Coffee Ring Effect Free TiO2 Nanotube Array for Quantitative Laser Desorption/Ionization Mass Spectrometry,ACS Applied Nano Materials

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Coffee Ring Effect Free TiO2 Nanotube Array for Quantitative Laser Desorption/Ionization Mass Spectrometry
ACS Applied Nano Materials ( IF 5.3 ) Pub Date : 2020-09-03 , DOI: 10.1021/acsanm.0c01858
Moon-Ju Kim ₁ , Jong-Min Park ₁ , Joo-Yoon Noh ₁ , Tae Gyeong Yun ₁ , Min-Jung Kang ₂ , Nam Su Ku ₃ , Eun Hye Lee ₄ , Kwang Hwan Park ₅ , Moo Suk Park ₄ , Sang-Guk Lee ₆ , Jae-Chul Pyun ₁

Affiliation

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.

中文翻译：

无咖啡环效应的TiO ₂纳米管阵列用于定量激光解吸/电离质谱

由于“咖啡环效应”引起的分析物分布不均匀，使用激光解吸/电离质谱（LDI-MS）进行的定量分析受到了限制。在这项研究中，提出了一种具有亲水点图案并被疏水区域包围的TiO ₂纳米管阵列（HB / HL图案化的TiO ₂ NTA），以均匀分布分析物并将其浓缩在样品点内。通过（1）电化学阳极氧化，（2）硅烷官能化和（3）在紫外线辐射下用光掩模进行亲水性图案化来制造HB / HL图案化的TiO ₂ NTA。抑制咖啡环对该可润湿性控制的TiO _2的影响通过分析物溶液向选择性可渗透的TiO ₂ NTA的毛细管渗透，从实验上阐明了NTA。在HB / HL图案的TiO ₂ NTA上干燥的荧光素的形态表明，荧光素沉积均匀，没有横向扩散。使用两种类型的败血症生物标志物溶血磷脂酰胆碱16：0（LPC 16：0）和LPC 18：0作为模型分析物证明了HB / HL模式的TiO ₂ NTA用于定量LDI-MS的可行性。此外，基于HB / HL模式的TiO ₂ NTA基质的LDI-MS可通过败血症阴性和阳性组的血清分析LPC 16：0和LPC 18：0应用于败血症的医学诊断。这些结果表明，HB / HL图案的TiO ₂NTA可以成为出色的定量分析平台。此外，基于HB / HL模式的TiO ₂ NTA基质的LDI-MS有可能成为脓毒症诊断的实用方法。

更新日期：2020-09-25

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