Non-targeted analysis and toxicity prediction for evaluation of photocatalytic membrane distillation removing organic contaminants from hypersaline oil and gas field-produced water.

Membrane distillation (MD) has received ample recognition for treating complex wastewater, including hypersaline oil and gas (O&G) produced water (PW). Rigorous water quality assessment is critical in evaluating PW treatment because PW consists of numerous contaminants beyond the targets listed in general discharge and reuse standards. This study evaluated a novel photocatalytic membrane distillation (PMD) process, with and without a UV light source, against a standard vacuum membrane distillation (VMD) process for treating PW, utilizing targeted analyses and a non-targeted chemical identification workflow coupled with toxicity predictions. PMD with UV light resulted in better removals of dissolved organic carbon, ammoniacal nitrogen, and conductivity. Targeted organic analyses identified only trace amounts of acetone and 2-butanone in distillates. According to non-targeted analysis, the number of suspects reduced from 65 in feed to 25-30 across all distillate samples. Certain physicochemical properties of compounds influenced contaminant rejection in different MD configurations. According to preliminary toxicity predictions, VMD, PMD with and without UV distillate samples, respectively contained 21, 22, and 23 suspects associated with critical toxicity concerns. Overall, non-targeted analysis together with toxicity prediction provides a competent supportive tool to assess treatment efficiency and potential impacts on public health and the environment during PW reuse.

Protonated α-N-Acetyl Galactose Glycopeptide Dissociation Chemistry.

We recently provided mass spectrometric, H/D labeling, and computational evidence of pyranose to furanose N-acetylated ion isomerization reactions that occurred prior to glycosidic bond cleavage in both O- and N-linked glycosylated amino acid model systems (Guan et al. Phys. Chem. Chem. Phys., 2021, 23, 23256-23266). These reactions occurred irrespective of the glycosidic linkage stereochemistry (α or ß) and the N-acetylated hexose structure (GlcNAc or GalNAc). In the present article, we test the generality of the preceding findings by examining threonyl α-GalNAc-glycosylated peptides. We utilize computational chemistry to compare the various dissociation and isomerization pathways accessible with collisional activation. We then interrogate the structure(s) of the resulting charged glycan and peptide fragments with infrared "action" spectroscopy. Isomerization of the original pyranose, the protonated glycopeptide [AT(GalNAc)A+H]+, is predicted to be facile compared to direct dissociation, as is the glycosidic bond cleavage of the newly formed furanose form, i.e., furanose oxazolinium ion structures are predicted to predominate. IR action spectra for the m/z 204, C8H14N1O5+, glycan fragment population support this prediction. The IR action spectra of the complementary m/z 262 peptide fragment were assigned as a mixture of the lowest-energy structures of [ATA+H]+ consistent with the literature. If general, the change to a furanose m/z 204 product ion structure fundamentally alters the ion population available for MS3 dissociation and glycopeptide sequence identification.

Sodium-cationized carbohydrate gas-phase fragmentation chemistry: influence of glycosidic linkage position.

We investigate the gas-phase structures and fragmentation chemistry of two isomeric sodium-cationized carbohydrates using combined tandem mass spectrometry, hydrogen/deuterium exchange experiments, and computational methods. Our model systems are the glucose-based disaccharide analytes cellobiose (ß-d-glucopyranosyl-(1 → 4)-d-glucose) and gentiobiose (ß-d-glucopyranosyl-(1 → 6)-d-glucose). These analytes show substantially different tandem mass spectra. We characterize the rate-determining barriers to both the glycosidic and structurally-informative cross-ring bond cleavages. Sodiated cellobiose produces abundant Y1 and B1 peaks. Our deuterium labelling and computational chemistry approach provides evidence for 1,6-anhydroglucose B1 ion structures rather than the 1,2-anhydroglucose and oxacarbenium ion structures proposed elsewhere. Unlike those earlier proposals, this finding is consistent with the experimentally observed Bn/Ym branching ratios. In contrast to cellobiose, sodiated gentiobiose primarily fragments by cross-ring cleavage to form various A2 ion types. Fragmentation is facilitated by ring-opening at the reducing end which enables losses of CnH2nOn oligomers. Deuterium labelling and theory enables rationalization of these processes. Theory and experiment also support the importance of consecutive fragmentation processes at higher collision energies.

Stereochemical Sequence Ion Selectivity: Proline versus Pipecolic-acid-containing Protonated Peptides.

Substitution of proline by pipecolic acid, the six-membered ring congener of proline, results in vastly different tandem mass spectra. The well-known proline effect is eliminated and amide bond cleavage C-terminal to pipecolic acid dominates instead. Why do these two ostensibly similar residues produce dramatically differing spectra? Recent evidence indicates that the proton affinities of these residues are similar, so are unlikely to explain the result [Raulfs et al., J. Am. Soc. Mass Spectrom. 25, 1705-1715 (2014)]. An additional hypothesis based on increased flexibility was also advocated. Here, we provide a computational investigation of the "pipecolic acid effect," to test this and other hypotheses to determine if theory can shed additional light on this fascinating result. Our calculations provide evidence for both the increased flexibility of pipecolic-acid-containing peptides, and structural changes in the transition structures necessary to produce the sequence ions. The most striking computational finding is inversion of the stereochemistry of the transition structures leading to "proline effect"-type amide bond fragmentation between the proline/pipecolic acid-congeners: R (proline) to S (pipecolic acid). Additionally, our calculations predict substantial stabilization of the amide bond cleavage barriers for the pipecolic acid congeners by reduction in deleterious steric interactions and provide evidence for the importance of experimental energy regime in rationalizing the spectra. Graphical Abstract ᅟ.

Cationized Carbohydrate Gas-Phase Fragmentation Chemistry.

We investigate the fragmentation chemistry of cationized carbohydrates using a combination of tandem mass spectrometry, regioselective labeling, and computational methods. Our model system is D-lactose. Barriers to the fundamental glyosidic bond cleavage reactions, neutral loss pathways, and structurally informative cross-ring cleavages are investigated. The most energetically favorable conformations of cationized D-lactose were found to be similar. In agreement with the literature, larger group I cations result in structures with increased cation coordination number which require greater collision energy to dissociate. In contrast with earlier proposals, the B n -Y m fragmentation pathways of both protonated and sodium-cationized analytes proceed via protonation of the glycosidic oxygen with concerted glycosidic bond cleavage. Additionally, for the sodiated congeners our calculations support sodiated 1,6-anhydrogalactose B n ion structures, unlike the preceding literature. This affects the subsequent propensity of formation and prediction of B n /Y m branching ratio. The nature of the anomeric center (α/ß) affects the relative energies of these processes, but not the overall ranking. Low-energy cross-ring cleavages are observed for the metal-cationized analytes with a retro-aldol mechanism producing the 0,2 A 2 ion from the sodiated forms. Theory and experiment support the importance of consecutive fragmentation processes, particularly for the protonated congeners at higher collision energies. Graphical Abstract ᅟ.

Proton Mobility in b2 Ion Formation and Fragmentation Reactions of Histidine-Containing Peptides.

A detailed energy-resolved study of the fragmentation reactions of protonated histidine-containing peptides and their b2 ions has been undertaken. Density functional theory calculations were utilized to predict how the fragmentation reactions occur so that we might discern why the mass spectra demonstrated particular energy dependencies. We compare our results to the current literature and to synthetic b2 ion standards. We show that the position of the His residue does affect the identity of the subsequent b2 ion (diketopiperazine versus oxazolone versus lactam) and that energy-resolved CID can distinguish these isomeric products based on their fragmentation energetics. The histidine side chain facilitates every major transformation except trans-cis isomerization of the first amide bond, a necessary prerequisite to diketopiperazine b2 ion formation. Despite this lack of catalyzation, trans-cis isomerization is predicted to be facile. Concomitantly, the subsequent amide bond cleavage reaction is rate-limiting.