Search results for: metallic complexes

Authors: Salem El-Tohami Ashoor

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Here we show that the reduction of [Cr(ArN(CH2)3NAr)2Cl2] (1) where (Ar = 2,6-Pri2C6H3) and in presence of NaCp (2) (Cp= C5H5 = cyclopentadien), with a center coordination η5 interaction between Cp as co-ligand and chromium metal center, this was optimization by using density functional theory (DFT) and then was comparing with experimental data, also other possibility of Cp interacted with ion metal were tested like η1 ,η2 ,η3 and η4 under optimization system. These were carried out under investigation of density functional theory (DFT) calculation, and comparing together. Other methods, explicitly including electron correlation, are necessary for more accurate calculations; MB3LYP ( Becke)( Lee–Yang–Parr ) level of theory often being used to obtain more exact results. These complexes were estimated of electronic energy for molecular system, because it accounts for all electron correlation interactions. The optimised of [Cr(ArN(CH2)3NAr)2(η5-Cp)] (Ar = 2,6-Pri2C6H3 and Cp= C5H5) was found to be thermally more stable than others of chromium cyclopentadienyl. By using Dewar-Chatt-Duncanson model, as a basis of the molecular orbital (MO) analysis and showed the highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital LUMO.

Keywords: Chromium(III) cyclopentadienyl complexes, DFT, MO, HOMO, LUMO

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Authors: Katarína Koňariková, Georgios A. Perdikaris, Lucia Andrezálová, Zdeňka Ďuračková, Lucia Laubertová, Helena Gbelcová, Ingrid Žitňanová

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Introduction: The continuous demand for new anti-cancer drugs has stimulated chemotherapeutic research based on the use of essential metalloelements with the aim to develop potential drugs with lower toxicity and higher antiproliferative activity against tumors. Copper(II) and its complexes play an important role as suitable species for antiproliferative tests. Objectives: The central objective of the current study was to investigate the potential in vitro anti-proliferative effects of N-salicylidene-L-glutamato copper (II) complexes and molecular mechanism of apoptosis induced by tested complexes. In our project we tested N-salicylidene-L-glutamato copper (II) complexes ZK1 - [Cu(N-salicylidene-L-glutamato)(H2O)2].H2O; MK0 - ([Cu2(N-sal-D,L-glu)2(isoquinoline)2].2H2O); MK1 - [Cu(N-salicylidene-5-methyl-L-glutamato)(H2O)].H2O; MK3 - transbis(ethanol)tetrakis(imidazol)Cu(II)(2+)bis(N-salicylidene-D,L-glutamato-N,O)-KO:KO´-(imidazol); MK5 - [Cu(N-salicylidene-D,L- glutamato)(2-methylimidazol] at concentration range 0.001-100 µmol/L against human colon carcinoma cell line HT-29 and human breast carcinoma cell line MCF-7. Methods: Viability was assessed by direct counting of 0.4% trypan blue dye-excluding cells after 24, 48 and 72 hour cultivations with or without copper complex and by MTT assay. To analyze the type of cell death and its mechanism induced by our copper complex we used different methods. To distinguish apoptosis from necrosis we used electrophoretic analysis, to study the activity of caspases 8 and 9 – luminometric analysis and caspase activity 3 colorimetric assay. Results: The observed anti-proliferative effect of the copper complexes appeared to be dose-, time- and cell line- dependent. Human colon carcinoma cells HT-29 appeared to be more sensitive to the complex MK0 ([Cu2(N-sal-D,L-glu)2(isoquinoline)2].2H2O) than to ZK1 ([Cu(N-salicylidene-L-glutamato)(H2O)2].H2O) and MK1 ([Cu(N-salicylidene-5-methyl-L-glutamato)(H2O)].H2O)). Human colon carcinoma cells HT-29 appeared to be more sensitive to the complex than human breast carcinoma cells MCF-7. IC50 decreased with time of incubation (24, 48 and 72h) for HT-29, but increased for MCF-7. By electrophoresis we found apoptotic cell death induced by our copper complexes in HT-29 at concentrations 1, 10, 50 and 100 µmol/L after 48h (ZK1) and 72h (MK0, MK1) and in MCF-7 we did not find apoptosis. We also studied molecular mechanism of apoptosis in HT-29 induced by copper complexes. We found active caspase 9 in HT-29 after ZK1 ([Cu(N-salicylidene-L-glutamato)(H2O)2].H2O) and MK1 ([Cu(N-salicylidene-5-methyl-L-glutamato)(H2O)].H2O)) influence and active caspase 8 after MK0 ([Cu2(N-sal-D,L-glu)2(isoquinoline)2].2H2O) influence. Conclusion: Our copper complexes showed cytotoxic activities against human colon carcinoma cells HT-29 and breast cancer cell line MCF-7 in vitro. Apoptosis was activated by mitochondrial pathway (intrinsic pathway) in case of ZK1 [Cu(N-salicylidene-L-glutamato)(H2O)2].H2O; MK1 [Cu(N-salicylidene-5-methyl-L-glutamato)(H2O)].H2O; MK3 - transbis(ethanol)tetrakis(imidazol)Cu(II)(2+)bis(N-salicylidene-D,L-glutamato-N,O)-KO:KO´-(imidazol) and MK5 - [Cu(N-salicylidene-D,L- glutamato)(2-methylimidazol] copper complexes and by death receptors (extrinsic pathway) in case of MK0 [Cu2(N-sal-D,L-glu)2(isoquinoline)2].2H2O copper complex in HT-29.

Keywords: apoptosis, copper complex, cancer, carcinoma cell line

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Authors: Khawar Ali

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We present the numerical study of unsteady hydromagnetic (MHD) flow and heat transfer characteristics of a viscous incompressible electrically conducting water-based hybrid metallic nanofluid (containing Cu-Au/ H₂O nanoparticles) between two orthogonally moving porous coaxial disks with suction. Different from the classical shooting methodology, we employ a combination of a direct and an iterative method (SOR with optimal relaxation parameter) for solving the sparse systems of linear algebraic equations arising from the FD discretization of the linearized self similar nonlinear ODEs. Effects of the governing parameters on the flow and heat transfer are discussed and presented through tables and graphs. The findings of the present investigation may be beneficial for the electronic industry in maintaining the electronic components under effectiveand safe operational conditions.

Keywords: heat transfer enhancement, hybrid metallic nanofluid, viscous dissipation and joule heating effect , Two dimensional flow

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Authors: Csilla Dudás, Éva Böszörményi, Bence Kutus, István Pálinkó, Pál Sipos

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In this study the behavior of alpha-D-isosaccharinate (2-hydroxymethyl-3-deoxy-D-erythro-pentonate, ISA−) in alkaline medium in the presence of calcium was studied. At first the Ca–ISA system was studied by Ca-ion selective electrode (Ca-ISE) in neutral medium at T = 25 °C and I = 1 M NaCl to determine the formation constant of the CaISA+ monocomplex, which was found to be logK = 1.01 ± 0.01 for the reaction of Ca2+ + ISA– = CaISA+. In alkaline medium pH potentiometric titrations were carried out to determine the composition and stability constant of the complex(es) formed. It was found that in these systems above pH = 12.5 the predominant species is the CaISAOH complex. Its formation constant was found to be logK = 3.04 ± 0.05 for the reaction of Ca2+ + ISA– + H2O = CaISAOH + H+ at T = 25 °C and I = 1 M NaCl. Solubility measurements resulted in data consistent with those of the potentiometric titrations. Temperature dependent NMR spectra showed that the slow exchange range between the complex and the free ligand is below 5 °C. It was also showed that ISA– acts as a multidentate ligand forming macrochelate Ca-complexes. The structure of the complexes was determined by using ab initio quantum chemical calculations.

Keywords: Ca-ISE potentiometry, calcium complexes, isosaccharinate ion, NMR spectroscopy, pH potentiometry

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Authors: Bo-Gaun Chen, Chiung-Hui Huang, Mei-Ching Chiang, Kuo-Hsing Lee, Chia-Chen Ho, Chin-Ping Huang, Chin-Heng Tien

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It is known that the natural dyeing of cloth results moderate color, but with poor color fastness. This study points out the correlation between the macroscopic color fastness of natural dye to the cotton fiber and the microscopic binding energy of dye molecule to the cellulose. With the additive metallic mordant, the new-formed coordination bond bridges the dye to the fiber surface and thus affects the color fastness as well as the color appearance. The density functional theory (DFT) calculation is therefore used to explore the most possible mechanism during the dyeing process. Finally, the experimental results reflect the strong effect of three different metal ions on the natural dyeing clothes.

Keywords: binding energy, color fastness, density functional theory (DFT), natural dyeing, metallic mordant

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Authors: Wei-Shan Wang, Klaus Vogel, Felix Gabler, Maik Wiemer, Thomas Gessner

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Metallic glasses, which are free of grain boundaries, have superior properties including large elastic limits, high strength, and excellent wear and corrosion resistance. Therefore, bulk metallic glasses (BMG) and thin film metallic glasses (TFMG) have been widely developed and investigated. Among various kinds of metallic glasses, Pd-Cu-Si TFMG, which has lower elastic modulus and better resistance of oxidation and corrosions compared to Zr- and Fe-based TFMGs, can be a promising candidate for MEMS applications. However, the study of Pd-TFMG membrane is still limited. This paper presents free-standing Pd-based metallic glass membranes with large area fabricated on wafer level for the first time. Properties of Pd-Cu-Si thin film metallic glass (TFMG) with various deposition parameters are investigated first. When deposited at 25°C, compressive stress occurs in the Pd76Cu6Si18 thin film regardless of Ar pressure. When substrate temperature is increased to 275°C, the stress state changes from compressive to tensile. Thin film stresses are slightly decreased when Ar pressure is higher. To show the influence of temperature on Pd-TFMGs, thin films without and with post annealing below (275°C) and within (370°C) supercooled liquid region are investigated. Results of XRD and TEM analysis indicate that Pd-TFMGs remain amorphous structure with well-controlled parameters. After verification of amorphous structure of the Pd-TFMGs, free-standing Pd-Cu-Si membranes were fabricated by depositing Pd-Cu-Si thin films directly on 200nm-thick silicon nitride membranes, followed by post annealing and dry etching of silicon nitride layer. Post annealing before SiNx removal is used to further release internal stress of Pd-TFMGs. The edge length of the square membrane ranges from 5 to 8mm. The effect of post annealing on Pd-Cu-Si membranes are discussed as well. With annealing at 370°C for 5 min, Pd-MG membranes are fully distortion-free after removal of SiNx layer. Results show that, by introducing annealing process, the stress-relief, distortion-free Pd-TFMG membranes with large area can be a promising candidate for sensing applications such as pressure and gas sensors.

Keywords: amorphous alloy, annealing, metallic glasses, TFMG membrane

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Authors: Mahboobeh Mohadeszadeh, Behzad Padidaran Moghaddam

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In order to measuring dinuclear molybdenum complexes formation constant First,the reactants and the products were optimized separately and then, their frequencies were measured. In next level , with using Hartree-fock (HF) and density functional theory (DFT) methods ,Theoretical studies on the geometrical parameters, electronic properties and vibrational frequencies of dinuclear molybdenum complexes [C40H44Mo2N2O20] were investigated . These calculations were performed with the B3LYP, BPV86, B3PW91 and HF theoretical method using the LANL2DZ (for Mo’s) + 6-311G (for others) basis sets. To estimate the error rate between theoretical data and experimental data, RSquare , SError and RMS values that according with the theoretical and experimental parameters found out DFT methods has more integration with experimental data compare to HF methods. In addition, through electron specification of compounds, the percentage of atomic orbital’s attendance in making molecular orbital’s, atoms electrical charge, the sustainable energy resulting and also HOMO and LUMO orbital’s energy achieved.

Keywords: geometrical parameters, hydrogen bonding, electronic properties, vibrational frequencies

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

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The electronic and magnetic properties of the cubic praseodymium oxides perovskites PrMnO3 were calculated using the density functional theory (DFT) with both generalized gradient approximation (GGA) and GGA+U approaches, where U is on-site Coulomb interaction correction. The results show a half-metallic ferromagnetic ground state for PrMnO3 in GGA+U approached, while semi-metallic ferromagnetic character is observed in GGA. The results obtained, make the cubic PrMnO3 a promising candidate for application in spintronics.

Keywords: first-principles, electronic properties, transition metal, materials science

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Authors: Sanjay Dhiraaj, Puneet Goyal, Aditya Kapoor, Gaurav Misra

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In electrocardiography, an ECG artefact is used to indicate something that is not heart-made. Although technological advancements have produced monitors with the potential of providing accurate information and reliable heart rate alarms, despite this, interference of the displayed electrocardiogram still occurs. These interferences can be from the various electrical gadgets present in the operating room or electrical signals from other parts of the body. Artefacts may also occur due to poor electrode contact with the body or due to machine malfunction. Knowing these artefacts is of utmost importance so as to avoid unnecessary and unwarranted diagnostic as well as interventional procedures. We report a case of ECG artefacts occurring due to patient warming blanket and its consequences. A 20-year-old male with a preoperative diagnosis of exstrophy epispadias complex was posted for surgery under epidural and general anaesthesia. Just after endotracheal intubation, we observed nonspecific ECG changes on the monitor. At a first glance, the monitor strip revealed broad QRs complexes suggesting a ventricular bigeminal rhythm. Closer analysis revealed these to be artefacts because although the complexes were looking broad on the first glance there was clear presence of normal sinus complexes which were immediately followed by 'broad complexes' or artefacts produced by some device or connection. These broad complexes were labeled as artefacts as they were originating in the absolute refractory period of the previous normal sinus beat. It would be physiologically impossible for the myocardium to depolarize so rapidly as to produce a second QRS complex. A search for the possible reason for the artefacts was made and after deepening the plane of anaesthesia, ruling out any possible electrolyte abnormalities, checking of ECG leads and its connections, changing monitors, checking all other monitoring connections, checking for proper grounding of anaesthesia machine and OT table, we found that after switching off the patient’s warming apparatus the rhythm returned to a normal sinus one and the 'broad complexes' or artefacts disappeared. As misdiagnosis of ECG artefacts may subject patients to unnecessary diagnostic and therapeutic interventions so a thorough knowledge of the patient and monitors allow for a quick interpretation and resolution of the problem.

Keywords: ECG artefacts, patient warming blanket, peri-operative arrhythmias, mobile messaging services

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Authors: Shidokht Rashiddadash, Mojtaba Sadighi, Soheil Dariushi

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Since sandwich structures are used in many areas ranging from ships, trains, automobiles, aircrafts, bridge and building, connecting sandwich structures is necessary almost in all industries. So application of metallic joints between sandwich panels is increasing. Various joining methods are available such as mechanically fastened joints (riveting or bolting) or adhesively bonded joints and choosing one of them depends on the application. In this research, sandwich specimens were fabricated with two different types of metallic connections with dissimilar geometries. These specimens included beams and plates and were manufactured using glass-epoxy skins and aluminum honeycomb core. After construction of the specimens, bending and low velocity impact tests were executed on them and the behaviors of specimens were discussed. Numerical models were developed using LS-DYNA software and validated with test results. Finally, parametric studies were performed on the thicknesses and lengths of two connections by employing the numerical models.

Keywords: connection, honeycomb, low velocity impact, sandwich panel, static test

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Authors: Tinebeb Tefera Ashene

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Glass facade systems have gained popularity in recent times. During an earthquake, building frames suffer large inter-story drifts, causing racking of building facade systems. A facade system is highly vulnerable and fails more frequently than a building with significant devastating effects. The usage of Metallic yield damper connections (Added Damping Stiffness) is proposed in this study to mitigate the aforementioned problems. Results showed as compared to control, usage of Metallic yield damper connections (Added-Damping-And-Stiffness) exhibited a reduction of connection deformation and axial force; differential displacement between frame and facade; and facade distortion by 44.35%, 43.33%, and 51.45% respectively. Also, employing proposed energy-absorbing connections reduced inter-story link joint drift by 71.11% and mitigated detrimental seismic effects on the entire building facade system.

Keywords: damper, energy dissipation, metallic yield, facades

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Authors: Kamalesh Kumar Singh

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Due to increasing trends of electronic waste, specially the ICT related gadgets, their green recycling is still a greater challenge. This article presents a two-stage, eco-friendly hydrometallurgical route for the recovery of gold from the delaminated metallic layers of waste mobile phone Printed Circuit Boards (PCBs). Initially, mobile phone PCBs are downsized (1x1 cm²) and treated with an organic solvent dimethylacetamide (DMA) for the separation of metallic fraction from non-metallic glass fiber. In the first stage, liberated metallic sheets are used for the selective dissolution of copper in an aqueous leaching reagent. Influence of various parameters such as type of leaching reagent, the concentration of the solution, temperature, time and pulp density are optimized for the effective leaching (almost 100%) of copper. Results have shown that 3M nitric acid is a suitable reagent for copper leaching at room temperature and considering chemical features, gold remained in solid residue. In the second stage, the separated residue is used for the recovery of gold by using sulphuric acid with a combination of halide salt. In this halide leaching, Cl₂ or Br₂ is generated as an in-situ oxidant to improve the leaching of gold. Results have shown that almost 92 % of gold is recovered at the optimized parameters.

Keywords: printed circuit boards, delamination, leaching, solvent extraction, recovery

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Authors: Emrah Ersoy, Yusuf Ozcatalbas

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The aim of this study is to investigate formability of Al based closed cell metallic foams at high temperature. The foam specimens with rectangular section were produced from AlMg1Si0.6TiH20.8 alloy preform material. Bending and free bending tests based on gravity effect were applied to foam specimens at high temperatures. During the tests, the time-angular deformation relationships with various temperatures were determined. Deformation types formed in cell walls were investigated by means of Scanning Electron Microscopy (SEM) and optical microscopy. Bending deformation about 90° was achieved without any defect at high temperatures. The importance of a critical temperature and deformation rate was emphasized in maintaining the deformation. Significant slip lines on surface of cell walls at tensile zones of bending specimen were observed. At high strain rates, the microcrack formation in boundaries of elongated grains was determined.

Keywords: Al alloy, Closed cell, Hot deformation, Metallic foam

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Authors: R. Chanajaree, D. Luanwiset, K. Pongpratea

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Dye removal is an environmental concern because the textile industries have been increasing by world population and industrialization. Adsorption is the technique to find adsorbents to remove dyes from wastewater. This method is low-cost and effective for dye removal. This work tries to develop effective adsorbents using the computational approach because it will be able to predict the possibility of the adsorbents for specific dyes in terms of binding free energies. The computational approach is faster and cheaper than the experimental approach in case of finding the best adsorbents. All starting structures of dyes and adsorbents are optimized by quantum calculation. The complexes between dyes and adsorbents are generated by the docking method. The obtained binding free energies from docking are compared to binding free energies from the experimental data. The calculated energies can be ranked as same as the experimental results. In addition, this work also shows the possible orientation of the complexes. This work used two experimental groups of the complexes of the dyes and adsorbents. In the first group, there are chitosan (adsorbent) and two dyes (reactive red (RR) and direct sun yellow (DY)). In the second group, there are poly(1,2-epoxy-3-phenoxy) propane (PEPP), which is the adsorbent, and 2 dyes of bromocresol green (BCG) and alizarin yellow (AY).

Keywords: dyes removal, binding free energies, quantum calculation, docking

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Authors: Ahmed Abada, Kadda Amara, Said Hiadsi, Bouhalouane Amrani

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Half-metallic properties of new predicted Mn2-based full Heusler alloys Mn2ZrSi and Mn2ZrGe have been studied by first-principles full-potential linearized augmented plane wave plus local orbital (FP-LAPW+lo) method based on density functional theory (DFT). Our investigation is focused on the structural, elastic, electronic and magnetic properties of these compounds. The AlCu2Mn-type structure is found to be energetically more favorable than the CuHg2Ti-type structure for both compounds and are half-metallic ferrimagnets (HMFIs) with total magnetic moments of 2.000 µB per formula unit, well consistent with Slater-Pauling rule (Mtot = ( 24 – Ztot ) µB). Calculations show that both the alloys have an indirect band gaps, in the majority-spin channel, with values of 0.505 eV and 0.278 eV for Mn2ZrSi and Mn2ZrGe, respectively. It was found that Mn2ZrSi and Mn2ZrGe preserved their half-metallicity for lattice constants range of 5.85–6.38 Å and 6.05–6.38 Å, respectively, and kept a 100% of spin polarization at the Fermi level. Moreover, the calculated formation energies and elastic constants confirm that these compounds are stable chemically and mechanically, and the good crystallographic compatibility with the lattice of semiconductors used industrially makes them promising magnetic materials in spintronic applications.

Keywords: first-principles calculations, full Heusler structure, half-metallic ferrimagnets, elastic properties

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Authors: P. Abachi, S. Karami, K. Purazrang

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The amorphous reinforcements (metallic glasses) can be considered as promising options for reinforcing light-weight aluminum and its alloys. By using the proper type of reinforcement, one can overcome to drawbacks such as interfacial de-cohesion and undesirable reactions which can be created at ceramic particle and metallic matrix interface. In this work, the Zr-based amorphous phase was produced via mechanical milling of elemental powders. Based on Miedema semi-empirical Model and diagrams for formation enthalpies and/or Gibbs free energies of Zr-Cu amorphous phase in comparison with the crystalline phase, the glass formability range was predicted. The composite was produced using the powder mixture of the aluminum and metallic glass and spark plasma sintering (SPS) at the temperature slightly above the glass transition Tg of the metallic glass particles. The selected temperature and rapid sintering route were suitable for consolidation of an aluminum matrix without crystallization of amorphous phase. To characterize amorphous phase formation, X-ray diffraction (XRD) phase analyses were performed on powder mixture after specified intervals of milling. The microstructure of the composite was studied by optical and scanning electron microscope (SEM). Uniaxial compression tests were carried out on composite specimens with the dimension of 4 mm long and a cross-section of 2 ˟ 2mm2. The micrographs indicated an appropriate reinforcement distribution in the metallic matrix. The comparison of stress–strain curves of the consolidated composite and the non-reinforced Al matrix alloy in compression showed that the enhancement of yield strength and mechanical strength are combined with an appreciable plastic strain at fracture. It can be concluded that metallic glasses (amorphous phases) are alternative reinforcement material for lightweight metal matrix composites capable of producing high strength and adequate ductility. However, this is in the expense of minor density increase.

Keywords: aluminum matrix composite, amorphous phase, mechanical alloying, spark plasma sintering

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Authors: T. Scattolin, E. Cavarzerani, F. Visentin, F. Rizzolio

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Organopalladium compounds have recently attracted attention for their high stability even under physiological conditions and, above all, for their remarkable in vitro cytotoxicity towards cisplatin-resistant cell lines. Among the organopalladium derivatives, those bearing at least one N-heterocyclic carbene ligand (NHC) and the Pd(II)-η³-allyl fragment have exhibited IC₅₀ values in the micro and sub-micromolar range towards several cancer cell lines in vitro and in some cases selectivity towards cancerous vs. non-tumorigenic cells. Herein, a selection of allyl and indenyl palladates were synthesized using a solvent-free method consisting of grinding the corresponding palladium precursors with different saturated and unsaturated azolium salts. All compounds have been fully characterized by NMR, XRD and elemental analyses. The intramolecular H, Cl interaction has been elucidated and quantified using the Voronoi Deformation Density scheme. Most of the complexes showed excellent cytotoxicity towards ovarian cancer cell lines, with I₅₀ values comparable to or even lower than cisplatin. Interestingly, the potent anticancer activity was also confirmed in a high-serous ovarian cancer (HGSOC) patient-derived tumoroid, with a clear superiority of this class of compounds over classical platinum-based agents. Finally, preliminary enzyme inhibition studies of the synthesized palladate complexes against the model TrxR show that the compounds have high activity comparable to or even higher than auranofin and classical Au(I) NHC complexes. Based on such promising data, further in vitro and in vivo experiments and in-depth mechanistic studies are ongoing in our laboratories.

Keywords: anticancer activity, palladium complexes, organoids, indenyl and allyl ligands

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Authors: Isik Cetintav, Cenk Misirli, Yilmaz Can

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This work investigates upsetting of the tri-metallic cylindrical billets both experimentally and analytically with a reduction ratio 30%. Steel, brass, and copper are used for the outer and outmost rings and aluminum for the inner core. Two different models have been designed to show material flow and the cavity took place over the two interfaces during forming after this reduction ratio. Each model has an outmost ring material as steel. Model 1 has an outer ring between the outmost ring and the solid core material as copper and Model 2 has a material as brass. Solid core is aluminum for each model. Billets were upset in press machine by using parallel flat dies. Upsetting load was recorded and compared for models and single billets. To extend the tests and compare with experimental procedure to a wider range of inner core and outer ring geometries, finite element model was performed. ABAQUS software was used for the simulations. The aim is to show how contact between outmost ring, outer ring and the inner core are carried on throughout the upsetting process. Results have shown that, with changing in height, between outmost ring, outer ring and inner core, the Model 1 and Model 2 had very good interaction, and the contact surfaces of models had various interface behaviour. It is also observed that tri-metallic materials have lower weight but better mechanical properties than single materials. This can give an idea for using and producing these new materials for different purposes.

Keywords: tri-metallic, upsetting, copper, brass, steel, aluminum

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Authors: K. V. Ramanaiah, R. Jagan, N. N. Murthy

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Trinuclear oxo-centered carboxylate-bridged iron complexes, [Fe3(µ3-O)(µ2-O2CR)L¬3]+/0 (where R = alkyl or aryl; L = H2O, ROH, Py, solvent) have attracted tremendous attention because of their interesting structural and magnetic properties, exhibit mixed-valent trapped and de-trapped states, and have bioinorganic relevance. The presence of a trinuclear iron binding center has been implicated in the formation of both bacterial and human iron storage protein, Ft. They are used as precursors for the synthesis of models for the active-site structures of non-heme proteins, hemerythrin (Hr), methane monooxygenase (MMO) and polyiron storage protein, ferritin (Ft). Used as important building blocks for the design and synthesis of supramolecules this can exhibit single molecular magnetism (SMM). Such studies have often employed simple and compact carboxylate ligands and the use of bulky carboxylates is scarce. In the present study, we employed two different type of sterically hindered carboxylates and synthesized a series of novel oxo-centered, carboxylate-bridged triiron complexes of general formula [Fe3(O)(O2CCPh3)6L3]X (L = H2O, 1; py, 2; 4-NMe2py, 3; X = ClO4; L = CH3CN, 4; X = FeCl4) and [Fe3(O)(O2C-anth)6L3]X (L = H2O, 5; X = ClO4; L = CH3OH, 6; X = Cl). Along with complex [Fe(OMe)2(O2CCPh3)]10, 7 was prepared by the self-assemble of anhydrous FeCl3, sodium triphenylacetate and sodium methoxide at ratio of 1:1:2 in CH3OH. The Electronic absorption spectra of these complexes 1-6, in CH2Cl2 display weak bands at near FTIR region (970-1135 nm, ε > 15M-1cm-1). For complex 7, one broad band centered at ~670nm and also an additional intense charge transfer (L→M or O→M) bands between 300 to 550nm observed for all the complexes. Paramagnetic 1H NMR is introduced as a good probe for the characterization of trinuclear oxo - cantered iron compounds in solution when the L ligand coordinated to iron varies as: H2O, py, 4-NMe2py, and CH3OH. The solution state magnetic moment values calculated by using Evans method for all the complexes and also solid state magnetic moment value of complex, 7 was calculated by VSM method, which is comparable with solution state value. These all magnetic moment values indicate there is a spin exchange process through oxo and carboxylate bridges in between two irons (d5). The ESI-mass data complement the data obtained from single crystal X-ray structure. Further purity of the compounds was confirmed by elemental analysis. Finally, structural determination of complexes 1, 3, 4, 5, 6 and 7 were unambiguously conformed by single crystal x-ray studies.

Keywords: decanuclear, paramagnetic NMR, trinuclear, uv-visible

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Authors: Kevin A. Droguett, Edwin G. Pérez, Denis Fuentealba, Margarita E. Aliaga, Angélica M. Fierro

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Supramolecular chemistry is a field of growing interest. Moreover, studying the formation of host-guest complexes between macrocycles and dyes is highly attractive due to their potential applications. Examples of the above are drug delivery, catalytic process, and sensing, among others. There are different dyes of interest in the literature; one example is the quinolinone derivatives. Those molecules have good optical properties and chemical and thermal stability, making them suitable for developing fluorescent probes. Secondly, several macrocycles can be seen in the literature. One example is the cucurbiturils. This water-soluble macromolecule family has a hydrophobic cavity and two identical carbonyl portals. Additionally, the thermodynamic analysis of those supramolecular systems could help understand the affinity between the host and guest, their interaction, and the main stabilization energy of the complex. In this work, two 7-(diethylamino) quinoline-2 (1H)-one derivative (QD1-2) and their interaction with cucurbit[7]uril (CB[7]) were studied from an experimental and in-silico point of view. For the experimental section, the complexes showed a 1:1 stoichiometry by HRMS-ESI and isothermal titration calorimetry (ITC). The inclusion of the derivatives on the macrocycle lends to an upward shift in the fluorescence intensity, and the pKa value of QD1-2 exhibits almost no variation after the formation of the complex. The thermodynamics of the inclusion complexes was investigated using ITC; the results demonstrate a non-classical hydrophobic effect with a minimum contribution from the entropy term and a constant binding on the order of 106 for both ligands. Additionally, dynamic molecular studies were carried out during 300 ns in an explicit solvent at NTP conditions. Our finding shows that the complex remains stable during the simulation (RMSD ~1 Å), and hydrogen bonds contribute to the stabilization of the systems. Finally, thermodynamic parameters from MMPBSA calculations were obtained to generate new computational insights to compare with experimental results.

Keywords: host-guest complexes, molecular dynamics, quinolin-2(1H)-one derivatives dyes, thermodynamics

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Authors: Majid Samavatian, Reza Gholamipour, Vahid Samavatian

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This study addresses the role of rejuvenation on the fluctuation of atomic-level stresses and nanoscale topological heterogeneity in ZrCuNiAl bulk metallic glass (BMG). Based on atomic force microscopy (AFM) results, the rejuvenation process leads to an increase in nanoscale spatial heterogeneity manifested by the intensification of the local viscoelastic response of the BMG nanostructure. It means that the rejuvenation process induces more loose-packing structures which behave towards an external load in a viscoelastic way. Hence, it is suggested that the alteration of such heterogeneity may be attributed to the variation of positional atomic rearrangement during the evolution of structural rejuvenation. On the other side, the synchrotron X-ray diffraction (XRD) results indicate that the rejuvenation intensifies the variation of internal stresses at the atomic level. This conclusion unfolds that the increase of atomic-level stresses during rejuvenation induces structural disordering and nanoscale heterogeneity in the amorphous material.

Keywords: bulk metallic glass, heterogeneity, rejuvenation, nanostructure

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Authors: Ahmed A. Abdel-Khalek, Reham A. Mohamed

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The kinetics of oxidation of the cobalt (II) complexes, [CoII(ADA)(Gly)(H2O)2]-, (ADA = N-(2-acetamido) iminodi-acetic acid and (Gly = Glycine) by periodate in aqueous acetate medium to cobalt (III) have been studied spectrophotometrically at 530 nm over the 30–50°C and a variety pH 4.57-5.25 range and I = 0.50 mol dm-3 under pseudo first order condition by taking large excess of oxidant [IO4-] and it obeys the following rate law: Rate=[CoII(ADA)(Gly)(H2O)2]-[H5IO6]{k4K6+(k5K7K5/[H+])}. Also, the kinetics of oxidation of the cobalt(II) complexes, [CoII(ADA)(Val)(H2O)2]- (ADA = N-(2-acetamido) iminodi-acetic acid and (Val = valine) by periodate in aqueous medium to cobalt (III) have been studied spectrophotometrically at 580 nm over the 30–50°C and a variety pH 4.3-5.12 range and I = 0.50 mol dm-3 under pseudo first order condition by taking large excess of oxidant [IO4-] and it obeys the following rate law: Rate=[CoII(ADA)(Val)(H2O)2]-[H5IO6]{k4K6+(k5K7K5/[H+])}

Keywords: periodate, oxidation, cobalt (II), glycine, valine acid, n-(2-acetamido imino-diacetato)

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Authors: Suzan Ghaddar, Aline Pinon, Manuel Gallardo-villagran, Mona Diab-assaf, Bruno Therrien, Bertrand Liagre

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Colorectal cancer (CRC) is the third most common cancer and exhibits a consistently rising incidence worldwide. Despite notable advancements in CRC treatment, frequent occurrences of side effects and the development of therapy resistance persistently challenge current approaches. Eventually, innovations in focal therapies remain imperative to enhance the patient’s overall quality of life. Photodynamic therapy (PDT) emerges as a promising treatment modality, clinically used for the treatment of various cancer types. It relies on the use of photosensitive molecules called photosensitizers (PS), which are photoactivated after accumulation in cancer cells, to induce the production of reactive oxygen species (ROS) that cause cancer cell death. Among commonly used metal-based drugs in cancer therapy, ruthenium (Ru) possesses favorable attributes that demonstrate its selectivity towards cancer cells and render it suitable for anti-cancer drug design. In vitro studies using distinct arene-Ru complexes, encapsulating porphin PS, are conducted on human HCT116 and HT-29 colorectal cancer cell lines. These studies encompass the evaluation of the antiproliferative effect, ROS production, apoptosis, cell cycle progression, molecular localization, and protein expression. Preliminary results indicated that these complexes exert significant photocytotoxicity on the studied colorectal cancer cell lines, representing them as promising and potential candidates for anti- cancer agents.

Keywords: colorectal cancer, photodynamic therapy, photosensitizers, arene-ruthenium complexes, apoptosis

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Authors: N. Touj, M. Sauthier, L. Mansour, N. Hamdi

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The palladium NHC complexes are one of the most interesting and widely investigated complexes in different catalytic transformations, especially C–C bond. Thus, the use of N-heterocyclic carbenes associated with palladium has been reported as efficient catalysts for the carbonyl coupling under mild and varied conditions. Herein, we report the synthesis, characterization, and cytotoxic activities of two new families of benzimidazolium salts. Then we studied the use of this class of benzimidazolium salts as a ligand in the carbonylative cross-coupling of 2-bromopyridine with different boronic acids under CO atmosphere to form unsymmetrical arylpyridine ketones.

Keywords: NHC-Pd(II) catalysts, carbonylative Suzuki cross-coupling reaction, arylboronic acids, 2-bromopyridine, unsymmetrical arylpyridine ketones

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Authors: Yasser M. Abd-elrhman, Mohamed A. Gepreel, Kiochi Nakamura, Ahmed Abd El-Moneim, Sengo Kobayashi, Mervat M. Ibrahim

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Titanium alloys are known as highly bio compatible metallic materials due to their high strength, low elastic modulus, and high corrosion resistance in biological media. Besides other important material features, the corrosion parameters and corrosion products are responsible for limiting the biological and chemical bio compatibility of metallic materials that produce undesirable reactions in implant-adjacent and/or more distant tissues. Electrochemical corrosion behaviors of novel beta titanium alloys, Ti-4.7Mo-4.5Fe, Ti-3Mo-0.5Fe, and Ti-2Mo-0.5Fe were characterized in naturally aerated Ringer’s solution at room temperature compared with common used biomedical titanium alloy, Ti-6Al-4V. The corrosion resistance of titanium alloys were investigated through open circuit potential (OCP), potentiodynamic polarization measurements and optical microscope (OM). A high corrosion resistance was obtained for all alloys due to the stable passive film formed on their surfaces. The new present alloys are promising metallic biomaterials for the future, owing to their very low elastic modulus and good corrosion resistance capabilities.

Keywords: titanium alloys, corrosion resistance, Ringer’s solution, electrochemical corrosion

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Authors: Roghaye Behroozi

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The development of functionalized metal complexes and nanomaterials has gained significant attention due to their potential in catalyzing selective oxidation and coupling reactions. These catalysts play a crucial role in various industrial and pharmaceutical processes, enhancing the efficiency, selectivity, and sustainability of chemical reactions. This research aims to design and synthesize new functionalized metal complexes and nanomaterials to explore their catalytic applications in the selective oxidation of alcohols and coupling reactions, focusing on improving yield, selectivity, and catalyst reusability. The study involves the synthesis of a nickel Schiff base complex stabilized within 41-MCM as a heterogeneous catalyst. A Schiff base ligand derived from glycine was used to create a tin (IV) metal complex characterized through spectroscopic techniques and computational analysis. Additionally, iron-based magnetic nanoparticles functionalized with melamine were synthesized for catalytic evaluation. Lastly, a palladium (IV) complex was prepared, and its oxidative stability was analyzed. The nickel Schiff base catalyst showed high selectivity in converting primary and secondary alcohols to aldehydes and ketones, with yields ranging from 73% to 90%. The tin (IV) complex demonstrated accurate structural and electronic properties, with consistent results between experimental and computational data. The melamine-functionalized iron nanoparticles exhibited efficient catalytic activity in producing triazoles, with enhanced reaction speed and reusability. The palladium (IV) complex displayed remarkable stability and low reactivity towards C–C bond formation due to its symmetrical structure. The synthesized metal complexes and nanomaterials demonstrated significant potential as efficient, selective, and reusable catalysts for oxidation and coupling reactions. These findings pave the way for developing environmentally friendly and cost-effective catalytic systems for industrial applications.

Keywords: catalysts, Schiff base complexes, metal-organic frameworks, oxidation reactions, nanoparticles, reusability

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Authors: Y. Benmalem , A. Abbad, W. Benstaali, T. Lantri

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Density functional theory is used to investigate the.the structural, electronic, and magnetic properties of the cubic anti-perovskites InNNi3 and ZnNNi3. The structure of antiperovskite also called (perovskite-inverse) identical to the perovskite structure of the general formula ABX3, where A is a main group (III–V) element or a metallic element, B is carbon or nitrogen, and X is a transition metal, displays a wide range of interesting physical properties, such as giant magnetoresistance. Elastic and electronic properties were determined using generalized gradient approximation (GGA), and local spin density approximation (LSDA) approaches, ), as implemented in the Wien2k computer package. The results show that the two compounds are strong ductile and satisfy the Born-Huang criteria, so they are mechanically stable at normal conditions. Electronic properties show that the two compounds studied are metallic and non-magnetic. The studies of these compounds have confirmed the effectiveness of the two approximations and the ground-state properties are in good agreement with experimental data and theoretical results available.

Keywords: anti-perovskites, elastic anisotropy, electronic band structure, first-principles calculations

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Authors: S. Belakry, D. Fasquelle, A. Rolle, E. Capoen, R. N. Vannier, J. C. Carru

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Solid oxide fuel cells (SOFCs) are promising devices for energy conversion due to their high electrical efficiency and eco-friendly behavior. Their performance is not only influenced by the microstructural and electrical properties of the electrodes and electrolyte but also depends on the interactions at the interfaces. Nowadays, commercial SOFCs are electrically efficient at high operating temperatures, typically between 800 and 1000 °C, which restricts their real-life applications. The present work deals with the objectives to reduce the operating temperature and to develop cost-effective intermediate-temperature solid oxide fuel cells (IT-SOFCs). This work focuses on the development of metal-supported solid oxide fuel cells (MS-IT-SOFCs) that would provide cheaper SOFC cells with increased lifetime and reduced operating temperature. In the framework, the local company TIBTECH brings its skills for the manufacturing of porous metal supports. This part of the work focuses on the physical, chemical, and electrical characterizations of porous metallic supports (stainless steel 316 L and FeCrAl alloy) under different exposure conditions of temperature and atmosphere by studying oxidation, mechanical resistance, and electrical conductivity of the materials. Within the target operating temperature (i.e., 500 to 700 ° C), the stainless steel 316 L and FeCrAl alloy slightly oxidize in the air and H2, but don’t deform; whereas under Ar atmosphere, they oxidize more than with previously mentioned atmospheres. Above 700 °C under air and Ar, the two metallic supports undergo high oxidation. From 500 to 700 °C, the resistivity of FeCrAl increases by 55%. But nevertheless, the FeCrAl resistivity increases more slowly than the stainless steel 316L resistivity. This study allows us to verify the compatibility of electrodes and electrolyte materials with metallic support at the operating requirements of the IT-SOFC cell. The characterizations made in this context will also allow us to choose the most suitable fabrication process for all functional layers in order to limit the oxidation of the metallic supports.

Keywords: stainless steel 316L, FeCrAl alloy, solid oxide fuel cells, porous metallic support

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Authors: Igor B. Sivaev

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Design of molecular machines is an extraordinary growing and very important area of research that it was recognized by awarding Sauvage, Stoddart and Feringa the Nobel Prize in Chemistry in 2016 'for the design and synthesis of molecular machines'. Based on the type of motion being performed, molecular machines can be divided into two main types: molecular motors and molecular switches. Molecular switches are molecules or supramolecular complexes having bistability, i.e., the ability to exist in two or more stable forms, among which may be reversible transitions under external influence (heating, lighting, changing the medium acidity, the action of chemicals, exposure to magnetic or electric field). Molecular switches are the main structural element of any molecular electronics devices. Therefore, the design and the study of molecules and supramolecular systems capable of performing mechanical movement is an important and urgent problem of modern chemistry. There is growing interest in molecular switches and other devices of molecular electronics based on transition metal complexes; therefore choice of suitable stable organometallic unit is of great importance. An example of such unit is bis(dicarbollide) complexes of transition metals [3,3’-M(1,2-C₂B₉H₁₁)₂]ⁿ⁻. The control on the ligand rotation in such complexes can be reached by introducing substituents which could provide stabilization of certain rotamers due to specific interactions between the ligands, on the one hand, and which can participate as Lewis bases in complex formation with external metals resulting in a change in the rotation angle of the ligands, on the other hand. A series of isomeric methyl sulfide derivatives of cobalt bis(dicarbollide) complexes containing methyl sulfide substituents at boron atoms in different positions of the pentagonal face of the dicarbollide ligands [8,8’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻, rac-[4,4’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ and meso-[4,7’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ were synthesized by the reaction of CoCl₂ with the corresponding methyl sulfide carborane derivatives [10-MeS-7,8-C₂B₉H₁₁)₂]⁻ and [10-MeS-7,8-C₂B₉H₁₁)₂]⁻. In the case of asymmetrically substituted cobalt bis(dicarbollide) complexes the corresponding rac- and meso-isomers were successfully separated by column chromatography as the tetrabutylammonium salts. The compounds obtained were studied by the methods of ¹H, ¹³C, and ¹¹B NMR spectroscopy, single crystal X-ray diffraction, cyclic voltammetry, controlled potential coulometry and quantum chemical calculations. It was found that in the solid state, the transoid- and gauche-conformations of the 8,8’- and 4,4’-isomers are stabilized by four intramolecular CH···S(Me)B hydrogen bonds each one (2.683-2.712 Å and 2.709-2.752 Å, respectively), whereas gauche-conformation of the 4,7’-isomer is stabilized by two intramolecular CH···S hydrogen bonds (2.699-2.711 Å). The existence of the intramolecular CH·S(Me)B hydrogen bonding in solutions was supported by the 1H NMR spectroscopy. These data are in a good agreement with results of the quantum chemical calculations. The corresponding iron and nickel complexes were synthesized as well. The reaction of the methyl sulfide derivatives of cobalt bis(dicarbollide) with various labile transition metal complexes results in rupture of intramolecular hydrogen bonds and complexation of the methyl sulfide groups with external metal. This results in stabilization of other rotational conformation of cobalt bis(dicarbollide) and can be used in design of molecular switches. This work was supported by the Russian Science Foundation (16-13-10331).

Keywords: molecular switches, NMR spectroscopy, single crystal X-ray diffraction, transition metal bis(dicarbollide) complexes, quantum chemical calculations

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Authors: Min-Ju Jo, Min-Young Um, Moonsung Choi, Sooim Shin

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Type 2 diabetes (T2D) is characterized by insulin resistance, the inability of β-cell and the dysfunction of mitochondria. To characterize effects of Cassia tora extract on mitochondrial dysfunction related T2D, the reduced glutathione level, amount of mitochondrial complexes and activities of mitochondrial complexes were measured. Three groups of mice were modeled; a control group was fed a normal diet, a diabetic group was fed a diabetic diet high in fat and carbohydrates, and a third group was fed a diabetic diet + 70% ethanol extracted Cassia tora seeds for 12 weeks. The amount of mitochondria was determined by Bradford assay after isolation of mitochondria in liver from each group. During isolation of mitochondria, cytosolic fractions of the tissue were collected to measure the reduced glutathione level. Interestingly, high level of the reduced glutathione was observed in Cassia tora treated group and decreased activities of mitochondrial complexes in Cassia tora treated group compared to the diabetic diet group. It indicates that Cassia tora has the potential to increase the reduced form of glutathione functioned as an important antioxidant in cells, and to reduce mitochondrial metabolic compensatory mechanism.

Keywords: antioxidant, Cassia tora, diabetes, electron transport chain, glutathione, mitochondria, spectrophotometry

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