Separation and detection of oxidation products of fluorodeoxyglucose and glucose by high-performance liquid chromatography-electrospray ionisation mass spectrometry

2-Deoxy-2-[18F]fluoro-D-glucose ([18F] FDG), the most popular positron emitting radiopharmaceutical, may oxidise by autoradiolysis in aqueous solution. The aim of this work was to use LC-MS for determination of the oxidation products of fluorodeoxyglucose and glucose (Glc) obtained by oxidation with Fenton's reagent. Asahipak NH2P-50 polyamide silica column and acetonitrile-0.025% aqueous ammonium formate (80:20 (v/v)) eluent were utilised with an Agilent 1100 HPLC-MS instrument. Ten major oxidation products of FDG and Glc were separated and identified by mass spectrometry: 2-fluorogluconic acid, 2-fluoroglucuronic acid, 2-oxoerythronic acid, arabinose, arabonic acid, araburonic acid, erythrose, erythrulose, gluconic acid, and glucuronic acid. The most intensive electrospray ionisation signals were found in the negative ion spectra and were due to HCOO- adducts, the other acids being in their lactone forms.     

Supramolecular helical mesomorphic polymers. Chiral induction through H-bonding

The work described here concerns a challenge of general interest in supramolecular chemistry: the achievement of chiral helical organizations with controlled structures. This work provides a strategy to obtain supramolecular polymers in which a chiral helical conformation has been induced by a noncovalent association, that is, through hydrogen bonding. Polycatenar 2,4,6-triarylamino-1,3,5-triazines, which organize into columnar mesophases and are susceptible to H-bonding interactions, were chosen as a starting point to build up the chiral supramolecular structure. The stacking of these mesogens has been forced to wind in a helical way by means of H-bond association with (R)-3-methyladipic acid, within the mesophase. The optically active columnar organization has been studied in depth by optical microscopy, differential scanning calorimetry (DSC), X-ray diffraction, and circular dichroism. Formation of stable complexes between the triazine units and (R)-3-methyladipic acid has also been investigated by means of NMR diffusion-ordered spectroscopy (DOSY) experiments in chloroform.     

Determination of liposoluble vitamins in cooked meals, milk and milk products by liquid chromatography

A method for the simultaneous determination of liposoluble vitamins in cooked meals was established. Saponification was performed with 50% (w/v) KOH at 80 degrees C, and ascorbic acid was added as antioxidant. The subsequent extraction was carried out with diethyl ether. This was followed by a liquid chromatographic separation on a reversed-phase C18 column with methanol-water (94:6, v/v as the mobile phase. Retinyl acetate was used as the internal standard. The analytical parameters linearity, detection limit (0.19 and 8.33 microg/100 g for retinol and alpha-tocopherol, respectively), precision of the method (RSD=5.24 and 6.99% for retinol and alpha-tocopherol, respectively) and recovery assays (95.6 and 96.5% for retinol and alpha-tocopherol, respectively) show that the method studied is useful for measuring these compounds in foods and cooked meals.     

Peptoids as source of compounds eliciting antibacterial activity

N-Alkylglycine oligomers (peptoids) constitute a family of non-natural peptidomimetics attractive for the early drug discovery process because of their physicochemical features, easy of adaptation to combinatorial chemistry approaches and their proteolytic stability. Consequently, peptoid libraries have found application for discovering hits against a wide diversity of pharmaceutical targets, among which different examples of antibacterials are found. In the present work, research efforts addressed towards the identification of peptoids as antibacterial agents are discussed.     

Indene and pseudoazulene discotic liquid crystals: a synthetic and structural study

Several new liquid-crystalline indene and pseudoazulene systems are reported. These molecules give rise to either columnar hexagonal mesophases and/or columnar plastic phases. The unique nature of these compounds stems from their non-classical discotic structure. Although the molecules have rigid aromatic cores, they lack terminal tails and instead the polarizable atoms (S, halogens) or polar groups (CN, CO) act as unusual soft parts. On the basis of many structurally related materials, we conclude that for this type of compound molecular stacking in the solid state is a prerequisite for the appearance of a columnar mesophase, although other intermolecular interactions within the layers are also important in establishing liquid-crystalline order. The behavior reported for these mesomorphic molecules opens up new possibilities in the search for related molecular interactions that might be useful for the construction of supramolecular architectures with particular properties.     

Efficiency of decomposition procedures for the determination of some elements in soils by atomic spectroscopic methods

Nine decomposition procedures for soil samples, such as via acid mixtures and fusion in open systems and microwave and autoclave dissolution (in closed systems under elevated temperature and pressure) were assessed using certified soil reference materials. The determination of various elements in solutions was performed by FAAS and ICP-OES and the results were compared with certified values and with direct current arc OES analysis. Received: 3 March 1997 / Revised: 30 May 1997 / Accepted: 3 June 1997     

Differential pulse adsorptive stripping voltammetry of osmium-modified peptides

Complexes of osmium tetroxide with nitrogen ligands were developed and used in our laboratory as probes of the DNA structure. Here, we show that the complex of osmium tetroxide with 2,2'-bipyridine (Os,bipy) can be used for modification and electrochemical detection of proteins at neutral pH. Salmon luteinizing hormone (SLH) containing two tryptophan (Trp) residues and human luteinizing hormone (HLH) containing one Trp were modified by Os,bipy and measured by differential pulse adsorptive stripping voltammetry (DPAdSV) at a hanging mercury drop electrode (HMDE). The intensity of the DPAdSV catalytic signals corresponded to the number of Trp residues in the peptide molecule. Decreasing pH of the background electrolyte from 6.6 to 3.8 led to the increase of DPAdSV signals, suggesting that at pH 3.8, the DPAdSV detection limit might be well below 1 ng/ml. Our results suggest that Os,bipy is potentially useful for chemical modification of proteins.     

Development of piezoelectric immunosensors for measurement of albuminuria

The development of piezoelectric immunosensors for human serum albumin (HSA) is reported. The piezoelectric crystals were modified either with monoclonal antibody AL-01 (direct assay) or with HSA (competitive assay). Measurements were carried out in the flow-through mode. Affinity interaction between albumin and the antibody was characterised. With immobilised antibody and HSA in solution, the kinetic association rate constant k(a) was 18 100 l mol(-1) s(-1) and the dissociation constant k(d) was 0.00369 s(-1). For the opposite arrangement (immobilised HSA), a slower dissociation was observed, k(d) was 0.00085 s(-1). A competitive assay for HSA was developed with working range of 1-5 mug ml(-1) and a total time for one analysis equal to 17 min. Samples of urine were analysed after tenfold dilution. The developed system was successfully evaluated on real samples from diabetic patients and the obtained results correlated well with the standard reflectometric assay of proteins in urine.     

Atmospheric pressure electrospray ionization mass spectra of glucose and 2-fluorodeoxyglucose for quantitative analysis of 2-fluorodeoxyglucose by high-performance liquid chromatography

2-Fluoro-2-deoxy-D-glucose (FDG) labeled by fluorine-18 is the most widely used radiopharmaceutical for positron emission tomography (PET). For high-performance liquid chromatography (HPLC)/MS assay and quality control, the mass spectra of FDG and glucose (Glc) in organic + water solutions were studied by flow injection analysis (FIA) and in a chromatographic eluate. In acetonitrile (MeCN) + 0.025% ammonium formate (NH(4)HCO(2)) solvent (80 : 20), electrospray ionisation (ESI) of glucose-FDG provides M.NH(4)(+) and 2M.Na(+) (M = Glc or FDG) as the most intense positive ions. Formation of the latter ions and also of M.MeCN.Na(+) and 2MeCN. Na(+) is typical of the presence of NaCl in the ESI inlet. The positive ions include heavier ions corresponding to the impurities separated by HPLC and also to the cross-ring fragmentation of complexes (2FDG. aMeCNX)L, where a = 0 or 1, L is either Na(+) or NH(4)(+) and X is a fragmented pyranose or anhydropyranose residue. The second most abundant Glc negative ion is m/z = 359 which was interpreted as (2GlcH(+))(). The negative-ion spectrum of FDG has dominating lines due to FDG.HCO(2)() ions at m/z 227 and also (2FDGH(+))() at m/z 363. The m/z 363 signal is suppressed in the presence of NaCl at a molar ratio of 4 : 1 to NH(4)HCO(2), while the ions at m/z 217 and 219, i.e. FDG.Cl(), become three times more intense than FDG.HCO(2)(). The latter ion appears to be most suitable as an analytical signal for chemical analysis of FDG at m/z 226 and 227. Limits of FDG quantitation (LOQ) of 19 ng and 21 ng were found for the 200(+) and 227() ion signals, respectively, and are wholly adequate for verification of total FDG content in radiopharmaceuticals.     

Incorporation of stable organic radicals into cyclotriphosphazene: preparation and characterization of mono- and diradical adducts

Stable cyclotriphosphazenes 4 and 5, incorporating one and two carbon radical centers, respectively, have been easily prepared and characterized. EPR spectroscopic studies in fluid solution at room temperature were carried out for both compounds and also for diradical 5 in frozen solvent matrixes. Spectral results are consistent with a triplet or degenerate singlet triplet ground state for 5. Reductive cyclic voltammetry shows a redox couple, being monoelectronic for 4 and bielectronic for 5.