Investigating the potential of pyrazine dioxide based-compounds as organic electrodes for batteries.

Understanding structure-property relationship in redox-active molecular species is of central importance in various fields, including many medicinal and chemical applications. The quest for performant organic electrodes in the context of energy storage calls for pioneering studies to develop new and possibly optimal materials. Beyond modifying the molecular design of the existing compounds through functionalization, expansion of the search enabling the advent of efficient new backbones can potentially lead to breakthroughs in this research area. The number of already identified families able to constitute negative organic electrodes is much lower than that of their positive counterparts, which calls for finding ways to bridge this gap. To expand the dataset of known predicted redox potentials and in view of reaching an educated guess about the abilities of some eventual new redox active electrodes, we examined the properties of pyrazine N,N'-dioxide (PZDO) and its fully methylated functionalized derivative (TeMePzDO). The aspects and mechanisms driving the various features characteristic of these compounds were unraveled through molecular and periodic DFT calculations combined with accurate electronic structure analysis. The predicted molecular redox/crystalline intercalation potentials lead to the classification of PZDO and TeMePzDO systems within the class of negative electrodes, with features that are significantly appealing compared to those of some existing systems with backbones suited for such kind of application.

Ciguatera poisonings: A global review of occurrences and trends.

Ciguatera Poisoning (CP) is the most prevalent, phycotoxin related seafood poisoning across the globe, affecting between 10,000 and 50,000 people annually. This illness results from the consumption of seafood contaminated with lipid soluble toxins known as ciguatoxins (CTXs) that are produced by benthic dinoflagellates in the genera Gambierdiscus and Fukuyoa. The present work reviews the global occurrence of CP events and outbreaks, based on both scientific and gray literature. Ciguatera prevalence is significantly underestimated due to a lack of recognition of ciguatera symptoms, limited collection of epidemiological data on a global level, and reticence to report ciguatera in CP-endemic regions. Analysis of the time-series data available for a limited number of countries indicates the highest incidence rates are consistently reported from two historical CP-endemic areas i.e., the Pacific and Caribbean regions, a situation due in part to the strong reliance of local communities on marine resources. Ciguatera-related fatalities are rare (<0.1% of reported cases). The vast majority of outbreaks involve carnivorous fish including snappers, groupers, wrasses, and barracudas. Since 2000, an expansion of the geographical range of CP has been observed in several areas like Macaronesia and east and southeast Asia. In some of these locales, random surveys confirmed the presence of CTXs in locally sourced fish, consistent with the concurrent report of novel CP incidents (e.g., Canary Islands, Madeira, Selvagens Islands, New South Wales). One characteristic of outbreaks occurring in Asia is that they often present as large disease clusters due to group consumption of a single contaminated fish. Similar observations are reported from the Indian Ocean in the form of shark poisoning outbreaks which often lead to singular types of CP characterized by a high fatality rate. Other atypical forms of CP linked to the consumption of marine invertebrates also have been documented recently. Owing to the significant health, socioeconomic and socio-cultural impacts of ciguatera, there is an urgent need for increased, standardized, coordinated efforts in ciguatera education, monitoring and research programs. Several regional and international initiatives have emerged recently, that may help improve patients' care, data collection at a global scale, and risk monitoring and management capabilities in countries most vulnerable to CP's toxic threat.

High quality factor photonic cavity for dark matter axion searches.

Searches for dark matter axions involve the use of microwave resonant cavities operating in a strong magnetic field. Detector sensitivity is directly related to the cavity quality factor, which is limited, until recently, to the use of non-superconducting metals by the presence of the external magnetic field. In this paper, we present a cavity of novel design whose quality factor is not affected by a magnetic field. It is based on a photonic structure by the use of sapphire rods. The quality factor at cryogenic temperature is in excess of 5 × 105 for a selected mode.

A cryogenic magneto-optical device for long wavelength radiation.

We present here a small-scale liquid helium immersion cryostat with an innovative optical setup suitable to work in long wavelength radiation ranges and under an applied magnetic field. The cryostat is a multi-stage device with several shielding in addition to several optical stages. The system has been designed with an external liquid nitrogen boiler to reduce liquid bubbling. The optical and mechanical properties of the optical elements were calculated and optimized for the designed configuration, while the optical layout has been simulated and optimized among different configurations based on the geometry of the device. The final design has been optimized for low-noise radiation measurements of proximity junction arrays under an applied magnetic field in the wavelength range λ = 250 µm-2500 µm.

Axion Search with a Quantum-Limited Ferromagnetic Haloscope.

A ferromagnetic axion haloscope searches for dark matter in the form of axions by exploiting their interaction with electronic spins. It is composed of an axion-to-electromagnetic field transducer coupled to a sensitive rf detector. The former is a photon-magnon hybrid system, and the latter is based on a quantum-limited Josephson parametric amplifier. The hybrid system consists of ten 2.1 mm diameter yttrium iron garnet spheres coupled to a single microwave cavity mode by means of a static magnetic field. Our setup is the most sensitive rf spin magnetometer ever realized. The minimum detectable field is 5.5×10^{-19} T with 9 h integration time, corresponding to a limit on the axion-electron coupling constant g_{aee}≤1.7×10^{-11} at 95% C.L. The scientific run of our haloscope resulted in the best limit on dark matter axions to electron coupling constant in a frequency span of about 120 MHz, corresponding to the axion-mass range 42.4-43.1 µeV. This is also the first apparatus to perform a wide axion-mass scanning by only changing the static magnetic field.

Ciguatera poisoning in French Polynesia: insights into the novel trends of an ancient disease.

Ciguatera is a non-bacterial seafood poisoning highly prevalent in French Polynesia where it constitutes a major health issue and a major threat to food sustainability and food security for local populations. Ciguatera results from the bioaccumulation in marine food webs of toxins known as ciguatoxins, originating from benthic dinoflagellates in the genera Gambierdiscus and Fukuyoa. Ciguatera is characterized by a complex array of gastrointestinal, neurological and cardiovascular symptoms. The effective management of patients is significantly hampered by the occurrence of atypical forms and/or chronic sequelae in some patients, and the lack of both a confirmatory diagnosis test and a specific antidote. In addition, recent findings have outlined the implication of novel species of the causative organisms as well as new vectors, namely marine invertebrates, in ciguatera outbreaks. Another novel trend relates to the geographical expansion of this disease to previously unaffected areas, not only in certain island groups of French Polynesia but also in temperate regions worldwide, as a likely consequence of the effects of climate change.

Risk factors for recurrent wheezing in the first year of life in the city of Córdoba, Argentina.

BACKGROUND: Wheezing is a very common respiratory symptom in infants. The prevalence of wheezing in infants, conducted in developed countries shows prevalence rates ranging between 20% and 30%. However, we do not know the risk factors in our population of wheezing infants. METHODS: A standardised written questionnaire (WQ-P1-EISL) in infants between 12 and 18 months of age residing in the city of Cordoba was used; population/sample included 1031 infants. Recurrent wheezing (RW) was defined as three or more episodes of wheezing reported by the parents during the first 12 months of life. Data obtained were coded in Epi-Info™ (version 7) and statistically analysed with SPSS (version 17.5) software in Spanish. Parametric tests (one-way ANOVA) were performed for identifying significantly associated variables. RESULTS: The prevalence of wheezing infants was 39.7%; recurrent wheezing 33%; and severe wheezing 14.7%; 13.7% had pneumonia before the first year and of these 6.3% were hospitalised, multiple variables as risk factors for wheezing were found such as: >6 high airway infections and bronchiolitis in the first three months of life, smokers who smoke in the home among other risk factors and protective factors in those who have an elevated socioeconomic status. CONCLUSION: It is known that persistent respiratory problems in children due to low socioeconomic status is a risk factor for wheezing, pneumonia and could be a determining factor in the prevalence and severity of RW in infants. Research suggests that there are areas for improvement in the implementation of new educational strategies.

Electronic structure and energy decomposition analyses as a tool to interpret the redox potential ranking of naphtho-, biphenyl- and biphenylene-quinone isomers.

By calling on modelling approaches we have performed a comparative study on the redox properties of various naphtho-, biphenyl- and biphenylene-quinone isomers. These different compounds exhibit as a whole a redox potential range between 2.09 and 2.90 V vs. Li+/Li. A specific methodology was used to decrypt the interplay among isomerism, aromaticity and antiaromaticity modifications and the stabilization/destabilization effects due to other molecular components on this key electrochemical feature for electrode materials of batteries. In particular, energy decomposition analysis, within the Quantum Theory of Atoms in Molecules, along with the electron and electron spin population changes upon reduction nicely rationalise the observed potential trends. While 1,2- and 2,3-isomers show the highest/lowest redox potential in the biphenylene-quinone series, a reverse trend is observed for the naphtho-quinone, the compound having the two carbonyl groups on distinct rings being characterized by an intermediate value in both cases. There is instead almost no differentiation between 1,2 and 2,3 isomers for the biphenyl-quinone family.

Engineering of unsubstituted quinoid-like frameworks enabling 2 V vs. Li(+)/Li redox voltage tunability and related derivatives.

A criterion for redox voltage tuning (0.96-2.96 V vs. Li(+)/Li) was derived from DFT calculations on quinoneazine and analogues (C/O replacing N). As rationalized through spin-charge distributions and energetic criteria, high-low voltage implying a bridge with delocalized-localized bond nature mainly originates from ring stabilization. Established guidelines serve to propose optimal derivatives.

[Ciguatera and acute polyradiculoneuritis. Description of two cases in French Polynesia: immunoallergic hypothesis?]. / Ciguatéra et polyradiculonévrite aiguë a propos de deux cas en Polynésie française: hypothèse immuno-allergique?

Ciguatera is a foodborne poisoning caused by eating seafood from tropical and subtropical reef areas. According to official data from the local health department, cases of ciguatera in French Polynesia are estimated to involve 240 to 400 persons per 100 000 inhabitants. Associated with a wide spectrum of gastrointestinal, cardiovascular, nervous, and general signs, ciguatera is usually benign although some forms can lead to hospitalization. The purpose of this report is to describe two unusual cases involving patients who developed acute polyradiculoneuritis with Guillain-Barré-syndrome-like peripheral nervous system deficits on the seventh day of ciguatera after ingestion of moray eel. The hypothesis of an immune-allergic reaction is raised especially in the light of rapid improvement of the patient who received polyvalent immunoglobulin treatment.

Vibrational properties of hexagonal Ge(2)Sb(2)Te(5) from first principles.

Phonons at the Γ point and the Raman spectrum of the hexagonal Ge(2)Sb(2)Te(5) were computed within density functional perturbation theory. The three different stackings of the Ge/Sb planes proposed in the experimental literature were considered. The theoretical Raman spectrum is similar for the three stackings with a marginally better agreement with experiments for the structure proposed by Matsunaga et al (2004 Acta Crystallogr. B 60 685) which assumes a disorder in Ge/Sb site occupation. Although the large broadening of the experimental Raman peaks prevents discriminating among the different stackings, the assignment of the Raman peaks to specific phonons is possible because the main features of the spectrum are rather insensitive to the actual distribution of atoms in the Sb/Ge sublattices. On the basis of the energetics (including configurational entropy) two stackings seem plausible candidates for GST, but only the mixed stacking by Matsunaga et al reproduces the spread of Ge/Sb-Te bond lengths measured experimentally.

Severe seafood poisoning in French Polynesia: a retrospective analysis of 129 medical files.

We present a retrospective study of 129 medical files concerning seafood poisonings (SFPs) registered at the central hospital of Tahiti (French Polynesia) between 1999 and 2005. Even if during that period most of the described cases (96%) concerned the ichtyosarcotoxism ciguatera, it is interesting to note that we also registered three other SFPs: tetrodotoxism, carchatoxism and lyngbyatoxism due to the consumption of tetraodon/diodon species, sharks or sea turtles, respectively. In ciguatera, cardiovascular symptoms were the primary criteria of severity with bradycardia and hypotension observed at 75% and 43%, respectively. Neurological manifestations (such as cerebellar syndrome, language troubles, diplopia or polyradiculoneuritis), trouble and/or loss of consciousness and dyspnoea were secondary criteria of severity. Body temperature was reported under 36.5 degrees C in 48 of 80 documented files. This observation, which has not previously been described in humans, may be related to possible central effects of the ingested toxin. The last remark concerns two extremely severe cases of ciguatera fish poisoning in which physicians had suspected an inflammatory neuropathy called the Guillain-Barré syndrome (GBS). Even if it is premature to conclude any correlation between the intoxication and the appearance of GBS, it is interesting to note that in both pathologies, morphological disturbances of nerve fibres have been reported.

Chronic treatment with tetrahydrobiopterin reverses endothelial dysfunction and oxidative stress in hypercholesterolaemia.

BACKGROUND: Reduced availability of tetrahydrobiopterin (BH(4)), an essential cofactor of nitric oxide (NO) synthase (NOS), decreases NO production and increases reactive oxygen species. Both mechanisms contribute to atherosclerotic vascular disease. Although acute supplementation of BH(4) improves endothelial dysfunction, the effect of chronic BH(4) in humans is unknown. OBJECTIVE: To investigate the effect of chronic BH(4) supplementation on endothelial function and oxidative stress in hypercholesterolaemia. DESIGN: Randomised double-blind, placebo-controlled trial. SETTING: University Hospital. PATIENTS: 22 hypercholesterolaemic patients (low-density lipoprotein (LDL) >4.5 mmol/l) were randomised to 4 weeks of oral BH(4) (400 mg twice daily) or placebo. Age-matched healthy volunteers served as controls. MAIN OUTCOME MEASURES: Endothelium-dependent and -independent vasodilatation was assessed by venous occlusion plethysmography. To elucidate the mechanisms of BH(4) effect, NO release and superoxide anion (O(2)(-)) production were measured in human aortic endothelial cells exposed to native LDL (2.6 mmol cholesterol/l). RESULTS: BH(4) plasma levels were significantly increased by oral supplementation. NO-mediated vasodilatation to acetylcholine was reduced in patients compared with controls and restored by BH(4). No effect of BH(4) on endothelium-independent vasodilatation was seen. Furthermore, 8-F(2 )isoprostane plasma levels, a marker of vascular oxidative stress, were reduced by BH(4). In LDL-treated endothelial cells, BH(4) levels and NO release were reduced and O(2)(-) production increased compared with control cells. Exogenous BH(4) normalised NO and O(2)(-) production. CONCLUSIONS: In hypercholesterolaemia, endothelial dysfunction and oxidative stress can be reversed by chronic oral treatment with BH(4). Thus, BH(4) availability is essential for maintaining NO synthesis and low O(2)(-) production by endothelial NOS in vivo, and may provide a rational therapeutic approach to prevent cardiovascular disease.

Histochemical study of cardiac mast cells degranulation and collagen deposition: interaction with the cathecolaminergic system in the rat.

Although their role in the cardiovascular system is still largely unknown, mast cells are present in the myocardium of both experimental animals and humans. Interestingly, cathecolaminergic nerve fibres and mast cells are often described in close morphological and functional interactions in various organs. In the present study we investigated the effects of chronic interference with beta-adrenergic receptors (via either sympathectomy or beta-blockade) on cardiac mast cell morphology/activation and on interstitial collagen deposition. In rats subjected to chemical sympathectomizy with the neurotoxin 6-hydroxydopamine (6-OHDA) we observed a significant increase of mast cell density, and in particular of degranulating mast cells, suggesting a close relationship between the cardiac catecholaminergic system and mast cell activation. In parallel, chronic 6-OHDA treatment was associated with increased collagen deposition. The influence of the beta-adrenergic receptor component was investigated in rats subjected to chronic propranolol administration, that caused a further significant increase in mast cell activation associated with a lower extent of collagen deposition when compared to chemical sympathectomy. These data are the first demonstration of a close relationship between rat cardiac mast cell activation and the catecholaminergic system, with a complex interplay with cardiac collagen deposition. Specifically, abrogation of the cardiac sympathetic efferent drive by chemical sympathectomy causes mast cell activation and interstitial fibrosis, possibly due to the local effects of the neurotoxin 6-hydroxydopamine. In contrast, beta-adrenergic blockade is associated with enhanced mast cell degranulation and a lower extent of collagen deposition in the normal myocardium. In conclusion, cardiac mast cell activation is influenced by beta-adrenergic influences.

Subcutaneous enoxaparin following thrombolysis and intravenous unfractionated heparin in ST-elevation acute myocardial infarction: safety and efficacy of low vs full dose.

AIM: In ST-segment elevation myocardial infarction (STEMI) treated with fibrin-specific thrombolytic agents, early intravenous unfractionated heparin (UFH) is warranted. Low molecular weight heparin Enoxaparin currently represents an alternative to UFH, to be used until hospital discharge. Since optimal dosing of subcutaneous Enoxaparin is not standardized, we conducted an observational study to compare safety and efficacy of low (4,000 U once daily) vs full dose (100 U/kg twice daily) regimens. METHODS: All STEMI patients successfully treated with tenecteplase and intravenous UFH and referred to the Catheterization Laboratory between June 2002-November 2003 for predischarge coronary angiography, were evaluated. The primary end-point was the composite of hemorrhages and residual angina/reinfarction during Enoxaparin administration, whereas secondary end-points were occurrence of venous thromboembolism (VTE) during Enoxaparin administration, and infarct-related artery (IRA) patency rate at predischarge coronary angiography. RESULTS: Out of 123 patients, 57 (M/F 45/12, mean age 65.8+/-8.1 years) received low dose, and 66 (men/women 45/21, mean age 62.6+/-11.8 years) full dose subcutaneous Enoxaparin. The incidence of the composite primary end-point was comparable in both groups (19% vs 26%; P=NS). Also, null was the occurrence of VTE, whereas the IRA patency rate did not significantly differ in the 2 groups (84% vs 86% TIMI 3 and 11% vs 9% TIMI 2 flow grades; P=NS). CONCLUSIONS: In patients with STEMI undergoing successful recanalization with tenecteplase and intravenous UFH, low dose subcutaneous Enoxaparin appears preferable to full dose, in the light of comparable safety and clinical efficacy and superior easiness of use.

Spontaneous rupture of non-parasitic hepatic cyst.

Intrahepatic cysts are generally classified as congenital, traumatic, infectious or neoplastic. Non-parasitic hepatic cysts (NPHCs) include simple cysts and adult polycystic liver disease in which the liver is diffusely occupied by cysts. NPHCs usually reach a large size before causing symptoms, unless a complication such as rupture, bleeding, infection, obstructive jaundice or neoplastic transformation occurs. We report the case of a 67-year-old man with spontaneous rupture of simple liver cyst. The clinical pictures and the unusual ultrasound features of this rare condition are discussed.

Endothelial function and postprandial lipemia.

It is widely recognised that post-prandial lipoproteins play a role in the development of atherosclerosis, but the mechanisms underlying this role are unclear. An attractive working hypothesis is that the pathogenetic link is endothelial dysfunction. The available data seem to corroborate this theory and recognise triggering by oxidative stress, but some of the evidence is still contradictory.

Body composition, fat distribution and metabolic characteristics in lean and obese women with polycystic ovary syndrome.

The polycystic ovary syndrome (PCOS), characterized by chronic anovulation and hyperandrogenism, has many features of metabolic syndrome and can be considered a metabolic disease. Approximately 50% of patients with PCOS are overweight or obese with abdominal fat accumulation. Some metabolic alterations and abdominal fat distribution have also been reported in lean women with PCOS. The aim of this study was to evaluate the effect, if any, of obesity on metabolic features, body composition and fat distribution in patients with PCOS. Body composition and abdominal fat distribution (evaluated by DEXA), waist circumference, blood pressure, lipid profile, glucose tolerance and homeostasis model assessment index were determined in 23 lean [mean age 23 +/- 5 yr, mean body mass index (BMI) 22 +/- 2 kg/m2] and 27 overweight-obese (mean age 21 +/- 5 yr, mean BMI 32 +/- 5 kg/m2) patients with PCOS and in 20 age- and weight-matched eumenorrhoic women. Patients exhibited slight but non-significant differences in metabolic parameters, waist circumference, blood pressure and total and abdominal fat content compared with weight-matched controls. None of the lean subjects suffered from metabolic syndrome according to the National Cholesterol Education Program--Adult Treatment Panel III (NCEP-ATPIII) criteria as opposed to 10 overweight-obese patients and three overweight-obese control subjects (37% and 33.3% of each subgroup, respectively). Our data do not show significant metabolic alterations in lean PCOS women. Results indicate that obesity seems to underpin the metabolic alterations exhibited by the overweight-obese patients. However, since women with PCOS are at increased cardiovascular risk, further studies are needed to evaluate metabolic alterations and body composition in these patients.

Voiding dysfunction in x-linked adrenoleukodystrophy: symptom score and urodynamic findings.

PURPOSE: Adrenoleukodystrophy is an x-linked genetic disorder characterized by the breakdown of the myelin sheath surrounding nerve cells in the brain and progressive dysfunction of the adrenal gland with 6 possible phenotypes. Lower urinary tract symptoms affect the quality of life of these patients but only sporadic cases have been previously studied by urodynamics. We report to our knowledge the first series in the literature looking at the prevalent pattern. MATERIALS AND METHODS: A total of 14 children and adults 8 to 53 years old (average age 30) with different phenotypes were referred for evaluation. Of the patients 6 had adrenomyeloneuropathy without cerebral involvement (C-) 3 had the adult cerebral form, 3 had the childhood cerebral form, 1 had cerebral involvement (C+) and 1 was asymptomatic. All patients were submitted to a screening protocol, consisting of the self-administered short form questionnaire International Conference on Incontinence Questionnaire-Short Form (ICIQ-SF) and a 3-day voiding diary. Patients were divided in group 1-no urinary symptoms, ICIQ-SF score 0 and no further investigation (3); group 2-frequency/urgency, ICIQ-SF score 1 to 5, uroflowmetry and post-voiding residual urine (4); and group 3-voiding symptoms and incontinence, ICIQ-SF score greater than 5, standard urodynamic examination (7). RESULTS: A neurogenic overactive bladder was the prevalent urodynamic finding (6 of 7 patients), while hypocontractility was found in 1 case. CONCLUSIONS: Vesicosphincteric dysfunction can be explained by spinal and/or cerebral involvement in the different neurological forms of adrenoleukodystrophy. Attempts at treatment with anticholinergics and neuromodulation in 4 of our patients provided temporary benefit with clear subjective amelioration of symptoms and improved quality of life.