Suzuki–Miyaura coupling reaction in water in the presence of robust palladium immobilized on modified magnetic Fe3O4 nanoparticles as a recoverable catalyst

Aryl halides and especially inactive aryl chlorides were coupled to benzenoid aromatic rings in a Suzuki–Miyaura coupling reaction in the absence of organic solvents and toxic phosphine ligands. The reaction was catalysed by a recoverable magnetic nanocatalyst, Pd@Fe₃O₄, in aqueous media. This method is green, and the catalyst is easily removed from the reaction media using an external magnetic field and can be re‐used at least 10 times without any considerable loss in its activity. The catalyst was characterized using scanning and transmission electron microscopies, thermogravimetric analysis, inductively coupled plasma spectroscopy, Fourier transform infrared spectroscopy, CHN analysis, X‐ray diffraction and vibrating sample magnetometry.     

Electrochemical investigation of gel polymer electrolytes based on poly(methyl methacrylate) and dimethylacetamide for application in Li-ion batteries

In the present work, gel polymer electrolytes (GPEs) were prepared using poly(methyl methacrylate) (PMMA), lithium perchlorate (LiClO₄) and dimethylacetamide as a plasticizer. Solution-casting technique was used to fabricate GPEs containing different weight percentage of PMMA. The degree of crystallinity of GPE samples was studied by X-ray diffraction (XRD) analysis. Fourier transform infrared (FT-IR) spectroscopy was applied to study the level of interactions between lithium salt and PMMA in the prepared GPEs. Electrochemical properties were studied by electrochemical impedance spectroscopy, linear sweep voltammetry and DC polarization techniques. Lithium ion conductivity of GPEs was determined by calculating the bulk resistance of polymer electrolytes from Nyquist plot. Increasing PMMA content of GPEs resulted in an improvement in the electrochemical potential window from 4.2 to 4.5 V. The highest lithium transference number (0.42) and also the best electrochemical properties were obtained for GPE containing 0.75 M LiClO₄ and 10 wt% PMMA. Scanning electron microscopy images of the optimized GPE showed a porous and heterogeneous surface structure which is desirable for application in Li-ion batteries.     

NH4I-catalyzed chalcogen(S/Se)-functionalization of 5-membered N-heteroaryls under metal-free conditions

Herein, we described the NH₄I-catalyzed CH bond chalcogenation of N-heteroaryls in the presence of a minimum amount of DMSO/H₂O/acetic acid as additives (2.5/2.5/1?M equiv., respectively), under metal-free conditions. Under optimized conditions, a wide variety of sulfenyl/selenyl imidazo[1,2-α]pyridines were prepared in very good yields. Moreover, the present approach was also highly efficient for the chalcogenation of different 5-membered N-heteroaryls, e.g., indole, imidazothiazole, indazole and imidazopyrimidine derivatives.     

Atrane complexes chemistry as a tool for obtaining trimodal UVM-7-like porous silica

Abstract

The use of atrane complexes as hydrolytic precursors enables the homogeneous incorporation of manganese (25 ≤ Si/Mn ≤ 48) throughout the porous walls of the nanoparticles of a surfactant-templated bimodal mesoporous silica (UVM-7). The subsequent leaching of the manganese nanodomains allows adding controlled microporosity to the host silica framework. The resulting final silica material presents three pore systems structured at different length scales: interparticle textural-type macroporosity (ca. 43.2 nm), ordered intraparticle mesoporosity (ca. 2.63 nm; after template removal), and well-dispersed microporosity (< 2 nm; as consequence of the lixiviation of the Mn-rich domains). The good dispersion of the guest element (Mn) in the silica intermediate provided by the atrane route is responsible for the disordered but regular microporosity achieved.     

Polarographic behaviour of salicylaldehyde-2-pyridylhydrazone and its copper(II) complex

The polarographic behaviour of salicylaldehyde-2-pyridylhydrazone (SAPH) has been studied in aqueous buffer solution containing 40% ethanol using DC and DP polarographic methods. In the pH range 1.8–7.5 the observed single irreversible reduction wave is assigned to the splitting of the N-N bond and reduction of C=N centre. In alkaline medium, a second wave appears at a more negative potential due to the reduction of the salicylaldehyde which is formed by hydrolytic decomposition of the SAPH molecule. The effect of pH on the limiting current andE _1/2 as well as the reduction mechanism are discussed and compared with similar compounds. The kinetic parameters of the electrode reaction have been calculated.The analytical properties of the copper(II)-SAPH system is described. The complex gave rise to a single irreversible well-defined wave (E _1/2=–0.58 V at pH=5.2). The reaction process is diffusion controlled. A method is suggested for the determination of Cu(II) in presence of different metal ions as the difference in theirE _1/2 values is sufficient for the purpose.This work is taken partly from the M. Sc. Thesis of Jamal S. Shalabi     

Theoretical conformational analysis of opiate peptides Leu-Enkephalin (H-Tyr-Gly-Gly-Phe-Leu-OH) and its two thioamide analogs (H-Tyr-Glyψ[CSNH]Gly-Phe-Leu-OH) and (H-Tyr-Gly-Glyψ[CSNH]Phe-Leu-OH)

In order to find informations on the native structure of the Leu-Enkephalin opiate peptide, the parent peptide and its two thioamide analogs (Thio-Gly2)Leu-Enkephalin and (Thio-Gly3)Leu-Enkephalin were studied by the theoretical method PEPSEA. This comparative conformational analysis showed that the active conformation is a β turn structure centered on Gly3 and Phe4. Moreover, this study showed also that the more active analog (Thio-Gly2)Leu-Enk has a lower tendency to adopt this structure. Consequently, its high activity can only be explained by its long lifetime due to its resistance to enzymatic hydrolysis, following the substitution of the amide linkage by the thioamide one. The weakly active analog (Thio-Gly3)Leu-Enk does not adopt this structure and prefers instead a β turn structure centered on Gly2 and Gly3. This study also confirmed the importance of the distances between the Tyr and Phe residues at positions 1 and 4, and that of the terminal Tyrosine N-H group which must be free of any intramolecular hydrogen bond in order to be available in the molecular recognition process.     

The detection and location estimation of disasters using Twitter and the identification of Non-Governmental Organisations using crowdsourcing

This paper provides the humanitarian community with an automated tool that can detect a disaster using tweets posted on Twitter, alongside a portal to identify local and regional Non-Governmental Organisations (NGOs) that are best-positioned to provide support to people adversely affected by a disaster. The proposed disaster detection tool uses a linear Support Vector Classifier (SVC) to detect man-made and natural disasters, and a density-based spatial clustering of applications with noise (DBSCAN) algorithm to accurately estimate a disaster’s geographic location. This paper provides two original contributions. The first is combining the automated disaster detection tool with the prototype portal for NGO identification. This unique combination could help reduce the time taken to raise awareness of the disaster detected, improve the coordination of aid, increase the amount of aid delivered as a percentage of initial donations and improve aid effectiveness. The second contribution is a general framework that categorises the different approaches that can be adopted for disaster detection. Furthermore, this paper uses responses obtained from an on-the-ground survey with NGOs in the disaster-hit region of Uttar Pradesh, India, to provide actionable insights into how the portal can be developed further.

     

The metal-to-ligand charge-transfer luminescences of ruthenium(II)-polypyridine-tetraam(m)ine complexes. Support for the interconvertibility of optical and thermal (kinetic) Franck-Condon parameters

This is the first report of the metal-to-ligand charge-transfer (MLCT) emission spectra of the bis-ethylenediamine- and tetraammine-bipyridineruthenium(II) complexes. The emission maxima occur at 800 and 840 nm, respectively, at 77 K in DMSO/H(2)O glasses. The MLCT excited states of these complexes have short lifetimes (less than 50 ns), and as a consequence, the emission intensities are very small. The energies of the emission maxima are very close to those expected on the basis of the difference in reduction potentials of the metal and ligand (DeltaE(1/2)) and the values of the reorganizational free energies (chi(r)) of the vertical transitions estimated from the electron-transfer self-exchange reactions of the complexes (hnu(max)(em) congruent with FDeltaE(1/2) - chi(r), where F is Faraday's constant). The low energy of the emissions is in large part a consequence of the substantial contributions of the reorganizational free energies.     

Switched system modeling and robust steering control of the tail end phase in a hot strip mill

In this article, a robust steering control for the last phase of the rolling process in a hot strip mill is proposed. This phase, called tail end phase, may be modelled as a linear switched system. The switchings make the system unstable and the task of the tail end steering control consists in guaranteeing the safety of the industrial plant. The system involves a two time scales dynamics. Hence, the singular perturbation method is used in order to design the control law. The controller has to take into account the physical variations of the rolled products and an uncertainty in the switching time. Results concerning the ArcelorMittal hot strip mill of Eisenhüttenstadt are presented.     

Study of Kinetic Freeze-Out Parameters as a Function of Rapidity in pp Collisions at CERN SPS Energies

We used the blast wave model with the Boltzmann–Gibbs statistics and analyzed the experimental data measured by the NA61/SHINE Collaboration in inelastic (INEL) proton–proton collisions at different rapidity slices at different center-of-mass energies. The particles used in this study were π+, π−, K+, K−, and p¯. We extracted the kinetic freeze-out temperature, transverse flow velocity, and kinetic freeze-out volume from the transverse momentum spectra of the particles. We observed that the kinetic freeze-out temperature is rapidity and energy dependent, while the transverse flow velocity does not depend on them. Furthermore, we observed that the kinetic freeze-out volume is energy dependent, but it remains constant with changing the rapidity. We also observed that all three parameters are mass dependent. In addition, with the increase of mass, the kinetic freeze-out temperature increases, and the transverse flow velocity, as well as kinetic freeze-out volume decrease.