Synthesis, characterization, electrochemistry and spectroelectrochemistry of novel soluble porphyrazines bearing unsaturated functional groups

Metalloporphyrazines with a 2-methyl-2-pentenyl group fused to each pyrrole unit were synthesized starting with the corresponding unsaturated dicarbonitrile derivative. The new compounds were characterized by elemental analysis together with FTIR, ¹H-NMR, and UV-Vis spectroscopy and via voltammetric and spectrochemical methods. Electrochemical and spectroelectrochemical measurements demonstrate that while metal-free and magnesium porphyrazines gave common porphyrazine (Pz) ring-based electron-transfer reactions, incorporating redox active metal center, Co^II, into the porphyrazine core extended the redox activity of the ring system with reversible metal-based reduction and oxidation couples of the metal center in addition to the common Pz ring-based electron transfer processes. The unsaturated functional groups of the porphyrazines did not alter the common electrochemical behavior of the complexes. An in situ electrocolorimetric method, based on the 1931 CIE (Commission Internationale de l’Eclairage) system of colorimetry, was applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for possible electrochromatic applications.     

The use of polyacrylamide-aluminosilicate composites for thorium adsorption

The adsorption of Th⁴⁺ ions was studied on composites of polyacrylamide (PAAm) with montmorillonite (Mt), clinoptilolite (Z) and zeolite Y (ZY), and after phytic acid (Phy) modification.The monolayer adsorption capacity was 0.33 and 0.65 mol kg^? 1 for PAAm-Mt and PAAm-Mt-Phy, 0.07, 0.21 and 0.60 mol kg^? 1 for Z, PAAm-Z and PAAm-Z-Phy, and 0.74, 0.89 and 1.18 mol kg^? 1 for ZY, PAAm-ZY and PAAm-ZY-Phy. The enthalpy and entropy changes were positive for all adsorbents. The adsorption kinetics followed the pseudo-second order model indicating that the rate controlling step was chemical adsorption by ion exchange. The reusability tests for five uses proved that the PAAm-Mt and PAAm-Z were reusable and complete recovery of the adsorbed ions was possible. ZY and the composites modified with Phy were not reusable. The presence of foreign metal cations did not influence the Th⁴⁺ adsorption. The adsorbed Th⁴⁺ onto the columns was effectively recovered with diluted HNO₃.     

Synthesis,photophysics, photochemistry and fluorescence quenching studies on highly soluble substituted oxo-titanium(IV) phthalocyanine complexes

The synthesis, photophysical and photochemical properties of soluble 3,4-(methylendioxy)-phenoxy substituted oxo-titanium(IV) phthalocyanines (4–6) are reported for the first time. The new compounds have been characterized by elemental analysis, FT-IR, ¹H NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for fluorescence lifetimes and fluorescence, photodegradation and singlet oxygen quantum yields, of these compounds in dimethylsulfoxide (DMSO) and toluene. The effects of the position of the substituents and solvent effect on the photophysical and photochemical parameters of the oxo-titanium(IV) phthalocyanines (4–6) are also reported. The fluorescence of the substituted oxo-titanium(IV) phthalocyanine complexes (4–6) is effectively quenched by 1,4-benzoquinone (BQ) in both DMSO and toluene.     

A deep learning-based CEP rule extraction framework for IoT data

The Journal of Supercomputing - With the recent developments in Internet of Things (IoT), the number of sensors that generate raw data with high velocity, variety, and volume is tremendously...     

TPS3: A privacy preserving data collection protocol for smart grids

Smart grid (SG) allows for two-way communication between the utility and its consumers and hence they are considered as an inevitable future of the traditional grid. Since consumers are the key component of SGs, providing security and privacy to their personal data is a critical problem. In this paper, a security protocol, namely TPS3, is based on Temporal Perturbation and Shamir’s Secret Sharing (SSS) schemes that are proposed to ensure the privacy of SG consumer’s data. Temporal perturbation is employed to provide temporal privacy, while the SSS scheme is used to ensure data confidentiality. Temporal perturbation adds random delays to the data collected by smart meters, whereas the SSS scheme fragments these data before transmitting them to the data collection server. Joint employment of both schemes makes it hard for attackers to obtain consumer data collected in the SG. The proposed protocol TPS3 is evaluated in terms of privacy, reliability, and communication cost using two different SG topologies. The performance evaluation results clearly show that the TPS3 protocol ensures the privacy and reliability of consumer data in SGs. The results also show that the tradeoff between the communication cost and security of TPS3 is negligible.     

Adsorptive features of chitosan entrapped in polyacrylamide hydrogel for Pb2+, UO2(2+), and Th4+

Chitosan (Ch) was entrapped in polyacrylamide (PAA) by direct polymerization of acrylamide in a suspension of Ch. The adsorptive features of PAA-Ch and Ch were then investigated for Pb2+, UO2(2+), and Th4+ in view of dependency on ion concentration, temperature, and kinetics. Additional considerations were also given to their ion selectivity and reusability. Isotherms were L and H type of Giles classification and evaluated with reference to Langmuir, Freundlich, and Dubinin-Radushkevich (DR) models. PAA-Ch had higher adsorption capacity than Ch for all studied ions so that the sequences were Th4+>Pb2+>UO2(2+) concordantly with their affective ionic charges. The affinity of Ch in PAA increased for Pb2+ and UO2(2+) but did not change for Th4+. The values of enthalpy and entropy changed were positive for all studied ions for both Ch and PAA-Ch. The negative free enthalpy change value indicated that the adsorption process is spontaneous in the sequence of Th4+>or=Pb2+>UO2(2+). Free energy values derived from DR model implied that the sorption process is the ion exchange. Well compatibility of adsorption kinetics to the pseudosecond-order model predicate that the rate-controlling step is a chemical sorption. The study for ion selectivity showed that both Ch and PAA-Ch had the highest affinity to Pb2+. The reusability tests for Ch and PAA-Ch for Pb2+ for five uses showed that complete recovery of the ion was possible. The studied features of PAA-Ch suggest that the material should be considered as a new adsorbent. It is envisaged that the use of Ch in PAA will enhance practicality and effectiveness of Ch in separation and removal procedures.