The synergetic effect of an aqua ligand and metal site on the performance of single-atom catalysts in H2O2 synthesis: a density functional theory study.

Studying the effect of the coordination field on the catalytic property is critical for the rational design of outstanding electrocatalysts for H2O2 synthesis. Herein, via density functional theory (DFT) calculations and ab initio molecular dynamic (AIMD) simulations, we built an effective computational framework to identify the synergetic effect of an aqua ligand and metal ion on the 2e- ORR catalytic performance under gas condition and aqua solvent. Specifically, the screening results of 29 single-atom catalysts (SACs), TM@C6N6 (TM = transition metal), indicated that Cu@C6N6 features excellent catalytic property with thermal stability, lowest 2e- ORR overpotential (0.02 V) and high selectivity of 99.99%. Once an aqua ligand binds with the Cu site, the activity is reduced to the overpotential of 0.42 V and the selectivity decreased slightly (99.98%) due to the reduction of the adsorption strength for the reaction intermediates. A combination of geometric structures and electronic properties revealed that such changes are correlated with the charge of the Cu site. Furthermore, based on molecular orbital theory, the essence of the high catalytic property deeply lies in the effect of the moderate electron back donation bond (dyz & dxz→) between Cu and O2. This work will provide a route to better design high-performance SACs for H2O2 synthesis effectively.

Characteristic fragmentation behavior of tobacco-specific N-nitrosamines using electrospray ionization multistage tandem mass spectrometry incorporating deuterium labeling.

RATIONALE: Tobacco-specific N-nitrosamines (TSNAs) mainly include 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), N-nitrosonornicotine (NNN), N-nitrosoanabasine (NAB) and N-nitrosoanatabine (NAT) that are formed from tobacco alkaloids during the curing process and contained in tobacco and tobacco smoke. They are linked with carcinogenesis. Analytical methods for quality control of products and determination of their metabolites are therefore of great importance. METHODS: The characteristic fragmentation behaviors of tobacco-specific TSNAs have been studied by electrospray ionization multistage tandem mass spectrometry. The deutero-labeled TSNA compounds have also been employed to clarify the fragmentation mechanism, which further confirms the proposed fragmentation patterns. RESULTS: Detailed analysis of the resultant fragments shows there are two different kinds of fragmentation patterns with the general fragment backbone of pyrrolidine or piperidine rings. In one route, pyrrolidine or piperidine rings undergo direct fragmentation and form some stable intermediates without affecting the parent rings. The other, however, involves ring opening and then ring closure at the pyridine-2 carbon atom to form multi-membered rings. CONCLUSIONS: This characteristic fragmentation behavior therefore provides useful information on identification of TSNAs that may be used to monitor such kinds of compound in the biological metabolism.

Cooperatively interface role of surface atoms and aqueous media on single atom catalytic property for H2O2 synthesis.

Direct electrosynthesis of hydrogen peroxide (H2O2) from H2 and O2 is a promising alternative to currently industrial Riedl-Pfleiderer route. Utilizing a combination of density functional theory (DFT) and ab-initio-molecular dynamic simulation (AIMD), we presented an effective computational framework to identify the cooperative role of surface atoms(e.g. O, N and S) and aqueous media on catalytic performance of single-atom catalysts (SACs) supported Nb2C MXenes. Computational results shown that both Ni/Nb2CN2 and Co/Nb2CS2 have low overpotentials of 0.17 V and 0.20 V, and the barrier of 0.89 eV and 0.67 eV for 2e- ORR under gas phase, respectively, while in aqueous phase, hydrogen bond framework on the surface promotes the transfer of proton, resulting in the lower 2e- ORR overpotential (0.05 V) in Co/Nb2CS2 and lower barrier (almost 0.01 eV) for rate-determining step (RDS) in Ni/Nb2CN2. Electronically, we found that the less-electronegativity N and S relative to O more benefit to mediate the activation degree of O2 on SACs and thereby improve catalytic selectivity. Thus, it is concluded that both surface atom and aqueous medium synergistically promote catalytic property for H2O2 synthesis.

Amino acid homochirality may be linked to the origin of phosphate-based life.

Phosphorylation has to have been one of the key events in prebiotic evolution on earth. In this article, the emergence of phosphoryl amino acid 5'-nucleosides having a P-N bond is described as a model of the origin of amino acid homochirality and Genetic Code. It is proposed that the intramolecular interaction between the nucleotide base and the amino acid side-chain influences the stability of particular amino acid 5'-nucleotides, and the interaction also selects for the chirality of amino acids. The differences between L: - and D: -conformation energies (DeltaE (conf)) are evaluated by DFT methods at the B3LYP/6-31G(d) level. Although, as expected, these DeltaE (conf) values are not large, they do give differences in energy that can distinguish the chirality of amino acids. Based on our calculations, the chiral selection of the earliest amino acids for L: -enantiomers seems to be determined by a clear stereochemical/physicochemical relationship. As later amino acids developed from the earliest amino acids, we deduce that the chirality of these late amino acids was inherited from that of the early amino acids. This idea reaches far back into evolution, and we hope that it will guide further experiments in this area.

Benzyl 2,5-dioxopyrrolidin-1-yl carbonate.

The asymmetric unit of the title compound, C(12)H(11)NO(5), contains two independent mol-ecules with similar geometric parameters but different orientations of the phenyl rings. The mol-ecular packing is stabilized by weak nonclassical C-H⋯O hydrogen-bonding inter-actions.

Negative ion electrospray ionization mass spectrometry of nucleoside phosphoramidate monoesters: elucidation of novel rearrangement mechanisms by multistage mass spectrometry incorporating in-source deuterium labelling.

Several O-2',3'-isopropylideneuridine-O-5'-phosphoramidate monoesters were synthesized and analyzed by negative ion electrospray ionization tandem mass spectrometry (ESI-MS(n)). Two kinds of novel rearrangement reactions were observed due to the difference in the amino acid in the nucleoside phosphoramidate monoesters, and possible mechanisms were proposed. One involves a five-membered cyclic transition state. The other is formation of a stable five-membered ring intermediate by Michael addition. Results were confirmed by tandem mass spectrometry and isotopically labeled hydrogen atoms. Furthermore, the internal hydrogen exchange between active hydrogen and methyl acrylate in the heated capillary of the mass spectrometer was found. The characteristic fragmentation behavior in ESI-MS may be used to monitor this kind of compounds in the biological metabolism.