Identification of Apigenin Metabolites in Rat Liver Perfusate by Column Switching High Performance Liquid Chromatography/Electrospray Ionization Mass Spectrometry

Summary.  A selective column switching high performance liquid chromatographic method has been used for the simultaneous determination of apigenin and metabolites in rat liver perfusate. This new method clearly separated apigenin and the metabolites with high resolution. The structures of metabolites were proposed based on selective ion recording and full scan analysis by electrospray ionization mass spectrometry. Corresponding author. E-mail: basly@pharma.unilim.fr Received May 15, 2002; accepted (revised) September 13, 2002     

Intramolecular interactions of L‐phenylalanine: Valence ionization spectra and orbital momentum distributions of its fragment molecules

Intramolecular interactions between fragments of L ‐phenylalanine, i.e., phenyl and alaninyl, have been investigated using dual space analysis (DSA) quantum mechanically. Valence space photoelectron spectra (PES), orbital energy topology and correlation diagram, as well as orbital momentum distributions (MDs) of L ‐phenylalanine, benzene and L ‐alanine are studied using density functional theory methods. While fully resolved experimental PES of L ‐phenylalanine is not yet available, our simulated PES reproduces major features of the experimental measurement. For benzene, the simulated orbital MDs for 1e_1g and 1a_2u orbitals also agree well with those measured using electron momentum spectra. Our theoretical models are then applied to reveal intramolecular interactions of the species on an orbital base, using DSA. Valence orbitals of L ‐phenylalanine can be essentially deduced into contributions from its fragments such as phenyl and alaninyl as well as their interactions. The fragment orbitals inherit properties of their parent species in energy and shape (ie., MDs). Phenylalanine orbitals show strong bonding in the energy range of 14‐20 eV, rather than outside of this region. This study presents a competent orbital based fragments‐in‐molecules picture in the valence space, which supports the fragment molecular orbital picture and building block principle in valence space. The optimized structures of the molecules are represented using the recently developed interactive 3D‐PDF technique. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011     

Relativistic effects in spectroscopy and photophysics of heavy-metal complexes illustrated by spin–orbit calculations of [Re(imidazole)(CO)3(phen)]+

Spin–orbit coupling (SOC) is an essential factor in photophysics of heavy transition metal complexes. By enabling efficient population of the lowest triplet state and its strong emission, it gives rise to a very interesting photophysical behavior and underlies photonic applications such as organic light emitting diodes (OLED) or luminescent imaging agents. SOC affects excited-state characters, relaxation dynamics, radiative and nonradiative decay pathways, as well as lifetimes and reactivity. We present a new photophysical model based on mixed-spin states, illustrated by relativistic spin–orbit TDDFT and MS-CASPT2 calculations of [Re(imidazole)(CO)₃(1,10-phenanthroline)]⁺. An excited-state scheme is constructed from spin–orbit (SO) states characterized by their energies, double-group symmetries, parentages in terms of contributing spin-free singlets and triplets, and oscillator strengths of corresponding transitions from the ground state. Some of the predictions of the relativistic SO model on the number and nature of the optically populated and intermediate excited states are qualitatively different from the spin-free model. The relativistic excited-state model accounts well for electronic absorption and emission spectra of Re^I carbonyl diimines, as well as their complex photophysical behavior. Then, we discuss the SO aspects of photophysics of heavy metal complexes from a broader perspective. Qualitative SO models as well as previous relativistic excited-state calculations are briefly reviewed together with experimental manifestations of SOC in polypyridine and cyclometallated complexes of second- and third row d⁶ metals. It is shown that the relativistic SO model can provide a comprehensive and unifying photophysical picture.     

Modulating the photophysical properties of azamacrocyclic europium complexes with charge-transfer antenna chromophores

Two europium complexes with bis(bipyridine) azamacrocyclic ligands featuring pendant arms with or without π-conjugated donor groups are synthesized and fully characterized by theoretical calculations and NMR spectroscopy. Their photophysical properties, including two-photon absorption, are investigated in water and in various organic solvents. The nonfunctionalized ligand gives highly water-stable europium complexes featuring bright luminescence properties but poor two-photon absorption cross sections. On the other hand, the europium complex with an extended conjugated antenna ligand presents a two-photon absorption cross section of 45 GM at 720 nm but is poorly luminescent in water. A detailed solvent-dependent photophysical study indicates that this luminescence quenching is not due to the direct coordination of O-H vibrators to the metal center but to the increase of nonradiative processes in a protic solvent induced by an internal isomerization equilibrium.     

N-H···π hydrogen-bonding and large-amplitude tipping vibrations in jet-cooled pyrrole-benzene

The N-H···π hydrogen bond is an important intermolecular interaction in many biological systems. We have investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet cooled complex of pyrrole with benzene and benzene-d(6) (Pyr·Bz, Pyr·Bz-d(6)). DFT-D density functional, SCS-MP2 and SCS-CC2 calculations predict a T-shaped and (almost) C(s) symmetric structure with an N-H···π hydrogen bond to the benzene ring. The pyrrole is tipped by ω(S(0)) = ±13° relative to the surface normal of Bz. The N···ring distance is 3.13 ?. In the S(1) excited state, SCS-CC2 calculations predict an increased tipping angle ω(S(1)) = ±21°. The IR depletion spectra support the T-shaped geometry: The NH stretch is redshifted by -59 cm(-1), relative to the "free" NH stretch of pyrrole at 3531 cm(-1), indicating a moderately strong N-H···π interaction. The interaction is weaker than in the (Pyr)(2) dimer, where the NH donor shift is -87 cm(-1) [Dauster et al., Phys. Chem. Chem. Phys., 2008, 10, 2827]. The IR C-H stretch frequencies and intensities of the Bz subunit are very similar to those of the acceptor in the (Bz)(2) dimer, confirming that Bz acts as the acceptor. While the S(1)←S(0) electronic origin of Bz is forbidden and is not observable in the gas-phase, the UV spectrum of Pyr·Bz in the same region exhibits a weak 0 band that is red-shifted by 58 cm(-1) relative to that of Bz (38?086 cm(-1)). The origin appears due to symmetry-breaking of the π-electron system of Bz by the asymmetric pyrrole NH···π hydrogen bond. This contrasts with (Bz)(2), which does not exhibit a 0 band. The Bz moiety in Pyr·Bz exhibits a 6a band at 0 + 518 cm(-1) that is about 20× more intense than the origin band. The symmetry breaking by the NH···π hydrogen bond splits the degeneracy of the ν(6)(e(2g)) vibration, giving rise to 6a' and 6b' sub-bands that are spaced by ～6 cm(-1). Both the 0 and 6 bands of Pyr·Bz carry a progression in the low-frequency (10 cm(-1)) excited-state tipping vibration ω', in agreement with the change of the ω tipping angle predicted by SCS-MP2 and SCS-CC2 calculations.     

Modeling of Thin-Layer Chromatographic Separation of Androstane Isomers

JPC – Journal of Planar Chromatography – Modern TLC - Modeling of thin-layer chromatographic separation of androstane isomers to find the optimum mobile phase is described in this...