How Much Can We Trust Major Element Quantification in Bioapatite Investigation?

Bioapatite is probably the key factor in the unreplicated success of vertebrates. Chemical data on bioapatite composition can be achieved on a solid sample by using different analytical tools such as spectroscopic and spectrometric methods. As analytical outputs can be affected by the physical-chemical characteristics of the sample matrix, an internal standard is usually required to correct and validate the results. Bioapatite lattice can accommodate iso- and heterovalent substitutions during life or diagenesis varying its chemical composition through (geological) time. If on the one hand, this makes bioapatite a unique archive of physical and chemical information for both the living cycle and the events occurring after death, on the other, it excludes the identification of a sole internal standard. Here, we propose a method to measure major element concentration with specific care for P, Ca, Mg, Na, K, Si, Al, and Fe, which are the main substituent atoms in bioapatite, through homemade matrix-matched external calibration standards for laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). We tested the method on living and fossil shark teeth, critically comparing the results obtained using other analytical techniques and certified external standards. We demonstrated that matrix-matched calibration in LA-ICPMS is mandatory for obtaining a reliable chemical characterization even if factors such as matrix aggregation variability, diverse presence of volatile compounds, the fossilization footprint, and the instrumental variability can represent further variability parameters

Structural properties of adsorbent phyllosilicates rule the entrapping ability of intercalated iron-phenanthroline complex towards thiols

The interaction of volatile organic sulfur derivatives, such as 1-heptanethiol (C7H16S), with clay minerals treated with a μ-oxo Fe3+-phenanthroline 1:1 complex results strongly affected by crystal chemical properties of pristine mineral phases. In particular, two sepiolite clays with different structural features demonstrated significantly different ability to immobilize the Fe3+-phenanthroline complex at two pH values (pH = 5.4 and pH = 2.3). The most effective binding was obtained with sepiolite with higher structural disorder at pH 5.4. Accordingly, the resulting hybrid material showed also the greatest efficiency in removal of thiol in gas phase. A direct correlation can be established between the adsorption of the Fe3+-phenanthroline complex and the gas binding process at room temperature. In fact, 1-heptanethiol entrapping occurs via redox reactions between Fe3+ and a first thiol molecule to give the reduced Fe2+-phenanthroline complex and disulfide, followed by the binding of further thiols to the reduced metal centre. The extremely high amount of thiol immobilized by the hybrid material also suggests the co-presence of a catalytic mechanism that guarantees the reoxidation of Fe+2 to Fe+3 and the restoration of redox reactions with thiol. Investigation and conclusions were supported by the several experimental techniques: elemental analysis, X-ray powder diffraction analyses, UV–Vis measurements, FT-IR and NMR spectroscopies, thermogravimetric analyses

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

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

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

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

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

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

Interlayer-confined Cu(II) complex as an efficient and long-lasting catalyst for oxidation of H2s on montmorillonite

Removal of highly toxic H2S for pollution control and operational safety is a pressing need. For this purpose, a montmorillonite intercalated with Cu(II)-phenanthroline complex [Cu[(Phen)(H2O)2]2+ (Mt-CuPhen) was prepared to capture gaseous H2S under mild conditions. This hybrid material was simple to obtain and demonstrated an outstanding ability to entrap H2S at room temperature, retaining high efficiency for a very long time (up to 36.8 g of S/100 g Mt-CuPhen after 3 months of exposure). Sorbent and H2S uptake were investigated by elemental analysis, X-ray powder diffraction measurements, diffuse reflectance (DR) UV\u2013Vis and infrared spectroscopy, thermal analysis and evolved gas mass spectrometry, scanning electron microscopy equipped with energy-dispersive X-ray spectrometer, and X-ray absorption spectroscopy. The H2S capture was studied over time and a mechanism of action was proposed. The entrapping involves a catalytic mechanism in which [Cu[(Phen)(H2O)2]2+ acts as catalyst for H2S oxidation to S0 by atmospheric oxygen. The low cost and the long-lasting performance for H2S removal render Mt-CuPhen an extremely appealing trap for H2S removal and a promising material for many technological applications