully applied to investigate dissociation and hydration of their acid sites, the bands in the measured spectra have still been empirically assigned to local vibrations. We performed vibrational analysis of model compounds of the side chains of perfluorinated sulfonic acid ionomers by hybrid DFT calculation. On the basis of mean absolute errors in bond lengths and vibrational frequencies of triflic acid (CF(3)SO(3)H) calculated with various hybrid functionals and basis sets, PBE0/6-311G* gave the best results within affordable computational times and was applied for the model compounds. Most of the observed bands in the ATR-IR spectra of the model compounds were successfully reproduced by calculation of their dissociated sulfonate anions. New assignments were proposed for characteristic two peaks at around 970 and 1060 cm(-1) as combinations of SO(3) symmetric stretch and adjacent CCO bend in two opposite phases. Vibrational bands of doubly hydrogen-bonded acid dimer were also identified in the IR spectrum of "as-received" PFEESA which was not hydrated. These results would provide a new basis for application of vibrational spectroscopy of perfluorinated sulfonic acid ionomers on their structural changes with degree of hydration.

[Fundus photoplanimetry of the optic nerve head in the Sakurae Study].

PURPOSE: To explore the fundus photoplanimetric distribution of the optic nerve head in a population-based health survey conducted in Sakurae area, in Shimane, Japan(the Sakurae Study). METHODS: After the exclusion of poor quality images from the 1660 right eye-fundus photos obtained from the Sakurae Study in 1991, 1583 photos were digitized, and then were planimetrically analyzed using a newly developed computer software, CDSketch. The parameters calculated included vertical and horizontal cup-to-disc (C/D) ratios, superior and inferior rim-to-disc (R/D) ratios, disc and cup vertical-to-horizontal (V/H) ratios, and disc-macular distance-to-disc diameter (DM/DD) ratio. RESULTS: For the vertical and horizontal C/D, superior and inferior R/D, disc and cup V/H, and DM/DD ratios, mean values were calculated to be 0.58, 0.59, 0.20, 0.18, 1.11, 1.09, 2.60, respectively, and median values were calculated to be 0.58, 0.59, 0.19, 0.18, 1.11, 1.09, 2.57, respectively; no parameter showed any remarkably skewed distribution. The vertical C/D ratio was positively correlated with the cup V/H ratio, but was not correlated with the disc V/ H ratio. The vertical and horizontal C/D, and the disc and cup V/H ratios were negatively correlated with the DM/DD ratio. CONCLUSIONS: The distributions of the various optic nerve head parameters and their correlations in the Sakurae Study are reported. Both mean and median values of the vertical C/D ratio were approximately 0.6 in this study population. These values were larger than the previously reported C/D ratios obtained by direct ophthalmoscopic observations and/or by subjective methods.

Analysis of LOXL1 gene variants in Japanese patients with branch retinal vein occlusion.

PURPOSE: Previous studies have described a possible association between exfoliation syndrome (EX) and various ocular and systemic vascular disorders; however, the association between EX and branch retinal vein occlusion (BRVO) remains unclear. Because slit-lamp examination may overlook latent deposits of exfoliation materials, an ocular biopsy is usually needed for a precise diagnosis. We evaluated a possible association between EX and BRVO using lysyl oxidase-like 1 (LOXL1) gene variants as alternative markers for EX. METHODS: Allelic and genotypic frequencies of three LOXL1 variants (rs1048661, rs3825942, and rs2165241) were determined for 78 consecutive Japanese patients with BRVO (11 patients with exfoliation syndrome [EX+], 67 patients without exfoliation syndrome [EX-]), and 158 patients with cataract without EX (CT) as controls. RESULTS: The rs1048661 variant differed between the BRVO and CT groups in allelic and genotypic frequencies (p=0.0137 and p=0.0203, respectively). Subgroup analysis, compared to the CT group, showed that BRVO EX+ had significantly different allelic and genotypic frequencies of rs1048661 (p=0.00011 and p=0.000189, respectively), while BRVO EX- did not (p=0.175 and p=0.288, respectively). The frequencies of rs3825942 and rs2165241 did not differ between the BRVO and CT groups. CONCLUSIONS: No association was found between BRVO and EX if LOXL1 variants were used as disease markers for clinically undetectable EX. The results suggested that LOXL1 variants, well established markers for EX, are not likely genetic markers for BRVO in Japanese subjects.

Macular pigment changes in pseudophakic eyes quantified with resonance Raman spectroscopy.

PURPOSE: We examined changes in macular pigment optical density (MPOD) levels after cataract surgery and compared the MPOD between eyes with clear intraocular lenses (IOLs) and yellow-tinted IOLs. DESIGN: Prospective, comparative case series. PARTICIPANTS: The MPOD levels were measured in 480 eyes of 337 patients after cataract surgery. Among them, the data from 259 eyes (clear IOL group, 121 eyes; yellow-tinted IOL group, 138 eyes) of 259 Japanese patients were selected for statistical analyses on the basis of the inclusion criteria: a postoperative visual acuity (VA) of ≥0.8 and no fundus diseases. Only 1 eye of each patient was enrolled. Patients provided informed consent to participate in this study on the basis of the approval of the institutional review board before surgery. METHODS: The patients selected the type of IOL to be implanted. The MPOD levels were measured using resonance Raman spectroscopy on day 1 (baseline value); months 1, 3, and 6; and years 1 and 2 postoperatively. MAIN OUTCOME MEASURES: The difference in MPOD levels between the IOL groups was analyzed by unpaired t tests. The following parameters were analyzed by multiple regression analysis: age, gender, body mass index (BMI), smoking history, glaucoma, diabetes, preoperative VA, preoperative refractive error, and IOL power and type. RESULTS: We found no significant differences in the baseline characteristics between the 2 groups. Until 6 months postoperatively, the MPOD levels did not differ significantly between the groups. However, from 1 year onward, the levels were significantly higher in the yellow-tinted IOL group compared with the clear IOL group. By multiple regression analysis, 1 day postoperatively, older age and diabetes were correlated with lower MPOD levels; 1 year postoperatively and thereafter, however, lower MPOD levels were correlated with clear IOLs. CONCLUSIONS: Cataract surgery with clear IOLs induced a greater decrease in macular pigment levels compared with yellow-tinted IOLs during a longer follow-up period. These findings agreed with observations that excessive light exposure is associated inversely with MPOD, because clear IOLs transmit higher intensities of blue light than yellow-tinted IOLs.

Retinal risks of high-dose ornithine supplements: a review.

We reviewed the literature on ornithine supplementation and related topics. Nutritionists and physicians have reported that ornithine supplementation is useful. Paediatricians and biochemists have reported that ornithine is supplemented for NH(3) detoxification in the hyperornithinaemia-hyperammonaemia-homocitrullinuria (HHH) syndrome. In contrast, ophthalmic researchers have reported retinotoxicity associated with high-dose ornithine. In vivo and in vitro experiments have shown that high concentrations of ornithine or its metabolites are toxic to the retinal pigment epithelial (RPE) cells. Long-term (exceeding a few years) and high concentrations (exceeding 600 µmol/l) of ornithine in the blood induce retinal toxicity in gyrate atrophy of the choroid and retina (GA). Intermittent high levels of ornithine do not lead to retinal lesions. Constant blood ornithine levels between 250 and 600 µmol/l do not induce retinal lesions or cause a very slowly progressive retinal degeneration. Blood ornithine levels below 250 µmol/l do not produce retinal alteration. We concluded that short-term, low-dose or transient high-dose ornithine intake is safe for the retina; its nutritional usefulness and effect on NH(3) detoxification are supported by many researchers, but the effect may be limited; and long-term, high-dose ornithine intake may be risky for the retina. Patients with GA should avoid taking ornithine; amino acid supplementation should be administered carefully for patients with the HHH syndrome, relatives of patients with GA (heterozygotes) and subjects with RPE lesions; and blood ornithine levels and retinal conditions should be evaluated in individuals taking long-term, high-dose ornithine.

Proton transport properties in an ionic liquid having a hydroxyl group.

An ionic liquid having a hydroxyl group, choline bis(trifluoromethylsulfonyl)amide ([N(111(2OH))][N(Tf)(2)]), was synthesized to investigate the effect of hydroxyl groups on the proton transport. 1,1,1-Trifluoro-N-(trifluoromethylsulfonyl)methanesulfoneamide (HN(Tf)(2)) as a proton source was mixed with the choline derivative at various molar ratios. Their thermal properties, viscosities, and ionic conductivities were investigated. [N(111(2OH))][N(Tf)(2)] showed a melting point at 27 °C, and its thermal stability was higher than 400 °C. The viscosity of [N(111(2OH))][N(Tf)(2)]/HN(Tf)(2) mixtures increased as the acid molar fraction increased. The ionic conductivity of [N(111(2OH))][N(Tf)(2)] was 2.1 × 10(-3) S cm(-1) at 25 °C; the ionic conductivity monotonously decreased as the acid molar fraction increased. There was a clear correlation between the ionic conductivity and the viscosity for the mixtures of the choline derivative and the acid. PFG-NMR measurements were carried out to investigate the diffusion behavior of protons. Although the acid and the hydroxyl group were indistinguishable by (1)H NMR, the self-diffusion coefficient of the (1)H of the hydroxyl group and the acid was larger than those of other (1)H nuclei. This difference suggests that a fast intermolecular proton transfer exists between the hydroxyl group and the acid.

Water Electrolysis Using a Porous IrO2/Ti/IrO2 Catalyst Electrode and Nafion Membranes at Elevated Temperatures.

Porous IrO2/Ti/IrO2 catalyst electrodes were obtained by coating IrO2 on both sides of three types of porous Ti powder sheets (sample 1, sample 2, and sample 3) using different surface treatment methods, and a hydrogen evolution catalyst electrode was obtained by coating Pt/C on carbon gas diffusion layers. A Nafion115 membrane was used as an electrolyte for the membrane electrode assemblies (MEA). Water electrolysis was investigated at cell temperatures up to 150 °C, and the electrical characteristics of the three types of porous IrO2/Ti/IrO2 catalyst electrodes were investigated. The sheet resistance of sample 1 was higher than those of samples 2 and 3, although during water electrolysis, a high current density was observed due to the nanostructure of the IrO2 catalyst. In addition, the structural stabilities of Nafion and Aquivion membranes up to 150 °C were investigated by using small angle X-ray scattering (SAXS). The polymer structures of Nafion and Aquivion membranes were stable up to 80 °C, whereas the crystalline domains grew significantly above 120 °C. In other words, the initial polymer structure did not recover after the sample was heated above the glass transition temperature.