Comprehensive DFT and MO studies on glyoxilic acid oxime and related ions in gas phase and solution: Conformations,basicities and acidities

Density functional (BLYP, B3LYP and BHLYP) and highly correlated MP2 and CCSD(T) calculations have been performed to investigate conformers, energy barriers, intramolecular H-bond strength, gas-phase basicity and deprotonation energies of glyoxilic acid oxime (gao) and related ions in gas phase and in aqueous solution (SCRF-PCM method). BHLYP/6-311G(d,p) and B3LYP/6-31++G(d) predictions for the global minimum conformer of gao were consistent with experiment. BLYP level overestimated the H-bond and stabilized incorrectly the H-bonded conformer. The calculations in solution indicated destabilization of H-bonded conformers due to the small polarizability and weaken of the H-bond. The same global minimum structures in gas phase and aqueous solution were found for gao-neutral (ectt) and gao-dianion (e⁻²), whereas they were different for gao-anion because of the strong decrease of the conformational energies in solution. The global minimum structures of the neutral, anion and dianion of gao, obtained in solution, are in agreement with experiment. The gas-phase basicity (GB) and molecular electrostatic potential (MEP) calculations revealed the same sites for electrophilic attack, supported by the nature of HOMO: the carbonylic oxygen for the neutral, the carboxylic oxygen for the anion and the oxime nitrogen for the dianion. MEP results in gas phase and in solution suggested a region between the two atoms, but not on one atom in accordance with bidentate binding of gao ions to a metal. The BHLYP/6-31++G(d,p) molecular properties of gao were in best consistent with CCSD(T) results. The thermodynamical properties (GB and bond deprotonation energy) of gao were better estimated at B3LYP level.     

Spectroscopic and theoretical study of Cu(II), Zn(II), Ni(II), Co(II) and Cd(II) complexes of glyoxilic acid oxime

The paper presents a detailed experimental and theoretical study of five metal complexes of glyoxilic acid oxime (gaoH2), Cu(gaoH)2(H2O)2 (1), Zn(gaoH)2(H2O)2 (2), Co(gaoH)2(H2O)2 (3), Ni(gaoH)2(H2O)2 (4) and [Cd(gaoH)2(H2O)2].H2O (5). The electronic and vibrational spectra were measured and discussed as to the most sensitive to the M-L binding bands. Two different types of coordination were considered for gaoH- ligand: bidentate through the carboxylic oxygen and oxime nitrogen in 1-4 and mixed bidentate and bridging through the COO group in 5. It is shown that the spectral behavior of the nu(COO) modes can be used to predict bridging ligand coordination. DFT(B3LYP/6-31++G(d,p)) calculations on model compounds: neutral, anionic and radical forms of gao and Cu(gaoH)2, have been carried out to correlate geometries, electronic and vibrational structures. The results obtained were used to assist the electronic and vibrational analysis of the complexes studied. The effect of the metal-ligand interactions (electrostatic and covalent) on the geometry structure of the ligand was investigated.     

Two-dimensional pH-responsive printable smectic hydrogels

Anisotropic swelling and deswelling of smectic liquid crystal networks have been observed in response to pH changes.     

Advances on photosystem II investigation by measurement of delayed chlorophyll fluorescence by a phosphoroscopic methods

A method for data acquisition based on recording of light signal from a conventional phophoroscope fluorometer with high-speed digitalization is proposed to extract more information from a delayed chlorophyll a fluorescence (DF) signal. During the signal processing from all points registered by the fluorometer, we obtain simultaneously a large number of induction curves of DF decaying at different time ranges. In addition, it is possible to register a series of dark relaxation kinetics of DF, recorded at different moments during the induction period or at different temperatures. This allows the evaluation of the contribution of DF kinetic components during the induction period or at different temperatures and the comparison between DF signals registered with different phophoroscopes. With the phosphoroscope system used in this study, we have shown that the contribution of the millisecond components (with lifetimes 0.6 and 2-4 ms) predominates during the first second of the induction period. After 1 s of illumination, the amplitudes of the 0.6 ms and 2-4 ms components and of the slower one (with lifetime more than 10 ms) become approximately equal. The change in lifetime of the different components during the induction and during gradual heating is also observed. It is shown that all registered DF kinetic components have different temperature dependences.     

Stereospecific Nickel‐Catalyzed Cross‐Coupling Reactions of Alkyl Grignard Reagents and Identification of Selective Anti‐Breast‐Cancer Agents

Alkyl Grignard reagents that contain β‐hydrogen atoms were used in a stereospecific nickel‐catalyzed cross‐coupling reaction to form C(sp³)? C(sp³) bonds. Aryl Grignard reagents were also utilized to synthesize 1,1‐diarylalkanes. Several compounds synthesized by this method exhibited selective inhibition of proliferation of MCF‐7 breast cancer cells.     

Comprehensive Evaluation of Late Season Peach Varieties (Prunus persica L.): Fruit Nutritional Quality and Phytochemicals

Peaches are one of the most preferred seasonal fruits, and a reliable source of nutrients. They possess biologically active substances that largely differ among varieties. Hence, revealing the potential of several late season peaches is of present interest. Three commonly consumed varieties (“Flat Queen”; “Evmolpiya”; “Morsiani 90”) were studied in terms of nutritive and phytochemical content, as well as antioxidant activity with the use of reliable spectrophotometric and High Performance Liquid Chromatographic (HPLC) methods. An analysis of the soil was also made. The phytochemical data were subjected to principal component analysis in order to evaluate their relationship. The “Morsiani 90” variety had the highest minerals concentration (2349.03 mg/kg fw), total carbohydrates (16.21 g/100 g fw), and α-tocopherol (395.75 µg/100 g fresh weight (fw)). Similar amounts of TDF (approx. 3 g/100 g fw) were reported for all three varieties. “Flat Queen’s” peel extract was the richest in monomeric anthocyanins (2279.33 µg cyanidin-3-glucoside (C3GE)/100 g fw). The “Morsiani 90” variety extracts had the highest antioxidant potential, defined by 2,2-diphenil-1-picrylhydrazyl (DPPH), ferric-reducing antioxidant power (FRAP) and cupric ion-reducing antioxidant capacity (CUPRAC) assays.     

Heterogeneous Water Oxidation: Surface Activity versus Amorphization Activation in Cobalt Phosphate Catalysts

Is water oxidation catalyzed at the surface or within the bulk volume of solid oxide materials? This question is addressed for cobalt phosphate catalysts deposited on inert electrodes, namely crystallites of pakhomovskyite (Co₃(PO₄)₂?8 H₂O, Pak) and phosphate‐containing Co oxide (CoCat). X‐ray spectroscopy reveals that oxidizing potentials transform the crystalline Pak slowly (5–8 h) but completely into the amorphous CoCat. Electrochemical analysis supports high‐TOF surface activity in Pak, whereas its amorphization results in dominating volume activity of the thereby formed CoCat material. In the directly electrodeposited CoCat, volume catalysis prevails, but not at very low levels of the amorphous material, implying high‐TOF catalysis at surface sites. A complete picture of heterogeneous water oxidation requires insight in catalysis at the electrolyte‐exposed “outer surface”, within a hydrated, amorphous volume phase, and modes and kinetics of restructuring upon operation.     

A soft molecular 2Fe–2As precursor approach to the synthesis of nanostructured FeAs for efficient electrocatalytic water oxidation

An unprecedented molecular 2Fe–2As precursor complex was synthesized and transformed under soft reaction conditions to produce an active and long-term stable nanocrystalline FeAs material for electrocatalytic water oxidation in alkaline media. The 2Fe2As-centred β-diketiminato complex, having an unusual planar Fe₂As₂ core structure, results from the salt-metathesis reaction of the corresponding β-diketiminato Fe^IICl complex and the AsCO⁻ (arsaethynolate) anion as the monoanionic As⁻ source. The as-prepared FeAs phase produced from the precursor has been electrophoretically deposited on conductive electrode substrates and shown to act as a electro(pre)catalyst for the oxygen evolution reaction (OER). The deposited FeAs undergoes corrosion under the severe anodic alkaline conditions which causes extensive dissolution of As into the electrolyte forming finally an active two-line ferrihydrite phase (Fe₂O₃(H₂O)_x). Importantly, the dissolved As in the electrolyte can be fully recaptured (electro-deposited) at the counter electrode making the complete process eco-conscious. The results represent a new and facile entry to unexplored nanostructured transition-metal arsenides and their utilization for high-performance OER electrocatalysis, which are also known to be magnificent high-temperature superconductors.

A molecularly derived FeAs has been used as an electro(pre)catalyst for an efficient alkaline OER for the first time and subsequently, its active structure has been determined by quasi in situ X-ray absorption spectroscopy and ex situ methods.