Quantification of Volatile Aldehydes Deriving from In Vitro Lipid Peroxidation in the Breath of Ventilated Patients

Exhaled aliphatic aldehydes were proposed as non-invasive biomarkers to detect increased lipid peroxidation in various diseases. As a prelude to clinical application of the multicapillary column–ion mobility spectrometry for the evaluation of aldehyde exhalation, we, therefore: (1) identified the most abundant volatile aliphatic aldehydes originating from in vitro oxidation of various polyunsaturated fatty acids; (2) evaluated emittance of aldehydes from plastic parts of the breathing circuit; (3) conducted a pilot study for in vivo quantification of exhaled aldehydes in mechanically ventilated patients. Pentanal, hexanal, heptanal, and nonanal were quantifiable in the headspace of oxidizing polyunsaturated fatty acids, with pentanal and hexanal predominating. Plastic parts of the breathing circuit emitted hexanal, octanal, nonanal, and decanal, whereby nonanal and decanal were ubiquitous and pentanal or heptanal not being detected. Only pentanal was quantifiable in breath of mechanically ventilated surgical patients with a mean exhaled concentration of 13 ± 5 ppb. An explorative analysis suggested that pentanal exhalation is associated with mechanical power—a measure for the invasiveness of mechanical ventilation. In conclusion, exhaled pentanal is a promising non-invasive biomarker for lipid peroxidation inducing pathologies, and should be evaluated in future clinical studies, particularly for detection of lung injury.     

Switching the Mechanism of NADH Photooxidation by Supramolecular Interactions

A series of three Ru(II) polypyridine complexes was investigated for the selective photocatalytic oxidation of NAD(P)H to NAD(P)⁺ in water. A combination of (time-resolved) spectroscopic studies and photocatalysis experiments revealed that ligand design can be used to control the mechanism of the photooxidation: For prototypical Ru(II) complexes a ¹O₂ pathway was found. Rudppz ([(tbbpy)₂Ru(dppz)]Cl₂, tbbpy=4,4'-di-tert-butyl-2,2'-bipyridine, dppz=dipyrido[3,2-a:2′,3′-c]phenazine), instead, initiated the cofactor oxidation by electron transfer from NAD(P)H enabled by supramolecular binding between substrate and catalyst. Expulsion of the photoproduct NAD(P)⁺ from the supramolecular binding site in Rudppz allowed very efficient turnover. Therefore, Rudppz permits repetitive selective assembly and oxidative conversion of reduced naturally occurring nicotinamides by recognizing the redox state of the cofactor under formation of H₂O₂ as additional product. This photocatalytic process can fuel discontinuous photobiocatalysis.     

Tuning Thiophene with Phosphorus: Synthesis and Electronic Properties of Benzobisthiaphospholes

1,4‐Dimercapto‐2,5‐diphosphinobenzene and 3,6‐bis(hexyloxy)‐1,4‐dimercapto‐2,5‐diphosphinobenzene were synthesized and combined with various acid chlorides to obtain a series of benzobisthiaphospholes. Electrochemical and photophysical properties of the substituted benzobisthiaphospholes have been evaluated, and the observed reductions are more facile than the related benzothiaphospholes and 2,6‐diphenylbenzobisthiazole. A benzobisthiaphosphole with C₆H₄‐p‐CN substituents was reduced at E_1/2=?1.08 V (vs. saturated calomel electrode (SCE)). X‐ray diffraction data for several of these phosphorus heterocycles has been obtained, and DFT calculations at the B3LYP level have been performed.     

Frequency and temperature dependence of molecular and micromechanical transitions in PPO/PMMA/P(S-g-EO) blends

The frequency and temperature dependence of molecular and micromechanical transitions were studied in polymer blends with an interphase. The viscoelastic properties of poly(2,6-dimethyl-p-phenylene oxide) (PPO) and poly(methyl methacrylate) (PMMA) blends that were compatibilized by a poly(styrene-graft-ethylene oxide) (P(S-g-EO)) copolymer were studied by dynamic mechanical spectroscopy (DMS) and the experimental data were compared with an interlayer model. The addition of the copolymer resulted in a micromechanical transition, and the relation between the volume fraction of interphase, the activation energy of the micromechanical transition, and the micromechanical transition temperature was studied. A qualitative agreement between experiments and theory was achieved. The quantitative difference was explained by partial mixing of PPO and/or PMMA with the copolymer in the interphase. © 1996 John Wiley & Sons, Inc.     

New designer drugs N-(1-phenylcyclohexyl)-2-ethoxyethanamine (PCEEA) and N-(1-phenylcyclohexyl)-2-methoxyethanamine (PCMEA): Studies on their metabolism and toxicological detection in rat urine using gas chromatographic/mass spectrometric techniques

Studies are described on the metabolism and the toxicological detection of the phencyclidine-derived designer drugs N-(1-phenylcyclohexyl)-2-ethoxyethanamine (PCEEA) and N-(1-phenylcyclohexyl)-2-methoxyethanamine (PCMEA) in rat urine using gas chromatographic/mass spectrometric (GC/MS) techniques. The identified metabolites indicated that PCEEA and PCMEA were transformed to the same metabolites by N-dealkylation and O-dealkylation partially followed by oxidation of the resulting alcohol to the respective carboxylic acid and hydroxylation of the cyclohexyl ring at different positions and combinations of those. Finally, aromatic hydroxylation of the O-dealkylated metabolites was partially followed by hydroxylation of the cyclohexyl ring at different positions. All metabolites were partially excreted in conjugated form. The authors' systematic toxicological analysis (STA) procedure using full-scan GC/MS after acid hydrolysis, liquid-liquid extraction and microwave-assisted acetylation allowed the detection of an intake of a common drug users' dose both of PCEEA and PCMEA in rat urine. Assuming similar metabolism in humans, the STA should be suitable for proof of an intake of PCEEA and PCMEA in human urine, although their differentiation is not possible due to common metabolites.     

On ϵ productions for terminals in E0L forms

When working with E0L forms, equality of languages and of language families has traditionally been considered modulo the empty word ? to avoid trivial but cumbersome distinctions of cases. Despite this fact, the role of ?-productions is often significant in L form theory particular, it has previously been shown that vomplete forms must have ?-productions We strengthen this result by proving that vomplete forms must even have ?-productions for nonterminals. Based on this theorem we establish that there are E0L forms with the property that any form equivalent E0L form must generate the empty word. Thus, despite the fact that we define equality of languages modulo ?, we are still unable to ignore the presence of the empty word in languages when studying L forms. The proof of our main theorem is based on a number of lemmas which allow to show that certain E0L forms are not form equivalent. In view of the difficulty of proving or disproving form equivalence of arbitrary E0L forms (conjectured to be undecidable) these lemmas may well be of independent interest.     

Optical properties of fiber optics materials

The advances in optical waveguides have permitted a clear measurement of many glass properties normally obscured by impurities in conventional glasses. Among these is the intrinsic optical absorption in both the infrared and ultraviolet regions. The wavelength dependence and the statistical fluctuations of another intrinsic property, the refractive index, have also been determined in detail. Knowing accurately the foregoing characteristics of “pure” glasses, deviations due to additives are easier to detect. This has led to absorption determinations for atomic defects and selected impurities as well as for deliberate additions of other oxides.     

Matroid basis graphs. I

A matroid may be defined as a collection of sets, called bases, which satisfy a certain exchange axiom. The basis graph of a matroid has a vertex for each basis and an edge for each pair of bases that differ by the exchange of a single pair of elements. Two characterizations of basis graphs are obtained. The first involves certain local subgraphs and how they lie when the given graph is leveled with respect to distance from a particular vertex. The second involves the existence of a special mapping from the given graph to some “full” basis graph. It is also shown that in a natural sense all basis graphs are homotopically trivial.     

Isolation and purification oil glucuronides with preparative anion exchange chromatography in methanol

890 ml of urine of rats treated with [¹⁴C] 205–734 was desalted over an Amberlite XAD-2 adsorption column. The methanol extract dissolved in 10 ml methanol was injected onto an anion exchange column (Nucleosil 10 SB 250 × 16 mm i.d.) equilibrated in methanol. A gradient of decreasing methanol proportion versus a 0.2 M ammonium hydrogen carbonate buffer eluted a pure glucuronide of 205–734. Its structure was established by NMR, MS, UV, and IR analyses. This procedure is simple, rapid, and very selective for the compound of interest.