Logic of Determination of Objects (LDO): How to Articulate ��Extension�� with ��Intension�� and ��Objects�� with ��Concepts��

From a logical viewpoint, object is never defined, even by a negative definition. This paper is a theoretical contribution about object using a new constructivist logical approach called Logic of Determination of Objects founded on a basic operation, called determination. This new logic takes into account cognitive problems such as the inheritance of properties by non typical occurrences or by indeterminate atypical objects in opposition to prototypes that are typical completely determinate objects. We show how extensional classes, intensions, more and less determined objects, more or less typical representatives of a concept and prototypes are defined and organized, using a determination operation that constructs a class of indeterminate objects from an object representation of a concept called typical object.     

Giant magnetoimpedance in thin amorphous and nanocrystalline microwires

We present the results on Giant magneto-impedance effect (GMI) in amorphous and nanocrystalline microwires at frequencies until 4 GHz, paying special attention to tailoring the frequency and magnetic field dependence of the GMI effect. Correlation between magnetoelastic anisotropy and magnetic field dependences of diagonal and off-diagonal impedance components are observed.     

Reply to A Computational Evaluation of the Evidence for the Synthesis of 1,3‐Dimethylcyclobutadiene in Solid State and Aqueous Solution—Beyond the Experimental Reality

Following earlier reports on the photochemical synthesis of 1,3‐dimethylcyclobutadiene 8 , 10 in a protective host matrix, theoretical calculations for the formation of that adduct have been recently performed by Rzepa. 13 The author formulated criticisms based mainly on density functional theory calculations of ¹H NMR spectra. According to Rzepa the calculated spectra do not correspond with our measured spectra, which leads him to the conclusion that our interpretation is wrong, and that mainly cyclobutadiene has not been stabilized or even synthesized; we believe, however, that the initial model that Rzepa used for his calculations does not correspond to chemical reality or is at the very least a crude simplification of it, which implies that his calculations cannot match, in every point, our experimental spectra. Rzepa′s simplified models might be ‘reasonable’ from the theoretical point of view; however, in the case of assessment in the solid state, the theoretical setup does not force the system to preserve the confined stabilizing space defined by the crystalline matrix for encapsulated hosts in the solid state. Inversely, in the case of solution modeling, the theoretical setup is too rigid to properly assess the complex equilibria occurring in solution and to accurately determine the NMR spectra of exchanging species in solution. The inconsistency between our experimental results and the results of the theoretical models proposed by Rzepa is such that his conclusions are considered to be too far from experimental reality. Accurate modeling taking in account “reasonable” experimental details would be a worthwhile endeavor.     

Magnetic nanoparticles coated with polysaccharide polymers for potential biomedical applications

This study reports a two-steps route for obtaining magnetic nanoparticles–polysaccharide hybrid materials consisting of Fe₃O₄, NiFe₂O₄ and CuFe₂O₄ nanoparticles synthesis by coprecipitation method in the presence of a soft template followed by coating of ferrite nanoparticles of 8–10-nm size range with polysaccharide type polymers—sodium alginate or chitosan. Magnetic oxide nanoparticles and the corresponding hybrid materials were characterized by X-ray diffraction (XRD), Mössbauer spectroscopy, atomic absorption spectroscopy (AAS), FTIR spectroscopy, scanning and transmission electron microscopy (SEM and TEM) and specific surface area measurements. The vibrating sample magnetometry confirms the superparamagnetic properties of the synthesized ferrites and hybrids. Using this route, the percent of magnetic nanoparticles retained in chitosan-based hybrid materials is nearly double in comparison with that of sodium alginate–based materials. The biological activity tests on Escherichia coli ATCC 25922, Pseudomonas aeroginosa ATCC 27853, Staphylococcus aureus ATCC 25923 and Candida scotti microorganisms show the non-toxic properties of prepared hybrid materials.     

Anionic Bipyridyl Ligands for Applications in Metallasupramolecular Chemistry

The facile synthesis of anionic bipyridyl ligands with dinuclear clathrochelate cores is described. These metalloligands can be obtained in high yields by the reactions of M(ClO₄)₂(H₂O)₆ (M: Zn, Mn, or Co) with 4‐pyridylboronic acid and 2,6‐diformyl‐4‐methylphenol oxime or 2,6‐diformyl‐4‐tert‐butylphenol oxime, followed by deprotonation. The ligands are interesting building blocks for metallasupramolecular chemistry, as evidenced by the formation of a Pt‐based molecular square and four coordination polymers with 2D or 3D network structures. Competition experiments reveal that the utilization of anionic bipyridyl ligands can result in significantly more stable assemblies.     

Chemical Bonding in Molecules and Complexes Containing d-Elements Based on DFT

Summary. Metal–ligand bonding in transition metal halide molecules and complexes with different central ions, oxidations states, and coordination numbers: Cr^IIIX₆^3–, Cr^IVX₄, Cr^IIX₂ (X = F,Cl,Br,I), M^IIICl₆^3–(M = Mo,W), M^III(H₂O)₆³⁺(M = Cr,Co) and Re₂Cl₈^2– has been studied in terms of the Extended Transition State (ETS) energy patitioning scheme within the DFT and electron density analysis (the Laplacian of the electron density and the electronic localization function). Bonding is found to be dominated by ionicity in all cases, especially so for complexes with higher coordination numbers. Covalent contributions to the metal–ligand bond are found to be mainly due to the nd-electrons and to lesser extent due to the metal (n+1)s and (n+1)p-orbitals, contributions from (n+1)s increasing when going to lower coordination numbers. Metal–ligand bonding analysis have been used in order to check some concepts emerging from ligand field theory when applied to the spectroscopy and magnetism of transition metal complexes. It is pointed out that for complexes of high symmetry (MX₆, O_h, MX₄, T_d, and MX₂, D_h) electron density analyses gain interpretative power when partitioned into contributions from occupied orbitals of different symmetry.     

Reaction of C60 with KMnF4 : Isolation and characterization of a new isomer of C60F8 and re-evaluation of the structures of C60F7(CF3) and the known isomer of C60F8

The volatile fluorofullerene products of high-temperature reactions of C₆₀ with the ternary manganese(III, IV) fluorides KMnF₄, KMnF₅, A₂MnF₆ (A⁺ = Li⁺, K⁺, Cs⁺), and K₃MnF₆ were monitored as a function of reaction temperature, reaction time, and stoichiometric ratio by in situ Knudsen-cell mass spectrometry. When combined with fluorofullerene product ratios from larger-scale (bulk) screening reactions with the same reagents, an optimized set of conditions was found that yielded the greatest amount of C₆₀F₈ (KMnF₄/C₆₀ mol ratio 28-30, 470 °C, 4-5 h). Two isomers of C₆₀F₈ were purified by HPLC, one of which has not been previously reported. Quantum chemical calculations at the DFT level combined with 1D and 2D ¹⁹F NMR, FTIR, and FT-Raman spectroscopy indicate that the C₆₀F₈ isomer previously reported to be 1,2,3,8,9,12,15,16-C₆₀F₈ is actually 1,2,3,6,9,12,15,18-C₆₀F₈, making it the first high-temperature fluorofullerene with non-contiguous fluorine atoms. The new isomer, which was found to be 1,2,7,8,9,12,13,14-C₆₀F₈, is predicted to be 5.5 kJ mol⁻¹ more stable than 1,2,3,6,9,12,15,18-C₆₀F₈ at the DFT level. In addition, new DFT calculations and spectroscopic data indicate that the compound previously isolated from the high-temperature reaction of C₆₀ and K₂PtF₆ and reported to be 16-CF₃-1,2,3,8,9,12,15-C₆₀F₇ is actually 18-CF₃-1,2,3,6,8,12,15-C₆₀F₇.     

Toward sustainable energy: photocatalysis of Cr-doped TiO<Subscript>2</Subscript>: 2. effect of defect disorder

The present chain of five papers considers the concept of solar-to-chemical energy conversion using TiO₂-based semiconductors. The series reports the effect of chromium on the key performance-related properties of polycrystalline TiO₂ (rutile), including electronic structure, photocatalytic activity, intrinsic defect disorder, electrochemical coupling and surface versus bulk properties. In this work, we show that the effect of chromium on photocatalytic performance of TiO₂ depends on its elemental content and the related defect disorder that is determined by oxygen activity in the oxide lattice. At high oxygen activity, chromium leads to enhanced photocatalytic performance only for dilute solid solutions (up to 0.04–0.043 at.% Cr). Higher chromium content results in a decrease of photocatalytic activity below that for pure TiO₂, despite the observed substantial decrease of the band gap. The photocatalytic performance of Cr-doped TiO₂ annealed in reducing conditions is low within the entire studied range of compositions. The obtained results led to derivation of a theoretical model representing the mechanism of the light-induced reactivity of TiO₂ with water and the related charge transfer. The photocatalytic performance is considered in terms of a competitive effect of several key performance-related properties. The performance is predominantly influenced by the concentration of titanium vacancies acting as reactive surface sites related to anodic charge transfer.

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