Revisiting Disinfection Byproducts with Supercritical Fluid Chromatography-High Resolution-Mass Spectrometry: Identification of Novel Halogenated Sulfonic Acids in Disinfected Drinking Water.

High resolution mass spectrometry (HRMS) coupled to either gas chromatography or reversed-phase liquid chromatography is the generic method to identify unknown disinfection byproducts (DBPs) but can easily overlook their highly polar fractions. In this study, we applied an alternative chromatographic separation method, supercritical fluid chromatography-HRMS, to characterize DBPs in disinfected water. In total, 15 DBPs were tentatively identified for the first time as haloacetonitrilesulfonic acids, haloacetamidesulfonic acids, and haloacetaldehydesulfonic acids. Cysteine, glutathione, and p-phenolsulfonic acid were found as precursors during lab-scale chlorination, with cysteine providing the highest yield. A mixture of the labeled analogues of these DBPs was prepared by chlorination of 13C3-15N-cysteine and analyzed using nuclear magnetic resonance spectroscopy for structural confirmation and quantification. A total of 6 drinking water treatment plants utilizing various source waters and treatment trains produced sulfonated DBPs upon disinfection. Those were widespread in the tap water of 8 cities across Europe, with estimated concentrations up to 50 and 800 ng/L for total haloacetonitrilesulfonic acids and haloacetaldehydesulfonic acids, respectively. Up to 850 ng/L haloacetonitrilesulfonic acids were found in 3 public swimming pools. Considering the stronger toxicity of haloacetonitriles, haloacetamides, and haloacetaldehydes than the regulated DBPs, these newly found sulfonic acid derivatives may also pose a health risk.

Chemical Synthesis with Gaseous Molecular Ions: Harvesting [B12 Br11 N2 ]- from a Mass Spectrometer.

Mass spectrometry frequently reveals the existence of transient gas phase ions that have not been synthesized in solution or in bulk. These elusive ions are, therefore, often considered to be primarily of analytical value in fundamental gas phase studies. Here, we provide proof-of-concept that the products of ion-molecule reactions in mass spectrometers may be collected on surfaces to generate condensed matter and thus serve as building blocks to synthesize new compounds. The highly reactive fragment anion [B12 Br11 ]- was generated in a mass spectrometer and converted to [B12 Br11 N2 ]- in the presence of molecular nitrogen followed by its mass-selection and soft-landing on surfaces. The molecular structure of [B12 Br11 N2 ]- , which has not been synthetically obtained before, was confirmed by conventional methods of molecular analysis, including nuclear magnetic resonance and infrared spectroscopy. The [B12 Br11 N2 ]- ion is stable on surfaces and in solution at room temperature, but thermal annealing induces elimination of N2 and provides access to the highly reactive intermediate [B12 Br11 ]- in the condensed phase, which can be further used as a reagent, for example, for electrophilic aromatic substitutions. Thus, isolation of [B12 Br11 N2 ]- expands the repertoire of the available diazo ions that can be employed as versatile intermediates in various chemical transformations.

Probing a Hydrogen-π Interaction Involving a Trapped Water Molecule in the Solid State.

The detection and characterization of trapped water molecules in chemical entities and biomacromolecules remains a challenging task for solid materials. We herein present proton-detected solid-state Nuclear Magnetic Resonance (NMR) experiments at 100 kHz magic-angle spinning and at high static magnetic-field strengths (28.2 T) enabling the detection of a single water molecule fixed in the calix[4]arene cavity of a lanthanide complex by a combination of three types of non-covalent interactions. The water proton resonances are detected at a chemical-shift value close to zero ppm, which we further confirm by quantum-chemical calculations. Density Functional Theory calculations pinpoint to the sensitivity of the proton chemical-shift value for hydrogen-π interactions. Our study highlights how proton-detected solid-state NMR is turning into the method-of-choice in probing weak non-covalent interactions driving a whole branch of molecular-recognition events in chemistry and biology.

Experimental boundaries of the quantum rotor induced polarization (QRIP) in liquid state NMR.

The Haupt-effect is a rather seldom used hyperpolarization method. It is based on the interdependence between nuclear spin states and rotational states of nearly free rotating methyl groups having C3 symmetry. A sudden change in temperature from 4.2 K to room temperature by fast dissolution yields considerably enhanced (13)C and (1)H resonance signals. This phenomenon is now termed quantum rotor induced polarization. More than 40 substances have been studied by this approach in order to identify them as polarizable by the 'Haupt-effect in the liquid state'. Influencing factors have been analyzed systematically. It could be concluded that substances having a high tunneling frequency, which is due to a small and narrow potential barrier, are most likely to feature quantum rotor induced polarization-enhanced signals.

Hybrid Peptides Based on α-Aminoxy Acids as Antimicrobial and Anticancer Foldamers.

α-Aminoxy peptides represent an interesting group of peptidomimetics with high proteolytic stability and the ability to fold into specific, predictable secondary structures. Here, we present a series of hybrid peptides consisting of α-aminoxy acids and α-amino acids with cationic and aromatic, hydrophobic side chains in an alternating manner synthesized using an efficient protocol that combines solution- and solid-phase synthesis. 2D ROESY experiments with a representative hexamer suggested the presence of a 7/8 helical conformation in solution. Biological evaluation revealed a significant impact of the peptide chain length and the N-terminal cap on the antimicrobial and anticancer properties of this series of hybrid peptides. The Fmoc-capped peptide 6e displayed the most potent antimicrobial activity against a panel of Gram-negative and Gram-positive bacterial strains (e. g. against E. Coli: MIC=8 mg/L; S. aureus: MIC=4 mg/L).

Unexpected multiplet patterns induced by the Haupt-effect.

An NMR polarization up to a factor of 100 compared to the room temperature signal of a fully equilibrated sample and up/down multiplets are observed when 4-methyl-pyridine or toluene are taken rapidly from liquid helium temperatures to room temperature by dissolving in acetone-d6. These findings result from the inherent coupling between rotational and nuclear spin states in methyl groups which can act as quantum rotors. The temperature jump causes changes in rotational and spin energy level population due to symmetry rules that is known as the Haupt-effect.

Transfer of the Haupt-hyperpolarization to neighbor spins.

The NMR hyperpolarization observed for freely rotating methyl groups by exerting a temperature jump from 4.2 K to 298 K can be transferred to spins which have a spin, spin coupling with the carbon of the methyl group. First, a spin echo sequence readjusts the primary up/down signals to an in-phase multiplet. This in-phase magnetization is then decoupled and transferred by a simple COSY step using one scan. The polarization factors at the neighbor spins are about 50 by comparing their signal-to-noise ratio with the signal strength after full relaxation.