Synthesis and photophysical properties of meso-substituted bisporphyrins: comparative study of phosphorescence quenching for dioxygen sensing

The 4,6-bis(10-mesityl-5,15-di-p-tolylporpyrinyl)dibenzothiophene (H4DPSN) free base was obtained in five steps from commercially available materials. The metalation of DPSN2- with zinc(II), copper(II), and palladium(II) led to three new homobimetallic systems, (Zn)2DPSN, (Cu)2DPSN, and (Pd)2DPSN, respectively. The cofacial structures of these molecules offer the possibility of having dioxygen molecules inside the cavity for a period of time, allowing dynamic (collisional) phosphorescence quenching to be more efficient. The bimolecular excited-state deactivation rate constant for deactivation by dioxygen (kQ: (Pd)2DPB, 2.98x10(9); (Pd)2DPSN, 3.99x10(9); (Pd)2DPX, 6.94x10(9); (Pd)TPP, 8.95x10(9); (Pd)2DPS, 8.95x10(9) M-1 s-1) of (Pd)2DPSN, which exhibits an intense phosphorescence at 699 nm, was compared to those observed for (Pd)TPP, (Pd)2DPS, (Pd)2DPX, and (Pd)2DPB (TPP2-=tetraphenylporphyrin dianion, DPS4-=4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene tetraanion, DPX4-=4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene tetraanion, and DPB4-=1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene tetraanion). These collision-induced deactivation data were interpreted by estimating a series of physical parameters such as the surface area and bisporphyrin radii, the diffusion coefficient of the bismacrocycles, and the theoretical deactivation efficiency for the five compounds addressing the role of steric hindrance of the macrocycles on each other and the aryl groups at the meso positions. For sensing purposes, (Pd)2DPX is characterized by a Stern-Volmer constant kSV of 2.91x10(6) M-1, placing the lower detection limit for [O2] in solution at 0.58 ppm, which is better than that for (Pd)TPP (kSV=2.31x10(6) M-1; lower detection limit of 0.73 ppm), the classically used monoporphyrin complex.     

A theoretical investigation of the enantioselective hydrogenation mechanism of α-ketoesters

The enantioselective hydrogenation of α-ketoesters to α-hydroxyesters over Pt/Al₂O₃ catalysts modified by cinchona alkaloids is an interesting model reaction for the investigation of heterogeneous catalysis capable of producing optically active products. The aim of the present theoretical study is to rationalize the interaction between protonated cinchona alkaloids (modifiers) and methyl pyruvate (substrate) by investigating the possible weak complexes formed by these two species. For this purpose we use molecular mechanics and the AM1 semiempirical method. The optimization leads to two stable forms of the complexes, where the substrate is bound to the modifier via hydrogen bonding between the oxygen of the α-carbonyl of pyruvate and the quinuclidine nitrogen of the alkaloid. In such complexes the methyl pyruvate is transformed into a half-hydrogenated species which can be adsorbed on the platinum surface and, after hydrogenation, leads to methyl lactate product. The results show that adsorption of the complex leading to (R)-methyl lactate is more favorable than that of the corresponding system yielding (S)-methyl lactate, which may be the key for the enantio-differentiation.     

Synthesis and absolute configuration of clemastine and its isomers (author's transl)]

Synthesis and Absolute Configuration of Clemastine and its Isomers. Condensation of 4-chloro-α-methylbenzhydrylalkohol ( 1 ) with 2-(2-chloroethyl)-1-methylpyrrolidine ( 2 ) gave an isomeric mixture of 2-[2-(p-chloro-α-methyl-=-phenylbenzyloxy)ethyl]-1-methylpyrrolidine ( 3 ) and 4-(p-chloro-=-phenylbenzyloxy)-1-methyl-hexahydroazepin ( 4 ). The separation of the four possible optically active isomers of 3 is described and their absolute configuration established by degradation to (R)- and (S)-1-methyl-2-pyrrolidineethanol ( 6 ), respectively, and by an X-ray cristallographic analysis of the quarternary methiodide of the isomer 3-A . Clemastine (3-A) is (+)-(2R)-2-[2-((αR)-(p-chloro-α-methyl-α-phenylbenzyloxy)ethyl)]-1-methylpyrrolidine.     

Characterization of humic substances: Implications for trihalomethane formation

Humic substances are precursors of carcinogenic trihalomethanes (THMs) formed during disinfection by chlorination in water treatment processes. In an effort to understand the relationship between trihalomethane formation potential (THMFP) and physicochemical properties of humic substances, UV-visible absorbance, fluorescence in emission and synchronous scan modes, and NMR spectra were measured for several aquatic fulvic and humic acids. For comparison, a soil fulvic acid was also examined using these methods. The feasibility of the gradient modified spin-echo (GOSE) NMR experiment to selectively measure singlet resonances arising from isolated protons was examined. In addition, diffusion coefficients were measured for DMSO solutions of the fulvic acids using BPPLED and GOSE-edited pulse sequences. Although none of the methods tested produced results that correlated with THMFP, the GOSE intensities determined for different regions of the NMR spectra did reflect the relative abundance of different types of functional groups produced by lignin oxidation. In addition, the GOSE-edited diffusion results suggest that the isolated protons, those most reactive to chlorination, are more likely contained in the larger molecular weight fractions of fulvic acids.     

Identification of ochratoxin A in food samples by chemical derivatization and gas chromatography-mass spectrometry.

The contamination of foods with ochratoxin A can be determined very sensitively by high-performance liquid chromatography (HPLC) with fluorescence detection. A novel procedure is described to confirm OA-positive results quantitatively down to the HPLC detection limit of 0.1 ppb. For this, ochratoxin A in the sample extract is converted into its O-methylochratoxin A methyl ester derivative, which is identified subsequently by gas chromatography-mass spectrometry negative-ion chemical ionization and multiple ion detection modes using the hexadeuterated O-methyl-d3-ochratoxin A methyl-d3 ester derivative as internal standard for quantification. In the analysis of more than 60 contaminated samples, the procedure was found to be very accurate.     

Liquid chromatographic separation of the thyroid hormones

The liquid Chromatographic separation of 3,3',5-triiodothyronine, 3,3',5'-triiodothyronine, and thyroxine with a nonpolar stationary phase was studied as a function of pH, temperature, organic content of the mobile phase, and ionic strength using aqueous phosphate—acetonitrile, aqueous phosphate—methanol, and aqueous phosphate— n-propanol mobile phase systems. It was demonstrated that the quality of the thyroid hormone separations, as determined by normalized peak capacity values, was unchanged with temperature, remained relatively constant with increasing ionic strength, and was affected to the greatest extent by changes in pH and organic modifier content of the mobile phase. Chromatographic behavior of the compounds studied as a function of these variables was found to be consistent with existing Chromatographic theory and/or empirical observations. Recommended conditions are aqueous phosphate—methanol mobile phase, pH 2–5 (aqueous portion), and high temperature (60–70°C).     

Collisional depolarization of NO2 fluorescence as studied by Hanle effect measurements

We report on collisional depolarization of NO₂ fluorescence with use of Hanle effect (zero magnetic field level crossing) experiments. Single fine structure levels of NO₂ in several regions of the visible absorption spectrum predominantly near 593 nm and 514 nm are prepared by selective optical excitation and the depolarization of the fluorescence light versus a magnetic field is investigated. We find that the Hanle signal is in general a superposition of two Lorentzian shaped signals, each with a characteristic dependence on light intensity and NO₂ pressure. For NO₂ pressures >1 µ bar the collisional depolarization follows simple Stern-Volmer kinetics. However, an unusual pressure dependence is observed at NO₂ pressures <1 µ bar. In the same pressure range (<1 µ bar) we see also an unexpected resonance with significantly different properties as the Hanle signal.     

Activated alpha-alkyl-alpha-arylacetic acid enantiomers for stereoselective thin-layer chromatographic and high-performance liquid chromatographic determination of chiral amines

The separation of racemic benoxaprofen into the two benoxaprofen enantiomers by preparative high-performance liquid chromatography and the application of the activated enantiomers as derivatization reagents for the simultaneous stereoselective determination of chiral amines in biological material is described. Activated (+)- and (-)-benoxaprofen are both shown to be very sensitive and stable chiral fluorescence markers, applicable to thin-layer chromatography as well as to high-performance liquid chromatography.     

Materials and Methods

Materials and Methods Synthesis of thionyl chloride-activated succinamidopropyl-glass beads