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Sensitive and robust electrophoretic NMR: instrumentation and experiments.

Fredrik Hallberg1, István Furó, Pavel V Yushmanov

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Summary

This study introduces a novel electrophoretic NMR (eNMR) sample cell design that overcomes previous limitations. The new cell enhances sensitivity and enables accurate measurement of electrophoretic mobility by mitigating bulk flow effects.

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Area of Science:

  • Analytical Chemistry
  • Physical Chemistry
  • Spectroscopy

Background:

  • Electrophoretic NMR (eNMR) has faced challenges limiting its application.
  • Bulk flow effects (electro-osmosis, thermal convection), bubble formation, and RF noise have reduced sensitivity and reproducibility.
  • U-tube geometries in eNMR limit sensitivity and obscure the sign of electrophoretic mobility.

Purpose of the Study:

  • To develop an improved electrophoretic NMR (eNMR) sample cell.
  • To enhance NMR sensitivity and overcome limitations of previous eNMR designs.
  • To enable accurate measurement of electrophoretic mobility by compensating for bulk flow effects.

Main Methods:

  • A new electrophoretic sample cell using a vertical NMR tube with palladium electrodes was designed.
  • A radiofrequency filter was implemented to prevent RF noise pickup.
  • A parallel reference signal from a non-charged species and a CPMG-like pulse train were used for bulk flow compensation.

Main Results:

  • The new cell design achieved a signal-to-noise ratio one order of magnitude higher than previous U-tube cells.
  • The design retains the sign of the displacement-related signal phase, crucial for mobility determination.
  • A method for compensating electro-osmotic and thermal convection bulk flow effects was successfully demonstrated.

Conclusions:

  • The developed electrophoretic NMR sample cell significantly improves sensitivity and overcomes major technical hurdles.
  • This advancement facilitates more accurate and reliable measurements of electrophoretic mobility.
  • The compensation strategy offers a robust solution for mitigating bulk flow interferences in eNMR experiments.