Clustering of nucleosides in the presence of alkali metals: Biologically relevant quartets of guanosine,deoxyguanosine and uridine observed by ESI-MS/MS

Electrospray ionization (ESI) mass spectra of nucleosides, recorded in the presence of alkali metals, display alkali metal ion-bound quartets and other clusters that may have implications for understanding non-covalent interactions in DNA and RNA. The tetramers of guanosine and deoxyguanosine and also their metaclusters (clusters of clusters), cationized by alkali metals, were observed as unusually abundant magic number clusters. The observation of these species in the gas phase parallels previous condensed-phase studies, which show that guanine derivatives can form quartets and metaclusters of quartets in solution in the presence of metal cations. This parallel behavior and also internal evidence suggest that bonding in the guanosine tetramers involves the bases rather than the sugar units. The nucleobases thymine and uracil are known to form magic number pentameric adducts with K+, Cs+ and NH4+ in the gas phase. In sharp contrast, we now show that the nucleosides uridine and deoxythymidine do not form the pentameric clusters characteristic of the corresponding bases. More subtle effects of the sugars are evident in the fact that adenosine and cytidine form numerous higher order clusters with alkali metals, whereas deoxyadenosine and deoxycytidine show no clustering. It is suggested that hydrogen bonding between the bases in the tetramers of dG and rG are the dominant interactions in the clusters, hence changing the ribose group to deoxyribose (and vice versa) generally has little effect. However, the additional hydroxyl group of RNA nucleosides enhances the non-selective formation of higher-order aggregates for adenosine and cytidine and results in the lack of highly stable magic number clusters. Some clusters are the result of aggregation in the course of ionization (ESI) whereas others appear to be intrinsic to the solution being examined.     

Strategy of analysis for the estimation of the bioavailability of zinc in foodstuffs

After the application of simulated digestive fluids (gastric and intestinale fluid) as extraction solutions, AAS and differential pulse anodic-stripping voltammetry (DPASV) were used as analytical methods in combination with ion-exchange procedures for the determination of zinc species and total zinc contents. The ion exchange procedure and the shifting of electrochemical potentials as well as changes of the calibration slope after standard addition in the polarographic analysis allowed discriminating statements with regard to a possible resorption of zinc. On the basis of these methods, a strategy is presented for in vitro investigations of the bioavailability of zinc in foodstuffs.     

Detection of VX contamination in soil through solid-phase microextraction sampling and gas chromatography/mass spectrometry of the VX degradation product bis(diisopropylaminoethyl)disulfide

A solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) sampling and analysis method was developed for bis(diisopropylaminoethyl)disulfide (a degradation product of the nerve agent VX) in soil. A 30-min sampling time with a polydimethylsiloxane-coated fiber and high temperature alkaline hydrolysis allowed detection with 1.0 microg of VX spiked per g of agricultural soil. The method was successfully used in the field with portable GC-MS instrumentation. This method is relatively rapid (less than 1 h), avoids the use of complex preparation steps, and enhances analyst safety through limited use of solvents and decontamination of the soil before sampling.     

Fuzzy theory in analytical chemistry

The concept of fuzzy theory is described in order to provide the analyst with the means for dealing with vague statements, uncertain observations or the fuzziness of human perception and interpretation, in general. In a theoretical part, basic notions of fuzzy theory are given, such as types of membership functions, operations with fuzzy sets, definitions of fuzzy numbers, points, functions, and relations, and the use of linguistic variables. The difference between fuzziness and probability is outlined. The applications section demonstrates advantages of fuzzy theory methods compared to common mathematical methods with respect to data handling for calibration of analytical methods, to classification of Chromatographie and spectroscopic patterns, to component identification and multicomponent analysis, and to designing fuzzy expert systems for selection of analytical procedures.     

Encapsulated guest molecules in the dimer of octahydroxypyridine[4]arene

Recently a new type of calix[4]arenes has been synthesized via condensation of 2,6-dihydroxypyridine and a number of aldehydes. This type of pyridine[4]arenes forms capsules consisting of two single pyridine[4]arenes. These capsules can incorporate different guest molecules, like carboxylic acids and amides in this case. We proved that the guest acids really are incorporated inside the cavity of the capsules by electrospray mass spectrometry, NMR spectroscopy, and theoretical calculations.     

Novel methyl helianthrones as photosensitizers: synthesis and biological evaluation

A combination of light, oxygen and a photosensitizer is used to induce death of cancer cells by photodynamic therapy. In this study, we have synthesized several new methyl helianthrone derivatives and compared their phototoxicity with that of hypericin. In contrast to hypericin, methyl helianthrones are soluble in aqueous solutions and have a broad range of light absorbance, which allows the use of polychromatic light. Structural modifications of methyl helianthrone demonstrated that substitution of hydrogen atoms of methyl helianthrone at Positions 2 and 5 with Br atoms or methylation of its phenolic hydroxyls, significantly increases the corresponding singlet oxygen quantum yield and their phototoxicity toward alphaT3-1, M2R and LNCaP cells. The phototoxicity of some of these compounds was similar to that of hypericin. Methyl helianthrones, like hypericin, accumulated mainly in the perinuclear region as evident by confocal microscopy. Irradiation of cells pretreated with methyl helianthrone derivatives generates intracellular reactive oxygen species and lipid free radicals, as shown by a fluorescentic probe and electron paramagnetic resonance methods, respectively. The phototoxicity of these methyl helianthrones as well as their ability to oxidize membrane lipids were significantly decreased on addition of specific Type-II inhibitors, suggesting the involvement of singlet oxygen as the main oxidant.     

Bestimmung geringer Uranmengen nach Konzentrierung durch Extraktion und Anionenaustausch in einem tri-n-octylphoshinoxidhaltigen Lösungsmittelsystem

Zusammenfassung Auf Grund systematischer Untersuchungen des Verhaltens von Uran in verschiedenen wäßrig-organischen, Tri-n-octylphosphinoxid (TOPO) enthaltenden Lösungsmittelsystemen gegenüber verschiedenen Anionenformen des stark basischen Anionenaustauschers Dowex 1, X 8 wurde eine Methode zur Abtrennung des Urans entwickelt. Bei diesem Verfahren wird das Uran aus einer ascorbin-säurehaltigen, 1-n salzsauren Lösung mit 0,1-m TOPO in Diäthyläther extrahiert und aus einem Gemisch aus 50 Vol. % Äther (0,1-m an TOPO), 45 Vol. % Methylglykol und 5 Vol. % 12-n Salzsäure am Ionenaustauscher (Chloridform) adsorbiert. Nach Elution mit 1-n Salzsäure wird das Uran entweder fluorimetrisch oder spektrophotometrisch nach der Thiocyanatmethode bestimmt. Mit diesem Anionenaustauschverfahren ist eine Abtrennung des Urans von allen, seine fluorimetrische oder spektrophotometrische Bestimmung störenden Ionen und auch vom TOPO selbst möglich. Besonders wurde auf die spektrophotometrische Bestimmung des Urans bei Anwesenheit großer Molybdänmengen eingegangen und eine Methode zur Abtrennung dieses Elementes entwickelt.

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Determination of small amounts of uranium after concentrating through extraction and anionic exchange in a solvent agent system containing tri-n-octylphosphine oxide

Summary A method has been developed for the separation of uranium that is based on systematic studies of the behavior of uranium in various water-organic solvent systems containing tri-n-octylphosphine oxide (TOPO) towards various anion forms of the strongly basic anion exchanger Dowex 1, X 8. In this procedure, the uranium is extracted from a 1N hydrochlorid acid solution containing ascorbic acid into diethyl ether and adsorbed from a mixture consisting of 50 vol.% ether (0.1N in TOPO), 45 vol.% methylglycol and5 vol.% 12N hydrochloric acid on the ion exchanger (chlorid form). Following elution with 1M hydrochloric acid, the uranium is determined either fluorimetrically or spectrophotometrically by the thiocyanate method. By means of this anion exchange procedure, it is possible above all to separate the uranium from all ions interfering with its fluorimetric or spectrophotometric determination and also from TOPO itself. In particular, consideration is given to the spectrophotometric determination of the uranium in the presence of larger amounts of molybdenum, and a method was worked out for the removal of this element.

     

In situ NMR observation of mono- and binuclear rhodium dihydride complexes using parahydrogen-induced polarization

Starting from the binuclear complex [RhCl(NBD)]2 (NBD = 2,5-norbornadiene) in the presence of the phosphines L = PMe3, PMe2Ph, PMePh2, PEt3, PEt2Ph, PEtPh2, or P(n-butyl)3, various mononuclear dihydrides of the type Rh(H)2CIL3, i.e., those of the homogeneous hydrogenation catalysts RhCIL3, have been obtained upon addition of parahydrogen, and their 1H NMR spectra have been investigated using parahydrogen-induced polarization (PHIP). Furthermore, the two binuclear complexes (H)(Cl)Rh(PMe3)2(mu-Cl)(mu-H)Rh(PMe3) and (H)(Cl)Rh(PMe2Ph)2(mu-Cl)(mu-H)Rh(PMe2Ph) have been detected and characterized by means of this in situ NMR method. Analogous complexes with trifluoroacetate instead of chloride, i.e., Rh(H)2(CF3COO)L3, have been generated in situ starting from Rh(NBD)(acac) in the presence of trifluoroacetic acid in combination with the phosphines L = PPh3, PEt2Ph, PEt3, and P(n-butyl)3, and their 1H NMR parameters have been determined.     

The absolute configuration of peroxisomicines A1 and A2

Peroxisomicine A1 is a potentially antineoplastic compound isolated from the seeds of Karwinskia parvifolia. It is considered as a useful chemotype for the preparation of topoisomerase II targeted anticancer cells. Stereochemically, it is characterized by the presence of two stereocenters and a rotationally hindered and thus likewise stereogenic biaryl axis. In this contribution, the absolute configuration of peroxisomicine A1 and its epimer, peroxisomicine A2, was established by means of a five-step degradative procedure giving the respective R- and S-configured methyl 2-(2′-methyl-5′-oxotetrahydrofuryl)acetates. The configuration of the degradation product was obtained by means of optical rotation, ¹H NMR analysis using a chiral displacement reagent, and by experimental and quantum chemical circular dichroism (CD) investigations. Based on the results obtained here and considering our previous work on the relative configuration at centers versus axis of these compounds, peroxisomicine A1 resulted to be the P,3S,3′S-isomer and peroxisomicine A2 the P,3R,3′S-isomer.