Adsorbate interactions of Cu(II) in Cu(II)-exchanged K-L gallosilicate studied by CW and Pulsed electron spin resonance

The interactions of Cu(II) in Cu(II)-exchanged K-L gallosilicate with adsorbates containing coordinative nitrogens in ammonia, pyridine, aniline, acetonitrile and hydrazine, and with the adsorbates carbon monoxide, benzene, propanol and dimethyl sulfoxide are investigated by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies. These results are compared with those in Cu(II)-exchanged K-L aluminosilicate and the differences are discussed. Adsorption of ammonia produces a complex containing four molecules of ammonia based on resolved nitrogen superhyperfine interaction. Upon equilibrium with pyridine, Cu(II) forms a complex containing four molecules of pyridine in CuK-L gallosilicate and a complex containing only three molecules of pyridine in CuK-L aluminosilicate based on resolved nitrogen superhyperfine. Upon adsorption of aniline and acetonitrile, Cu(II) forms complexes containing two molecules of each in CuK-L gallosilicate based on resolved nitrogen superhyperfine. However, no resolved nitrogen superhyperfine between hydrazine and Cu(II) is seen. Adsorption of carbon monoxide, benzene, propanol and dimethyl sulfoxide causes changes in the ESR spectrum of Cu(II), indicating migration of Cu(II) into cation positions in the main channels where adsorbate coordination can occur. Cu(II) forms complexes with one molecule of benzene and two molecules of propanol based on ESEM data in both K-L gallosilicate and K-L aluminosilicate. However, Cu(II) interacts directly with one dimethyl sulfoxide in K-L aluminosilicate but only indirectly at a longer distance with one dimethyl sulfoxide in K-L gallosilicate based on ESEM data.     

Analysis of matrix nuclei spin flip satellite lines in EPR spectra: Application to trapped hydrogen atoms

The relative intensities and energy separation of allowed EPR lines of a paramagnetic species and partially forbidden spin flip satellite lines due to dipole-dipole coupling between the paramagnetic species and the matrix nuclei have been analyzed in a new way. The analysis allows one to determine both the distance to and the number of matrix nuclei that contribute to a given satellite transition. For hydrogen atoms trapped in a gamma-irradiated sulphuric acid glass at 77 K the analysis indicates that interaction occurs with four matrix protons at a distance of 2.15 Å. For trapped hydrogen atoms in phosphoric acid glass the analysis indicates interaction with four matrix protons at 2.37 Å.     

Condensed phase photoelectron asymmetry

Large directional asymmetries were observed in photoelectron distributions from core and valence levels in metals and adsorbate atoms. Intensities varied by factors up to 25 as the angle between A and p was varied. The energy dependence of asymmetry showed atomic behavior similar to that expected for free atoms, modified for the tendency p∥A.     

Bio-orthogonal affinity purification of direct kinase substrates

Protein phosphorylation is a major mechanism of post-translational protein modification used to control cellular signaling. A challenge in phosphoproteomics is to identify the direct substrates of each protein kinase. Herein, we describe a chemical strategy for delivery of a bio-orthogonal affinity tag to the substrates of an individual protein kinase. The kinase of interest is engineered to transfer a phosphorothioate moiety to phosphoacceptor hydroxyl groups on direct substrates. In a second nonenzymatic step, the introduced phosphorothioate is alkylated with p-nitrobenzylmesylate (PNBM). Antibodies directed against the alkylated phosphorothioate epitope recognize these labeled substrates, but not alkylation products of other cellular nucleophiles. This strategy is demonstrated with Cdk1/cyclinB substrates using ELISA, western blotting, and immunoprecipitation in the context of whole cell lysates.     

Electron spin echo at S-band: Nuclear modulations and decay in C60 powder

At S-band (≈ 3 GHz) the modulation amplitude of the Electron Spin Echo patterns is increased with respect to the amplitude at X-band: as a consequence, it is possible to reveal the presence of nuclei not detectable at X-band. In this paper the results obtained by running ESE experiments at S-band on a C₆₀ powder sample containing radicals are shown and discussed. The two- and three-pulse Electron Spin Echo patterns exhibit both¹³C modulation and proton modulation not detected at X-band. The experimental data are quantitatively analyzed by simulating the time-domain patterns and their Fourier transforms. It results that a noticeable amount of proton nuclei surrounds the intrinsic paramagnetic centers. On the basis of the analysis, a possible explanation of their existence is given.     

Polarity effects on wavelength dependence of the fluorescence quantum yield for indole

The change in fluorescence quantum yield for indole as a function of excitation wavelength between 250 and 220 nm is found to vary with the static dielectric constant of various alcohol—water mixtures at 296 K. The supports the intermediacy of a CTTS state in the photoionization process.