The direction of the dipole moments of furan,thiophen, and pyrrole: A controversial question

The report that the dipole moment in the five-membered heterocyclic rings, furan, thiophene, and pyrrole has the positive pole on the heteroatom is contradicted with arguments based on reactivity data, theoretical calculations and moment values of substituted derivatives. In actuality, the dipole moment in furan and thiophene is directed from the ring (positive pole) to the heteroatom (negative pole).     

Optical Anisotropy of Porphyrin Nanocrystals Modified by the Electrochemical Dissolution

Reflectance anisotropy spectroscopy (RAS) coupled to an electrochemical cell represents a powerful tool to correlate changes in the surface optical anisotropy to changes in the electrochemical currents related to electrochemical reactions. The high sensitivity of RAS in the range of the absorption bands of organic systems, such as porphyrins, allows us to directly correlate the variations of the optical anisotropy signal to modifications in the solid-state aggregation of the porphyrin molecules. By combining in situ RAS to electrochemical techniques, we studied the case of vacuum-deposited porphyrin nanocrystals, which have been recently observed dissolving through electrochemical oxidation in diluted sulfuric acid. Specifically, we could identify the first stages of the morphological modifications of the nanocrystals, which we could attribute to the single-electron transfers involved in the oxidation reaction; in this sense, the simultaneous variation of the optical anisotropy with the electron transfer acts as a precursor of the dissolution process of porphyrin nanocrystals.     

Driving Organic Nanocrystals Dissolution Through Electrochemistry

We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (Zn^II) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential.     

Compared EC-AFM Analysis of Laser-Induced Graphene and Graphite Electrodes in Sulfuric Acid Electrolyte

Flexible and economic sensor devices are the focus of increasing interest for their potential and wide applications in medicine, food analysis, pollution, water quality, etc. In these areas, the possibility of using stable, reproducible, and pocket devices can simplify the acquisition of data. Among recent prototypes, sensors based on laser-induced graphene (LIGE) on Kapton represent a feasible choice. In particular, LIGE devices are also exploited as electrodes for sensing in liquids. Despite a characterization with electrochemical (EC) methods in the literature, a closer comparison with traditional graphite electrodes is still missing. In this study, we combine atomic force microscopy with an EC cell (EC-AFM) to study, in situ, electrode oxidation reactions when LIGE or other graphite samples are used as anodes inside an acid electrolyte. This investigation shows the quality and performance of the LIGE electrode with respect to other samples. Finally, an ex situ Raman spectroscopy analysis allows a detailed chemical analysis of the employed electrodes.     

A Stable Porphyrin Functionalized Graphite Electrode Used at the Oxygen Evolution Reaction Potential

Many researches have been devoted to rechargeable power generators that can store (but also release) energy. This availability is ensured through (e. g.) the oxygen evolution reaction (OER). However, (i) large values of the overpotentials and (ii) a progressive detriment of the anode (graphite) electrode limit the ultimate device. In view of enhancing the electrode performances, graphite was protected by following different strategies, which oblige to follow precise preparation protocols. Here, we prove that a thin layer of free-base porphyrin molecules is able to protect the underneath graphite electrode from detriment even if many (about 100) electrochemical cycles are performed.     

Dynamic Multi-level Overlay Graphs for Shortest Paths

Multi-level overlay graphs represent a speed-up technique for shortest paths computation which is based on a hierarchical decomposition of a weighted directed graph G. They have been shown to be experimentally efficient, especially when applied to timetable information. However, no theoretical result on the cost of constructing, maintaining and querying multi-level overlay graphs in a dynamic environment is known. In this paper, we show theoretical properties of multi-level overlay graphs that lead us to the definition of a new data structure for the computation and the maintenance of an overlay graph of G while weight decrease or weight increase operations are performed on G. Our solution is theoretically faster than the recomputation from scratch and allows queries that can be performed more efficiently than running Dijkstra’s shortest paths algorithm on G. This work was partially supported by the Future and Emerging Technologies Unit of EC (IST priority – 6th FP), under contract no. FP6-021235-2 (project ARRIVAL).     

ARDESIA: A fast silicon drift detector X-ray spectrometer for synchrotron applications

ARDESIA, a four-channel X-ray spectrometer based on silicon drift detectors (SDDs), is presented. It has been developed for synchrotron applications targeting especially X-ray fluorescence (XRF) and X-ray absorption spectroscopy (XAS) with good energy resolution at high count rates (a few Mcps per second). The main target applications are XRF and XAFS techniques. The system features a 2 × 2 monolithic array of 5-mm-pitch SDDs cooled with a double Peltier scheme and coupled to a four-channel CUBE charge preamplifier. Different digital pulse processors allowing operation in Mcps per second count rates are employed. The results of preliminary characterization measurements performed at both the LNF DAΦNE-Light DXR1 beamline and the ESRF LISA BM-08 are reported, in particular, XRF measurements on low atomic number elements (down to the Carbon K-line, 270 eV) and extended X-ray absorption fine structure of trace materials in pyrite.     

A germanium photodetector array for the near infrared monolithically integrated with silicon CMOS readout electronics

Near infrared (NIR) detectors, operating in the 1.3–1.6 μm region, are key elements in a number of applications ranging from optical communications to remote sensing. InGaAs and Ge are currently the materials of choice for the fabrication of NIR detectors due to their good absorption and transport properties. However, as the required performances increase (bit-rate in optical communications, number of pixels in imaging, etc.), it becomes more and more important to reduce the separation from detectors and driving/biasing and amplifying electronics, by integrating the two components on the same chip.We demonstrate an array of NIR detectors monolithically integrated with standard silicon CMOS readout electronics. The employed low temperature process allowed the integration of the detectors as the last step of chip fabrication. The integrated micro-system consists of a linear array of 120×120 μm² pixels, an analog CMOS multiplexer and a transimpedance amplifier. The chip exhibits a good photoresponse in the NIR, with responsivities as high as 43 V/W at 1.3 μm, dark currents of 1 mA/cm² and inter-pixel cross-talk better than −20 dB.     

Statistical Characterization of Heterogeneous Dissolution Rates of Calcite from In situ and Real-Time AFM Imaging

Transport in Porous Media - The evolution of the surface topography of a calcite crystal subject to dissolution is documented through in situ real-time imaging obtained via atomic force microscopy...