Screening of Toxic Chemicals in a Single Drop of Human Whole Blood Using Ordered Mesoporous Carbon as a Mass Spectrometry Probe

Abstract

Surface-enhanced laser desorption/ionization (SELDI) is a versatile and high-throughput mass spectrometry (MS) technique that uses a probe for extraction, enrichment, desorption, and ionization of target analytes. Here we report ordered mesoporous carbon as a new SELDI probe for rapid screening and identification of trace amount of toxic chemicals in a single drop of human whole blood without complicated sample preparation procedures. We demonstrate that ordered mesoporous carbon not only can selectively enrich a wide variety of low-mass toxic compounds from whole blood samples but also can be used as an excellent matrix to assist the laser desorption/ionization process of small molecules with low background noise, high repeatability, and good salt tolerance. High sensitivity (detection limits at ppt levels) and good reproducibility for typical toxic compounds were obtained. With CMK-8 as a SELDI probe, we successfully identified and screened six perfluorinated compounds in a single drop of whole blood collected from workers in a perfluorochemical plant. The method was also validated with complex samples such as human urine and environmental water samples. With distinct advantages such as simplicity, rapidness, minimal sample requirement, and high reliability, this method keeps great promise for various aspects of application.H igh-throughput mass spectrometry (MS) techniques for toxic chemicals are highly desired in many fields such as modern healthcare, public safety, forensics, exposomics, and environmental health studies. 1−4 Surface-enhanced laser desorption/ ionization time-of-flight mass spectrometry (SELDI-TOF MS), a variant mode of matrix-assisted laser desorption/ionization (MALDI)-TOF MS, provides a potentially powerful tool for high-throughput screening. 5−7 SELDI-TOF MS uses a probe for extraction, enrichment, desorption, and ionization of target analytes. The probe is the key of SELDI technique and an ideal probe must satisfy two requirements: (1) it is capable of selectively capturing and enriching the target compounds from complex sample matrix, and (2) it can serve as a highly efficient matrix or surface to assist the LDI process in MS detection. However, only a few materials have been reported to be available as SELDI probes 8−13 due to such rigorous requirements. This seriously limits the application of the SELDI technique. Until now, SELDI-TOF MS has mainly gained applications in clinical proteomics, whereas its applications in other fields are rarely reported. Therefore, development of new probes with high sensitivity and selectivity is of great significance for the SELDI MS technique.Ordered mesoporous carbon, with intriguing properties such as well-ordered nanopore structure, ultrahigh surface area, tunable pore size, thermal and chemical stability has shown tremendous potentials in various fields, including separation, catalyst supports, adsorption, energy storage/conversion, and biomedical engineering. 13−17 In particular, the nanosized pore structure endows ordered mesoporous...

Negative ion laser desorption/ionization time‐of‐flight mass spectrometric analysis of small molecules by using nanostructured substrate as matrices

“…More recently, ordered mesoporous carbons were examined as matrix and the corresponding analytical approach so called surface‐enhanced laser desorption/ionization (SELDI) probe for high throughput screening and identification of trace amount of toxic chemicals in human whole blood was proposed (Figure ). In this work, several commercial mesoporous materials (CMK‐3, CMK‐8, SBA‐15, and MCM‐41) were compared and the results demonstrated that CMK‐8 has good performance in negative ion LDI‐TOF MS, which produced high sensitivity, low background noise in the low‐mass region, good reproducibility and high salt tolerance.…”

“…Scheme showing the procedures for the screening of toxic chemicals in a single drop of human whole blood. Reprinted with permission from Huang et al Copyright 2016 American Chemical Society…”

Nanomaterials as Assisted Matrix of Laser Desorption/Ionization Time-of-Flight Mass Spectrometry for the Analysis of Small Molecules

“…Recently, Huang et al [116] reported a LDI-TOF MS method for screening and identification of toxic compounds in a single drop of human whole blood by using highly ordered mesoporous carbon as both adsorbent and matrix (Figure 4). Among the studied materials including CMK-8, CMK-3, SBA-15, MCM-41, graphene and CHCA, CMK-8 provided the best performance for analysis of target compounds, such as bisphenol S (BPS), TBBPA, BDE-47, PCP, E2 and PFOS.…”

Recent progress in the application of nanomaterials in the analysis of emerging chemical contaminants

“…Some new carbon NMs have also emerged derived from their original forms by chemical modications, such as oxidation, 27,28 sulfonation, [29][30][31] and uorination. [32][33][34] New analogs of carbon NMs, such as graphynes, [35][36][37][38][39][40] graphene oxide nanoribbons (GONRs), 27,41 ordered mesoporous carbon, 42,43 and carbon nitride nanosheets, [44][45][46][47] have attracted increasing interest owing to their extraordinary physical and chemical properties. For ordered mesoporous carbon, its size-selective adsorption ability has been used to selectively enrich low-mass ECCs.…”

“…With CMK-8 as a SELDI probe, they successfully identied and screened six peruorinated compounds in a single drop of human whole blood without any complicated sample preparation procedure. The method provides a promising tool for high-throughput analysis of MS. 43 Recently, Huang et al prepared uorographene (FG) by a one-step exfoliation of uorographite. Based on the unique structure and self-assembly properties, FG was used as a MALDI matrix and SELDI probe with higher sensitivity and better reproducibility than other graphene-based materials.…”