title: Functionalized HgTe nanoparticles promote laser-induced solid phase ionization/dissociation for comprehensive glycan sequencing.
abstract: Glycoconjugates are ubiquitously present and play a critical role in various biological processes. Due to their low stability and incredibly high degree of structural diversity, the structural characterization of glycan generally requires chemical derivatization and sophisticated instrumentation. Herein, we report a method for complicated glycan characterization in a single assay by employing 2,5-dihydroxybenzoic acid functionalized mercury telluride nanoparticles (HgTe@DHB NPs) as a dual ionization-dissociation element in matrix-assisted laser desorption/ionization mass spectrometry. Using a linear glycan, HgTe@DHB NPs promote laser-induced extensive and intense dissociation of the glycan, superior to HgTe microparticles and other inorganic nanoparticles (TiO2, ZnO, and Mn2O3NPs). Abundant generation of diagnostic glycosidic (Y-, and B-type ions) and cross-ring cleavage (A-type ions) ions permits unambiguous determination of the composition, sequence, branching, and linkage of labile sialylated glycans. The general utility of this approach was demonstrated by the characterization of labile sialylated glycans and two sets of complicated isomeric glycans. This phenomenon was delineated further by investigating the NP's physico-chemical characteristics, revealing that their nanoscale-dependent thermodynamic properties, including UV absorption, photoelectron release dynamics and thermal energy, were the key to levitate temperature synergistically, thus inducing spontaneous glycan decomposition during the nanoparticle-assisted laser desorption-ionization process. Our results show that this "pseudo-MS/MS" obtained by HgTe@DHB can be beneficial for the analysis of biologically relevant and more complicated carbohydrates, without the need for chemical pre-derivatization and conventional tandem mass spectrometry.
authors.affiliation: Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan and Molecular Science and Technology Program, Taiwan International Graduate Program, Institute of Chemistry, Academia Sinica, Taiwan and Institute of Chemistry, Academia Sinica, Taipei, Taiwan. yujuchen@gate.sinica.edu.tw and Research Unit for Clean Technology, Indonesian Institute of Sciences, Bandung, Indonesia.
authors.forename: Indah
authors.initials: I
authors.lastname: Primadona
authors.affiliation: Genomics Research Center, Academia Sinica, Taipei, Taiwan. wer@gate.sinica.edu.tw.
authors.forename: Yin-Hung
authors.initials: YH
authors.lastname: Lai
authors.affiliation: Institute of Chemistry, Academia Sinica, Taipei, Taiwan. yujuchen@gate.sinica.edu.tw and Division of Chemistry, Caraga State University, Butuan city, Philippines.
authors.forename: Rey Y
authors.initials: RY
authors.lastname: Capangpangan
authors.affiliation: Institute of Chemistry, Academia Sinica, Taipei, Taiwan. yujuchen@gate.sinica.edu.tw.
authors.forename: Rofeamor P
authors.identifier: http://orcid.org/0000-0003-3080-8222
authors.initials: RP
authors.lastname: Obena
authors.affiliation: Institute of Chemistry, Academia Sinica, Taipei, Taiwan. yujuchen@gate.sinica.edu.tw.
authors.forename: Mei-Chun
authors.initials: MC
authors.lastname: Tseng
authors.affiliation: Department of Chemistry, National Taiwan University, Taipei, Taiwan.
authors.forename: Ming-Feng
authors.initials: MF
authors.lastname: Huang
authors.affiliation: Department of Chemistry, National Taiwan University, Taipei, Taiwan.
authors.forename: Huan-Tsung
authors.initials: HT
authors.lastname: Chang
authors.affiliation: Genomics Research Center, Academia Sinica, Taipei, Taiwan. wer@gate.sinica.edu.tw.
authors.forename: Shiou-Ting
authors.initials: ST
authors.lastname: Li
authors.affiliation: Genomics Research Center, Academia Sinica, Taipei, Taiwan. wer@gate.sinica.edu.tw.
authors.forename: Chung-Yi
authors.initials: CY
authors.lastname: Wu
authors.affiliation: Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan.
authors.forename: Wei-Ting
authors.initials: WT
authors.lastname: Chien
authors.affiliation: Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan.
authors.forename: Chun-Cheng
authors.initials: CC
authors.lastname: Lin
authors.affiliation: Genomics Research Center, Academia Sinica, Taipei, Taiwan. wer@gate.sinica.edu.tw.
authors.forename: Yi-Sheng
authors.initials: YS
authors.lastname: Wang
authors.affiliation: Institute of Chemistry, Academia Sinica, Taipei, Taiwan. yujuchen@gate.sinica.edu.tw and Department of Chemistry, National Taiwan University, Taipei, Taiwan.
authors.forename: Yu-Ju
authors.initials: YJ
authors.lastname: Chen
mesh_terms: D007834:Lasers; D017669:Mercury Compounds; D053768:Metal Nanoparticles; D011134:Polysaccharides / Q000032:analysis*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013691:Tellurium
chemical_list: D017669:Mercury Compounds; D011134:Polysaccharides; D013691:Tellurium