Coffee Ring Effect Free TiO2Nanotube Array for Quantitative Laser Desorption/Ionization Mass Spectrometry

Moon Ju Kim, Jong Min Park, Joo Yoon Noh, Tae Gyeong Yun, Min Jung Kang, Nam Su Ku, Eun Hye Lee, Kwang Hwan Park, Moo Suk Park, Sang Guk Lee, Jae Chul Pyun

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14 Citations (Scopus)


Quantitative analysis using laser desorption/ionization mass spectrometry (LDI-MS) has been limited because of the nonuniform distribution of analytes caused by the "coffee ring effect". In this study, a TiO2 nanotube array with hydrophilic dot patterns surrounded by hydrophobic areas (HB/HL-patterned TiO2 NTA) is presented to distribute analytes uniformly as well as to concentrate them within a sample spot. The HB/HL-patterned TiO2 NTA is fabricated by (1) electrochemical anodization, (2) silane functionalization, and (3) hydrophilic patterning with a photomask under ultraviolet radiation. Suppression of the coffee ring effect on this wettability-controlled TiO2 NTA is experimentally elucidated in terms of a capillary penetration of analyte solution into the selectively permeable TiO2 NTA. The morphology of a dried fluorescein on the HB/HL-patterned TiO2 NTA demonstrates homogeneous fluorescein deposition without lateral spreading. The feasibility of HB/HL-patterned TiO2 NTA for quantitative LDI-MS is demonstrated using two types of sepsis biomarkers, lysophosphatidylcholine 16:0 (LPC 16:0) and LPC 18:0 as model analytes. Further, LDI-MS based on the HB/HL-patterned TiO2 NTA matrix is applied to the medical diagnosis of sepsis by analyzing LPC 16:0 and LPC 18:0 with the sera from sepsis-negative and -positive groups. These results reveal that the HB/HL-patterned TiO2 NTA can be a remarkable platform for quantitative analysis. Furthermore, LDI-MS based on the HB/HL-patterned TiO2 NTA matrix has the potential to be a practical approach for sepsis diagnosis.

Original languageEnglish
Pages (from-to)9249-9259
Number of pages11
JournalACS Applied Nano Materials
Issue number9
Publication statusPublished - 2020 Sept 25

Bibliographical note

Funding Information:
This work was supported by the National Research Foundation of Korea [grant number: NRF-2020R1A2B5B01002187] and the Korea Institute of Science and Technology institutional program [grant number: 2E30480].

Publisher Copyright:
Copyright © 2020 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Materials Science(all)


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