Preparation and Photophysics of 2-(1-Pyrenyl)acrylic Acid and Its Methyl and 2′,2′,6′,6′-Tetramethyl-4′-Piperidyl Esters

Novel probes represented connection of pyrene as chromophore and sterically hindered amine stabilizers (HAS) in the form of esters of 2-(1-pyrenyl)acrylic acid were synthesized. HAS was in the form of parent amine (PAP) as well as stable nitroxyl radical form (PAP-NO^.). Photophysics of these probes were compared with their precursor as 2-(1-pyrenyl)acrylic acid (PAA) and its methyl ester (PAM). The fluorescence spectrum of PAA strongly depends on the acidity of the solution. The spectrum in neutral methanol indicates that it originates from the anionic form –COO⁻. Changes of acidity or basicity of methanol solution resulted in the changes of shape, position as well as the intensity of fluorescence band. This is due to the presence of protolytic equilibria, either in the ground state or in the singlet excited state, leading to the formation of molecular form –COOH and the cationic form –COOH₂⁺. The ester analogues did not show any changes in various pH conditions. Fluorescence of all probes depends on the polarity of solvents and the presence of oxygen. Intermolecular quenching was studied with external quenchers TEMPO and oxygen and the data were compared with the intramolecular quenching using 1′-oxo-2′,2′,6′,6′-tetramethyl-4′-piperidinyl-2-(1-pyrenyl)acrylate (PAP-NO^.).     

Reactivities of mixed organozinc and mixed organocopper reagents. Part 13 Kinetic study for phosphine‐catalyzed acylation of alkylarylzincs and effect of residual group on the transfer rate of alkyl group

Kinetics of reactions of di‐n‐butylzinc, n‐Bu₂Zn, and mixed n‐butyl(substituted phenyl)zinc reagents and n‐Bu(functional group (FG)?C₆H₄)Zn with benzoyl chloride in the presence of tri‐n‐butylphosphine have been investigated. Reaction rates of transferable n‐butyl group have been determined in tetrahydrofuran at 0 °C to compare the transfer rate of n‐butyl group in homo and mixed diorganozincs. Rate law is consistent with a third‐order reaction, which is first order in diorganozinc, benzoyl chloride, and n‐Bu₃P, and a mechanism was proposed. The lower reaction rate of n‐BuPhZn than that of n‐Bu₂Zn and negative reaction constant in Hammett plot are in accordance with the carbanionic charge of transferable n‐butyl group in the acylation reaction. These findings support the hypothesis that the reaction rate of transferable group, R_T, changes depending upon the residual group, R_R, in R_RR_TZn reagents. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation and characterization of titania based nanowires

A new method for preparation of titania nanowires with diameter around 10 nm and length up to 2–3 μm is described. The precursor was prepared from sodium titanate by adding ethylene glycole (EG) and heating at temperature of 198°C for 6 h under reflux. The sodium titanate glycolate formed by this way aggregated into 1D nanostructures and was subsequently transformed into titania glycolate during a chemical treatment with 98% sulfuric acid. Titania nanowires with variable amount of anatase and rutile were prepared by heating to temperatures in the range 350–1000°C. The precursor as well as titania based samples were characterized by X-ray diffraction, Infrared spectroscopy, Scanning electron microscopy, High resolution transmission microscopy, Thermogravimetry, Differential thermal analysis, Evolved gas analysis and Emanation thermal analysis. The nitrogen adsorption/desorption was used for surface area and porosity determination. The photoactivity of the prepared titania samples was assessed by the photocatalytic decomposition of 4-chlorophenol in an aqueous slurry under UV irradiation of 365 nm wavelength.     

Delayed resonator with acceleration feedback – Complete stability analysis by spectral methods and vibration absorber design

This paper deals with the problem of active vibration suppression using the concept of delayed resonator (DR) absorber with acceleration feedback. A complete dynamic analysis of DR and its coupling with a single degree of freedom mechanical system are performed. Due to the presence of a delay in the acceleration feedback, the dynamics of the resonator itself, as well as the dynamics of combined system are of ‘neutral’ character. On this system, spectral methods are applied to perform a complete stability analysis. Particularly, the method of cluster treatment of characteristic roots is used to determine stability boundaries in the space of the resonator parameters. Based on this analysis, a methodology to select the resonator parameters is proposed in order to guarantee desirable suppression characteristics and to provide safe stability margins. An example case study is included to demonstrate these analytical results.     

First-principles prediction and partial characterization of the vibrational states of water up to dissociation

A new, accurate, global, mass-independent, first-principles potential energy surface (PES) is presented for the ground electronic state of the water molecule. The PES is based on 2200 energy points computed at the all-electron aug-cc-pCV6Z IC-MRCI(8,2) level of electronic structure theory and includes the relativistic one-electron mass-velocity and Darwin corrections. For H₂¹⁶O, the PES has a dissociation energy of D₀ = 41 109 cm⁻¹ and supports 1150 vibrational energy levels up to 41 083 cm⁻¹. The deviation between the computed and the experimentally measured energy levels is below 15 cm⁻¹ for all the states with energies less than 39 000 cm⁻¹. Characterization of approximate vibrational quantum numbers is performed using several techniques: energy decomposition, wave function plots, normal mode distribution, expectation values of the squares of internal coordinates, and perturbing the bending part of the PES. Vibrational normal mode labels, though often not physically meaningful, have been assigned to all the states below 26 500 cm⁻¹ and to many more above it, including some highly excited stretching states all the way to dissociation. Issues to do with calculating vibrational band intensities for the higher-lying states are discussed.     

Response of bare 1-3 piezocomposite array to localized electrical excitation

The theoretical response of a 1-3 piezocomposite plate submitted to localized electrical excitation was studied with the theory of guided waves. The theoretical modeling was based on the global matrix method, and the piezocomposite material was considered as a homogeneous medium. To validate the theoretical results, experimental displacement measurements were performed with an interferometric probe on two piezocomposite plates, one with a single element and one with an array of electrodes. The measured response on the single-element plate was mainly supported by the S0 and S3 modes of the plate. Homogenization limits of the composite in terms of frequency and wave number are defined on the basis of data from this sample. Within these limits, the piezocomposite material operates as a homogeneous medium, and comparison between theoretical and experimental results allows the equivalent electroacoustic parameters to be evaluated. A second sample was measured to study the effects of the electrode array on the electroacoustic response of the plate. Two kinds of electrical excitation were studied.     

Investigation of 2-aminoethanethiol as corrosion inhibitor for steel using response surface methodology (RSM)

The inhibition efficiency of 2-aminoethanethiol (2-AEE) has been investigated against steel corrosion in 0.1 M HCl solution. The effect of temperature, pH, and concentration were studied with the help of potentiodynamic measurement, electrochemical impedance spectroscopy, scanning electron microscopy, and atomic absorption spectroscopy techniques. The potential of zero charge (E_pzc) studies showed that the adsorption occurs via ?SH group; the metal surface is positively charged in corrosive test solution. The adsorptive interaction is evaluated, and best correlation was obtained with Langmuir isotherm. 2-AEE was shown to have significant inhibition efficiency against steel corrosion. The response surface methodology was employed to explain the relation between pH, inhibitor concentration, and the efficiency. The regression analysis was realized for development of an equation between independent variables and the output. The success of fitting model was tested with basic statistical arguments, residual and variance analysis, T and F tests, and R ² value. The statistical evaluations showed that the obtained polynomial equation can be successfully used for optimization of applications involving the use of 2-AEE as inhibitor.     

Photoinduced decarboxylation of 9‐oxo‐6,9‐dihydro[1,2,5]selenadiazolo[3,4‐f]quinoline‐8‐carboxylic acid

Photoinduced reactions of 9‐oxo‐6,9‐dihydro[1,2,5]selenadiazolo[3,4‐f]quinoline‐8‐carboxylic acid (SeQCA) were investigated in alkaline media (aqueous NaOH solutions) by electron paramagnetic resonance (EPR) spectroscopy, following the in situ formation of paramagnetic species. According to UV–Vis and nuclear magnetic resonance investigations, protonation (pH ≈ 11) and deprotonation (pH ≈ 13) of the imino hydrogen of the 4‐pyridone moiety has to be considered, reflected also in the different EPR spectra observed upon irradiation. Photoinduced generation of radicals was found only for carboxylate substituted SeQCA; other studied selenadiazoloquinolone derivatives, together with those substituted at the C(8) position (R = H, COOCH₂CH₃, COOCH₃, COCH₃ or CN), did not generate paramagnetic species during exposure. Consequently, photodecarboxylation was suggested as the decisive step, accompanied by the decomposition of the selenadiazole ring, resulting in the formation of ortho‐hydroxylate anions. EPR parameters elucidated from experimental EPR spectra obtained at pH ≈ 11 and pH ≈ 13 indicate the formation of oxygen‐centered radicals at the decarboxylated 4‐pyridone ring. EPR spin trapping experiments with nitromethane confirmed a very effective photoinduced electron transfer from all the selenadiazoloquinolones investigated. Copyright © 2011 John Wiley & Sons, Ltd.     

Preservation of the Pt(100) surface reconstruction after growth of a continuous layer of graphene

Scanning tunneling microscopy shows that a layer of graphene can be grown on the hex-reconstructed Pt(100) surface and that the reconstruction is preserved after growth. A continuous sheet of graphene can be grown across domain boundaries and step edges without loss of periodicity or change in direction. Density functional theory calculations on a simple model system support the observation that the graphene can have different rotation angles relative to the hex-reconstructed Pt surface. The graphene sheet direction can be changed by incorporating pentagon-heptagon defects giving rise to accommodation of edge dislocations. The defect formation energy and the induced buckling of the graphene have been characterized by DFT calculations.     

Mössbauer Study of Oxygenated Iron-Phthalocyanines,a Precursor of Magnetic Storage Material

⁵⁷Fe transmission Mössbauer spectroscopy and X-ray diffractometry were used to study rc="/content/tr0100567828m028/xxlarge945.gif" alt="agr" align="BASELINE" BORDER="0">- and rc="/content/tr0100567828m028/xxlarge946.gif" alt="beta" align="MIDDLE" BORDER="0">-polymorphs of iron phthalocyanines (FePc) to get information about their oxygenation in connection with controlled pyrolysis of flat layered phthalocyanines initiated by radicals at relatively low temperatures, to form acicular carbide particles encaged in carbon. Mössbauer spectroscopy and XRD revealed that the oxygenation of both rc="/content/tr0100567828m028/xxlarge945.gif" alt="agr" align="BASELINE" BORDER="0">- and rc="/content/tr0100567828m028/xxlarge946.gif" alt="beta" align="MIDDLE" BORDER="0">-polymorphs of FePc was successfully achieved. New Mössbauer spectral components (doublets) appeared upon the oxygenation in both rc="/content/tr0100567828m028/xxlarge945.gif" alt="agr" align="BASELINE" BORDER="0"> and rc="/content/tr0100567828m028/xxlarge946.gif" alt="beta" align="MIDDLE" BORDER="0"> FePc. This can be attributed to iron microenvironments containing oxygen between the layers of iron phthalocyanines.