Characterization of new Pt(IV)–thiazole complexes: Analytical,spectral, molecular modeling and molecular docking studies and applications in two opposing pathways

New thiazole derivatives were synthesized and fully characterized, then coordinated with PtCl₄ salt. Also, the newly synthesized Pt(IV) complexes were investigated analytically (elemental and thermogravimetric analyses), spectrally (infrared, UV–visible, mass, ¹H NMR, ¹³C NMR, X‐ray diffraction) as well as theoretically (kinetics, modeling and docking). The data extracted led to the establishment of the best chemical and structural forms. Octahedral geometry was the only formula proposed for all complexes, which is favorable for d⁶ systems. The molecular ion peaks from mass spectral analysis coincide with all analytical data, confirming the molecular formula proposed. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) allowed discrimination of features between crystalline particles and other amorphous morphology. By applying Gaussian09 as well as HyperChem 8.2 programs, the best structural forms were obtained, as well as computed significant parameters. Computed parameters such as softness, hardness, surface area and reactivity led us towards application in two opposing pathways: tumor inhibition and oxidation activation. The catalytic oxidation for CO was conducted over PtO₂, which was yielded from calcination of the most reactive complex. The success of catalytic role for synthesized PtO₂ was due to its particulate size and surface morphology, which were estimated from XRD patterns and SEM images, respectively. The antitumor activity was tested versus HCT‐116 and HepG‐2 cell lines. Mild toxicity was recorded for two of the derivatives and their corresponding complexes. This degree of toxicity is more favorable in most cases, due to exclusion of serious side effects, which is coherently attached with known antitumor drugs.     

Study on crystalline properties of Er-Si-O compounds in relation to Er-related 1.54 μm photoluminescence and electrical properties

Er-Si-O crystalline compounds, which exhibit superlattice structures and sharp and strong Er-related 1.54 μm photoluminescence (PL) spectra at room temperature have been formed by self-assembling growth mechanism. Oxidation of the starting materials which have Si and Er at an atomic ratio of 2:1 are prepared and then oxidation and succeeding high-temperature annealing in Ar above 1250 °C cause a self-assembled superlattice-structured Er-Si-O crystalline compounds. The control of the ratio of Si and Er, as well as the following oxidation and annealing processes, is found to be sensitive to the crystalline properties, PL spectra and electrical properties. In this study, Er-Si-O crystalline thin films are formed on Si substrates by sol-gel and MOMBE methods, and their crystalline properties such as crystalline orientation and concentration ratio of Er, Si and O are investigated. Crystalline Er-Si-O films of high orientation are successfully grown on Si(1 0 0) and its inclined surface. The PL and excitation spectra, fluorescence decay and the electrical properties are found to be strongly related to the crystalline properties. Excess O causes a broader 1.54 μm PL spectra, slower fluorescence decay, lower carrier-mediated excitation and higher resistivity. A precise control of O is found to be necessary to grow superlattice-structured Er-Si-O compounds, which are semiconducting and are excitable via carrier-mediated excitation mechanism.     

Polyaniline/12-phosphotungstic acid/V<Subscript>2</Subscript>O<Subscript>5</Subscript> nanocomposite and its platinum analog as oxygen reduction electrocatalysts

A guest-host nanocomposite based on electroconducting polyaniline doped with 12-phosphotungstic acid and V₂O₅ as well as its bifunctional analog containing not more than 5 mass% nanosized platinum were obtained. A study was carried out on the structure of these nanocomposites, their redox characteristics, and electrocatalytic activity in the reduction of oxygen. These nanocomposites were found to display catalytic properties in the electrochemical reduction of oxygen, while the presence of even a slight amount of nanosized platinum in the bifunctional composite leads to a significant increase in its electrocatalytic activity. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 5, pp. 307–314, September–October, 2007.     

EXAFS study of liposome-encapsulated cisplatin

The anticancer agent cisplatin encapsulated in sterically stabilized liposomes is studied with extended X-ray absorption fine structure (EXAFS) method. Analysis of local atomic structure around Pt atoms clearly indicates that the liposome-encapsulated drug is chemically stable and does not hydrolyze. Cisplatin forms a supersaturated solution in the liposome interior at a concentration about eight-fold above its aqueous solubility.     

Effect of borohydride as reducing agent on the structures and electrochemical properties of Pt/C catalyst

In this paper, we found that boron deposited on the surface of support when sodium borohydride used as reducing agent during the preparation of Pt/C catalyst. The deposition of boron markedly reduces particle size of Pt, raises electrochemical active surface (EAS) area of catalyst and electrochemical activity for hydrogen evolution or oxygen reduction reaction (ORR) compared with which prepared using other reducing agents (hydrogen and formaldehyde).     

Materials for spintronic: Room temperature ferromagnetism in Zn–Mn–O interfaces

In this paper we study the room temperature ferromagnetism reported on Mn-doped ZnO and ascribed to spin polarization of conduction electrons. We experimentally show that the ferromagnetic behaviour is associated to the coexistence of Mn³⁺ and Mn⁺⁴ in MnO₂ grains where diffusion of Zn promotes the Mn⁴⁺→Mn³⁺ reduction. Potential uses of this material in spintronic devices are analysed.     

Crack path instabilities in DCDC experiments in the low speed regime

We studied the low speed fracture regime (10⁻⁴-10⁻⁹ m s⁻¹) in different glassy materials (soda-lime glass, glass ceramics) with variable but controlled length scale of heterogeneity. The chosen mechanical system enabled us to work in pure mode I (tensile) and at a fixed load on double cleavage drilled compression specimen. The internal residual stresses of studied samples were carefully relaxed by appropriate thermal treatment. By means of optical and atomic force microscopy techniques fracture surfaces have been examined. We have shown for the first time that the crack front line underwent an out-of-plane oscillating behavior as a result of a reproducible sequence of instabilities. The wavelength of such a phenomenon is in the micrometer range and its amplitude in the nanometer range. These features were observed for different glassy materials providing that a typical length scale characterizing internal heterogeneities was lower than a threshold limit estimated to few nanometers. This effect is the first clear experimental evidence of crack path instabilities in the low speed regime in a uniaxial loading experiment. This phenomenon has been interpreted by referring to the stability criterion for a straight crack propagation as presented by Adda-Bedia et al. [Phys. Rev. Lett. 76 (1996) 1497].     

Reactivities of tetraalkyltin complexes toward Pt/HY zeolite

Tetraalkyltin complexes, SnR₄ (R = Me, Et, Pr, Bu) could react with Pt/HY at 193, 243, 273 and 333 K, respectively. The reactions occurred on the surface of the zeolite and the organotin grafted zeolites were characterized in detail. The framework and the microporous structure of the grafted Pt/HY zeolites were retained. However, the modified zeolites showed better size selectivity in the absorption of hydrocarbons.     

Analysis of atomic arrangement in magnetic Fe–Pt nanoparticles

The order parameter S of Fe–Pt nanoparticles is estimated from X-ray diffraction (XRD) patterns. The total intensity of a diffraction peak is obtained by Rietveld analysis as well as simply integrating the intensity. The Rietveld analysis is found to provide a plausible value of S even for a sample showing an XRD pattern with broad and overlapped peaks. Another order parameter Q, which is obtained from Mössbauer spectra, is introduced, and it is confirmed that Q is equivalent to the probability of Fe atoms being in the L1₀-type atomic arrangement. The coercivity of Fe–Pt nanoparticles is directly proportional to Q, while it vanishes at S=0.4, indicating that the magnetic property of Fe–Pt nanoparticles has a closer relationship to Q than S.     

Combinatorial computational chemistry approach of tight-binding quantum chemical molecular dynamics method to the design of the automotive catalysts

Recently, we have developed a new tight-binding quantum chemical molecular dynamics program “Colors” for combinatorial computational chemistry approach. This methodology is based on our original tight-binding approximation and realized over 5000 times acceleration compared to the conventional first-principles molecular dynamics method. In the present study, we applied our new program to the simulations on various realistic large-scale models of the automotive three-way catalysts, ultrafine Pt particle/CeO₂(111) support. Significant electron transfer from the Pt particle to the CeO₂(111) surface was observed and it was found to strongly depend on the size of the Pt particle. Furthermore, our simulation results suggest that the reduction of the Ce atom due to the electron transfer from the Pt particle to the CeO₂ surface is a main reason for the strong interaction of the Pt particle and CeO₂(111) support.