Skip to main content
Log in

NH2NH-MOF: a reaction matrix for the specific determination of small aldehydes by MALDI-MS

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

Efficient determination of aldehydes by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is hampered mainly by the low mass and unstable nature of analytes. In the present work, we propose a combined strategy of a reactive metal–organic framework (MOF) matrix for the derivatization and detection of aldehydes. A novel reactive MOF matrix (NH2NH-MOF) was synthesized in two steps. First, NR3+-MOF was synthesized via Cu2+ and the quaternary amine ligand 4,4′-bipyridinium, 1,1″-(1,2-ethanediyl)bis-, dibromide (PyEtBr). Then, -NHNH2 was introduced to NR3+-MOF through electrostatic adsorption between the -NR3+ and -HSO3 of 4-hydrazinylbenzenesulfonic acid to synthesize NH2NH-MOF. The acid–base chemistry of NH2NH-MOF led to uniform cocrystallization of the aldehyde-matrix mixtures and helped to achieve the detection of low-weight aldehydes with good relative standard deviations (RSDs = 0.07–12.35%). It was confirmed that this strategy can accurately quantify formaldehyde, valeraldehyde, and benzaldehyde with good linearity (r > 0.97). Furthermore, this strategy was applied to quantitatively detect benzaldehyde in wastewater, thus showing potential applications in environmental pollutant detection.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1.
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Abushareeda W, Lyris E, Kraiem S, Al Wahaibi A, Alyazidi S, Dbes N, Lommen A, Nielen M, Horvatovich PL, Alsayrafi M, Georgakopoulos C (2017) Gas chromatographic quadrupole time-of-flight full scan high resolution mass spectrometric screening of human urine in antidoping analysis. J Chromatogr B 1063:74–83

    Article  CAS  Google Scholar 

  2. Alipanahpour DE, Ghaedi M, Asfaramb A (2017) Optimization and modeling of pre-concentration and determination of dyes based on ultrasound assisted-dispersive liquid-liquid microextraction coupled with derivative spectrophotometry. Ultrason Sonochem 34:27–36

    Article  Google Scholar 

  3. Dil EA, Ghaedi M, Asfaram A, Zare F, Mehrabi F, Sadeghfar F (2017) Comparison between dispersive solid-phase and dispersive liquid-liquid micro-extraction combined with spectrophotometric determination of malachite green in water samples based on ultrasound-assisted and preconcentration under multi-variable experimental design optimization. Ultrason Sonochem 39:374–383

    Article  Google Scholar 

  4. Shigeri Y, Yasuda A, Sakai M, Ikeda S, Arakawa R, Sato H, Kinumi T (2015) Hydrazide and hydrazine reagents as reactive matrices for matrix-assisted laser desorption/ionization mass spectrometry to detect steroids with carbonyl groups. Eur J Mass Spectrom 21(2):79–90

    Article  CAS  Google Scholar 

  5. Shigeri Y, Yasuda A, Sakai M, Ikeda S, Arakawa R, Sato H, Kinumi T (2016) 2-Hydrazinoquinoline: a reactive matrix for matrix-assisted laser desorption/ionization mass spectrometry to detect gaseous carbonyl compounds. Eur J Mass Spectrom 22(2):83–90

    Article  CAS  Google Scholar 

  6. Liu HL, Chang YJ, Fan T, Gu ZY (2016) Two-dimensional metal-organic framework nanosheets as a matrix for laser desorption/ionization of small molecules and monitoring enzymatic reactions at high salt concentrations. Chem Commun 52(88):12984–12987

    Article  CAS  Google Scholar 

  7. Monopoli A, Calvano CD, Nacci A, Palmisano F (2014) Boronic acid chemistry in MALDI MS: a step forward in designing a reactive matrix with molecular recognition capabilities. Chem Commun 50(33):4322–4324

    Article  CAS  Google Scholar 

  8. Zhao XY, Guo C, Huang Y, Huang LL, Ma G, Liu YQ, He Q, Wang HW, Chen KS, Pan YJ (2019) Combination strategy of reactive and catalytic matrices for qualitative and quantitative profiling of N-glycans in MALDI-MS. Anal Chem 91(14):9251–9258

    Article  CAS  Google Scholar 

  9. Ling L, Xiao CS, Ma Y, Jiang LY, Wang S, Guo LM, Jiang SM, Guo XH (2019) 2-Phenyl-3-(p-aminophenyl) acrylonitrile: a reactive matrix for sensitive and selective analysis of glycans by MALDI-MS. Anal Chem 91(14):8801–8807

    Article  CAS  Google Scholar 

  10. Lin Z, Cai ZW (2018) Negative ion laser desorption/ionization time-of-flight mass spectrometric analysis of small molecules by using nanostructured substrate as matrices. Mass Spec Rev 37(5):681–696

    Article  CAS  Google Scholar 

  11. Lu MH, Yang XQ, Yang YX, Qin PG, Wu XR, Cai ZW (2017) Nanomaterials as assisted matrix of laser desorption/ionization time-of-flight mass spectrometry for the analysis of small molecules. Nanomaterials 7(4):87

    Article  Google Scholar 

  12. Yuan N, Gong XR, Sun WD, Yu CH (2021) Advanced applications of Zr-based MOFs in the removal of water pollutants. Chemosphere 267:128863

    Article  CAS  Google Scholar 

  13. Yang J, Yang YW (2020) Metal-organic frameworks for biomedical applications. Small 16(10):1906846

    Article  CAS  Google Scholar 

  14. Daglar H, Gulbalkan HC, Avci G, Aksu GO, Altundal OF, Altintas C, Erucar I, Keskin S (2021) Effect of metal-organic framework (MOF) database selection on the assessment of gas storage and separation potentials of MOFs. Angew Chem Int Ed 60(14):7828–7837

    Article  CAS  Google Scholar 

  15. Garai M, Yavuz CT (2021) Robust mesoporous Zr-MOF with Pd nanoparticles for formic-acid-based chemical hydrogen storage. Matter 4(1):10–12

    Article  CAS  Google Scholar 

  16. Singh C, Mukhopadhyay S, Hod I (2021) Metal-organic framework derived nanomaterials for electrocatalysis: recent developments for CO2 and N2 reduction. Nano Convergence 8(1):1

    Article  Google Scholar 

  17. Amiripour F, Ghasemi S, Azizi SN (2021) Design of turn-on luminescent sensor based on nanostructured molecularly imprinted polymer-coated zirconium metal-organic framework for selective detection of chloramphenicol residues in milk and honey. Food Chem 347:129034

    Article  CAS  Google Scholar 

  18. Ma Q, Chu SS, Li H, Guo J, Zhang Q, Lin ZQ, Wang JP, Che QD (2021) Bi-component MOF-derived high-sensitive triethylamine gas sensors based on MoO3/ZnMoO4/CoMoO4 hierarchical structures effectuated by tunable surface/interface transfer behavior. J Mater Sci 56(13):7906–7919

    Article  CAS  Google Scholar 

  19. Shih YH, Chien CH, Singco B, Hsu CL, Lin CH, Huang HY (2013) Metal-organic frameworks: new matrices for surface-assisted laser desorption-ionization mass spectrometry. Chem Commun 49(43):4929–4931

    Article  CAS  Google Scholar 

  20. Feng D, Xia Y (2018) Covalent organic framework as efficient desorption/ionization matrix for direct detection of small molecules by laser desorption/ionization mass spectrometry. Anal Chim Acta 1014:58–63

    Article  CAS  Google Scholar 

  21. Li J, Peng YL, Liu Y, Li WW, Jin Y, Tang ZT, Duan YX (2014) Investigation of potential breath biomarkers for the early diagnosis of breast cancer using gas chromatography-mass spectrometry. Clin Chim Acta 436:59–67

    Article  CAS  Google Scholar 

  22. Guadagni R, Miraglia N, Simonelli A, Silvestre A, Lamberti M, Feola D, Acampora A, Sannolo N (2011) Solid-phase microextraction–gas chromatography-mass spectrometry method validation for the determination of endogenous substances: urinary hexylaldehyde and heptanal as lung tumor biomarkers. Anal Chim Acta 701(1):29–36

    Article  CAS  Google Scholar 

  23. Abdelhamid HN (2018) Nanoparticle assisted laser desorption/ionization mass spectrometry for small molecule analytes. Microchim Acta 185:200

    Article  Google Scholar 

  24. Shi CY, Deng CH (2016) Recent advances in inorganic materials for LDI-MS analysis of small molecules. Analyst 141(10):2816–2826

    Article  CAS  Google Scholar 

  25. Kim J (2015) Sample preparation for matrix-assisted laser desorption/ionization mass spectrometry. Mass Spectrom Lett 6:27–30

    Article  Google Scholar 

  26. Alexovic M, Dotsikas Y, Bober P, Sabo J (2018) Achievements in robotic automation of solvent extraction and related approaches for bioanalysis of pharmaceuticals. J Chromatogr B 1092:402–421

    Article  CAS  Google Scholar 

  27. Abushareeda W, Vonaparti A, Al Saad K, Almansoori M, Meloug M, Saleh A, Aguilera R, Angelis Y, Horvatovich PL, Lommen A, Alsayrafi M, Georgakopoulos C (2018) High resolution full scan liquid chromatography mass spectrometry comprehensive screening in sports antidoping urine analysis. J Pharm Biomed Anal 151:10–24

    Article  CAS  Google Scholar 

  28. Xu M, Yang SS, Gu ZY (2018) Two-dimensional metal-organic framework nanosheets: a rapidly growing class of versatile nanomaterials for gas separation, MALDI-TOF matrix and biomimetic applications. Chem Eur J 24(57):15131–15142

    Article  CAS  Google Scholar 

  29. Da HJ, Yang CX, Yan XP (2019) Cationic covalent organic nanosheets for rapid and selective capture of perrhenate: an analogue of radioactive pertechnetate from aqueous solution. Environ Sci Technol 53(9):5212–5220

    Article  CAS  Google Scholar 

  30. Wang J, Han PP, Xia Y (2019) A cationic metal-organic framework for the highly efficient removal of thiocyanate from water. Microporous Mesoporous Mater 287:107–113

    Article  CAS  Google Scholar 

  31. Hu YN, Chen D, Zhang TY, Ding J, Feng YQ (2020) Use of ammonium sulfite as a post-column derivatization reagent for rapid detection and quantification of aldehydes by LC-MS. Talanta 206:120172

    Article  CAS  Google Scholar 

  32. Qiao Z, Perestrelo R, Reyes-Gallardo EM, Lucena R, Cardenas S, Rodrigues J, Camara JS (2015) Octadecyl functionalized core-shell magnetic silica nanoparticle as a powerful nanocomposite sorbent to extract urinary volatile organic metabolites. J Chromatogr A 1393:18–25

    Article  CAS  Google Scholar 

  33. Liu JF, Yuan BF, Feng YQ (2015) Determination of hexanal and heptanal in human urine using magnetic solid phase extraction coupled with in-situ derivatization by high performance liquid chromatography. Talanta 136:54–59

    Article  CAS  Google Scholar 

Download references

Funding

Financial support was obtained from the National Natural Science Foundation of China (21874073) and the NCC Fund (NCC2020PY11).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Yan Xia.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Highlights

• NH2NH-MOF was synthesized, providing a new reactive matrix that possesses molecular recognition properties.

• Selective recognition of small aldehydes was achieved in complex samples with good accuracy.

• An MOF matrix was developed with built-in recognition capabilities, providing new ideas for the functional expansion of MOFs.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 1.10 MB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zheng, R., Yang, Y. & Xia, Y. NH2NH-MOF: a reaction matrix for the specific determination of small aldehydes by MALDI-MS. Microchim Acta 189, 51 (2022). https://doi.org/10.1007/s00604-021-05143-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-021-05143-y

Keywords

Navigation