Dong Cao

Polydopamine-Coated Magnetic Nanoparticles for Enrichment and Direct Detection of Small Molecule Pollutants Coupled with MALDI-TOF-MS

Polydopamine-coated Fe(3)O(4) nanoparticles (Fe(3)O(4)@PDA NPs) were synthesized and applied as matrix for the detection of pollutants by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The synthesis of Fe(3)O(4)@PDA NPs was accomplished in 30 min by in situ polymerization of dopamine without any toxic reagent. Using Fe(3)O(4)@PDA NPs as matrix of MALDI-TOF, eleven small molecule pollutants (molecular weight from 251.6 to 499.3), including Benzo(a)pyrene (BaP), three perfluorinated compounds (PFCs), and seven antibiotics, were successfully detected in either positive or negative reflection mode without background interference. Furthermore, the Fe(3)O(4)@PDA NPs can also enrich trace amounts of hydrophobic target, such as BaP, from solution to nanoparticles surface. Then the Fe(3)O(4)@PDA-BaP can be isolated through magnetic sedimentation step and directly spotted on the stainless steel plate for MALDI measurement. With Fe(3)O(4)@PDA NPs as adsorbent and matrix, we also realized the analysis of BaP in tap water and lake water samples. Thus, a magnetic solid-phase extraction (MSPE)-MALDI-TOF-MS method was established for the measurement of BaP.

Molecular-Scale Investigation with ESI-FT-ICR-MS on Fractionation of Dissolved Organic Matter Induced by Adsorption on Iron Oxyhydroxides

Adsorption by minerals is a common geochemical process of dissolved organic matter (DOM) which may induce fractionation of DOM at the mineral-water interface. Here, we examine the molecular fractionation of DOM induced by adsorption onto three common iron oxyhydroxides using electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). Ferrihydrite exhibited higher affinity to DOM and induced more pronounced molecular fractionation of DOM than did goethite or lepidocrocite. High molecular weight (>500 Da) compounds and compounds high in unsaturation or rich in oxygen including polycyclic aromatics, polyphenols and carboxylic compounds had higher affinity to iron oxyhydroxides and especially to ferrihydrite. Low molecular weight compounds and compounds low in unsaturation or containing few oxygenated groups (mainly alcohols and ethers) were preferentially maintained in solution. This study confirms that the double bond equivalence and the number of oxygen atoms are valuable parameters indicating the selective fractionation of DOM at mineral and water interfaces. The results of this study provide important information for further understanding the behavior of DOM in the natural environment.

Comprehensive characterization of natural organic matter by MALDI- and ESI-Fourier transform ion cyclotron resonance mass spectrometry

Natural organic matter (NOM) is a complex and non-uniform mixture of organic compounds which plays an important role in environmental processes. Due to the complexity, it is challenging to obtain fully detailed structural information about NOM. Although Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) has been demonstrated to be a powerful tool for providing molecular information about NOM, multiple ionization methods are needed for comprehensive characterization of NOM at the molecular level considering the ionizing selectivity of different ionization methods. This paper reports the first use of matrix assisted laser desorption/ionization (MALDI) method coupled with FT-ICR-MS for molecular characterization of NOM within a mass range of 200-800 Da. The mass spectral data obtained by MALDI were systematically compared with data generated by electrospray ionization (ESI). It showed that complementary molecular information about NOM which could not be detected by ESI, were provided by MALDI. More unsaturated and aromatic constituents of NOM with lower O/C ratio (O/C ratio<0.5) were preferentially ionized in MALDI negative mode, whereas more polar constituents of NOM with higher O/C ratio were preferentially ionized in ESI negative mode. Molecular anions of NOM appearing at even m/z in MALDI negative ion mode were detected. The results show that NOM molecules with aromatic structures, moderate O/C ratio (0.7>O/C ratio>0.25) and lower H/C ratio were liable to form molecular anions at even m/z, whereas those with higher H/C ratio are more likely to form deprotonated ions at odd m/z. It is speculated that almost half of the NOM molecules identified by MALDI may be aromatic or condensed aromatic compounds with special groups which are liable to absorb electron from other molecules to generate free radical anions during MALDI ionization.

Ion Accumulation Time Dependent Molecular Characterization of Natural Organic Matter Using Electrospray Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Natural organic matter (NOM) is a complex organic mixture and plays a crucial role in environmental processes. By using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), detailed molecular information on NOM could be achieved. In this paper, ion accumulation time (IAT), a key parameter of FTICR-MS for complex mixture detection, was the focus, and its effect on the molecular characterization of NOM by FTICR-MS was systematically investigated. A notable feature of selective detection of NOM molecules by FTICR-MS with different IAT was observed. Most of the polar molecules with high O/C ratio (O/C ratio >0.5) could be easily detected by FTICR-MS with a short IAT, but extending IAT led to the ion intensities of these molecules decreasing or even disappearing. Meanwhile, a large number of unsaturated and aromatic molecules with low O/C ratio (O/C ratio <0.6) and low polarity, all of which could not be observed with a short IAT, were remarkably detected by extending IAT. Results also revealed that the unsaturated and aromatic molecules, which could only be observed by extending the IAT, were not generated by the fragmentation of molecules in NOM or from the dissociation of NOM aggregations but originally existed in NOM samples. The selective detection of NOM molecules caused by IAT extension was possibly attributed to their different polarity and different stability in the collision cell. On the basis of these results, a novel strategy of combining mass spectrometric data of NOM obtained with different IAT by FTICR-MS was proposed. With this strategy, more than 4715 CHO-molecular formulas were assigned, where about 2000 more formulas were obtained in comparison with using a short IAT (2733 CHO-molecular formulas identified) solely. The strategy is simple and robust and can be used as an alternative method to obtain more molecular information on NOM in the environment.

Solid-phase extraction-stepwise elution (SPE-SE) procedure for isolation of dissolved organic matter prior to ESI-FT-ICR-MS analysis

Characterization of dissolved organic matter (DOM) at the molecular level will greatly improve our understanding of its bio-geochemical role in controlling the fate of contaminants in the environment, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is the most powerful analytical technique for this purpose. Before FT-ICR-MS analysis, isolation, desalination and concentration of DOM are necessary, and solid-phase extraction (SPE) is the most widely applied pretreatment procedure. However, some molecular information is lost using conventional SPE methods. Here, we propose a novel strategy of SPE enrichment using stepwise elution (SPE-SE). Compounds in DOM were divided into three fractions by this SPE-SE procedure according to their polarity and ionization efficiency. The diversity of DOM molecules identified by ESI-FT-ICR-MS using SPE-SE exceeded those using conventional SPE methods by more than 50%. This method is feasible and has the potential to be used as a pretreatment strategy for complex DOM matrixes prior to ESI-FT-ICR-MS analysis, especially for those rich in nitrogenous molecules, carbohydrates, lipids and/or aromatic compounds.

Discovery of a Novel Polyfluoroalkyl Benzenesulfonic Acid around Oilfields in Northern China

The existence of more than 3000 per- and polyfluoroalkyl substances (PFASs) on the global market has prompted the identification and hazard characterization of hitherto unknown PFASs. In the present study, a novel PFAS, sodium p-perfluorous nonenoxybenzenesulfonate (OBS), was identified using Orbitrap MS/MS in water samples around a suspected application area, Daqing Oilfield, China. The peak OBS concentration was 3.2 × 103 ng/L in a sample taken near the oil well with the longest production history in Daqing. The concentrations of OBS and contribution to the sum of PFASs in surface waters displayed considerable variation among the three sampling areas (mean levels at 6.9, 50, and 5.6 × 102 ng/L with mean percentages at 9.8%, 45%, and 69% in the background, new and old oilfield areas respectively) confirming that the density of oil wells and the oil production history are important factors influencing OBS contamination in the studied areas. A preliminary assessment of acute toxicity and environmental fate indicates that OBS exhibits similar toxicity and environmental persistence to perfluorooctanesulfonic acid (PFOS). The widespread occurrence of OBS, in conjunction with its potential hazard properties, underscores the need to further study on the bioaccumulation and potential for human exposure.

N-doped graphene quantum dots as a novel highly-efficient matrix for the analysis of perfluoroalkyl sulfonates and other small molecules by MALDI-TOF MS

N-doped graphene quantum dots (N-GQDs) were synthesized by a facile, rapid method based on a time-efficient bottom-up strategy. In addition, solid-phase extraction (SPE) was, for the first time, applied to the purification of N-GQDs, which was very time-efficient compared to the traditional dialysis method and facilitated the removal of salts and the obtention of N-GQDs with homogeneous size. The as-prepared N-GQDs, with good solubility in both organic solvents and water, were successfully employed as a novel matrix for the analysis of perfluoroalkyl sulfonates (PFSs) and other small molecules by MALDI-TOF MS. Compared with conventional matrices, N-GQDs displayed a superior efficiency, less background interferences, high sensitivity and good repeatability. The presence of polymorphous nitrogen species in GQDs and the π-conjugated structure contributed to an enhanced desorption/ionization efficiency. The homogeneity of the material provided a good repeatability. Furthermore, quantitative detection of perfluorooctane sulfonate (PFOS) in environmental samples was successfully determined by MALDI-TOF MS using N-GQDs; this suggests that N-GQDs have a potential to play an important role in the rapid, sensitive and precise analysis of trace levels of organic pollutants, such as PFSs. Thus, it is of great interest to broaden this method to apply it to the analysis of other small-molecular weight organic pollutants in the future.

Covalent-Organic Frameworks as Adsorbent and Matrix of SALDI-TOF MS for the Enrichment and Rapid Determination of Fluorochemicals

An imine-linked two-dimensional covalent organic framework, via the condensation of 1, 3, 5-triformylbenzene and p-phenylenediamine (COF-LZU1) is used as both adsorbent and matrix of SALDI-TOF MS for the rapid analysis of fluorochemicals. COF-LZU1 can efficiently assist the laser desorption/ionization of fluorochemicals and function well in negative ion modes without background interference. COF-LZU1 with large surface area, high porosity and suitable hydrophobicity, also can enrich trace amounts of fluorochemicals from solution effectively and quickly through hydrophobic interaction. Therefore, COF-LZU1-solid-phase extraction (SPE) enrichment is combined with SALDI-TOF MS measurement to provide the rapid and high sensitive analysis of fluorochemicals in water samples. The LODs of fluorochemicals can reach ppt or subppt levels. Besides, this method shows robust anti-interference ability. With the assistance of COF-LZU1, trace levels of fluorochemicals could be quantitatively and sensitively analyzed from environmental water samples in a rapid, sensitive and convenient way.