Organometallic-Constructed Tip-Based Dual Chemical Sensing by Tip-Enhanced Raman Spectroscopy for Diabetes Detection

Abstract

Tip-enhanced Raman spectroscopy (TERS) is capable of probing specific molecular information with high sensitivity, but dual chemical sensing remains a challenge. Another major hindrance to TERS chemical detection in biosamples such as blood is the interference from the strong absorptions of biomolecules. Herein, we report the preparation of an organometallic-conjugated TERS tip. We demonstrate that organometallic chemistry can be perfectly coupled with TERS for dual-molecule sensing. The unique Raman signals generated by the organometallic compound circumvent signal interference from the biomolecules in blood, allowing the rapid analysis of two important molecules (glucose and thiol) in ultralow volume (50 nL) samples. This enabled a correlation between the thiol and glucose levels in the blood of nondiabetic and diabetic patients to be drawn.

Selective excitation of one among the three peaks of tip‐enhanced Raman spectroscopy by a shaped ultrafast laser pulse

“…Combining the utility of scanning probe microscopy and Raman scattering, tip‐enhanced Raman spectroscopy (TERS) has become an ultrasensitive detection technique, and it is widely used in the fields of atomic structure, catalytic processes, and the redox behavior of single molecules . The selective Raman enhancement has been studied through the modifications and functionalization of TERS probes and controlling of surface plasmon polarizations and light polarizations .…”

Probing Molecular-Scale Oxidative Generation of Quinone Methides and Their Transformation Using Tip-Enhanced Raman Spectroscopy

“…Operando/in situ studies of tip-enhanced Raman spectroscopy (TERS) have contributed significantly toward understanding molecular-scale chemical interactions. − This technique offers high chemical sensitivity and excellent spatial resolution . TERS has been implemented in liquid environments to investigate chemical reactions and surface chemistry under ambient conditions. , Recent progress in TERS has led to its application in electrochemistry, revealing chemical transformations.…”

“…TERS has been implemented in liquid environments to investigate chemical reactions and surface chemistry under ambient conditions. , Recent progress in TERS has led to its application in electrochemistry, revealing chemical transformations. In our recent studies, we employed the TERS technique to characterize the reaction modes of transition metal complexes with biomolecules . Based on the change in the TERS spectrum, the dominant chemical transformation of transition metal complexes was identified.…”

“…A very aggressive phenotype called hormone-independent breast cancer displays high resistance to tamoxifen . Much research as of late has focused on the utilization of ferrocene to modify the effects of biologically active molecules. − Ferrocifen, a ferrocenyl-based tamoxifen that forms when a ferrocene moiety replaces a phenyl group in tamoxifen, exhibits an improved toxicity (in preclinical evaluation for the treatment of cancer) . The teams of Gerard and Vessières have proposed that the effectiveness of ferrocene is highly correlated with the formation of ferrocenyl quinone methide metabolites that is mediated by ferrocene to facilitate ferrocene phenol activation. , QM metabolites, possibly a cytotoxic species, undergo formation at rather mild oxidation potentials in the presence of ferrocene.…”

“…In our recent studies, we employed the TERS technique to characterize the reaction modes of transition metal complexes with biomolecules. 7 Based on the change in the TERS spectrum, the dominant chemical transformation of transition metal complexes was identified. This feature has also been implemented in biosensing applications.…”