Lipase-mediated deracemization of secondary 1-phenyl-substituted propargylic alcohols of different topology

Acetylation of (±)-1-phenylnon-2-yn-1-ol, (±)-1-phenylhept-1-yn-3-ol, and (±)-1-phenylundec-4-yn-3-ol ((±)-5) in the presence of lipase from Candida cylindracea (CCL) proceeds slowly to give products with ee 20%. The acetates of these alcohols are hydrolyzed in the presence of porcine pancreatic lipase (PPL) equally unsatisfactorily. The (⁶-arene)tricarbonylchromium complex of alcohol (±)-5 is acetylated in the presence of CCL up to 22% conversion to give (R)-acetate whose oxidative decomplexation followed by saponification results in alcohol (R)-(–)-5 with ee 95%. The configuration of alcohols (–)-5 and (+)-5 was determined by NMR spectroscopy of their esters with (R)- and (S)-Mosher"s acids.     

Synthesis of alkyl (α-phenylthioalkenyl) ketones containing a (Z)-trisubstituted olefinic fragment

Warren"s method, which has been proposed for the synthesis of -phenylthiodialkyl ketones, appeared to be inefficient for the preparation of their alkenyl alkyl analogs. The latter were prepared in good yields by alkenylation of alkyl phenylthiomethyl ketones with alkenyl bromides.     

A Negative Deviation from Stern–Volmer Equation in Fluorescence Quenching

A negative deviation from the normal Stern-Volmer equation shown in the fluorescence quenching of doxorubicin by adenosine 5' monophosphate is interpreted in terms of doxorubicin exists in two different conformers in the ground state. An estimate of the Stem-Volmer constant for the excited-state quenching is about 218 M(-1). The fluorescence decay of free doxorubicin is a bi-exponential in polar protic and polar aprotic solvents. In the presence of adenosine 5' monophosphate, doxorubicin shows a tri-exponential decay in water.     

Spectroscopic Study on the Photophysical Properties of Lanthanide Complexes with 2, 2′-Bipyridine-N, N′-dioxide

Five novel lanthanide (Eu3+, Tb3+, Gd3+, Sm3+ and Dy3+) complexes with 2, 2'-bipyridine-N, N'-dioxide (bipyO2) were synthesized and characterized by elemental analysis, IR spectrum. The triplet state energy of bipy O2 was determined to be 22275 cm(-1) with the phosphorescence spectrum of bipy O2 and its gadolinium complex. The photophysical properties of these complexes indicated that the triplet state energy of the ligand is suitable for the sensitization of the luminescence of Eu3+, Tb3+, Sm3+ and Dy3+, especially of Tb3+.     

Measurement of RLT and ATL in the 4He(e, e’p)3H reaction at pmiss of 130-300 MeV/ c

We have measured the ⁴He(e, ep)³H reaction at missing momenta of 130-300 MeV/c using the three-spectrometer facility at the Mainz microtron MAMI. Data were taken in perpendicular kinematics to allow us to determine the response function R_LT and the asymmetry term A_TL. The data are compared to both relativistic and non-relativistic calculations.     

Effects of phonon-phonon coupling on low-lying states in neutron-rich Sn isotopes

Starting from an effective Skyrme interaction we present a method to take into account the coupling between one- and two-phonon terms in the wave functions of excited states. The approach is a development of a finite rank separable approximation for the quasiparticle RPA calculations proposed in our previous work. The influence of the phonon-phonon coupling on energies and transition probabilities for the low-lying quadrupole and octupole states in the neutron-rich Sn isotopes is studied.     

Beta-decay of 71Co and 73Co

A decay spectroscopy study of the neutron-rich cobalt isotopes has been performed using fragmentation of a ⁸⁶Kr³⁶⁺ beam and the new LISE2000 spectrometer at GANIL. For ⁷¹Co and ⁷³Co, the -delayed radiation has been observed for the first time, and the half-lives were found to be 79(5) ms and 41(4) ms, respectively. Features of the decay are discussed qualitatively in terms of nuclear models.     

Sol-Gel Synthesis of Transparent Alumina Gel and Pure Gamma Alumina by Urea Hydrolysis of Aluminum Nitrate

-Alumina was synthesized by a sol-gel method with the aluminum ion hydrolysis control performed by urea. The initial saturated Al³⁺/urea solution presented urea coordinated with the aluminum ion, as shown in the ¹³C NMR and ²⁷Al NMR spectra and longitudinal relaxation times, T ₁, from the latter. The substitution of water molecules in the Al³⁺ coordination shell by urea controlled the hydrolysis process and provided an extensive nucleation during the initial steps of the aluminum hydroxide formation due to urea thermolysis at 90°C. The resulting sol, composed of Al(OH)₃ nanoparticles, coalesced and became a transparent gel permeated by a solution of urea and the polycation ion [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺. The freshly prepared gel was transformed, under heating at 300°C, directly to -alumina, characterized by FTIR, ²⁷Al-MAS-NMR and S_BET techniques, without - or -phases, as a consequence of the high degree of homogeneity of the -alumina precursor.     

Capillary Coated with Layer-by-Layer Assembly of γ-Zirconium Phosphate/ Lysozyme Nanocomposite Film for Open Tubular Capillary Electrochromatography Chiral Separation

A new capillary coating of alternate -zirconium phosphate lysozyme fabricated for open-tubular electrochromatography enantioseparation. The chiral compounds D, L-tryptophan tested were enantiomerically resolved. The influences brought by experimental parameters, such as organic modifier, temperature, applied voltage and pH of running buffer on the performance of the column, were investigated.