Characterization of partially transesterified poly(beta-hydroxyalkanoate)s using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the characterization of a partially transesterified poly(beta-hydroxyalkanoate), PHA, polymer produced by the bacterial strain Alcaligenes eutrophus using saponified vegetable oils as the sole carbon sources. The transesterification was carried out separately under acidic and basic conditions to obtain PHA oligomers weighing less than 10 kDa. The intact oligomers were detected in their cationized [M + Na](+) and [M + K](+) forms by MALDI-TOFMS. A composition analysis, using the MALDI-TOF spectra, indicate that the oligomers obtained via acid catalysis were terminated with a methyl 3-hydroxybutyrate end group, and those obtained by base catalysis had a methyl crotonate (olefinic) termination. In addition to HB (hydroxy butyrate), the oligomers were found to contain a small percentage of HV (hydroxy valerate). This was independently confirmed using gas chromatography/mass spectrometry (GC/MS). In comparison, the analysis of a commercial PHA polymer, transesterified under identical conditions, only showed the presence of HB, i.e. a pure PHB homopolymer. Copyright 1999 John Wiley & Sons, Ltd.     

On the preparation of fluorine-18 labelled XeF(2) and chemical exchange between fluoride ion and XeF(2)

A recent report claims to have prepared [18F]XeF2 by exchange between a large stoichiometric excess of XeF2 and no-carrier-added 18F-, as salts of the [2,2,2-crypt-M+] (M = K or Cs) cations, in CH2Cl2 or CHCl3 solvents at room temperature. Attempts to repeat this work have proven unsuccessful and have led to a critical reinvestigation of chemical exchange between fluoride ion, in the form of anhydrous [N(CH3)4][F] and [2,2,2-crypt-K][F], and XeF2 in dry CH2Cl2 and CH3CN solvents. It was shown, by use of 19F and 1H NMR spectroscopies, that [2,2,2-crypt-K][F] rapidly reacts with CH3CN solvent to form HF2-, and with CH2Cl2 solvent to form HF2-, CH2ClF, and CH2F2 at room temperature. Moreover, XeF2 rapidly oxidizes 2,2,2-crypt in CH2Cl2 solvent at room temperature to form HF and HF2-. Thus, the exchange between XeF2 and no-carrier-added 18F- reported in the prior work arises from exchange between XeF2 and HF/HF2-, and does not involve fluoride ion. However, naked fluoride ion has been shown to undergo exchange with XeF2 under rigorously anhydrous and HF-free conditions. A two-dimensional 19F-19F EXSY NMR study demonstrated that [N(CH3)4][F] exchanges with XeF2 in CH3CN solvent, but exchange of HF2- with either XeF2 or F- is not detectable under these conditions. The exchange between XeF2 and F- is postulated to proceed by the formation of XeF3- as the exchange intermediate.     

Standardization for oxygen isotope ratio measurement - still an unsolved problem

Numerous organic and inorganic laboratory standards were gathered from nine European and North American laboratories and were analyzed for their delta(18)O values with a new on-line high temperature pyrolysis system that was calibrated using Vienna standard mean ocean water (VSMOW) and standard light Antartic precipitation (SLAP) internationally distributed reference water samples. Especially for organic materials, discrepancies between reported and measured values were high, ranging up to 2 per thousand. The reasons for these discrepancies are discussed and the need for an exact and reliable calibration of existing reference materials, as well as for the establishment of additional organic and inorganic reference materials is stressed. Copyright 1999 John Wiley & Sons, Ltd.     

Cyclotri(λ3-phosphazane) (XPNMe)3: Darstellung,NMR-Spektren und Struktur

Ausgehend vom trihalogensubstituierten Cyclotri(λ³-phosphazan) 1 lassen sich die Derivate 2—12 in glatter Reaktion darstellen. Die sterische Belastbarkeit des Sechsring-systems hat mit X = NEt₂ in 11 ihre Grenze erreicht, für X = N? iPr₂ tritt nur noch Monosubstitution zu 13 ein, die aber eine Weitersubstitution mit sterisch weniger anspruchsvollen Resten, z. B. auch zu den Bicyclen 14—16 nicht ausschließt. Die NMR-spektroskopischen Daten legen eine Sesselkonformation der Cyclophosphazanringe nahe, wobei die diequatorial-axiale bzw. diaxial-equatoriale Konfiguration der Phosphoratome ( c, d ) als thermodynamisch günstigere Alternative zu a oder b verwirklicht ist. Es wird erstmals über eine Ringkontraktion vom Sechs- zum Vierring in der Reihe der Cyclo(λ³-phosphazane) berichtet. Cyclotri(λ³-phosphazanes) (XPNMe)₃: Preparation, NMR-Data, and Structure Cyclotri(λ³-phosphazanes) 2–12 are easily prepared from the trihalogeno substituted 1 . For steric reasons there is only a monosubstitution with X = N? iPr₂ to 13 , which nevertheless may be further substituted by sterically less demanding substituents to give e.g. the bicyclic compounds 14—16 . From NMR spectroscopic data a chair conformation of the six membered ring seems probable with the substituents at phosphorus being located either diequatorially axially ( c ) or vice versa ( d ) rather than a or b . A thermal ring contraction from a six to a four membered ring in the series of cyclo(λ³-phosphazanes) is reported for the first time.     

Stereocomplementary bioreduction of alpha,beta-unsaturated dicarboxylic acids and dimethyl esters using enoate reductases: enzyme- and substrate-based stereocontrol

Asymmetric bioreduction of alpha,beta-unsaturated dicarboxylic acids, such as 2-methylmaleic/fumaric and 2-methylenesuccinic acid, as well as the corresponding dimethyl esters, using three cloned enoate reductases furnished 2-methylsuccinic acid or dimethyl 2-methylsuccinate, respectively. Opposite stereoisomeric products were obtained in up to >99% ee either by choice of the enzyme or by using E/Z-configurated substrates. Cofactor-recycling systems (NADH/FDH/formate, NADH/GDH/glucose or NADPH/G6PDH/glucose-6-phosphate) only worked in presence of a divalent metal ion, such as Ca2+, Mg2+, or Zn2+.     

Molecular distribution of some commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Nonylphenol ethoxylates (NPEs) belong to a group of nonionic surfactants that are collectively referred to as alkylphenol ethoxylates (APEs). APEs find widespread use in heavy-duty commercial and household cleaning formulations, shampoos, and industrial processing, i.e. textile manufacture. Their environmental impact depends on the molecular distribution and the extent of their biodegradation in municipal sewage systems, waterways and rivers. We have established two sample preparation methods that have enabled the determination of the molecular distributions of six commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS). In both methods, alpha-cyano-4-hydroxycinnamic acid, dissolved in acetonitrile/tetrahydrofuran, was used as the matrix. In one set of experiments, the NPEs were dissolved in an acetonitrile/tetrahydrofuran solvent system prior to mixing with the matrix solution, and the resulting MALDI-TOF mass spectra produced mostly sodiated molecules [M + Na](+). The NPEs, all having the formula 4-(C(9)H(19))-C(6)H(4)-(OCH(2)CH(2))(n)-OH, are Surfonic (R)N-95, N-100, N-102, N-120, N-150 and N-300. Surfonic N-95 and N-100 gave n values of 5-20; Surfonic N-102, N-120, N-150, and N-300 gave n values of 5-21, 5-22, 8-25 and 15-40, respectively. In order to develop a sample preparation method that could be used with less polar NPEs, we dissolved the NPEs (except N-300) in pentane prior to mixing with the matrix solution, and found that the MALDI spectral quality was unaffected by the solvent systems. Copyright 1999 John Wiley & Sons, Ltd.     

Syntheses and X-ray crystal structures of alpha- and beta-[XeO2F][SbF6], [XeO2F][AsF6], [FO2XeFXeO2F][AsF6], and [XeF5][SbF6)].XeOF4 and computational studies of the XeO2F+ and FO2XeFXeO2F+ cations and related species

Reactions of XeO2F2 with the strong fluoride ion acceptors, AsF5 and SbF5, in anhydrous HF solvent give rise to alpha- and beta-[XeO2F][SbF6], [XeO2F][AsF6], and [FO2XeFXeO2F][AsF6]. The crystal structures of alpha-[XeO2F][SbF6] and [XeO2F][AsF6] consist of trigonal-pyramidal XeO2F+ cations, which are consistent with an AXY2E VSEPR arrangement, and distorted octahedral MF6- (M = As, Sb) anions. The beta-phase of [XeO2F][SbF6] is a tetramer in which the xenon atoms of four XeO2F+ cations and the antimony atoms of four SbF6- anions are positioned at alternate corners of a cube. The FO2XeFXeO2F+ cations of [FO(2)XeFXeO2F][AsF6] are comprised of two XeO2F units that are bridged by a fluorine atom, providing a bent Xe- - -F- - -Xe arrangement. The angle subtended by the bridging fluorine atom, a xenon atom, and the terminal fluorine atom of the XeO2F group is bent toward the valence electron lone-pair domain on xenon, so that each F- - -XeO2F moiety resembles the AX(2)Y(2)E arrangement and geometry of the parent XeO2F2 molecule. Reaction of XeF6 with [H3O][SbF6] in a 1:2 molar ratio in anhydrous HF predominantly yielded [XeF5][SbF6].XeOF4 as well as [XeO2F][Sb2F11]. The crystal structure of the former salt was also determined. The energy-minimized, gas-phase MP2 geometries for the XeO2F+ and FO2XeFXeO2F+ cations are compared with the experimental and calculated geometries of the related species IO2F, TeO2F-, XeO2(OTeF5)+, XeO2F2, and XeO2(OTeF5)2. The bonding in these species has been described by natural bond orbital and electron localization function analyses. The standard enthalpies and Gibbs free energies for reactions leading to XeO2F+ and FO2XeFXeO2F+ salts from MF5 (M = As, Sb) and XeO2F2 were obtained from Born-Haber cycles and are mildly exothermic and positive, respectively. When the reactions are carried out in anhydrous HF at low temperatures, the salts are readily formed and crystallized from the reaction medium. With the exception of [XeO2F][AsF6], the XeO2F+ and FO2XeFXeO2F+ salts are kinetically stable toward dissociation to XeO2F2 and MF5 at room temperature. The salt, [XeO2F][AsF6], readily dissociates to [FO2XeFXeO2F][AsF6] and AsF5 under dynamic vacuum at 0 degree C. The decompositions of XeO2F+ salts to the corresponding XeF+ salts and O2 are exothermic and spontaneous but slow at room temperature.     

On-line delta(18)O measurement of organic and inorganic substances

A method for the automated sample conversion and on-line oxygen isotope ratio (delta(18)O) determination for organic and inorganic substances is presented. The samples are pyrolytically decomposed at 1400 degrees C in the presence of nickelized graphite. With the system presented organic as well as inorganic samples such as nitrates, sulphates and phosphates of 50-100 &mgr;g O can be analyzed for their delta(18)O values with a standard deviation usually better than 0.5 per thousand. Additionally, carbon isotope ratios of organic substances and nitrogen isotope ratios of inorganic nitrogenous compounds are available in the same sample run. Data for international and some inter-laboratory reference materials are presented to show the accuracy and reliability of the method. The effect of some additives on the CO yield was checked for substances which do not pyrolyze completely. Copyright 1999 John Wiley & Sons, Ltd.