Tags

Type your tag names separated by a space and hit enter

In situ calibration of Direct Analysis in Real Time-mass spectrometry for direct quantification: Urine excretion rate index creatinine as an example.
Talanta 2019; 201:134-142T

Abstract

Ambient ionization in open environment brings a capability of a coupled mass spectrometry to detect target molecules in situ. However, it is limited to qualitative and semi-quantitative analysis. By coupling of an ambient ionization-based Direct Analysis in Real Time (DART) with high-resolution quadrupole time-of-flight mass spectrometry (QTOF/MS), we observe that, in one-chemical system, the target molecule displays a non-linear response in MS signal vs concentration, accompanying with large variation in MS signal, suggesting two obstacles for quantification to be overcome. Surprisingly, in a two-chemical system, we observe an apparent suppression effect. We prove that, due to this observed suppression effect, a fluctuant response in the MS signal of the stable isotope-labeled analogue can immediately reflect the change in the analyte concentration and ionization efficiency. For example, by taking advantage of this effect, even the analyte of different concentrations despairingly displayed similar signals would be accurately calibrated through the suppression of the internal stable isotope standard. This puts an important foundation on accurate and linear quantitation of analytes in complex matrix using DART-MS assay. Moreover, we for the first time demonstrate an application of in situ calibration of DART-MS for direct and accurate quantification of target molecule (creatinine) in highly complex samples (human urine) without any pre-separation. The quantification is also validated using HPLC-UV analysis (n = 38). At last, we show that stable isotope-labeled-creatinine (m/z 117.0850 amu) can be used for simultaneous in situ calibration of some other urinary metabolites with a mass/charge ratio varying from 120.069 amu to 333.125 amu.

Authors+Show Affiliations

State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, China.Chemical Analysis Group, Agilent Technologies, Beijing, 100102, China.ASPEC Technologies Limited, Beijing, 100101, China.ASPEC Technologies Limited, Beijing, 100101, China.State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, China; University of Chinese Academy of Sciences, Beijing, 100049, China. Electronic address: hlwang@rcees.ac.cn.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31122403

Citation

Zhang, Ning, et al. "In Situ Calibration of Direct Analysis in Real Time-mass Spectrometry for Direct Quantification: Urine Excretion Rate Index Creatinine as an Example." Talanta, vol. 201, 2019, pp. 134-142.
Zhang N, Lu M, Duan X, et al. In situ calibration of Direct Analysis in Real Time-mass spectrometry for direct quantification: Urine excretion rate index creatinine as an example. Talanta. 2019;201:134-142.
Zhang, N., Lu, M., Duan, X., Liu, C. C., & Wang, H. (2019). In situ calibration of Direct Analysis in Real Time-mass spectrometry for direct quantification: Urine excretion rate index creatinine as an example. Talanta, 201, pp. 134-142. doi:10.1016/j.talanta.2019.03.092.
Zhang N, et al. In Situ Calibration of Direct Analysis in Real Time-mass Spectrometry for Direct Quantification: Urine Excretion Rate Index Creatinine as an Example. Talanta. 2019 Aug 15;201:134-142. PubMed PMID: 31122403.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - In situ calibration of Direct Analysis in Real Time-mass spectrometry for direct quantification: Urine excretion rate index creatinine as an example. AU - Zhang,Ning, AU - Lu,Meiling, AU - Duan,Xiaokun, AU - Liu,Charles C, AU - Wang,Hailin, Y1 - 2019/04/04/ PY - 2018/12/24/received PY - 2019/03/23/revised PY - 2019/03/27/accepted PY - 2019/5/25/entrez PY - 2019/5/28/pubmed PY - 2019/6/18/medline KW - Direct analysis in real time KW - Direct quantification KW - Stable isotope-labeled creatinine KW - Urinary creatinine SP - 134 EP - 142 JF - Talanta JO - Talanta VL - 201 N2 - Ambient ionization in open environment brings a capability of a coupled mass spectrometry to detect target molecules in situ. However, it is limited to qualitative and semi-quantitative analysis. By coupling of an ambient ionization-based Direct Analysis in Real Time (DART) with high-resolution quadrupole time-of-flight mass spectrometry (QTOF/MS), we observe that, in one-chemical system, the target molecule displays a non-linear response in MS signal vs concentration, accompanying with large variation in MS signal, suggesting two obstacles for quantification to be overcome. Surprisingly, in a two-chemical system, we observe an apparent suppression effect. We prove that, due to this observed suppression effect, a fluctuant response in the MS signal of the stable isotope-labeled analogue can immediately reflect the change in the analyte concentration and ionization efficiency. For example, by taking advantage of this effect, even the analyte of different concentrations despairingly displayed similar signals would be accurately calibrated through the suppression of the internal stable isotope standard. This puts an important foundation on accurate and linear quantitation of analytes in complex matrix using DART-MS assay. Moreover, we for the first time demonstrate an application of in situ calibration of DART-MS for direct and accurate quantification of target molecule (creatinine) in highly complex samples (human urine) without any pre-separation. The quantification is also validated using HPLC-UV analysis (n = 38). At last, we show that stable isotope-labeled-creatinine (m/z 117.0850 amu) can be used for simultaneous in situ calibration of some other urinary metabolites with a mass/charge ratio varying from 120.069 amu to 333.125 amu. SN - 1873-3573 UR - https://www.unboundmedicine.com/medline/citation/31122403/In_situ_calibration_of_Direct_Analysis_in_Real_Time-mass_spectrometry_for_direct_quantification:_Urine_excretion_rate_index_creatinine_as_an_example L2 - https://linkinghub.elsevier.com/retrieve/pii/S0039-9140(19)30350-9 DB - PRIME DP - Unbound Medicine ER -