A Facile Route to Flavone-3-Carboxamides and Flavone-3-Carboxylates via Palladium-Catalyzed Amino- and Aryloxy-Carbonylation Reactions.

A library of C-3 functionalized flavones was successfully provided via palladium-catalyzed amino- and aryloxycarbonylation reactions of 3-iodoflavone (), under mild conditions. This methodology showed good functional group tolerance using a variety of amines and phenols, under an atmospheric pressure of carbon monoxide as a carbonyl source. While the flavone-3-carboxamides () were produced in 22-79%, the flavone-3-carboxylates () were obtained in excellent yields (up to 88%), under identical reaction conditions, just by switching -nucleophiles to -nucleophiles.

Identification of a Chimera Mass Spectrum of Isomeric Lipid A Species Using Negative Ion Tandem Mass Spectrometry.

The toxic nature of bacterial endotoxins is affected by the structural details of lipid A, including the variety and position of acyl chains and phosphate group(s) on its diglucosamine backbone. Negative-ion mode tandem mass spectrometry is a primary method for the structure elucidation of lipid A, used independently or in combination with separation techniques. However, it is challenging to accurately characterize constitutional isomers of lipid A extracts by direct mass spectrometry, as the elemental composition and molecular mass of these molecules are identical.

Synthesis of Chroman-2,4-diones via Ring-Opening/Ring-Closing Reaction Involving Palladium-Catalyzed Intramolecular Aryloxycarbonylation.

Palladium-catalyzed aminocarbonylation of 3-iodochromone was studied in the presence of primary and secondary amines using atmospheric pressure of carbon monoxide as a carbonyl source. This procedure successfully provided a library of chromone-3-carboxamides and 3-substituted chroman-2,4-diones in 40 to 92% isolated yields. The reaction proceeded via highly chemoselective aminocarbonylation (up to 100%) in the presence of secondary amines by using monodentate or bidentate phosphine ligands.

Complete Structural Elucidation of Monophosphorylated Lipid A by CID Fragmentation of Protonated Molecule and Singly Charged Sodiated Adducts.

Lipid A, the inflammatory portion of lipopolysaccharides (LPS, endotoxins), is the main component of the outer membrane of Gram-negative bacteria. Its bioactivity in humans and animals is strictly related to its chemical structure. In the present work, the fragmentation patterns of the singly charged monosodium [M + Na] and disodium [M - H + 2Na] adducts, as well as the protonated form of monophosphorylated lipid A species were investigated in detail using positive-ion electrospray ionization-based tandem (MS/MS) and multistage mass spectrometry (MS) with low-energy collision-induced dissociation (CID).

Comparative Study on Grape Berry Anthocyanins of Various Teinturier Varieties.

The red-fleshed grape cultivars, called teinturier or dyer grapes, contain anthocyanins in both the skin and flesh. These phenolic compounds exhibit excellent coloring ability, and as antioxidants, they are important bioactive compounds in food crops. In this work, anthocyanin patterns of grape berries of fifteen teinturier varieties collected from the gene bank located at Pécs in the southwest of Hungary were compared.

Study on the CID Fragmentation Pathways of Deprotonated 4'-Monophosphoryl Lipid A.

Lipid A, the membrane-bound phosphoglycolipid component of bacteria, is held responsible for the clinical syndrome of gram-negative sepsis. In this study, the fragmentation behavior of a set of synthetic lipid A derivatives was studied by electrospray ionization multistage mass spectrometry (ESI-MS), in conjunction with tandem mass spectrometry (MS/MS), using low-energy collision-induced dissociation (CID). Genealogical insight about the fragmentation pathways of the deprotonated 4'-monophosphoryl lipid A structural analogs led to proposals of a number of alternative dissociation routes that have not been reported previously.

NACE-ESI-MS/MS method for separation and characterization of phosphorylation and acylation isomers of lipid A.

Lipid A represents a heterogeneous group of bacterial outer membrane phosphoglycolipids, which play a major role in the pathogenesis of Gram-negative sepsis. The number and position of phosphoryl and acyl groups in lipid A molecules are key structural determinants in their bioactivities. In this study, a NACE-ESI-MS/MS method was developed for the simultaneous analysis of lipid A isomers possessing a different degree of phosphorylation and acylation.

Characterization of complex, heterogeneous lipid A samples using HPLC-MS/MS technique III. Positive-ion mode tandem mass spectrometry to reveal phosphorylation and acylation patterns of lipid A.

In this study, we report the detailed analysis of the fragmentation patterns of positively charged lipid A species based on their tandem mass spectra obtained under low-energy collision-induced dissociation conditions of an electrospray quadrupole time-of-flight mass spectrometer. The tandem mass spectrometry experiments were performed after the separation of the compounds with a reversed-phase high performance liquid chromatography method. We found that both, phosphorylated and nonphosphorylated lipid A molecules can be readily ionized in the positive-ion mode by adduct formation with triethylamine added to the eluent.

Mass Spectrometry for Profiling LOS and Lipid A Structures from Whole-Cell Lysates: Directly from a Few Bacterial Colonies or from Liquid Broth Cultures.

Lipopolysaccharides (LPSs, endotoxins) are components of the outer cell membrane of most Gram-negative bacteria and can play an important role in a number of diseases of bacteria, including Gram-negative sepsis. The hydrophilic carbohydrate part of LPSs consists of a core oligosaccharide (in the case of an R-type LPS or lipooligosaccharide, LOS) linked to an O-polysaccharide chain (in the case of an S-type LPS), which is responsible for O-specific immunogenicity. The hydrophobic lipid A anchor is composed of a phosphorylated diglucosamine backbone to which varying numbers of ester- and amide-linked fatty acids are attached and this part of the LPSs is associated with endotoxicity.

Characterization of complex, heterogeneous lipid A samples using HPLC-MS/MS technique II. Structural elucidation of non-phosphorylated lipid A by negative-ion mode tandem mass spectrometry.

Non-phosphorylated lipid A species confer reduced inflammatory potential for the bacteria. Knowledge on their chemical structure and presence in bacterial pathogens may contribute to the understanding of bacterial resistance and activation of the host innate immune system. In this study, we report the fragmentation pathways of negatively charged, non-phosphorylated lipid A species under low-energy collision-induced dissociation conditions of an electrospray ionization quadrupole time-of-flight instrument.

Characterization of complex, heterogeneous lipid A samples using HPLC-MS/MS technique I. Overall analysis with respect to acylation, phosphorylation and isobaric distribution.

We established a new reversed phase-high performance liquid chromatography method combined with electrospray ionization quadrupole time-of-flight tandem mass spectrometry for the simultaneous determination and structural characterization of different lipid A types in bacteria (Escherichia coli O111, Salmonella adelaide O35 and Proteus morganii O34) showing serological cross-reactivity. The complex lipid A mixtures (obtained by simple extraction and acid hydrolysis of the outer membrane lipopolysaccharides) were separated and detected without phosphate derivatization. Several previously unidentified ions were detected, which differed in the number and type of acyl chains and number of phosphate groups.

Structural background for serological cross-reactivity between bacteria of different enterobacterial serotypes.

The structure of the oligosaccharide repeating units of endotoxins from Gram-negative bacteria is characteristic for the different serogroups and serotypes of bacteria. Detailed examination of the cross-reactions of three enterobacterial serotypes, Proteus morganii O34, Escherichia coli O111, and Salmonella enterica sv. Adelaide O35, was performed using sensitive tests (ELISA, immunoblotting).

Structural characterization of bacterial lipopolysaccharides with mass spectrometry and on- and off-line separation techniques.

The focus of this review is the application of mass spectrometry to the structural characterization of bacterial lipopolysaccharides (LPSs), also referred to as "endotoxins," because they elicit the strong immune response in infected organisms. Recently, a wide variety of MS-based applications have been implemented to the structure elucidation of LPS. Methodological improvements, as well as on- and off-line separation procedures, proved the versatility of mass spectrometry to study complex LPS mixtures.

Effect of electrolyte pH on CIEF with narrow pH range ampholytes.

CIEF of components following sequential injection of ampholytes and the sample zone offers unique advantages for analysis. The most important one of these is the efficient separation of amphoteric compounds having pIs outside the pH range of the ampholytes applied, but the resolution of the components can be increased by an adequate setup in the injection protocol. In this study, the effect of the pH of the anolyte and catholyte on the selectivity and speed of the isoelectric focusing was investigated.

Sequential injection setup for capillary isoelectric focusing combined with MS detection.

Capillary isoelectric focusing in the presence of electroosmosis with sequential injection of carrier ampholytes and sample was found to be suitable for MS detection. The separate injection of the sample and the ampholytes provides good condition to suppress and overcome the undesirable effect of the presence of ampholytes in MS. By the appropriate selection of ampholyte solutions, whose pH range not necessarily covers the pI values of the analytes, the migration of the components can be controlled, and the impact of the ampholytes on MS detection is decreased.

Structural variability of endotoxins from R-type isogenic mutants of Shigella sonnei.

The structural variations in the rough-type endotoxins [lipopolysaccharides (LPSs)] of Shigella sonnei mutant strains (S. sonnei phase II-4303, R41, 562H and 4350) were investigated by Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and tandem MS. A series of S.

Determination of polyphenolic compounds by liquid chromatography-mass spectrometry in Thymus species.

Polyphenolic compounds represent a wide group of phytochemicals, including well-known subgroups of phenolic acids, flavonoids, natural dyes, lignans etc., which are produced by plants. These natural bioactive compounds possess a variety of beneficial effects including antioxidant and anticarcinogenic activities, protection against coronary diseases as well as antimicrobial properties.

Vanadium(IV,V) complexes of D-saccharic and mucic acids in aqueous solution.

The vanadium(IV,V) complexes formed with two aldaric acids (D-saccharic or D-glucaric acid, and mucic or galactaric acid) in aqueous solution were characterised by employing pH-potentiometry, EPR, multinuclear NMR and UV-VIS spectroscopy. The stoichiometry and stability constants of the complexes formed were determined at 25 degrees C and ionic strength I= 0.2 mol dm(-3)(KCl).

N,N'-ethylenebis(pyridoxylideneiminato) and N,N'-ethylenebis(pyridoxylaminato): synthesis, characterization, potentiometric, spectroscopic, and DFT studies of their vanadium(IV) and vanadium(V) complexes.

The Schiff base N,N'-ethylenebis(pyridoxylideneiminato) (H(2)pyr(2)en, 1) was synthesized by reaction of pyridoxal with ethylenediamine; reduction of H(2)pyr(2)en with NaBH(4) yielded the reduced Schiff base N,N'-ethylenebis(pyridoxylaminato) (H(2)Rpyr(2)en, 2); their crystal structures were determined by X-ray diffraction. The totally protonated forms of 1 and 2 correspond to H(6)L(4+), and all protonation constants were determined by pH-potentiometric and (1)H NMR titrations. Several vanadium(IV) and vanadium(V) complexes of these and other related ligands were prepared and characterized in solution and in the solid state.

The effects of Al(III) speciation on the activity of trypsin.

The effects of the different forms of Al(III) on the catalytic activity of the serine protease trypsin were studied. Enzyme activity was measured by BAEE assay in the presence of AlCl(3), Al(III):lactic acid 1:3, Al(III):maltol 1:3 or Al(III):nitrilotriacetic acid (NTA) 1:1 at a nominal Al(III) concentration of 0.01 M, and the ligand alone at pH 7.