Layer charge and heavy metals structures in hydrated 2 : 1 silicates:state of the art and new advances on cadmium

This study will discuss how layer charge can affect chemical speciation and topology of heavy metals adsorbed to 2:1 layer silicates, by providing: i) an overview of literature data; ii) experimental data on Cd complexes adsorbed by 2:1 layer silicates with different layer charge (montmorillonite and vermiculite); iii) a comparison between our results and literature data. This study will also be supported by several different experimental techniques such as chemical and thermal analyses, X-ray powder diffraction and X-ray absorption spectroscopy.Based on our data Cd atoms were found to complex water molecules in both clay minerals and to show four-fold coordination in montmorillonite (CdO distances of 2.24 Å) and six-fold coordination in vermiculite (CdO distances of 2.16 and 2.28 Å). Furthermore our models clearly suggest that Cd mainly bonds to interlayer water, without neglecting the more limited, but still significant, Cd multinuclear surface complexes at the octahedral broken edges. Both clay minerals show H2O/Cd ratio, as evidenced by thermal analyses, drastically higher than expected from X-ray adsorption spectroscopy data, thus implying that most of the water molecules are only loosely coordinated to interlayer cations

High prevalence of patent foramen ovale in migraine with aura

In this study we evaluated the presence of patent foramen ovale (PFO) in a cohort of 25 consecutive patients suffering from migraine with aura (MA) during an attack presenting to the emergency ward of an Italian hospital. Patients underwent brain magnetic resonance imaging (MRI) with contrast medium, routine coagulation tests, contrast transcranial echocolour–coded sonography (c–TCCS) and transoesophageal echocardiography (TEE). Of the enrolled patients, 88.7% showed a PFO according to the c–TCCS test, whereas only in 72% TEE confirmed the presence of PFO. This discordance could be due to the fact that c–TCCS is more sensitive even with shunts with minimal capacity also located in the pulmonary vasculature. After surgical treatment of the PFO, MA disappeared within two months. Also, the treatment with warfarin as well as with acetylsalicylic acid and flunarizine was able to dramatically reduce the frequency of migraine attacks. These data indicate a higher prevalence of PFO in MA vs. normal population (OR=2.92) and could suggest that the presence of arteriovenous (AV) shunts could represent a trigger for MA attacks as well as for stroke, but more studies are needed to confirm this preliminary hypothesis

Consensus recommendations for transcranial color-coded duplex sonography for the assessment of intracranial arteries in clinical trials on acute stroke

BACKGROUND AND PURPOSE: Transcranial color-coded duplex sonography has become a standard diagnostic technique to assess the intracranial arterial status in acute stroke. It is increasingly used for the evaluation of prognosis and the success of revascularization in multicenter trials. The aim of this international consensus procedure was to develop recommendations on the methodology and documentation to be used for assessment of intracranial occlusion and for monitoring of recanalization. METHODS: Thirty-five experts participated in the consensus process. The presented recommendations were approved during a meeting of the consensus group in October 2008 in Giessen, Germany. The project was an initiative of the German Competence Network Stroke and performed under the auspices of the Neurosonology Research Group of the World Federation of Neurology. RESULTS: Recommendations are given on how examinations should be performed in the time-limited situation of acute stroke, including criteria to assess the quality of the acoustic bone window, the use of echo contrast agents, and the evaluation of intracranial vessel status. The important issues of the examiners' training and experience, the documentation, and analysis of study results are addressed. One central aspect was the development of standardized criteria for diagnosis of arterial occlusion. A transcranial color-coded duplex sonography recanalization score based on objective hemodynamic criteria is introduced (consensus on grading intracranial flow obstruction [COGIF] score). CONCLUSIONS: This work presents consensus statements in an attempt to standardize the application of transcranial color-coded duplex sonography in the setting of acute stroke research, aiming to improve the reliability and reproducibility of the results of future stroke studies

high quality genomic dna from human whole blood and mononuclear cells

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Light-Triggered Electron Transfer between a Conjugated Polymer and Cytochrome C for Optical Modulation of Redox Signaling

Protein reduction/oxidation processes trigger and finely regulate a myriad of physiological and pathological cellular functions. Many biochemical and biophysical stimuli have been recently explored to precisely and effectively modulate intracellular redox signaling, due to the considerable therapeutic potential. Here, we propose a first step toward an approach based on visible light excitation of a thiophene-based semiconducting polymer (P3HT), demonstrating the realization of a hybrid interface with the Cytochrome c protein (CytC), in an extracellular environment. By means of scanning electrochemical microscopy and spectro-electrochemistry measurements, we demonstrate that, upon optical stimulation, a functional interaction between P3HT and CytC is established. Polymer optical excitation locally triggers photoelectrochemical reactions, leading to modulation of CytC redox activity, either through an intermediate step, involving reactive oxygen species formation, or via a direct photoreduction process. Both processes are triggered by light, thus allowing excellent spatiotemporal resolution, paving the way to precise modulation of protein redox signaling

Autonomous Non-Equilibrium Self-Assembly and Molecular Movements Powered by Electrical Energy

The ability to exploit energy autonomously is one of the hallmarks of life. Mastering such processes in artificial nanosystems can open technological opportunities. In the last decades, light- and chemically driven autonomous systems have been developed in relation to conformational motion and self-assembly, mostly in relation to molecular motors. In contrast, despite electrical energy being an attractive energy source to power nanosystems, its autonomous harnessing has received little attention. Herein we consider an operation mode that allows the autonomous exploitation of electrical energy by a self-assembling system. Threading and dethreading motions of a pseudorotaxane take place autonomously in solution, powered by the current flowing between the electrodes of a scanning electrochemical microscope. The underlying autonomous energy ratchet mechanism drives the self-assembly steps away from equilibrium with a higher energy efficiency compared to other autonomous systems. The strategy is general and might be extended to other redox-driven systems

Low-flow ischemia and hypoxia stimulate apoptosis in perfused rat hearts independently of reperfusion

Post-ischemic reperfusion leads to apoptosis-linked loss of myocytes in cultured cells and in vivo. We tested the hypothesis that apoptosis develops without reperfusion in Langendorff-perfused hearts exposed to either low-flow ischemia (LFI) or hypoxia (H). Rat hearts were perfused with aminoacid-enriched Krebs- Henseleit buffer and exposed for 6 h to LFI (flow=2 ml/min, PO2=500\ub150mmHg, mean\ub1SD), H (10ml/min, 120\ub115mmHg), or control conditions (C, 10ml/min, 500\ub150mmHg). At selected times, DNA-fragmentation was measured by agarose-gel electrophoresis and in situ TUNEL assay. After 6 h, the ratio (TUNEL-positi- ve)/(total nuclei) was 0.620\ub10.027, 0.615\ub10.005, 0.404\ub10.021 in LFI, H and C, respectively. The ratio was 0.813\ub10.021 in hearts exposed to 90 min global no-flow ischemia and reperfused (5 h). To assess the role of membrane-diffusible factors, separate experiments were performed recirculating the medium and exposing hearts to LFI or H as above. The degree of apoptosis was the same in both the recirculating and non-recirculating modes. Thus, apoptosis develops by similar extents and in a time-dependent fashion in crystalloid-perfused rat hearts during LFI or H at the same oxygen shortage (flow\u2022PO2), even without the reperfusion

Electrochemical Characterization and CO2 Reduction Reaction of a Family of Pyridazine-Bridged Dinuclear Mn(I) Carbonyl Complexes

Three recently synthesized neutral dinuclear carbonyl manganese complexes with the pyridazine bridging ligand, of general formula [Mn2(μ-ER)2(CO)6(μ-pydz)] (pydz = pyridazine; E = O or S; R = methyl or phenyl), have been investigated by cyclic voltammetry in dimethylformamide and acetonitrile both under an inert argon atmosphere and in the presence of carbon dioxide. This family of Mn(I) compounds behaves interestingly at negative potentials in the presence of CO2. Based on this behavior, which is herein discussed, a rather efficient catalytic mechanism for the CO2 reduction reaction toward the generation of CO has been hypothesized

Field emission properties of carbon nanotube arrays grown in porous anodic alumina

AbstractCarbon nanotubes (CNTs), with their excellent electronic properties and extremely high aspect ratio, represent an ideal material for building electron sources based on field emission. Fowler‐Nordheim equation describes quite successfully the field emission phenomenon, especially for single or isolated tips. However, some complications arise when populations of CNTs are considered, where collective effects and large variability in the emitters features influence the measured I–V characteristics. In this work, the emission properties of multi‐walled CNTs grown within ordered anodic alumina templates are investigated. These CNT matrices produce current densities up to some tens of mA/cm2, and the field enhancement factor for collective emission sources can be estimated. Such material can be modelled as an ordered and uniform array of emitters and a simulation of the electrostatic field on the emission tips can be done in order to evaluate the field enhancement factor and its dependence on various geometries. This allows comparing predictions from simulation and experimental measurements, in a direct way. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim

An unexpected evolution of symptomatic mild middle cerebral artery (MCA) stenosis: asymptomatic occlusion

<p>Abstract</p> <p>Background</p> <p>The intracranial localization of large artery disease is recognized as the main cause of ischemic stroke in the world, considering all countries, although its global burden is widely underestimated. Indeed it has been reported more frequently in Asians and African-American people, but the finding of intracranial stenosis as a cause of ischemic stroke is relatively common also in Caucasians. The prognosis of patients with stroke due to intracranial steno-occlusion is strictly dependent on the time of recanalization. Moreover, the course of the vessel involvement is highly dynamic in both directions, improvement or worsening, although several data are derived from the atherosclerotic subtype, compared to other causes.</p> <p>Case description</p> <p>We report the clinical, neurosonological and neuroradiological findings of a young woman, who came to our Stroke Unit because of the abrupt onset of aphasia during her work. An urgent neurosonological examination showed a left M1 MCA stenosis, congruent with the presenting symptoms; magnetic resonance imaging confirmed this finding and identified an acute ischemic lesion on the left MCA territory. The past history of the patient was significant only for a hyperinsulinemic condition, treated with metformine, and a mild overweight. At this time a selective cerebral angiography was not performed because of the patient refusal and she was discharged on antiplatelet and lipid-lowering therapy, having failed to identify autoimmune or inflammatory diseases. Within 1 month, she went back to our attention because of the recurrence of aphasia, lasting about ten minutes. Neuroimaging findings were unchanged, but the patient accepted to undergo a selective cerebral angiography, which showed a mild left distal M1 MCA stenosis.</p> <p>During the follow-up the patient did not experienced any recurrence, but a routine neurosonological examination found an unexpected evolution of the known MCA stenosis, i.e. left M1 MCA occlusion. Neuroradiological imaging did not identify new lesions of the brain parenchyma and a repeated selective cerebral angiography confirmed the left M1 MCA occlusion.</p> <p>Conclusions</p> <p>Regardless of the role of metabolic and/or inflammatory factors on the aetiology of the intracranial stenosis in this case, the course of the vessel disease was unexpected and previously unreported in the literature at our knowledge.</p