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Highly efficient analysis of underivatized carbohydrates using monolithic-silica-based capillary hydrophilic interaction (HILIC) HPLC

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Abstract

A polyacrylamide (PAAm)-modified monolithic silica capillary column of increased phase ratio, 200T-PAAm, for hydrophilic interaction liquid chromatography (HILIC) was prepared. The column showed high separation efficiency, with a theoretical plate height H = 7–20 μm at a linear velocity, u = 1–7 mm/s. From a kinetic plot analysis, it was expected that the monolithic column could provide three times faster separation than particle-packed HILIC columns under a pressure limit at 20 MPa. HILIC coupled with electrospray ionization (ESI)–mass spectrometry (HILIC-ESI-MS) using the 200T-PAAm column was employed for the analysis of underivatized carbohydrates to achieve fast and efficient separations of mixtures containing mono-, di-, and trisaccharides within 5 min. Under single MS full scan mode, 200 pg of oligosaccharides was detected by the system. The limit of detection (LOD) of the LC-ESI-MS/MS system was determined using selected reaction monitoring (SRM) to be as low as 3.2 ng/mL (attomol level) for nonreducing saccharides. The system was successfully applied to the detection of disaccharides in extracts of plant, such as corn, soybean, and Arabidopsis thaliana.

HILIC-ESI-MS provides a high-efficiency separation and sensitive detection of underivatized carbohydrate oligomers, e.g., the homologs of glucose (1) up to maltoheptaose (7)

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Acknowledgement

We acknowledge the financial support from a Grant-in-Aid for Scientific Research funded by the Ministry of Education, Sports, Culture, Science and Technology, No. 17350036 and No. 19550088. We appreciate Dr. Vladimir V. Tolstikov, University of California at Davis, for helpful discussion. Mr. K. Horie thanks the Kyoto Institute of Technology for a scholarship of the Engineer Training and Research Innovation Program. The support by Nacalai Tesque, GL Sciences and Merck KGaA, Darmstadt, are also gratefully acknowledged.

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Author notes

  1. Kanta Horie

    Present address: Eisai Co. Ltd., Tsukuba, Ibaraki, 3002635, Japan

  2. Nabil Saad

    Present address: KineMed, Inc., Emeryville, CA, 94608, USA

  3. Ken Hosoya

    Present address: Tohoku University, Sendai, Japan

Authors and Affiliations

  1. Department of Biomolecular Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto, 606-8585, Japan

    Tohru Ikegami, Kanta Horie, Ken Hosoya & Nobuo Tanaka

  2. Genome Center, University of California at Davis, East Health Sciences Drive, Davis, CA, 95616-8816, USA

    Nabil Saad & Oliver Fiehn

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  1. Tohru Ikegami
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  2. Kanta Horie
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Correspondence to Tohru Ikegami.

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Ikegami, T., Horie, K., Saad, N. et al. Highly efficient analysis of underivatized carbohydrates using monolithic-silica-based capillary hydrophilic interaction (HILIC) HPLC. Anal Bioanal Chem 391, 2533–2542 (2008). https://doi.org/10.1007/s00216-008-2060-6

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  • DOI: https://doi.org/10.1007/s00216-008-2060-6

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