Anode Catalysts in Anion-Exchange-Membrane Electrolysis without Supporting Electrolyte: Conductivity, Dynamics, and Ionomer Degradation.

Anion-exchange-membrane water electrolyzers (AEMWEs) in principle operate without soluble electrolyte using earth-abundant catalysts and cell materials and thus lower the cost of green H2 . Current systems lack competitive performance and the durability needed for commercialization. One critical issue is a poor understanding of catalyst-specific degradation processes in the electrolyzer. While non-platinum-group-metal (non-PGM) oxygen-evolution catalysts show excellent performance and durability in strongly alkaline electrolyte, this has not transferred directly to pure-water AEMWEs. Here, AEMWEs with five non-PGM anode catalysts are built and the catalysts' structural stability and interactions with the alkaline ionomer are characterized during electrolyzer operation and post-mortem. The results show catalyst electrical conductivity is one key to obtaining high-performing systems and that many non-PGM catalysts restructure during operation. Dynamic Fe sites correlate with enhanced degradation rates, as does the addition of soluble Fe impurities. In contrast, electronically conductive Co3 O4 nanoparticles (without Fe in the crystal structure) yield AEMWEs from simple, standard preparation methods, with performance and stability comparable to IrO2 . These results reveal the fundamental dynamic catalytic processes resulting in AEMWE device failure under relevant conditions, demonstrate a viable non-PGM catalyst for AEMWE operation, and illustrate underlying design rules for engineering anode catalyst/ionomer layers with higher performance and durability.

Three-Electrode Study of Electrochemical Ionomer Degradation Relevant to Anion-Exchange-Membrane Water Electrolyzers.

Among existing water electrolysis (WE) technologies, anion-exchange-membrane water electrolyzers (AEMWEs) show promise for low-cost operation enabled by the basic solid-polymer electrolyte used to conduct hydroxide ions. The basic environment within the electrolyzer, in principle, allows the use of non-platinum-group metal catalysts and less-expensive cell components compared to acidic-membrane systems. Nevertheless, AEMWEs are still underdeveloped, and the degradation and failure modes are not well understood. To improve performance and durability, supporting electrolytes such as KOH and K2CO3 are often added to the water feed. The effect of the anion interactions with the ionomer membrane (particularly other than OH-), however, remains poorly understood. We studied three commercial anion-exchange ionomers (Aemion, Sustainion, and PiperION) during oxygen evolution (OER) at oxidizing potentials in several supporting electrolytes and characterized their chemical stability with surface-sensitive techniques. We analyzed factors including the ionomer conductivity, redox potential, and pH tolerance to determine what governs ionomer stability during OER. Specifically, we discovered that the oxidation of Aemion at the electrode surface is favored in the presence of CO32-/HCO3- anions perhaps due to the poor conductivity of that ionomer in the carbonate/bicarbonate form. Sustainion tends to lose its charge-carrying groups as a result of electrochemical degradation favored in basic electrolytes. PiperION seems to be similarly negatively affected by a pH drop and low carbonate/bicarbonate conductivity under the applied oxidizing potential. The insight into the interactions of the supporting electrolyte anions with the ionomer/membrane helps shed light on some of the degradation pathways possible inside of the AEMWE and enables the informed design of materials for water electrolysis.

Perceived Centrality in Social Networks Increases Women's Expectations of Confronting Sexism.

This article integrates the study of intergroup relations and social network cognition, predicting that women who occupy central (vs. peripheral) advice network positions are more likely to confront a coworker's gender-biased comment. Study 1 offers correlational evidence of the predicted link between perceived advice network centrality and confronting among employed women, uniquely in advice (but not communication) networks. Study 2 replicates and investigates two possible mechanisms-perceptions of the situation as public and perceived risk of confronting. Study 3 rules out order effects and tests an additional mechanism (expectations of the network members). Study 4 is an experiment that shows people expect central (vs. peripheral) women to confront more, even when she is lower (vs. equal) power. Study 5 replicates the core hypothesis in retrospective accounts of women's responses to real workplace gender bias. Study 6 compares multiple potential mechanisms to provide greater insight into why centrality reliably predicts confrontation.

Evidence for blatant dehumanization of mental illness and its relation to stigma.

People with mental illness face stigma, and due to their low social status, they may also face blatant dehumanization that denies their status as fully evolved human beings. In the current research, three studies documented the existence of blatant dehumanization of mental illness. Study 1 (N = 112) showed that participants rated people with mental illness in general as being significantly less human than other dehumanized social groups such as Mexican immigrants and Muslims. Study 2 (N = 158) showed that dehumanization occurs for specific mental disorders but that the level of dehumanization varies widely among disorders. Study 3 (N = 223) documented significant correlations between dehumanization of mental illness and standard measures of stigma such as fear, pity, and social distance. Overall, the results establish the relevance of blatant dehumanization to mental illness stigma and suggest new directions for understanding stigma.

Analysis of electro-permeation of hydrogen in metallic alloys.

A reaction-diffusion type modelling framework is presented to analyse both electro-permeation (EP) and thermal desorption spectrometry (TDS) measurements of hydrogen in metallic alloys. It is assumed that the kinetics of hydrogen motion is governed by diffusion through the lattice, along with trapping/detrapping at specific sites such as dislocations, grain boundaries, etc. It is shown that the trapping and detrapping rates are typically much faster than the diffusion rate, and consequently a simplification of the governing equations suffices such that local equilibrium exists between lattice and trapped hydrogen. Using this local equilibrium assumption, we then present an asymptotic analysis of the governing kinetic equation for the EP test. This asymptotic analysis reveals that four regimes of behaviour exist, ranging from negligible trapping to the complete filling of deep traps. The analysis suggests that EP tests should be so-arranged that three regimes of behaviour are spanned, in order to extract the relevant material properties associated with hydrogen transport. The numerical solutions presented in this study support the asymptotic analysis. The hydrogen kinetics framework is also deployed to analyse both EP and TDS tests on the same martensitic steel. The EP measurements all lie in regime I and are thus insufficient to uniquely determine both the trap density and binding energy. Reasonable agreement is obtained between measurements and numerical predictions of TDS tests using parameters estimated from the EP tests. Further improvements in measurements are required to confirm the fidelity of this modelling approach.This article is part of the themed issue 'The challenges of hydrogen and metals'.

Objective measurement of erythema in psoriasis using digital color photography with color calibration.

BACKGROUND: Traditional metrics for evaluating the severity of psoriasis are subjective, which complicates efforts to measure effective treatments in clinical trials. METHODS: We collected images of psoriasis plaques and calibrated the coloration of the images according to an included color card. Features were extracted from the images and used to train a linear discriminant analysis classifier with cross-validation to automatically classify the degree of erythema. The results were tested against numerical scores obtained by a panel of dermatologists using a standard rating system. RESULTS: Quantitative measures of erythema based on the digital color images showed good agreement with subjective assessment of erythema severity (κ = 0.4203). The color calibration process improved the agreement from κ = 0.2364 to κ = 0.4203. CONCLUSION: We propose a method for the objective measurement of the psoriasis severity parameter of erythema and show that the calibration process improved the results.

Intended intramuscular gluteal injections: are they truly intramuscular?

CONTEXT: In patients with obesity, intramuscular injections may be deposited subcutaneously due to an increase in gluteal fat. We aimed to use abdominal CT done in our institute for gluteal fat thickness to test our hypothesis. MATERIALS AND METHODS: After IRB approval, CT scans of the abdomen and pelvis of the past 6 months were analyzed. The thickness of gluteal region subcutaneous fat was measured in a standardized manner. RESULTS: Out of 700 CT scans, studied, 476 were males and 224 were females. The average gluteal fat thickness was 2.34 cm +/- 1 cm. The average fat thickness in males was 1.98 cm +/- 0.98 cm whereas in females was 3.0 cm +/- 1.2 cm. Subcutaneous granulomas were seen in 17 cases and one injection granuloma in the intramuscular plane. CONCLUSION: A significant number of female patients had increased gluteal fat thickness beyond the reach of routinely used needles. The medications in these patients will thus be unintentionally injected to subcutaneous plane, possibly altering the pharmacokinetics.

Metastases to the thyroid presenting as a metabolically inactive incidental thyroid nodule with stable size in 15 months.

Though the thyroid gland has a rich vascular supply, incidence of metastatic disease from distant organs is rare. Here we present an unusual case of metastases to the thyroid with several interesting features. A 63-year-old male with history of adenocarcinoma of the right lobe lung (5 years prior to presentation), treated with surgery and chemotherapy, followed by new adenosquamous lung cancer in the left lobe of the lung (one year prior to presentation), treated surgically followed by adjuvant chemotherapy, was referred to Endocrinology section for evaluation of an incidental thyroid nodule on CT chest. Ultrasound (US) of the thyroid revealed a complex, predominantly hypoechoic lesion measuring 1.8 cm within the lower pole of the right thyroid lobe and a subcentimeter lesion in the left lobe of the thyroid. Review of prior CT chests showed that the lesion in the right lobe was stable for 15 months, with no evidence of a hypermetabolic lesion on PET scan. The subcentimeter lesion was not seen on prior CT scans. US guided fine needle aspiration (FNA) and pathology of the lobectomy of the thyroid confirmed adenosquamous carcinoma. Interesting features in this case are that the thyroid metastases occurred without any evidence of synchronous lesions elsewhere, the size was stable over 15 months, and the lesions were metabolically inactive.

Interleukin 5 is protective during sepsis in an eosinophil-independent manner.

RATIONALE: The immune response in sepsis is characterized by overt immune dysfunction. Studies indicate immunostimulation represents a viable therapy for patients. One study suggests a potentially protective role for interleukin 5 (IL-5) in sepsis; however, the loss of eosinophils in this disease presents a paradox. OBJECTIVES: To assess the protective and eosinophil-independent effects of IL-5 in sepsis. METHODS: We assessed the effects of IL-5 administration on survival, bacterial burden, and cytokine production after polymicrobial sepsis. In addition, we examined the effects on macrophage phagocytosis and survival using fluorescence microscopy and flow cytometry. MEASUREMENTS AND MAIN RESULTS: Loss of IL-5 increased mortality and tissue damage in the lung, IL-6 and IL-10 production, and bacterial burden during sepsis. Therapeutic administration of IL-5 improved mortality in sepsis. Interestingly, IL-5 administration resulted in neutrophil recruitment in vivo. IL-5 overexpression in the absence of eosinophils resulted in decreased mortality from sepsis and increased circulating neutrophils and monocytes, suggesting their importance in the protective effects of IL-5. Furthermore, novel data demonstrate IL-5 receptor expression on neutrophils and monocytes in sepsis. IL-5 augmented cytokine secretion, activation, phagocytosis, and survival of macrophages. Importantly, macrophage depletion before the onset of sepsis eliminated IL-5-mediated protection. The protective effects of IL-5 were confirmed in humans, where IL-5 levels were elevated in patients with sepsis. Moreover, neutrophils and monocytes from patients expressed the IL-5 receptor. CONCLUSIONS: Taken together, these data support a novel role for IL-5 on noneosinophilic myeloid populations, and suggest treatment with IL-5 may be a viable therapy for sepsis.

Regulatory role of miR-2909 in cell-mediated immune response.

Keeping in view the micromanagement of immune response by micro RNAs, the present study was directed to explore the role of miR-2909 in the differentiation and maturation of T-lymphocytes within the population of normal human peripheral blood mononuclear cells maintained in in vitro culture. The results of such a study revealed that miR-2909 had the inherent capacity to significantly increase Treg (CD4+CD25+Foxp3+) cell population and dominant Th1-type cytokine (especially with decrease in IL-4 level and higher levels of INF-ß and INF-γ) profile. Based upon these results, we propose that miR-2909 may modulate native immunity in general and help in providing protective immunity against viral infections in particular.

Infraorbital ethmoid (Haller's) cells: a panoramic radiographic study.

OBJECTIVE: Haller's cells or infraorbital ethmoid cells refer to the ethmoidal pneumatization of the superior aspect of the maxillary sinus and floor of the orbit. The clinical importance of these entities initiated this study with an aim to determine the prevalence and characteristics of Haller's cells on panoramic radiographs. METHODS: The study group comprised 600 healthy adults of both genders with an age range of 18-60 years. One panoramic radiograph for each of the patients was made and interpreted for the presence of Haller's cells. The data collected were subjected to statistical analysis: frequencies/percentages, descriptive statistics, χ(2) test and cross-tabulation (contingency table analysis) to obtain the results. RESULTS: Haller's cells were noted in 96 patients, accounting for a prevalence of 16%. Of these patients, 77.1% were unilateral while 22.9% were bilateral. Among 96 cases, a total of 204 cells were found. The majority of the cells were round or ovoid in shape. The unilocular type of Haller's cells occurring unilaterally was statistically significant. CONCLUSION: This study has attempted to explore the characteristics of Haller's cells on panoramic radiographs. A description of Haller's cells on these radiographs may prove vital in enumerating the differential diagnosis for patients afflicted with intractable orofacial pain and reduce the risk of untoward intraoperative complications during endonasal procedures.

Telomerase inhibition potentiates the effects of genotoxic agents in breast and colorectal cancer cells in a cell cycle-specific manner.

Previous studies have shown that telomerase facilitates DNA-damage repair and cell survival following stress. It is not clear how telomerase promotes DNA repair, or whether short-term telomerase inhibition, combined with genotoxic stress, can be exploited for cancer therapy. Here, we show that transient inhibition of telomerase activity by the specific inhibitor, GRN163L, increases the cytotoxicity of some, but not all, DNA-damaging agents. Such synergistic inhibition of growth requires the use of DNA-damaging agents that are toxic in the S/G(2) phase of the cell cycle. Notably, inhibition of Ataxia Telangiectasia Mutated (ATM) kinase, together with telomerase inhibition, synergistically increases the cytotoxicity induced by the G(2)-specific topoisomerase II inhibitor etoposide. By varying the timing of telomerase inhibition, relative to the timing of DNA damage, it is apparent that the prosurvival functions of telomerase occur at early stages of DNA damage recognition and repair. Our results suggest that the protective role of telomerase in cell cycle-restricted DNA damage repair could be exploited for combined anticancer chemotherapy.

Annular vesiculobullous eruptions in type 2 reaction in borderline lepromatous leprosy: a case report.

An untreated case of BL presented with clinical features of type 2 reaction (T2R) confirmed by histopathology. The case was a 18-year-old female with borderline lepromatous leprosy who developed annular vesiculobullous eruptions oversome of the pre-existing plaques on arms and upper back along with fever and severe neuritis after a short course of ofloxacin intake prescribed for urinary tract infection. In addition to the above lesions, some of the existing lesions showed acute exacerbation characterized by erythema, oedema, tenderness and vesiculobullous eruption. This can be considered as an example of leprous exacerbation as described in older literature. T2Rs are common in lepromatous leprosy and not so uncommonly are observed in borderline lepromatous leprosy. The vesiculobullous and crusted lesions developing over the existing borderline plaques, some of them presenting in an annular pattern in T2R in the form of leprous exacerbation, have been reported rarely in the literature.

Serology in autoimmune pancreatitis.

Autoimmune pancreatitis (AIP) is the pancreatic manifestation of a systemic immune-driven, inflammatory process that can involve organs such as the bile duct, salivary glands and lymph nodes, in addition to the pancreas. Many of the presenting signs and symptoms of AIP, including painless jaundice, weight loss and mild epigastric pain, are characteristic of pancreatic adenocarcinoma; thus, obtaining an accurate diagnosis to avoid unnecessary surgery is imperative. AIP responds very well to steroid treatment, although it may recur in up to 20% to 40% of cases. The diagnostic criteria for AIP are histological, radiographic, clinical and laboratory-based in nature. Although no international consensus on diagnostic criteria has yet been made, some of the diagnostic features of AIP include elevated gamma globulin, immunoglobulin, and, in particular, immunoglobulin G4 fraction (IgG4). The search for a distinct serological marker of AIP has included antibodies to a wide range of antigenic stimuli. To date, there have been studies of AIP and antibodies to lactoferrin, carbonic anhydrase isoforms II and IV, pancreatic secretory trypsin inhibitor (PSTI or SPINK) as well as to less sensitive or specific markers of autoimmunity, such as antinuclear antibody and rheumatoid factor. Although there are some preliminary strengths of association with PSTI antibodies, none of these biomarkers appears to be sensitive or specific enough to serve as distinctive evidence of AIP. At the current time, elevations of IgG4 to greater than 280 mg/dL remain the most reliable and reproducible indicator that a patient has AIP.

Late postpartum eclampsia at five weeks post-delivery.

Postpartum eclampsia is a serious and unexpected complication. A relative increase in the incidence of postpartum eclampsia has been noted in the last few years. Late postpartum eclampsia, though initially controversial, is now recognised up to four weeks after delivery. We present such a case occurring in a 26-year-old woman. This patient, who had undergone lower segment caesarean section due to pregnancy-induced hypertension, presented with typical features of postpartum eclampsia 34 days after an asymptomatic interval.

The Misgav Ladach method: a step forward in the operative technique of caesarean section.

INTRODUCTION: Caesarean delivery remains the most common intraperitoneal surgical procedure in obstetric and gynaecologic practice. Since time immemorial there have been countless efforts to improve the technique of caesarean section. One such innovative breakthrough technique is the Misgav Ladach method of caesarean of section. The objective of this trial was to compare the intraoperative and short-term postoperative outcomes between the conventional and the Misgav-Ladach technique for caesarean section. MATERIALS AND METHOD: The randomized prospective comparative study was carried out in the department of Obstetrics and Gynaecology, B.P Koirala Institute of Health Sciences, Dharan Nepal. Four hundred patients were randomized to either Misgav Ladach or the Conventional method of caesarean section. Only term pregnancies with singleton foetuses' were included whereas pregnancies with previous caesarean section were excluded from the study. The study period was from September 2001 to September 2004. RESULT: There was not much difference in the demographic variables between the two groups. The age of the patients ranged between 18-40 years. The mean age of patients in Misgav Ladach and conventional group was 24.5 and 23.6 years respectively. Foetal distress was the commonest indication for caesarean section followed by non progress of labour. The mean incision to delivery interval, operating time and blood loss in the Misgav Ladach group was 1 minute 30 seconds, 16 minutes and 35 0ml as compared to 3 minutes, 28 minutes and 600 ml in the conventional group respectively. 3.5%of patients in the Misgav Ladach group showed febrile morbidity as compared to 7% in the conventional group. 19% from conventional group and only 4%from Misgav Ladach group required added analgesia. Almost equal number of patients (10-12) in each group experienced significant headache.).0.1%in the Misgav group and 5% in the Conventional group required post operative blood transfusion. Four patients from the conventional group had their wound gaped. The number of neonates requiring intensive care was sixteen (8% ) in the conventional group and 3 (1.5%) in the Misgav group.6.5% from conventional group and 2% from Misgav Ladach group required maternal intensive care admissions. CONCLUSION: Misgav-Ladach technique has been be associated with shorter operative time, quicker recovery, and lesser need for postoperative medications, when compared with traditional caesarean section. It has also been shown to be more cost-effective. A further advantage of the technique may be the shorter time taken for the delivery of the child.

Signaling through CD14 attenuates the inflammatory response to Borrelia burgdorferi, the agent of Lyme disease.

Lyme disease is a chronic inflammatory disorder caused by the spirochetal bacterium, Borrelia burgdorferi. In vitro evidence suggests that binding of spirochetal lipoproteins to CD14, a pattern recognition receptor expressed on monocytes/macrophages and polymorphonuclear cells, is a critical requirement for cellular activation and the subsequent release of proinflammatory cytokines that most likely contribute to symptomatology and clinical manifestations. To test the validity of this notion, we assessed the impact of CD14 deficiency on Lyme disease in C3H/HeN mice. Contrary to an anticipated diminution in pathology, CD14(-/-) mice exhibited more severe and persistent inflammation than did CD14(+/+) mice. This disparity reflects altered gene regulation within immune cells that may engender the higher bacterial burden and serum cytokine levels observed in CD14(-/-) mice. Comparing their in vitro stimulatory activity, live spirochetes, but not lysed organisms, were a potent CD14-independent stimulus of cytokine production, triggering an exaggerated response by CD14(-/-) macrophages. Collectively, our in vivo and in vitro findings support the provocative notion that: 1) pattern recognition by CD14 is entirely dispensable for elaboration of an inflammatory response to B. burgdorferi, and 2) CD14-independent signaling pathways are inherently more destructive than CD14-dependent pathways. Continued study of CD14-independent signaling pathways may provide mechanistic insight into the inflammatory processes that underlie development of chronic inflammation.