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.

Paraneoplastic Neuromyelitis Optica Spectrum Disorder Related to Glucose-regulated Protein 78 (GRP78) Autoantibodies in a Patient with Lynch Syndrome-associated Colorectal Cancer.

Neuromyelitis optica spectrum disorders have been previously reported in a paraneoplastic context, although there is no clear consensus on their pathogenesis. We herein report a case of aquaporin-4 antibody-positive neuromyelitis optica spectrum disorder in a 64-year-old woman with colorectal cancer. She underwent tumor resection, resulting in serum aquaporin-4 antibody titers subsequently becoming negative. Serum samples were also positive for glucose-regulated protein 78 antibody, which has recently been suggested to be a novel factor in the disruption of the blood-brain barrier. Serological and pathological investigations in this case highlight the role and involvement of aquaporin-4 and glucose-regulated protein 78 antibodies in paraneoplastic conditions.

Vertically Oriented Metallic Heterodimer Array Semiembedded in Flat Conductive Carbon Film for Electrochemical Application.

General synthesis of a highly oriented metallic heterodimer array based on a selective electrodeposition technique onto a metal nanoparticle-embedded carbon film is proposed, which enables the preparation of heterodimers with a wide variety of metal combinations. This method requires no surfactant, capping agent, organic solvent, or heat treatment. As a representative metal combination, a nickel (Ni)/palladium (Pd) heterodimer array was prepared by selective electrodeposition of Ni nanoparticles (Ni NPs) on top of partially exposed Pd NPs embedded in carbon film electrodes fabricated by a cosputtering technique. Such a selective electrodeposition becomes possible by utilizing the difference in electrodeposition overpotentials between carbon and Pd NP surfaces. X-ray photoelectron spectroscopy revealed a charge transfer from Ni NPs to Pd NPs, implying that the catalytic and optical properties can be expected to be controllable. The formed heterodimer array structure was mechanically stable against ultrasonication in ethanol for over 1 h because most parts of the Pd NPs were tightly embedded in the carbon film. After conversion from Ni to nickel hydroxide (Ni(OH)2), the electrode showed high electrocatalytic activity toward glucose oxidation, with a higher turnover rate and lower overpotential compared to Ni(OH)2 electrodeposited on pure carbon film electrodes.

Lipophilic probe behavior in microemulsions evaluated by fluorescence correlation spectroscopy.

We evaluated the dispersion and diffusion of fluorescent-labeled lipophilic vitamin E (VE) in microemulsions (MEs) including water-in-oil (W/O) type ME, oil-in-water (O/W) type ME, and bicontinuous ME (BME), using fluorescence correlation spectroscopy (FCS). We prepared a fluorescent ATTO 488 or BODIPY group labeled VE (VE-ATTO or VE-BODIPY). VE-ATTO possesses lipophilic and hydrophilic parts, while VE-BODIPY consists solely of the lipophilic part. The VE-ATTO dissolved in heptane solution as an oil phase appeared hot pink in color due to the solvatochromism effect under room light and almost no fluorescent signal, which was unlike the VE-ATTO dissolved in ME solutions and all the VE-BODIPY solutions (typical fluorescent green color). The FCS measurement proved that VE-BODIPY diffuses faster than VE-ATTO. This is presumably because the "surfactant-like" VE-ATTO is localized and trapped at the micro-water/micro-oil interface of the MEs, while the VE-BODIPY exists in the ME phase and macro-oil phase with good dispersion. These results demonstrate that FCS is a powerful tool for the rapid evaluation of the lipophilic probe behavior in heterogeneous ME solutions.

Cardioembolic Stroke Due to Cardiac Sarcoidosis Diagnosed by Pathological Evaluation of the Retrieved Thrombus.

A 70-year-old woman undergoing glucocorticoid therapy for cardiac sarcoidosis was brought to our hospital with the sudden onset of right hemiplegia and aphasia. Brain magnetic resonance imaging showed a high diffusion-weighted imaging signal in the left frontotemporal lobe and disruption of blood flow in the M1 segment of the left middle cerebral artery. Hence, she underwent thrombolysis and mechanical thrombectomy, resulting in marked improvement in her neurological symptoms. A pathologic evaluation of the thrombus suggested its cardiogenicity, and the absence of any obvious abnormality other than a left ventricular aneurysm indicated stroke due to a cardioembolic etiology secondary to cardiac sarcoidosis.

Lipophilic Vitamin E Diffusion through Bicontinuous Microemulsions.

We studied the diffusion properties of lipophilic vitamin E (VE) through bicontinuous microemulsions (BME) using both electrochemical and fluorescence correlation spectroscopy (FCS) measurements. We investigated the effect of different composition ratios of micro-water and micro-oil phases in BMEs (W/OBME). When we employed the BME with a lower W/OBME value of 40/60 (oil-rich BME) as an electrolyte solution, we obtained a larger current response from VE at a fluorinated nanocarbon film electrode. Further voltammetric studies revealed that a higher VE diffusion coefficient was observed in the oil-rich BME. The FCS results also exhibited faster diffusion through the oil-rich BME, which played a significant role in accelerating the VE diffusion probably due to the widening of the micro-oil phase pathway in the BME. Moreover, the effect of increasing the VE diffusion was pronounced at the interface between the electrode surface and the BME solution. These results indicate that controlling the conditions of the BME as the measurement electrolyte is very effective for achieving superior electrochemical measurements in a BME.

Hybrid Carbon Film Electrodes for Electroanalysis.

Carbon materials have been widely used for electrochemical analysis and include carbon nanotubes, graphene, and boron-doped diamond electrodes in addition to conventional carbon electrodes, such as those made of glassy carbon and graphite. Of the carbon-based electrodes, carbon film has advantages because it can be fabricated reproducibly and micro- or nanofabricated into electrodes with a wide range of shapes and sizes. Here, we report two categories of hybrid-type carbon film electrodes for mainly electroanalytical applications. The first category consists of carbon films doped or surface terminated with other atoms such as nitrogen, oxygen and fluorine, which can control surface hydrophilicity and lipophilicity or electrocatalytic performance, and are used to detect various electroactive biochemicals. The second category comprises metal nanoparticles embedded in carbon film electrodes fabricated by co-sputtering, which exhibits high electrocatalytic activity for environmental and biological samples including toxic heavy metal ions and clinical sugar markers, which are difficult to detect at pure carbon-based electrodes.

Suppression of Surface Oxygen on Nanocarbon Film Electrodes for Maintaining Electrode Activity.

We investigated sputtered nanocarbon films with respect to the effect of suppressing surface oxygen on their electrochemical properties. The nanocarbon film consisted of nanocrystallites with mixed sp2 and sp3 bonds formed by unbalanced magnetron sputtering. Ultraviolet/ozone (UV/O3) irradiation and electrochemical pretreatment (ECP) were conducted to change the surface oxygen concentration of nanocarbon film. X-ray photoelectron spectroscopy (XPS) measurements revealed that nanocarbon films with different amounts of surface oxygen could be prepared. In addition, we observed no significant increase of the surface roughness (Ra) at the angstrom level after treatments, owing to a stable structure containing 40% of sp3 bonds. The electrode characteristics, including the potential window and electrochemical properties for some redox species, such as Ru(NH3)63+/2+, were investigated. Some electrochemical measurements of zinc ions (Zn2+) and hydrogen peroxide (H2O2) showed that the electrochemical reaction was improved by suppressing the surface oxygen. These results clearly indicated that the low surface oxygen concentration plays an important role in these electrochemical reactions.

Stand-Alone Semi-Solid-State Electrochemical Systems Based on Bicontinuous Microemulsion Gel Films.

Bicontinuous microemulsion (BME)-based hydrogel films were integrated with screen-printed electrodes (SPEs) comprising working, counter, and reference electrodes to form stand-alone, semi-solid-state electrochemical systems that do not require an outer electrolyte solution. The gel network of the BME hydrogel only exists in the microaqueous phase and retains the structure of the entire BME gel. Following gelation, a microaqueous phase with sufficient ionic strength ensured effective ionic conductivity, even in thin gel films. This enabled the electrochemical reaction to proceed using a thin gel film as an electrolyte solution. However, an intact micro-oil phase with no gel network enabled efficient extraction from an external oil solution and exhibited rapid electrochemistry that was comparable to that of a BME solution. Cyclic voltammograms of lipophilic redox species in oil using the gel-integrated SPE system demonstrated successfully in the oil itself and in the air with dropped oil onto the system.

Controlling Surface Oxygen Concentration of a Nanocarbon Film Electrode for Improvement of Target Analytes.

A nanocarbon film consisting of nanocrystallites with mixed sp2 and sp3 bonds formed by unbalanced magnetron sputtering, was studied with respect to changes in the characteristics caused by the surface oxygen concentration. An electrochemical pretreatment (ECP) was conducted to change the surface oxygen concentration of the nanocarbon film. X-ray photoelectron spectroscopy (XPS) measurements revealed that nanocarbon films with different amounts of surface oxygen could be prepared. In addition, we observed no significant increase of surface roughness (Ra) at the angstrom level after ECP, owing to a stable structure containing 40% of sp3 bonds. The electrode characteristics, including the potential window, and electrochemical properties for some redox species, such as Ru(NH3)63+/2+, Fe(CN)63-/4- and some biomolecules, were investigated. The anodic potential limit became wider and ΔEp of Fe(CN)63-/4- became smaller at the treated nanocarbon film electrode than those of the as-deposited nanocarbon film electrode. Based on these results, we realized to measure uridylic acid (UMP) and inosine triphosphate (ITP) with a high oxidation potential by direct oxidation, which was difficult to measure at the as-deposited nanocarbon film electrode.

[Investigation into the Effect of Shitei Extract, a Traditional Chinese Medicine Formulation, on Hiccups].

Hiccups are occasionally experienced by most individuals, and although not life-threatening, they may leadto a decline in quality of life. Shitei extract(shitei, persimmon calyx)may be usedfor the treatment of hiccups. The effects of shitei extract were investigatedin patients admittedto the Japanese RedCross Musashino Hospital between October 2011 andM ay 2016. Numerous prescriptions for shitei extract were reportedin the Department of Respiratory Organs andNeurosurgery. The primary causes of hiccups were chemotherapy andbrain disease. Of 149 patients, 107(71.8%)sufferedfrom hiccups. None of the patients reported adverse events related to the administration of shitei extract. The incidence of hiccups was significantly higher in patients with brain disease(p=0.0075), treatedwith chemotherapy for cancer(p=0.0402), or requiring the insertion of a gastric tube(p=0.0065). Among those treatedwith chemotherapy for cancer, shitei extract was effective against hiccups in 82.0% patients(45 of 55). Furthermore, four patients receivedprophylaxis with shitei extract for the prevention of hiccups after chemotherapy. In conclusion, these results indicate that shitei extract is an effective and safe therapeutic drug for the treatment of hiccups. In particular, shitei extract was effective in the prevention of hiccups after chemotherapy.

Electrochemical performance at sputter-deposited nanocarbon film with different surface nitrogen-containing groups.

Carbon materials containing nitrogen have been extensively studied as electrode materials for use in non-platinum cathodes of fuel cells due to their high electrocatalytic activity for oxygen reduction. The activity is strongly dependent on the structure of surface nitrogen-containing functional groups. Carbon film containing nitrogen is also suitable for analytical applications because of its low background noise and its electrocatalytic activity, which is superior to that of pure carbon film. Here, we fabricated sputter-deposited nanocarbon film with a nitrogen-containing group and estimated the efficacy of a surface nitrogen-containing group for detecting biomolecules. Two types of carbon films, one rich in graphite-like nitrogen-containing bonds and the other rich in pyridine-like bonds, were successfully fabricated without changing their nitrogen concentration, sp2/sp3 ratio or surface flatness. The carbon film rich in pyridine-like bonds shows a positive oxygen reduction peak of about 250 mV compared with pure carbon film and is also 200 mV more positive compared with film with graphite-like nitrogen-containing bonds. This indicates that pyridine-like bonds contribute more effectively to electrocatalytic activity than graphite-like nitrogen-containing bonds. For detecting biomolecules, carbon film rich in pyridine-like bonds also exhibits more negative peak potentials for the oxidation of NADH and l-ascorbic acid, suggesting that carbon film rich in pyridine-like bonds will show improved performance for detecting electroactive biomolecules.

Increased electrode activity during geosmin oxidation provided by Pt nanoparticle-embedded nanocarbon film.

The musty odor compound geosmin was electrochemically detected by using Pt nanoparticle (PtNP)-embedded nanocarbon (Pt-C) films formed with unbalanced magnetron (UBM) co-sputtering. The sputtered Pt components formed NPs (typically 1.53-4.75 nm in diameter) spontaneously in the carbon films, owing to the poor intermiscibility of Pt with carbon. The surface concentrations of PtNPs embedded in the nanocarbon film were widely controllable (Pt = 4.8-35.9 at%) by regulating the target powers of the Pt and carbon individually. The obtained film had a flat surface (Ra = 0.17-0.18 nm) despite the fact the PtNPs were partially exposed at the surface. Compared with a Pt film electrode, some Pt-C films exhibited higher electrode activity against geosmin although the surface Pt concentrations of these Pt-C films were much lower than that of the Pt film electrode, thanks to the wider potential window and lower background current that resulted from the ultraflat and stable carbon-based film prepared by UBM co-sputtering. Computational experiments revealed that the theoretical oxidation potential (Eox) value for geosmin was relatively similar to that obtained in electrochemical experiments using our Pt-C film electrode. Moreover, we also theoretically estimated the possible oxidation site of geosmin molecules and the advantage of the NP shape of the electroactive Pt parts as regards the electrochemical oxidation of geosmin. We successfully used the Pt-C film (10.6 at%) electrode to detect geosmin in combination with HPLC at a low detection limit of 100 ng L-1.

Uneventful Pregnancy and Delivery after Thrombolysis Plus Thrombectomy for Acute Ischemic Stroke: Case Study and Literature Review.

BACKGROUND: Intravenous thrombolysis with recombinant tissue plasminogen activator and endovascular mechanical thrombectomy are known to be the most effective treatments in the acute phase of ischemic stroke. However, the safety of intravenous systemic thrombolysis with recombinant tissue plasminogen and endovascular mechanical thrombectomy during pregnancy is not well-confirmed. We describe a case of an uneventful pregnancy and delivery after thrombolysis plus endovascular mechanical thrombectomy for acute ischemic stroke. MATERIALS AND METHODS: The patient's medical records were reviewed retrospectively. A comprehensive systemic literature search of the PubMed database was conducted. CASE PRESENTATION: A 36-year-old woman at 21 weeks gestation presented with a sudden headache, dysarthria, and right hemiparesis. Magnetic resonance angiography revealed occlusion of the left internal carotid artery. Recombinant tissue plasminogen activator was administered intravenously 193 minutes after symptom onset, and endovascular mechanical thrombectomy was started immediately. Recanalization of her left internal carotid artery was achieved. The patient continued to experience mild hemiparesis after the initial treatment and started rehabilitation. The fetus remained in satisfactory condition during the pregnancy and was delivered at 38 weeks without obvious maternal or neonatal complications. No apparent abnormality has been observed in the newborn in the first year of life. CONCLUSIONS: Intravenous recombinant tissue plasminogen and endovascular mechanical thrombectomy could be considered as treatment for acute ischemic stroke during pregnancy unless high risks of hemorrhage or preterm labor are expected.

Brain volume loss is present in Japanese multiple sclerosis patients with no evidence of disease activity.

No evidence of disease activity-3 (NEDA-3), defined as absence of clinical relapse, disability progression, and brain magnetic resonance imaging (MRI) activity, has emerged as the therapeutic target of disease-modifying therapy for multiple sclerosis (MS). However, recent studies have revealed that NEDA-3 might not be sufficient to prevent cognitive deterioration and predict long-term disability. In addition to NEDA-3, brain atrophy has recently been recognized as a pivotal biomarker that is closely associated to disability in patients with MS. This retrospective observational study included 22 Japanese MS patients with relatively mild disease (median expanded disability status scale = 1.75). Fifteen patients (68%) received disease-modifying therapy (DMT), including interferon (IFN)-ß (n = 6), IFN-ß, or azathioprine followed by fingolimod (n = 4), fingolimod (n = 4), and IFN-ß followed by natalizumab (n = 1). It revealed that 14 (64.6%) patients achieved NEDA-3 in the 2-year observational period. However, nine (64.3%) of the patients with NEDA-3 were revealed to have a significant BVL, defined as ≥ 0.4% per year. Importantly, these nine patients included all patients receiving IFN-ß therapy (n = 6), whereas patients without BVL included none of these patients. Conversely, patients treated with fingolimod following IFN-ß did not have significant BVL. These results indicate that evaluation of NEDA-4 is encouraged especially in patients with IFN-ß therapy in MS clinical practice in Japan although Japanese MS patients have generally been thought to possess a milder disease including brain atrophy compared to their Western counterparts.

Association between Delirium and Prehospitalization Medication in Poststroke Patients.

PURPOSE: Medication is an important risk factor for delirium; however, the association between delirium and prehospitalization medication is unclear. We investigated the association between prestroke medication and poststroke delirium. MATERIALS AND METHODS: All patients hospitalized in the stroke care unit from September 2011 to September 2012 were selected, and their delirium symptoms, patient information, and pre- and poststroke medications were analyzed. Delirium was defined as a score of 4 or higher on the Intensive Care Delirium Screening Checklist. Factors that were related to delirium were extracted using univariate analysis, and the independent risk factors were determined using multivariate analysis. RESULTS: Of the 269 patients analyzed, 97 (36%) experienced delirium. Univariate analysis revealed significant differences between the delirium and nondelirium groups in age, dementia, previous cerebrovascular disease, craniotomy, all insertion-tube types, and 6 categories of prestroke medication. Prestroke polypharmacy was associated with poststroke delirium (P = .002). Multivariate analysis showed that taking antianxiety agents or sleep aids was an independent risk factor for delirium (odds ratio: 3.17, 95% confidence interval: 1.16-8.82). CONCLUSIONS: The present study suggests that prestroke medication affects the onset of poststroke delirium. These findings can contribute to the prediction and prevention of this condition.

Clinical validity of the Japanese version of WAIS-III short forms: Adaptation for patients with mild neurocognitive disorder and dementia.

We investigated the Japanese WAIS-III short form utility in mild neurocognitive disorder and dementia. Our sample consisted of 108 old patients (ages: 65-89; mean age = 78.3). Fifteen short forms (SFs) and full-scale (FS) IQs were compared. The SFs included Dyads (SF1, SF2), Triads (SF3), Tetrads (SF4, SF5, SF6, SF7), Pentad (SF8), Six-subtest (SF9), Seven-subtests (SF10(a)(b), SF11(a)(b), SF12), and Nine-subtest (SF13). Correlations between SFIQs and FSIQ were all significant. Significant differences also were found in paired t-test between FSIQ and 5 SFIQs (SF2: t = -4.16, SF5: t = -7.06, SF7; t = 2.59, SF10(a): t = 2.56, SF12: t = -4.82; p < .05). On the point of clinical accuracy, two SFs led to an appropriate estimated IQ (SF11(a): 84.3%, SF13: 91.7%; within 95% confidence interval and 2 standard error of measurements of FSIQ). However, SF13 was considered to still have a long administration time. The present results suggest that SF11(a) could be the most useful to estimate IQ for Japanese speaking patients with mild neurocognitive disorder and dementia. SF11(a) consists of seven subtests of Similarities, Arithmetic, Digit Span, Information, Picture Completion, Digit Symbol-Coding, and Matrix Reasoning (Ryan & Ward, 1999), and the formula (Axelrod et al., 2001) should be adopted to convert scaled scores into estimated IQ scores.

Atrial fibrillation type matters: greater infarct volume and worse neurological defects seen in acute cardiogenic cerebral embolism due to persistent or permanent rather than paroxysmal atrial fibrillation.

Aims: Some studies have shown that the type of atrial fibrillation (AF), whether paroxysmal AF (PAF) or persistent or permanent AF (PeAF), affects the incidence of ischaemic stroke. This study sought to determine the relationship between the AF pattern and the severity and brain volume of infarction in an AF population including transient ischaemic attack (TIA) patients. Methods and results: This was a retrospective observational study. We studied 161 consecutive patients who were admitted to our stroke care unit with cardiogenic embolism or TIA related to non-valvular AF (age 79 ± 9.5, 78 females, and 87 PAF patients). We evaluated the differences in severity and infarct volume between the types of AF. Additionally, we divided the patients into three groups according to severe stroke (n = 38), TIA (n = 28), and those who were neither (stroke, n = 95) for the assessment of the predictors of severe stroke and TIA. Persistent or permanent atrial fibrillation patients with acute cardiogenic stroke or TIA had worse peak National Institute of Health Stroke Scale (NIHSS) scores [PAF median 4 (range 3-14), PeAF 17 (5.8-25); P < 0.0001] and worse NIHSS scores at discharge [PAF 2.0 (1-7), PeAF 11 (3-22); P < 0.0001]. Their infarct brain volume assessed by computed tomography or magnetic resonance imaging was also larger [PAF 4.4 (1.1-32) mL, PeAF 64 (6.9-170) mL; P < 0.0001]. Multivariate analysis of severe stroke vs. non-severe stroke patients showed that having PeAF was the only independent predictor of severe stroke [odds ratio (OR) 4.27, 95% confidence interval (CI) 1.91-10.2; P = 0.0003]. Comparison of TIA vs. non-TIA patients showed that PeAF (OR 0.120, 95% CI 0.0230-0.444; P = 0.0008) and anticoagulant use (OR 8.24, 95% CI 2.15-40.8; P = 0.0018) were independent predictors of TIA. Conclusion: Cardiogenic emboli due to non-valvular PeAF are associated with a worse acute clinical course and greater volume of infarction than those due to PAF.

On-Chip Evaluation of DNA Methylation with Electrochemical Combined Bisulfite Restriction Analysis Utilizing a Carbon Film Containing a Nanocrystalline Structure.

This paper reports an on-chip electrochemical assessment of the DNA methylation status in genomic DNA on a conductive nanocarbon film electrode realized with combined bisulfite restriction analysis (COBRA). The film electrode consists of sp2 and sp3 hybrid bonds and is fabricated with an unbalanced magnetron (UBM) sputtering method. First, we studied the effect of the sp2/sp3 ratio of the UBM nanocarbon film electrode with p-aminophenol, which is a major electro-active product of the labeling enzyme from p-aminophenol phosphate. The signal current for p-aminophenol increases as the sp2 content in the UBM nanocarbon film electrode increases because of the π-π interaction between aromatic p-aminophenol and the graphene-like sp2 structure. Furthermore, the capacitative current at the UBM nanocarbon film electrode was successfully reduced by about 1 order of magnitude thanks to the angstrom-level surface flatness. Therefore, a high signal-to-noise ratio was achieved compared with that of conventional electrodes. Then, after performing an ELISA-like hybridization assay with a restriction enzyme, we undertook an electrochemical evaluation of the cytosine methylation status in DNA by measuring the oxidation current derived from p-aminophenol. When the target cytosine in the analyte sequence is methylated (unmethylated), the restriction enzyme of HpyCH4IV is able (unable) to cleave the sequence, that is, the detection probe cannot (can) hybridize. We succeeded in estimating the methylation ratio at a site-specific CpG site from the peak current of a cyclic voltammogram obtained from a PCR product solution ranging from 0.01 to 1 nM.