Visible Light Spectroscopy of Liquid Solutes from Femto- to Attoliter Volumes inside a Single Nanofluidic Channel

TL;DR

This paper introduces Nanofluidic Scattering Spectroscopy (NSS), a technique that enables visible light spectroscopy of liquid solutes in nanochannels with attoliter volumes, providing accurate spectral fingerprints and concentration measurements.

Contribution

The study demonstrates NSS's capability to perform spectroscopic analysis at nanoliter to attoliter scales with high accuracy, suitable for continuous flow and real-time applications.

Findings

Achieved spectroscopic measurements in volumes as small as attoliters.

Accurately determined solute concentrations and molar extinction coefficients.

Validated NSS against literature values for dye molar extinction coefficients.

Abstract

UV-Vis spectroscopy is a workhorse in analytical chemistry that finds application in life science, organic synthesis and energy technologies like photocatalysis. In its traditional implementation with cuvettes, it requires sample volumes in the milliliter range. Here, we show how Nanofluidic Scattering Spectroscopy, NSS, which measures visible light scattered from a single nanochannel in a spectrally resolved way, can reduce this sample volume to the attoliter range for solute concentrations in the mM regime, which corresponds to as few as 105 probed molecules. The connection of the nanochannel to a microfluidic in-and outlet system enables such measurements in continuous flow conditions, and the integrated online optical reference system ensures their long-term stability. On the examples of the non-absorbing solutes NaCl and H2O2, and the dyes Brilliant Blue, Allura Red and Fluorescein, we demonstrate that spectral fingerprints can be obtained with good accuracy and that solute concentrations inside the nanochannel can be determined based on NSS-spectra. Furthermore, by applying a reverse Kramers-Kronig transformation to NSS-spectra, we show that the molar extinction coefficient of the dye solutes can be extracted with excellent agreement with the literature values. These results thus advertise NSS as a versatile tool for the spectroscopic analysis of solutes in situations where nanoscopic sample volumes, as well as continuous flow measurements, are critical, e.g., in single particle catalysis or nanoscale flow cytometry.