Rapid and highly sensitive determination of unexpected diquat and paraquat in biological fluids by electro-enhanced SPME-SERS

Poisoning with diquat (DQ) and paraquat (PQ) herbicides has been a public health problem. Unfortunately, rapid detection in biofluids remains challenging. Herein, a hyphenated approach of electro-enhanced adsorption, solid-phase microextraction, and surface-enhanced Raman spectroscopy (EE−SPME−SERS) was exploited for rapid and sensitive in situ analysis of DQ and PQ in human urine and plasma. A porous Ag fiber with an Au layer (p-Ag/Au fiber) was fabricated with multi-functions (SERS substrate, SPME sorbent, and working electrode). Clear trends could be observed between signal intensity and concentration of DQ or PQ with high reproducibility. The method detection limits (MDLs) calculated from the characteristic peak of DQ were 0.064 ppb and 0.65 ppb in urine and plasma, respectively. Corresponding MDLs for DQ and PQ in urine and plasma were 0.036 ppb and 0.35 ppb, respectively. The whole process of “extracting and detecting” was completed within 4 min with satisfactory recoveries. Notably, the EE−SPME−SERS technique could easily realize in situ analysis of DQ and PQ in biofluids with good selectivity, which is practical in clinical diagnosis. This EE−SPME−SERS method provides a potential avenue for efficient pretreatment and in situ poison detection in biological samples. [Display omitted] •Ultrafast EE-SPME-SERS method for in situ analyzing diquat and paraquat in biofluids.•Low detection limits ranging from 0.034 ppb to 0.65 ppb.•Good selectivity based on electrochemical adsorption.•p-Ag/Au fiber to realize hyphenation of enrichment, extraction, and SERS detection.