Hydrogen bond networks in gas-phase complex anions.

Hydrogen bond networks (HBNs) have piqued the interest of the scientific community due to their crucial roles in nature. However, HBNs that are isolated from complicated backgrounds for unraveling their characteristics are still scarce. Herein, we propose that HBNs exist in complex anions formed between α-cyclodextrin (α-CD) and four benzoic acids (RBAs) in the gas phase. The complex anions are facilely extracted from solutions via the electrospray ionization technique, and subsequently activated through collision for the investigation of their transition dynamics. It is revealed that the generation of deprotonated α-CD and neutral RBAs is the unexpected dominant dissociation pathway for all the four complex anions, and the complex anions formed from more acidic RBAs exhibit higher stabilities. These dissociation results are successfully explained by the cooperative stretching dynamics of the proposed HBNs that are formed involving the intramolecular HBN of α-CD and the intermolecular hydrogen bonds (HBs) between α-CD and RBAs. Furthermore, the rarely observed low barrier HBs (LBHBs) are suggested to be present in the HBNs. It is believed that the present complex anions can serve as a facilely accessible and informative model for studying HBNs in the future.

Identifying a selective oligopeptide clamp in the gas phase.

Oligopeptide foldamers are promising as minimalist functional analogues to proteins. Herein, we report a versatile and cost-effective experimental scheme in the gas phase that can facilely identify selective oligopeptides and unambiguously resolve the corresponding folding conformations. Based on this methodology, a stereoselective oligopeptide clamp targeting ß2-blockers is successfully identified.

Noncovalently Tagged Gas Phase Complex Ions for Screening Unknown Contaminant Metabolites in Plants.

Screening the metabolites of emerging organic contaminants (EOCs) from complicated biological matrices is an important but challenging task. Although stable isotope labeling (SIL) is frequently used to facilitate the identification of contaminant metabolites from redundant interfering components, the isotopically labeled reagents are expensive and difficult to synthesize, which greatly constrains the application of the SIL method. Herein, a new online noncovalent tagging method was developed for screening the metabolites of 1H-benzotriazol (BT) based on the characteristic structural moieties reserved in the metabolites. By selecting ß-cyclodextrin (ß-CD) as a macrocyclic tagging reagent, metabolites with the reserved moiety were expected to exhibit a characteristic shift of the mass-to-charge ratio (Δm/z = 1134.3698) after being noncovalently tagged by ß-CD. Based on the characteristic mass shift, the suspected features were reduced by 1 order of magnitude, as numerous interfering species that could not be effectively tagged by ß-CD were excluded. From these suspected features, two metabolites of BT that have not been reported before were successfully screened out. The significant characteristic mass shift caused by the noncovalent tagging method is easier to identify with more confidence than the previously reported SIL method. Besides, noncovalent tagging reagents can be much more accessible and less expensive than isotopically labeled reagents. Hence, this online noncovalent tagging method can be an intriguing alternative to the conventional SIL method.

Valence-dependent catalytic activities of iron terpyridine complexes for pollutant degradation.

Herein, iron-terpyridine complexes with the iron centers at different initial valence states were utilized as homogeneous catalysts for the degradation of phenol in water. The iron(iii)-terpyridine complex induced the formation of more high-valent iron-oxo centers and hydroxyl radicals than the iron(ii)-terpyridine complex, leading to a higher catalytic activity.