Search results for: metallic complexes

Authors: Tassia Batista Pessato, Francielli Pires Ribeiro Morais, Fernanda Guimaraes Drummond Silva, Flavia Maria Netto

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Proteins and phenolic compounds can interact mainly by hydrophobic interactions. Those interactions may lead to structural changes in both molecules, which in turn could affect positively or negatively their functional and nutritional properties. Here, the structural changes of whey proteins (WPI) due to interaction with caffeic acid (CA) were investigated by intrinsic and extrinsic fluorescence. The effects of protein-phenolic compounds interactions on the total phenolic content and antioxidant activity were also assessed. The WPI-CA complexes were obtained by mixture of WPI and CA stock solutions in deionized water. The complexation was carried out at room temperature during 60 min, using 0.1 M NaOH to adjust pH at 7.0. The WPI concentration was fixed at 5 mg/mL, whereas the CA concentration varied in order to obtain four different WPI:CA molar relations (1:1; 2:1; 5:1; 10:1). WPI and phenolic solutions were used as controls. Intrinsic fluorescence spectra of the complexes (mainly due to Trp fluorescence emission) were obtained at λex = 280 nm and the emission intensities were measured from 290 to 500 nm. Extrinsic fluorescence was obtained as the measure of protein surface hydrophobicity (S0) using ANS as a fluorescence probe. Total phenolic content was determined by Folin-Ciocalteau and the antioxidant activity by FRAP and ORAC methods. Increasing concentrations of CA resulted in decreasing of WPI intrinsic fluorescence. The emission band of WPI red shifted from 332 to 354 nm as the phenolic concentration increased, which is related to the exposure of Trp residue to the more hydrophilic environment and unfolding of protein structure. In general, the complexes presented lower S0 values than WPI, suggesting that CA hindered ANS binding to hydrophobic sites of WPI. The total phenolic content in the complexes was lower than the sum of two compounds isolated. WPI showed negligible AA measured by FRAP. However, as the relative concentration of CA increased in the complexes, the FRAP values enhanced, indicating that AA measure by this technique comes mainly from CA. In contrast, the WPI ORAC value (82.3 ± 1.5 µM TE/g) suggest that its AA is related to the capacity of H+ transfer. The complexes exhibited no important improvement of AA measured by ORAC in relation to the isolated components, suggesting complexation partially suppressed AA of the compounds. The results hereby presented indicate that interaction of WPI and CA occurred, and this interaction caused a structural change in the proteins. The complexation can either hide or expose antioxidant sites of both components. In conclusion, although the CA can undergo an AA suppression due to the interaction with proteins, the AA of WPI could be enhanced due to protein unfolding and exposure of antioxidant sites.

Keywords: bioactive properties, milk proteins, phenolic acids, protein-phenolic compounds complexation

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Authors: Srinivasa Reddy Mallampati, Byoung Ho Lee, Yoshiharu Mitoma, Simion Cristian

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In recent years, environmental nanotechnology has risen to the forefront and the new properties and enhanced reactivates offered by nanomaterial may offer a new, low-cost paradigm to solving complex environmental pollution problems. This study assessed the synthesis and application of multi-functioned nano-size metallic calcium (nMC) composite for detoxification of hazardous inorganic (heavy metals (HMs)/organic chlorinated/brominated compound (CBCs) contaminants in automobile shredder residue (ASR). ASR residues ball milled with nMC composite can achieve about 90-100% of HMs immobilization and CBCs decomposition. The results highlight the low quantity of HMs leached from ASR residues after treatment with nMC, which was found to be lower than the standard regulatory limit for hazardous waste landfills. The use of nMC composite in a mechanochemical process to treat hazardous ASR (dry conditions) is a simple and innovative approach to remediate hazardous inorganic/organic cross-contaminates in ASR.

Keywords: nano-sized metallic calcium, automobile shredder residue, organic/inorganic contaminants, immobilization, detoxification

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Authors: Tomasz Dubiel, Tadeusz Balawender, Miroslaw Osetek

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The paper presents the influence of non-metallic inclusions on the multi-stage forging process and the mechanical properties of the dodecagon socket bolt used in the automotive industry. The detected metallurgical defect was so large that it directly influenced the mechanical properties of the bolt and resulted in failure to meet the requirements of the mechanical property class. In order to assess the defect, an X-ray examination and metallographic examination of the defective bolt were performed, showing exogenous non-metallic inclusion. The size of the defect on the cross-section was 0.531 [mm] in width and 1.523 [mm] in length; the defect was continuous along the entire axis of the bolt. In analysis, a FEM simulation of the multi-stage forging process was designed, taking into account a non-metallic inclusion parallel to the sample axis, reflecting the studied case. The process of defect propagation due to material upset in the head area was analyzed. The final forging stage in shaping the dodecagonal socket and filling the flange area was particularly studied. The effect of the defect was observed to significantly reduce the effective cross-section as a result of the expansion of the defect perpendicular to the axis of the bolt. The mechanical properties of products with and without the defect were analyzed. In the first step, the hardness test confirmed that the required value for the mechanical class 8.8 of both bolt types was obtained. In the second step, the bolts were subjected to a static tensile test. The bolts without the defect gave a positive result, while all 10 bolts with the defect gave a negative result, achieving a tensile strength below the requirements. Tensile strength tests were confirmed by metallographic tests and FEM simulation with perpendicular inclusion spread in the area of the head. The bolts were damaged directly under the bolt head, which is inconsistent with the requirements of ISO 898-1. It has been shown that non-metallic inclusions with orientation in accordance with the axis of the bolt can directly cause loss of functionality and these defects should be detected even before assembling in the machine element.

Keywords: continuous casting, multi-stage forging, non-metallic inclusion, upset bolt head

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Authors: Issam Lakdhar, Akram Alhussein, Juan Creus

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With the huge increase in world energy consumption, researchers are working to find other alternative sources of energy instead of fossil fuel one causing many environmental problems as the production of greenhouse effect gases. Hydrogen is considered a green energy source, which its combustion does not cause environmental pollution. The transport and the storage of the gas molecules or the other products containing this smallest chemical element in metallic structures (pipelines, tanks) are crucial issues. The dissolve and the permeation of hydrogen into the metal lattice lead to the formation of hydride phases and the embrittlement of structures. To protect the metallic structures, a surface treatment could be a good solution. Among the different techniques, magnetron sputtering is used to elaborate micrometric coatings capable of slowing down or stop hydrogen permeation. In the plasma environment, the deposition parameters of new thin-film metallic glasses Al-Ti-W were optimized and controlled in order to obtain, hydrogen barrier. Many characterizations were carried out (SEM, XRD and Nano-indentation…) to control the composition and understand the influence of film microstructure and chemical composition on the hydrogen permeation through the coatings. The coating performance was evaluated under two hydrogen production methods: chemical and electrochemical (cathodic protection) techniques. The hydrogen quantity absorbed was experimentally determined using the Thermal-Desorption Spectroscopy method (TDS)). An ideal ATW thin film was developed and showed excellent behavior against the diffusion of hydrogen.

Keywords: thin films, hydrogen, PVD, plasma technology, electrochemical properties

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Authors: Saroj Poudel, Joshua Mancini, Douglas Pike, Jennifer Timm, Alexei Tyryshkin, Vikas Nanda, Paul Falkowski

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On the early Earth, protein-metal complexes likely harvested energy from a reduced environment. These complexes would have been precursors to the metabolic enzymes of ancient organisms. Hydrogenase is an essential enzyme in most anaerobic organisms for the reduction and oxidation of hydrogen in the environment and is likely one of the earliest evolved enzymes. To attempt to reinvent a precursor to modern hydrogenase, we computationally designed a short thirteen amino acid peptide that binds the often-required catalytic transition metal Nickel in hydrogenase. This simple complex can achieve hundreds of hydrogen evolution cycles using light energy in a broad range of temperature and pH. Biophysical and structural investigations strongly indicate the peptide forms a di-nickel active site analogous to Acetyl-CoA synthase, an ancient protein central to carbon reduction in the Wood-Ljungdahl pathway and capable of hydrogen evolution. This work demonstrates that prior to the complex evolution of multidomain enzymes, early peptide-metal complexes could have catalyzed energy transfer from the environment on the early Earth and enabled the evolution of modern metabolism

Keywords: hydrogenase, prebiotic enzyme, metalloenzyme, computational design

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Authors: I. Hilia, C. Hange, F. Hakala, M. Matheus, C. Jansen, J. Hidinwa, O. Awofolu

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The article reports on the occurrences, level, and mobility of selected trace metals in environmental samples. The conceptual basis was to examine the possible influence of anthropogenic activities and the impact on human and environmental health. Environmental samples (soil, plant and lower animal) were randomly collected from stratified study/sampling areas, preserved and pre-treated before analysis. Mineral acid digestion procedure was employed for the isolation of metallic contents in samples, and elemental qualitative and quantitative analysis was by ICP-OES. Analytical protocol was validated through the quality assurance process and was found acceptable with quantitative metallic recoveries in the range of 85-90%; hence considered applicable for the analyses of environmental samples. The mean concentration of analysed metals in soil samples ranged from 53.2- 2532.8 mg/kg (Cu); 59.5- 2020.1 mg/kg (Zn); 1.80 – 21.26 mg/kg (Cd) and 19.6- 140.9 mg/kg (Pb). The mean level in grass samples ranged from 9.33 – 38.63 mg/kg (Cu); 64.20-105.18 mg/kg (Zn); 0.28–0.73 mg/kg (Cd) and 0.53 -16.26 mg/kg (Pb) while the mean level in lower animal sample (beetle) varied from 9.6 - 105.3 mg/kg (Cu); 134.1-297.2 mg/kg (Zn); 0.63 – 3.78 (Cd) and 8.0 – 29.1 mg/kg (Pb) across sample collection points (SCPs) 1-4 respectively. Metallic transfer factors (TFs) were in the order Zn >Cd > Cu > Pb with metal Pollution Indices (MPIs) in the order SCP1 > SCP2 > SCP3 > SCP4. About 60-70 % of analysed metals were above the maximum allowable limits (MALs) in soil and plant samples. Results obtained revealed the general prevalence of analysed metals at all sampled sites with indication of metallic mobility across the food chain which portrayed dire consequences for environmental and human health. Systematic environmental remediation and pollution abatement strategies are recommended.

Keywords: trace metals, pollution, human health, Incidences, ICP-OES

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Authors: Dai Yizheng, Chen-Yang Zhang

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As station-city integration has been widely accepted as a strategy for mixed-use development, a quantitative analysis of the functional characteristics of urban complexes based on station-city integration is urgently needed. Taking 15 railway stations in European, North American, and East Asian cities as the research objects, this study analyzes their functional proportion, functional positioning, and functional correlation with respect to four categories of functional facilities for both railway passenger flow and subway passenger flow. We found that (1) the functional proportion of urban complexes was mainly concentrated in three models: complementary, dominant, and equilibrium. (2) The mathematical model affected by the functional proportion was created to evaluate the functional positioning of an urban complex at three scales: station area, city, and region. (3) The strength of the correlation between the functional area and passenger flow was revealed via data analysis using Pearson’s correlation coefficient. Finally, the findings of this study provide a valuable reference for research on similar topics in other countries that are developing station-city integration.

Keywords: urban complex, station-city integration, mixed-use, function, quantitative analysis

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Authors: R. Berrached, H. Ait Mahamed, A. Iddou

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Water pollution is nowadays a serious problem, due to the increasing scarcity of water and thus to the impact induced by such pollution on the human health. Various techniques are made use of to deal with water pollution. Among the most used ones, some can be enumerated: the bacterian bed, the activated mud, the Lagunage as biological processes and coagulation-floculation as a physic-chemical process. These processes are very expensive and an treatment efficiency which decreases along with the increase of the initial pollutants’ concentration. This is the reason why research has been reoriented towards the use of a process by adsorption as an alternative solution instead of the other traditional processes. In our study, we have tempted to exploit the characteristics of two metallic hydroxides Al and Fe to purify contaminated water by two industrial dyes SBL blue and SRL-150 orange. Results have shown the efficiency of the two materials on the blue SBL dye.

Keywords: metallic hydroxydes, industrial dyes, purificatıon,

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Authors: B. Bouadjemi, S. Bentata, W. Benstaali, A. Abbad, T. Lantri, A. Zitouni

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The purpose of this study was to investigate the structural,electronic and magnetic properties of the cubic praseodymium oxides perovskites PrMnO3. It includes our calculations based on the use of the density functional theory (DFT) with both generalized gradient approximation (GGA) and GGA+U approaches, The spin polarized electronic band structures and densities of states as well as the integer value of the magnetic moment of the unit cell (6 μB) illustrate that PrMnO3 is half-metallic ferromagnetic. The study prove that the compound is half-metallic ferromagnetic however the results obtained, make the cubic PrMnO3 a promising candidate for application in spintronics.

Keywords: cubic, DFT, electronic properties, magnetic moment, spintronics

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Authors: S. Forel, F. Bouanis, L. Catala, I. Florea, V. Huc, F. Fossard, A. Loiseau, C. Cojocaru

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Single wall carbon nanotubes are seen as excellent candidate for application on nanoelectronic devices because of their remarkable electronic and mechanical properties. These unique properties are highly dependent on their chiral structures and the diameter. Therefore, structure controlled growth of SWNTs, especially directly on final device’s substrate surface, are highly desired for the fabrication of SWNT-based electronics. In this work, we present a new approach to control the diameter of SWNTs and eventually their chirality. Because of their potential to control the SWNT’s chirality, bi-metalics nanoparticles are used to prepare alloy nanoclusters with specific structure. The catalyst nanoparticles are pre-formed following a previously described process. Briefly, the oxide surface is first covered with a SAM (self-assembled monolayer) of a pyridine-functionalized silane. Then, bi-metallic (Fe-Ru, Co-Ru and Ni-Ru) complexes are assembled by coordination bonds on the pre-formed organic SAM. The resultant alloy nanoclusters were then used to catalyze SWNTs growth on SiO2/Si substrates via CH4/H2 double hot-filament chemical vapor deposition (d-HFCVD). The microscopy and spectroscopy analysis demonstrate the high quality of SWNTs that were furthermore integrated into high-quality SWNT-FET.

Keywords: nanotube, CVD, device, transistor

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Authors: B. Bouadjemi, S. Bentata, W. Benstaali, A. Abbad, T. Lantri, A. Zitouni

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The purpose of this study was to investigate the structural,electronic and magnetic properties of the cubic praseodymium oxides perovskites PrMnO3. It includes our calculations based on the use of the density functional theory (DFT) with both generalized gradient approximation (GGA) and GGA+U approaches, The spin polarized electronic band structures and densities of states aswellas the integer value of the magnetic moment of the unit cell (6 μB) illustrate that PrMnO3 is half-metallic ferromagnetic. The study shows that the robust half-metallicity makes the cubic PrMnO3 a promising candidate for application in spintronics.

Keywords: Perovskite, DFT, electronic properties, Magnetic moment, half-metallic

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Authors: A. Zitouni, S. Bentata, B. Bouadjemi, T. Lantri, W. Benstaali, A. Zoubir, S. Cherid, A. Sefir

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The structural, electronic, and magnetic properties of transition metal Co and Mn doped zinc-blende semiconductor CdTe were calculated using the density functional theory (DFT) with both generalized gradient approximation (GGA). We have analyzed the structural parameters, charge and spin densities, total and partial densities of states. We find that the Co and Mn doped zinc blende CdTe show half-metallic behavior with a total magnetic moment of 6.0 and 10.0 µB, respectively.The results obtained, make the Co and Mn doped CdTe a promising candidate for application in spintronics.

Keywords: first-principles, half-metallic, diluted magnetic semiconductor, magnetic moment

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Authors: A. Bruce Janati, Muhammad Umair Khan, Naif Alghassab, Ibrahim Alzeir, Assem Mahmoud, M. Sammour

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Rationale: Lennox-Gastaut syndrome(LGS) is an electro-clinical syndrome composed of the triad of mental retardation, multiple seizure types, and the characteristic generalized slow spike-wave complexes in the EEG. In this article, we report on two patients with LGS whose brain MRI showed dysgenesis of corpus callosum(CC). We review the literature and stress the role of CC in the genesis of secondary bilateral synchrony(SBS). Method: This was a clinical study conducted at King Khalid Hospital. Results: The EEG was consistent with LGS in patient 1 and unilateral slow spike-wave complexes in patient 2. The MRI showed hypoplasia of the splenium of CC in patient 1, and global hypoplasia of CC combined with Joubert syndrome in patient 2. Conclusion: Based on the data, we proffer the following hypotheses: 1-Hypoplasia of CC interferes with functional integrity of this structure. 2-The genu of CC plays a pivotal role in the genesis of secondary bilateral synchrony. 3-Electrodecremental seizures in LGS emanate from pacemakers generated in the brain stem, in particular the mesencephalon projecting abnormal signals to the cortex via thalamic nuclei. 4-Unilateral slow spike-wave complexes in the context of mental retardation and multiple seizure types may represent a variant of LGS, justifying neuroimaging studies.

Keywords: EEG, Lennox-Gastaut syndrome, corpus callosum , MRI

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Authors: Lishuang Ma

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Charge transfer (CT) complex, also known as Electron donor-acceptor (EDA) complex, has received attentions increasingly in the field of synthetic chemistry community, due to the CT complex can absorb the visible light through the intermolecular charge transfer excited states, various of catalyst-free photochemical transformations under mild visible-light conditions. However, a number of fundamental questions are still ambiguous, such as the origin of visible light absorption, the photochemical and photophysical properties of the CT complex, as well as the detailed mechanism of the radical coupling pathways mediated by CT complex. Since these are critical factors for target-specific design and synthesis of more new-type CT complexes. To this end, theoretical investigations were performed in our group to answer these questions based on multiconfigurational perturbation theory. The photo-induced fluoroalkylation reactions are mediated by CT complexes, which are formed by the association of an acceptor of perfluoroalkyl halides RF−X (X = Br, I) and a suitable donor molecule such as β-naphtholate anion, were chosen as a paradigm example in this work. First, spectrum simulations were carried out by both CASPT2//CASSCF/PCM and TD-DFT/PCM methods. The computational results showed that the broadening spectra in visible light range (360-550nm) of the CT complexes originate from the 1(σπ*) excitation, accompanied by an intermolecular electron transfer, which was also found closely related to the aggregate states of the donor and acceptor. Moreover, from charge translocation analysis, the CT complex that showed larger charge transfer in the round state would exhibit smaller charge transfer in excited stated of 1(σπ*), causing blue shift relatively. Then, the excited-state potential energy surface (PES) was calculated at CASPT2//CASSCF(12,10)/ PCM level of theory to explore the photophysical properties of the CT complexes. The photo-induced C-X (X=I, Br) bond cleavage was found to occur in the triplet state, which is accessible through a fast intersystem crossing (ISC) process that is controlled by the strong spin-orbit coupling resulting from the heavy iodine and bromine atoms. Importantly, this rapid fragmentation process can compete and suppress the backward electron transfer (BET) event, facilitating the subsequent effective photochemical transformations. Finally, the reaction pathways of the radical coupling were also inspected, which showed that the radical chain propagation pathway could easy to accomplish with a small energy barrier no more than 3.0 kcal/mol, which is the key factor that promote the efficiency of the photochemical reactions induced by CT complexes. In conclusion, theoretical investigations were performed to explore the photophysical and photochemical properties of the CT complexes, as well as the mechanism of radical coupling reactions mediated by CT complex. The computational results and findings in this work can provide some critical insights into mechanism-based design for more new-type EDA complexes

Keywords: charge transfer complex, electron transfer, multiconfigurational perturbation theory, radical coupling

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Authors: Arslan Usman, Abdul Sattar, Hamid Latif, Afshan Ashfaq, Muhammad Rafique, Martin Koch

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Two-dimensional materials have promising applications in optoelectronic and photonics; MoS₂ is the pioneer 2D material in the family of transition metal dichalcogenides. Its optical, optoelectronic, and structural properties are of practical importance along with its exciton dynamics. Exciton, along with exciton complexes, plays a vital role in realizing quantum devices. MoS₂ monolayers were synthesized using chemical vapour deposition (CVD) technique on SiO₂ and hBN substrates. Photoluminescence spectroscopy (PL) was used to identify the monolayer, which also reflects the substrate based peak broadening due to screening effects. In-plane and out of plane characteristic vibrational modes E¹₂g and A₁g, respectively, were detected in a different configuration on the substrate. The B-excitons and trions showed a dominant feature at low temperatures due to electron-phonon coupling effects, whereas their energies are separated by 100 meV.

Keywords: 2D materials, photoluminescence, AFM, excitons

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Authors: Belete B. Beyene, Ayenew M. Mihirteu, Misganaw T. Ayana, Amogne W. Yibeltal

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Modification of synthetic porphyrins is one of the promising strategies in an attempt to get molecules with desired properties and applications. Here in, we report synthesis, photophysical characterization and antibacterial activity of 5, 10, 15, 20-tetrakis-(4- methoxy carbonyl phenyl) porphyrin M(II); where M = Co, Fe, Ni, Zn. Metallation of the ligand was confirmed by using UV–Vis spectroscopy and ESI-Ms measurement, in which the number of Q bands in absorption spectra of the ligand decreased from four to one or two as a result of metal insertion to the porphyrin core. The antibacterial activity study of the complexes toward two Gram-positive (Staphylococcus aureus (S. aureus) and Streptococcus pyogenes (s. pyogenes)) and two Gram-negative (Escherichia coli (E. coli) and Klebsiella pneumoniae (K. pneumoniae)) bacteria by disc diffusion method showed a promising inhibitory activity. The complexes exhibited highest activities at highest concentration and were better than the activity of free base ligand, the salts, and blank solution. This could be explained on the basis of Overton's concept of cell permeability and Tweed's Chelation theory. An increased lipo-solubility enhances the penetration of the complexes into the lipid membrane and interferes with the normal activities of the bacteria. Our study, therefore, showed that the growth inhibitory effect of these metalloporphyrins is generally in order of ZnTPPCOOMe > NiTPPCOOMe > CoTPPCOOMe> FeTPPCOOMe, which may be attributed to the better lipophilicity and binding of the complex with the cellular components.

Keywords: porphyrins, metalloporphyrins, spectral property, antibacterial activity, synthesis

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Authors: Joanna Drzeżdżon, Marzena Białek

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Polyolefins are a group of materials used today in all areas of life. They are used in the food, domestic and other industries. In particular, polyethylene and polypropylene have found application in the production of packaging materials, pipes, containers, car parts as well as elements of medical equipment, e.g. syringes. Optimization of the polymerization and oligomerization processes of selected olefins is a very important stage before the technological implementation of polyolefin production. The purpose of the studies is to determine the conditions for ethylene polymerization as well as 3-buten-2-ol and 2-chloro-2-propen-1-ol oligomerization with the use of oxovanadium(IV) dipicolinate complexes with N-heterocyclic ligands. Additionally, the studies aims to determine the catalytic activities of the dipicolinate oxovanadium(IV) complexes with N-heterocyclic ligands in the studied polymerization and oligomerization processes.

Keywords: buten-2-ol, dipicolinate, ethylene, polymerization, oligomerization, vanadium

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Authors: Eslam Dabbish, Fortuna Ponte, Stefano Scoditti, Emilia Sicilia, Gloria Mazzone

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The medical techniques based on the use of light for activating the drug are occupying a prominent place in the cancer treatment due to their selectivity that contributes to reduce undesirable side effects of conventional chemotherapy. Among these therapeutic treatments, photodynamic therapy (PDT) and photoactivated chemotherapy (PACT) are emerging as complementary approaches for selective destruction of neoplastic tissue through direct cellular damage. Both techniques rely on the employment of a molecule, photosensitizer (PS), able to absorb within the so-called therapeutic window. Thus, the exposure to light of otherwise inert molecules promotes the population of excited states of the drug, that in PDT are able to produce the cytotoxic species, such as 1O2 and other ROS, in PACT can be responsible of the active species release or formation. Following the success of cisplatin in conventional treatments, many other transition metal complexes were explored as anticancer agents for applications in different medical approaches, including PDT and PACT, in order to improve their chemical, biological and photophysical properties. In this field, several crucial characteristics of candidate PSs can be accurately predicted from first principle calculations, especially in the framework of density functional theory and its time-dependent formulation, contributing to the understanding of the entire photochemical pathways involved which can ultimately help in improving the efficiency of a drug. A brief overview of the outcomes on some platinum and ruthenium-based PSs proposed for the application in the two phototherapies will be provided.

Keywords: TDDFT, metal complexes, PACT, PDT

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Authors: Akila Tayeb-Benmachiche, Saber-Mustapha Zendaoui, Salah-Eddine Bouaoud, Bachir Zouchoune

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The variation of the metal coordination site in π-coordinated polycyclic aromatic hydrocarbons (PAH) corresponds to the haptotropic rearrangement or haptotropic migration in which the metal fragment MLn is considered as the moveable moiety that is shifted between two rings of polycyclic or heteropolycyclic ligands. These structural characteristics and dynamical properties give to this category of transition metal complexes a considerable interest. We have investigated the coordination and the haptotropic shifts of (CO)3Ti and CpV moieties over the phenanthridine aromatic system and according to the metal atom nature. The optimization of (CO)3Ti(PHND) and CpV(PHND), using the Amsterdam Density Functional (ADF) program, without a symmetrical restriction of geometry gives an η6 coordination mode of the C6 and C5N rings, which in turn give rise to a six low-lying deficient 16-MVE of each (CO)3Ti(PHND) and CpV(PHND) structure (three singlet and three triplet state structures for Ti complexes and three triplet and three quintet state structures for V complexes). Thus, the η6–η6 haptotropic migration of the metal fragment MLn from the terminal C6 ring to the central C5N ring has been achieved by a loss of energy. However, its η6–η6 haptotropic migration from central C5N ring to the terminal C6 rings has been accomplished by a gain of energy. These results show the capability of the phenanthridine ligand to adapt itself to the electronic demand of the metal in agreement with the nature of the metal–ligand bonding and demonstrate that this theoretical study can also be applied to large fused π-systems.

Keywords: electronic structure, bonding analysis, density functional theory, coordination chemistry haptotropic migration

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Authors: Amit Kumar, Davide Lionetti, Victor Day, James Blakemore

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Capture and activation of the water-soluble uranyl dication (UO22+) remains a challenging problem, as few rational approaches are available for modulating the reactivity of this species. Here, we report the divergent synthesis of heterobimetallic complexes in which UO22+ is held in close proximity to a range of redox-inactive metals by tailored macrocyclic ligands. Crystallographic and spectroscopic studies confirm assembly of homologous UVI(μ-OAr)2Mn+ cores with a range of mono-, di-, and trivalent Lewis acids (Mn+). X-ray diffraction (XRD) and cyclic voltammetry (CV) data suggest preferential binding of K+ in an 18-crown-6-like cavity and Na+ in a 15-crown-5-like cavity, both appended to Schiff-base type sites that selectively bind UO22+. CV data demonstrate that the UVI/UV reduction potential in these complexes shifts positive and the rate of electron transfer decreases with increasing Lewis acidity of the incorporated redox-inactive metals. Moreover, spectroelectrochemical studies confirm the formation of [UV] species in the case of monometallic UO22+ complex, consistent with results from prior studies. However, unique features were observed during spectroelectrochemical studies in the presence of the K+ ion, suggesting new insights into electronic structure may be accessible with the heterobimetallic complexes. Overall, these findings suggest that interactions with Lewis acids could be effectively leveraged for rational tuning of the electronic and thermochemical properties of the 5f elements, reminiscent of strategies more commonly employed with 3d transition metals.

Keywords: electrochemistry, Lewis acid, macrocycle, uranyl

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Authors: Amine Rezzoug, Said Abdi, Nadjet Bouhelal, Ismail Daoud

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This paper investigates the application of metallic coatings on high fiber volume fraction carbon/epoxy polymer matrix composites. For the grip of the metallic layer, a method of modifying the surface of the composite by introducing a mixture of copper and steel powder (filler powders) which can reduce the impact of thermal spray particles. The powder was introduced to the surface at the time of the forming. Arc spray was used to project the zinc coating layer. The substrate was grit blasted to avoid poor adherence. The porosity, microstructure, and morphology of layers are characterized by optical microscopy, SEM and image analysis. The samples were studied also in terms of hardness and erosion resistance. This investigation did not reveal any visible evidence damage to the substrates. The hardness of zinc layer was about 25.94 MPa and the porosity was around (∼6.70%). The erosion test showed that the zinc coating improves the resistance to erosion. Based on the results obtained, we can conclude that thermal spraying allows the production of protective coating on PMC. Zinc coating has been identified as a compatible material with the substrate. The filler powders layer protects the substrate from the impact of hot particles and allows avoiding the rupture of brittle carbon fibers.

Keywords: arc spray, coating, composite, erosion

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Authors: Parul Kapoor, Dheeraj Bhardwaj

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Delhi and other Indian cities accommodate thousands of Central Government employees in housing complexes called ‘General Pool Residential Accommodation’ (GPRA), located in prime parcels of the city. These residential colonies are now undergoing redevelopment at a massive scale, significantly impacting the ecology of the surrounding areas. Essentially, these colonies were low-rise, low-density planned developments with a dense tree cover and minimal parking requirements. But with increasing urbanisation and spike in parking demand, the proposed built form is an aggregate of high-rise gated complexes, redefining the skyline of the city which is a huge departure from the mediocre setup of Low-rise Walk-up apartments. The complexity of these developments is further aggravated by the need for parking which necessitates cutting huge number of trees to accommodate multiple layers of parking beneath the structures thus sidelining the authentic character of these areas which is laden with a dense tree cover. The aftermath of this whole process is the generation of a huge carbon footprint on the surrounding areas, which is unaccounted for, in the planning and design practice. These developments are currently planned as mix-use compounds with large commercial built-up spaces which have additional parking requirements over and above the residential parking. Also, they are perceived as gated complexes and not as neighborhood units, thus project isolated images of high-rise, dense systems with little context to the surroundings. The paper would analyze case studies of GPRA Redevelopment projects in Delhi, and the lack of relevant development control regulations which have led to abnormalities and complications in the entire redevelopment process. It would also suggest policy guidelines which can establish comprehensive codes for effective planning of these settlements.

Keywords: gated complexes, GPRA Redevelopment projects, increased densities, huge carbon footprint, mixed-use development

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Authors: Vishnu V. Pillai, Sunil P. Lonkar, Akhil M. Abraham, Saeed M. Alhassan

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An effectual technology for wastewater treatment is a great demand now in order to encounter the water pollution caused by organic pollutants. Photocatalytic oxidation technology is widely used in removal of such unsafe contaminants. Among the semi-conducting metal oxides, robust and thermally stable TiO2 has emerged as a fascinating material for photocatalysis. Enhanced catalytic activity was observed for nanostructured TiO2 due to its higher surface, chemical stability and higher oxidation ability. However, higher charge carrier recombination and wide band gap of TiO2 limits its use as a photocatalyst in the UV region. It is desirable to develop a photocatalyst that can efficiently absorb the visible light, which occupies the main part of the solar spectrum. Hence, in order to extend its photocatalytic efficiency under visible light, TiO2 nanoparticles are often doped with metallic or non-metallic elements. Non-metallic doping of TiO2 has attracted much attention due to the low thermal stability and enhanced recombination of charge carriers endowed by metallic doping of TiO2. Amongst, sulfur doped TiO2 is most widely used photocatalyst in environmental purification. However, the most of S-TiO2 synthesis technique uses toxic chemicals and complex procedures. Hence, a facile, scalable and environmentally benign preparation process for S-TiO2 is highly desirable. In present work, we have demonstrated new and facile solid-state reaction method for S-TiO2 synthesis that uses abundant elemental sulfur as S source and moderate temperatures. The resulting nano-sized S-TiO2 has been successfully employed as visible light photocatalyst in methylene blue dye removal from aqueous media.

Keywords: ecofriendly, nanomaterials, methylene blue, photocatalysts

Procedia PDF Downloads 319

Authors: Priya Varshney, Soumya S. Mohapatra

Abstract:

Fabrication of anti-corrosion and self-cleaning superhydrophobic coatings for metallic surfaces which are regenerable and durable in the aggressive conditions has shown tremendous interest in materials science. In this work, the superhydrophobic coatings on metallic surfaces (aluminum, steel, copper) were prepared by two-step and one-step chemical etching process. In two-step process, roughness on surface was created by chemical etching and then passivation of roughened surface with low surface energy materials whereas, in one-step process, roughness on surface by chemical etching and passivation of surface with low surface energy materials were done in a single step. Beside this, the effect of etchant concentration and etching time on wettability and morphology was also studied. Thermal, mechanical, ultra-violet stability of these coatings were also tested. Along with this, regeneration of coatings and self-cleaning, corrosion resistance and water repelling characteristics were also studied. The surface morphology shows the presence of a rough microstuctures on the treated surfaces and the contact angle measurements confirms the superhydrophobic nature. It is experimentally observed that the surface roughness and contact angle increases with increase in etching time as well as with concentration of etchant. Superhydrophobic surfaces show the excellent self-cleaning behaviour. Coatings are found to be stable and maintain their superhydrophobicity in acidic and alkaline solutions. Water jet impact, floatation on water surface, and low temperature condensation tests prove the water-repellent nature of the coatings. These coatings are found to be thermal, mechanical and ultra-violet stable. These durable superhydrophobic metallic surfaces have potential industrial applications.

Keywords: superhydrophobic, water-repellent, anti-corrosion, self-cleaning

Procedia PDF Downloads 232

Authors: B. Bouadjemi, S. Bentata, W. Benstaali, A. Souidi, A. Abbad, T. Lantri, Z. Aziz, A. Zitouni

Abstract:

The electronic and magnetic structures of double perovskite Ba2MnMoO6 are systematically investigated using the first principle method of the Full Potential Linear Augmented Plane Waves Plus the Local Orbitals (FP-LAPW+LO) within the Local Spin Density Approximation (LSDA) and the Generalized Gradient Approximation (GGA). In order to take into account the strong on-site Coulomb interaction, we included the Hubbard correlation terms: LSDA+U and GGA+U approaches. Whereas half-metallic ferromagnetic character is observed due to dominant Mn spin-up and Mo spin-down contributions insulating ground state is obtained. The LSDA+U and GGA+U calculations yield better agreement with the theoretical and the experimental results than LSDA and GGA do.

Keywords: electronic structure, double perovskite, first principles, Ba2MnMoO6, half-metallic

Procedia PDF Downloads 409

Authors: B. Rajesh Kamath, J. Sundara Rajan, M. K. Veeraiah, M. Z. Kurian

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Insulation performance of a gas insulated system is severely affected by particle contaminants. These metallic particles adversely affect the characteristics of insulating system. These particles can produce surface charges due to partial discharge activities. These particles which are free to move enhance the local electric fields. This paper deals with the influence of conducting particle placed in a co-axial duct on the discharge characteristics of gas mixtures. Co-axial duct placed in a high pressure chamber is used for the purpose. A gas pressure of 0.1, 0.2 and 0.3 MPa have been considered with a 10:90 SF₆ and N₂ gas mixtures. The 2D and 3D histograms of clean duct and duct with copper particle are discussed in this paper.

Keywords: coaxial duct, gas insulated system, gas mixtures, metallic particle, partial discharges, histograms

Procedia PDF Downloads 354

Authors: S. M. Hamidi, M. Zamani

Abstract:

Magneto-plasmonic (MP) structures have turned into essential tools for the amplification of magneto-optical (MO) responses via the combination of MO activity and surface Plasmon resonance (SPR). Both the plasmonic and the MO properties of the resulting MP structure become interrelated because the SPR of the metallic medium. This interconnection can be modified the wave vector of surface plasmon polariton (SPP) in MP multilayer [1] or enhanced the MO activity [2- 3] and also modified the sensor responses [4]. There are several types of MP structures which are studied to enhance MO response in miniaturized configuration. In this paper, we propose a new MP structure based on the nano-metal grating and we investigate the MO and optical properties of this new structure. Our new MP structure fabricate by DC magnetron sputtering method and our home made MO experimental setup use for characterization of the structure.

Keywords: Magneto-plasmonic structures, magneto-optical effect, nano-garting

Procedia PDF Downloads 507

Authors: Jiwuer Jilili, Iogann Tolbatov, Mousumi U. Kahaly

Abstract:

Metal to insulator transition and interfacial magnetism of the LaNiO₃ based superlattice are main interest due to thickness dependent electronic response and tunable magnetic behavior. We investigate the structural, electronic, and magnetic properties of recently experimentally synthesized (LaNiO₃)n/(CaMnO₃)m superlattices with varying LaNiO₃ thickness using density functional theory. The effect of the on-site Coulomb interaction is discussed. In switching from zero to finite U value for Ni atoms, LaNiO₃ shows transitions from half-metallic to metallic character, while spinning ordering changes from paramagnetic to ferromagnetic (FM). For CaMnO₃, U < 3 eV on Mn atoms results in G-type anti-FM spin ordering whereas increasing U value yields FM ordering. In superlattices, metal to insulator transition was achieved with a reduction of LaNiO₃ thickness. The system with one layer of LaNiO₃ yields insulating character. Increasing LaNiO₃ to two layers and above results in the onset of the metallic character with a major contribution from Ni and Mn 3d eg states. Our results for interfacial ferromagnetism, induced Ni magnetic moments and novel antiferromagnetically coupled Ni atoms are consistent with the recent experimental findings. The possible origin of the emergent magnetism is proposed in terms of the exchange interaction and Anderson localization.

Keywords: density functional theory, interfacial magnetism, metal-insulator transition, Ni magnetism.

Procedia PDF Downloads 193

Authors: Sultan Ben Jaber

Abstract:

Optical properties of molecules exhibit dramatic changes when adsorbed close to nano-structure metallic surfaces such as gold and silver nanomaterial. This phenomena opened a wide range of research to improve conventional spectroscopies efficiency. A well-known technique that has an intensive focus of study is surface-enhanced Raman spectroscopy (SERS), as since the first observation of SERS phenomena, researchers have published a great number of articles about the potential mechanisms behind this effect as well as developing materials to maximize the enhancement. Infrared and Raman spectroscopy are complementary techniques; thus, surface-enhanced infrared absorption (SEIRA) also shows a noticeable enhancement of molecules in the mid-IR excitation on nonmetallic structure substrates. In the SEIRA, vibrational modes that gave change in dipole moments perpendicular to the nano-metallic substrate enhanced 200 times greater than the free molecule’s modes. SEIRA spectroscopy is promising for the characterization and identification of adsorbed molecules on metallic surfaces, especially at trace levels. IR reflection-absorption spectroscopy (IRAS) is a well-known technique for measuring IR spectra of adsorbed molecules on metallic surfaces. However, SEIRA spectroscopy sensitivity is up to 50 times higher than IRAS. SEIRA enhancement has been observed for a wide range of molecules adsorbed on metallic substrates such as Au, Ag, Pd, Pt, Al, and Ni, but Au and Ag substrates exhibited the highest enhancement among the other mentioned substrates. In this work, trace levels of 3,4-methylenedioxymethamphetamine (MDMA) have been detected using gold nanoparticles (AuNPs) substrates with surface-enhanced infrared absorption (SEIRA). AuNPs were first prepared and washed, then mixed with different concentrations of MDMA samples. The process of fabricating the substrate prior SEIRA measurements included mixing of AuNPs and MDMA samples followed by vigorous stirring. The stirring step is particularly crucial, as stirring allows molecules to be robustly adsorbed on AuNPs. Thus, remarkable SEIRA was observed for MDMA samples even at trace levels, showing the rigidity of our approach to preparing SEIRA substrates.

Keywords: surface-enhanced infrared absorption (SEIRA), gold nanoparticles (AuNPs), amphetamines, methylene dioxy- methamphetamine (MDMA), enhancement factor

Procedia PDF Downloads 36

Authors: Mohamed H. El-Newehy, Sameh M. Osman, Moamen S. Refat, Salem S. Al-Deyab, Ayman El-Faham

Abstract:

The two copolymers itaconic acid-methyl methacrylate and itaconic acid-acrylamide have been prepared in different ratio by radical copolymerization in the presence of azobisisobutyronitrile (AIBN) as initiator and using 2-butanone as reaction medium using microwave irradiation. The microwave technique is safe, fast, and gives high yield of the products with high purity in an optimum time, comparing to the traditional conventional heating. All the prepared copolymers were characterized by FT-IR, thermal analysis and elemental microanalysis. The itaconic acid-based copolymers showed a good sensitivity in alkaline media for scavenging Cu (II) and Pb (II). The chelation behavior of both Cu (II) and Pb (II) complexes were checked using FT-IR, thermogravimetric analysis (TGA), and differential scanning calorimetery (DSC). The infrared data are in a good agreement with the coordination through carboxylate-to-metal, in which the copolymers acting as a bidentate ligand.

Keywords: microwave synthesis, itaconic acid, copolymerization, scavenging, thermal stability

Procedia PDF Downloads 419