Tamm-Horsfall protein in humane urine: sex-dependent differences in the excretion and N-glycosylation pattern.

Tamm-Horsfall protein (THP) is a highly N-glycosylated protein from epithelial cells of the ascending limb of Henle loop. It is secreted into the urine as part of the innate immune response against uropathogenic pathogens. As women are more likely to suffer from urinary tract infections, biomedical studies were conducted to investigate sex-differences in THP excretion, as well as differences in the THP N-glycosylation pattern.

Unprotected Galactosamine as a Dynamic Key for a Cyclochiral Lock.

The discrimination of d-galactosamine (), representative of the amino-sugar class of compounds, has been probed through nano-ESI-FT-ICR mass spectrometry by isolating the relevant [·H·] proton-bound complexes with the enantiomers of the cyclochiral resorcin[4]arene and allowing them to react toward three primary amines ( = EtNH, PrNH, and ()- and ()-BuNH). The system under investigation presents several features that help to unveil the behavior of unprotected in such a supramolecular architecture: (i) the hydrophobic derivatization of the convex side forces the polar guest to be coordinated by the cyclochiral concave region; (ii) protonated d-galactosamine exists as an anomeric mixture, dynamically interconverting throughout the experimental time-window; and (iii) different basicities of allow the experiment to subtly tune the reactivity of the [·H·] complexes. Three [·H·] aggregate-types were found to exist, differing in both their origin and reactivity.

Reactions of an anionic chelate phosphane/borata-alkene ligand with [Rh(nbd)Cl], [Rh(CO)Cl] and [Ir(cod)Cl].

Borata-alkenes can serve as anionic olefin equivalent ligands in transition metal chemistry. A chelate ligand of this type is described and used for metal coordination. Deprotonation of the MesP(CH)B(CF) frustrated Lewis pair in the α-CH[B] position gave the methylene-bridged phosphane/borata-alkene anion.

What is the role of acid-acid interactions in asymmetric phosphoric acid organocatalysis? A detailed mechanistic study using interlocked and non-interlocked catalysts.

Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst-catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers.

Consecutive loss of two benzyl radicals from the [M + Na] adduct ions of pyrogallol tribenzyl ether and its derivatives.

The electrospray ionization-collision-induced dissociation mass spectra of nine pyrogallol tribenzyl ethers, 2-10, and a catechol dibenzyl ether, 11, that bear various functional groups or larger structural extensions have been studied with respect to the occurrence of a highly characteristic consecutive loss of two benzyl radicals from the sodiated molecular ions, [M + Na]. It is shown that this specific fragmentation reaction strongly dominates other fragmentation routes, such as loss of carbon monoxide, formaldehyde and water. In addition, elimination of benzaldehyde occurs as a minor fragmentation channel in most cases.

Chemical Modification and Detoxification of the Pseudomonas aeruginosa Toxin 2-Heptyl-4-hydroxyquinoline N-Oxide by Environmental and Pathogenic Bacteria.

2-Heptyl-4-hydroxyquinoline N-oxide (HQNO), a major secondary metabolite and virulence factor produced by the opportunistic pathogen Pseudomonas aeruginosa, acts as a potent inhibitor of respiratory electron transfer and thereby affects host cells as well as microorganisms. In this study, we demonstrate the previously unknown capability of environmental and pathogenic bacteria to transform and detoxify this compound. Strains of Arthrobacter and Rhodococcus spp.

Orthogonal Click Postfunctionalization of Alternating Copolymers Prepared by Nitroxide-Mediated Polymerization.

Nitroxide-mediated polymerization (NMP) was applied to prepare alternating copolymers using 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) 1 and ((6-trimethylsilyl)-hex-5-yn-1-yl)vinyl ether (THVE) 2 as monomers. The alternating sequence of the resulting poly(HFIPA-alt-THVE) 3 was proved by using tandem mass spectrometry (MS/MS) and further supported by H NMR spectroscopy. Alternating alkyne and activated ester moieties of copolymer 3 were further functionalized with organic azides and amines using sequential Cu-catalyzed azide-alkyne click (CuAAC) and amidation reactions, providing dually functionalized poly(acrylamide-alt-triazole) polymers 5.

Diastereoselective anodic hetero- and homo-coupling of menthol-, 8-methylmenthol- and 8-phenylmenthol-2-alkylmalonates.

Diastereoselective radical coupling was achieved with chiral auxiliaries. The radicals were generated by anodic decarboxylation of five malonic acid derivatives. These were prepared from benzyl malonates and four menthol auxiliaries.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry imaging of ochratoxin A and fumonisins in mold-infected food.

Rationale: Mycotoxins are toxic secondary metabolites produced by various fungi. Their distribution within contaminated material is of high interest to obtain insight into infection mechanisms and the possibility of reducing contamination during food processing.

Methods: Various vegetable foodstuffs were infected with fungi of the genera Fusarium and Aspergillus.

Glial Glycolysis Is Essential for Neuronal Survival in Drosophila.

Neuronal information processing requires a large amount of energy, indicating that sugars and other metabolites must be efficiently delivered. However, reliable neuronal function also depends on the maintenance of a constant microenvironment in the brain. Therefore, neurons are efficiently separated from circulation by the blood-brain barrier, and their long axons are insulated by glial processes.

Alternating copolymerization by nitroxide-mediated polymerization and subsequent orthogonal functionalization.

A novel method for the preparation of functionalized alternating copolymers is presented. Nitroxide-mediated polymerization of hexafluoroisopropyl acrylate with 7-octenyl vinyl ether provides the corresponding alternating polymer, which can be chemically modified using two orthogonal polymer-analogous reactions. A thiol-ene click reaction followed by amidation provides dual-functionalized alternating copolymers.

Analysis of free fatty acids by ultraviolet laser desorption ionization mass spectrometry using insect wings as hydrophobic sample substrates.

Physiologically relevant free fatty acids (FFAs) were analyzed by UV-laser desorption/ionization orthogonal extracting time-of-flight mass spectrometry (LDI-oTOF-MS). Dissected wings from Drosophila melanogaster fruit flies were used as the hydrophobic, laser energy strongly absorbing sample substrates. Using untreated substrates produces predominantly molecular [M + K](+) ions of the FFAs, whereas other alkali metal adducts can be generated by treating the wings with the corresponding alkali hydroxide before spotting of analyte.

Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation.

The unidirectional triple-hydrogen (3H) rearrangement of the radical cations of 3-aryl-1-propanols bearing an electron-rich substitutent in the para-position was investigated for the diastereomeric 2-(4-dimethylamino)benzylcyclohexanols and 2-(4-dimethylamino)-benzylcyclopentanols and confirmed to be a highly stereospecific feature. Whereas the standard electron ionization (EI) (70 eV) mass spectra of the trans-isomers exhibit very minor (approximately 2%-3%) albeit stereospecific peaks for the relevant C8H13N*+ ions (m/z 123), the metastable ion [mass-analyzed ion kinetic energy (MIKE)] spectra show these peaks with significant relative intensity (8%-17%). The respective cis-isomers do not undergo the 3H rearrangement, be it under standard or under metastable-ion conditions.

Enantioselective supramolecular devices in the gas phase. Resorcin[4]arene as a model system.

This review describes the state-of-art in the field of the gas-phase reactivity of diastereomeric complexes formed between a chiral artificial receptor and a biologically active molecule. The presented experimental approach is a ligand-displacement reaction carried out in a nano ESI-FT-ICR instrument, supported by a thermodynamic MS-study and molecular-mechanics and molecular-dynamics (MM/MD) computational techniques. The noncovalent ion-molecule complexes are ideal for the study of chiral recognition in the absence of complicating solvent and counterion effects.

Cyclochiral resorcin[4]arenes as effective enantioselectors in the gas phase.

The effect of cyclochirality of rccc-2,8,14,20-tetra-n-decyl-4,10,16,22-tetra-O-methylresorcin[4]arene (C) on the enantiodiscrimination of a number of chiral bidentate and tridentate aromatic and aliphatic biomolecules (G) has been investigated by nano-electrospray ionization (nano-ESI)-Fourier transform ion cyclotron resonance mass spectrometry. The experimental approach is based on the formation of diastereomeric proton-bound [C·H·G](+) complexes by nano-ESI of solutions containing an equimolar amount of quasi-enantiomers (C) together with the chiral guest (G) and the subsequent measurement of the rate of the G substitution by the attack of several achiral and chiral amines. In general, the heterochiral complexes react faster than the homochiral ones, except when G is an aminoalcoholic neurotransmitter whose complexes, beyond that, exhibit the highest enantioselectivity.

Unprecedented gas-phase chiroselective logic gates.

The gas-phase encounters between 2-aminobutane and proton-bound chiral resorcin[4]arene/nucleoside complexes behave in the gas phase as supramolecular "chiroselective logic gates" by releasing the nucleoside depending on the resorcin[4]arene and the 2-aminobutane configurations.

Interactions of vinca alkaloid subunits with chiral amido[4]resorcinarenes: a dynamic, kinetic, and spectroscopic study.

The stereoselectivity of the reaction between (R)-(-)-2-butylamine and the diastereomeric proton-bound complexes of (+)-catharanthine (C) or (-)-vindoline (V) with some chiral amido[4]resorcinarenes has been investigated in the gas phase by ESI-FT-ICR-MS. The reaction stereoselectivity (0.56 < k(homo)/k(hetero) < 16.

Gas-phase enantioselectivity of chiral N-linked peptidoresorc[4]arene isomers toward dipeptides.

The gas-phase enantioselectivity of cone N-linked peptidoresorc[4]arenes (generally symbolized as M) toward the homologue dipeptides (generally symbolized as A) has been evaluated by measuring the kinetics of the A release from the diastereomeric [M x H x A](+) complexes induced by (R)-(-)-2-butylamine (B). In most cases investigated, the heterochiral [M x H x A](+) complexes, namely those wherein the configuration of the A guest is opposite to that of the host M pendants, react faster (up to 5 times) than the homochiral analogues, wherein guest A guest has the same configuration of the host M pendants. The kinetic results, discussed in the light of previous MS and NMR evidence, indicate that both the efficiency and the enantioselectivity of the guest exchange reaction depend essentially on the structure and the relative stability of the diastereomeric [M x H x A](+) complexes.

Energetics and reaction mechanisms for the competitive losses of H2, CH4 and C2H4 from protonated methylbenzenes--implications to the methanol- to-hydrocarbons (MTH) process.

We report the unimolecular decomposition following collisional activation of protonated mono-, di- and trimethylbenzenes as a function of collision energy. The resulting energy-resolved mass spectra are then used for the quality control of high-level quantum chemical models of the respective potential energy surfaces. Distinction is made between direct dissociation products (CH(4) or H(2)) and indirect products (alkenes), since formation of the latter requires extensive rearrangement of the molecular skeleton.

SIRIUS: decomposing isotope patterns for metabolite identification.

Motivation: High-resolution mass spectrometry (MS) is among the most widely used technologies in metabolomics. Metabolites participate in almost all cellular processes, but most metabolites still remain uncharacterized. Determination of the sum formula is a crucial step in the identification of an unknown metabolite, as it reduces its possible structures to a hopefully manageable set.

A kinetic study of guest displacement reactions on a host-guest complex with a photoswitchable calixarene.

The displacement processes of several guests, incorporated in a calixarene host system, were investigated in the gas phase by electrospray ionization-Fourier transform-ion cyclotron resonance (ESI-FT-ICR) mass spectrometry. The complexes resulting from a resorcin[4]arene host with ammonia and sec-butylamine guests were isolated in an ICR-cell, separately using both states of the photoswitch as well as two reference systems for the open and closed forms of the photoswitchable host. The isolated complexes were forced to exchange the guest by using methylamine, ethylamine and sec-butylamine, resulting in different reaction rates for all the measured systems.

Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2*+ (E = N, P, As).

In context of an analysis of the effect of the central atom E of gaseous radical cations of phenyl pnictogens C(6)H(5)EH(2), E = N (1), P (2), and As (3), the mass spectrometric reactions of phenyl phosphane 2 have been re-investigated by D-labeling and by using methods of tandem mass spectrometry. The 70 eV mass spectrum of 2 shows the base peak for ion [M-2H](*+) and significant peaks for ions [M-H](+), [M-(2C,3H)](+), [M-PH] (*+), and [M-(C,P,2H)](+). Metastable 2(*+) fragments exclusively by loss of H(2), and the investigation of deuterated 2-d(2) shows that excessive H/D migrations occur before fragmentation.

Calixarenes as hosts for ammonium cations: a quantum chemical study and mass-spectrometric investigations.

Host-guest complexes of tetramethylcavitand with different ammonium cations were investigated by using a quantum chemical method at the density functional level (BP86, B3 LYP). The NH4+ cation is strongly bound to the host. Increasing methyl substitution at the cation decreases its inclination towards the complex formation.

Isomerization and fragmentation reactions of gaseous phenylarsane radical cations and phenylarsanyl cations. A study by tandem mass spectrometry and theoretical calculations.

The unimolecular reactions of radical cations and cations derived from phenylarsane, C6H5AsH2 (1) and dideutero phenylarsane, C6H5AsD2 (1-d2), were investigated by methods of tandem mass spectrometry and theoretical calculations. The mass spectrometric experiments reveal that the molecular ion of phenylarsane, 1*+, exhibits different reactivity at low and high internal excess energy. Only at low internal energy the observed fragmentations are as expected, that is the molecular ion 1*+ decomposes almost exclusively by loss of an H atom.