16502-02-6Relevant articles and documents
Chemical Tagging Assisted Mass Spectrometry Analysis Enables Sensitive Determination of Phosphorylated Compounds in a Single Cell
Ding, Jiang-Hui,Feng, Yu-Qi,Huang, Wei-Hua,Liu, Fei-Long,Yang, Xiao-Ke,Ye, Tian-Tian,Yin, Xiao-Ming,Yuan, Bi-Feng
, p. 6848 - 6856 (2021)
Polar phosphorylated metabolites are involved in a variety of biological processes and play vital roles in energetic metabolism, cofactor regeneration, and nucleic acid synthesis. However, it is often challenging to interrogate polar phosphorylated metabolites and compounds from biological samples. Liquid chromatography-mass spectrometry (LC/MS) now plays a central role in metabolomic studies. However, LC/MS-based approaches have been hampered by the issues of the low ionization efficiencies, low in vivo concentrations, and less chemical stability of polar phosphorylated metabolites. In this work, we synthesized paired reagents of light and heavy isotopomers, 2-(diazomethyl)phenyl)(9-methyl-1,3,4,9-tetrahydro-2H-pyrido[3,4-b]indol-2-yl)methanone (DMPI) and d3-(2-(diazomethyl)phenyl)(9-methyl-1,3,4,9-tetrahydro-2H-pyrido[3,4-b]indol-2-yl)methanone (d3-DMPI). The paired reagents of DMPI and d3-DMPI carry diazo groups that can efficiently and selectively react with the phosphate group on polar phosphorylated metabolites under mild conditions. As a proof of concept, we found that the transfer of the indole heterocycle group from DMPI/d3-DMPI to ribonucleotides led to the significant increase of ionization efficiencies of ribonucleotides during LC/MS analysis. The detection sensitivities of these ribonucleotides increased by 25-1137-fold upon DMPI tagging with the limits of detection (LODs) being between 7 and 150 amol. With the developed method, we achieved the determination of all the 12 ribonucleotides from a single mammalian cell and from a single stamen of Arabidopsis thaliana. The method provides a valuable tool to investigate the dynamic changes of polar phosphorylated metabolites in a single cell under particular conditions.
Dehydrogenation of N-Heterocycles by Superoxide Ion Generated through Single-Electron Transfer
Huang, Yuan-Qiong,Song, Hong-Jian,Liu, Yu-Xiu,Wang, Qing-Min
, p. 2065 - 2069 (2018/01/27)
Nitrogen-containing heteroarene motifs are found in numerous pharmaceuticals, natural products, and synthetic materials. Although several elegant methods for synthesis of these compounds through dehydrogenation of the corresponding saturated heterocycles have been reported, some of the methods are hampered by long reaction times, harsh conditions, and the need for catalysts that are not readily available. This work reports a novel method for dehydrogenation of N-heterocycles. Specifically, O2.? generated in situ acts as the oxidant for N-heterocycle substrates that are susceptible to oxidation through a hydrogen atom transfer mechanism. This method provides a general, green route to N-heteroarenes.
N-methylation of aromatic amines and N-heterocycles under acidic conditions with the TTT (1,3,5-trioxane-triethylsilane-trifluoroacetic acid) system
Popp, Tobias A.,Bracher, Franz
, p. 3333 - 3338 (2016/11/29)
A novel reductive N-methylation protocol under acidic conditions with the TTT (1,3,5-trioxane-triethylsilane-trifluoroacetic acid) system is disclosed. This method is highly specific for aromatic amines and several N-heterocycles (indoles and annulated analogues, phenoxazine, phenothiazine), insensitive to steric hindrance, and compatible with a wide range of functional groups. Further the N-methylation step can be combined with an in situ N-Boc deprotection. Compounds in which the nucleophilicity of the NH group is eliminated by protonation under the reaction conditions (aliphatic amines, azaarenes of noteworthy basicity) are inert. In several examples, it was demonstrated that the TTT system is complementary to other N-methylation protocols.
