Xiangfeng Chen

Metal–organic framework MIL-53(Al) as a solid-phase microextraction adsorbent for the determination of 16 polycyclic aromatic hydrocarbons in water samples by gas chromatography–tandem mass spectrometry

In this paper, the potential applications of metal-organic framework (MOF) materials as fiber coatings for the solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs) in water samples were explored. Fibers coated with MIL-53(Al, Cr, Fe) materials were fabricated by an adhesive method for SPME. The quantitation was performed by gas chromatography-tandem mass spectrometry (GC-MS/MS) using the multiple reaction monitoring mode. Among the three MIL-53(M) coatings, MIL-53(Al) showed the highest extraction efficiency towards PAHs under the current fabrication procedure. Under optimized conditions, the MIL-53(Al)-coated fiber showed good precision (relative standard deviation <12.5%), low detection limits (0.10 ng L(-1) to 0.73 ng L(-1), S/N = 3), and good linearity (R(2) > 0.98) for aqueous solutions containing 16 PAH . The fiber also offered high thermal and chemical stability. The method developed based on MIL-53(Al) SPME-GC-MS/MS was successfully applied in the analysis of real water samples. Based on the simulation results, the PAHs were adsorbed on MIL-53(Al) primarily through the hydrophobic and π-π interactions between PAHs and the organic linker of the material. The results presented in this paper indicate that water-stable MOF materials have great potential for the SPME of aromatic compounds in water samples.

Fe3O4@MOF core–shell magnetic microspheres for magnetic solid-phase extraction of polychlorinated biphenyls from environmental water samples

Fe3O4@MIL-100 core-shell magnetic microspheres were, for the first time, used as the sorbent for the magnetic solid-phase extraction (MSPE) of polychlorinated biphenyls at trace levels in environmental water samples. GC coupled with tandem MS was used for sample quantification and detection. The Box-Behnken design was used to determine the optimum extraction parameters influencing extraction efficiency through response surface methodology. Under the optimized conditions, the developed method showed good linearity within the range of 5-4000ngL(-1), low limits of detection (1.07-1.57ngL(-1); signal-to-noise ratio=3:1), and good extraction repeatability (relative standard deviation<12%; n=5). Environmental samples collected from the Yellow River, local lake, wastewater, and snow water were processed using the developed method. The results demonstrated that the Fe3O4@MOF core-shell magnetic microspheres are promising sorbents in the MSPE of aromatic pollutants from environmental water samples.

In situ hydrothermal growth of ytterbium-based metal–organic framework on stainless steel wire for solid-phase microextraction of polycyclic aromatic hydrocarbons from environmental samples

In this paper, we report the use of a porous ytterbium-based metal-organic framework (Yb-MOF) coating material with good thermal stability for the headspace solid-phase microextraction (HS-SPME) of polycyclic aromatic hydrocarbons (PAHs) from environmental samples. The Yb-MOF thin films, grown in situ on stainless steel wire in solution, exhibited high selectivity and sensitivity toward PAHs. Under the optimal conditions, the novel fibers achieved large enrichment factors (130-2288), low limits of detection (0.07-1.67ngL(-1)), and wide range of linearity (10-1000ngL(-1)) for 16 PAHs in the tested samples. The novel fiber was successfully used in the analysis of PAHs in real environmental samples. These results demonstrated that Yb-MOF is a promising coating material for the SPME of PAHs at trace levels from environmental samples.

Feasibility of metal-organic nanotubes [Cu3(μ3-O)(μ-OH)(triazolate)2]+-coated fibers for solid-phase microextraction of polychlorinated biphenyls in water samples.

Metal-organic nanotubes (MONTs), a novel class of hybrid materials, have attracted considerable attention because of their uniform and fixed internal diameters, impressive topological structures, and versatile applications. However, to the best of our knowledge, no studies on MONTs coating fabrication for solid-phase microextraction are yet available. The aim of this work is to investigate the feasibility of using [Cu3(μ3-O)(μ-OH)(triazolate)2]+ as a solid-phase microextraction coating material to enrich trace levels of polychlorinated biphenyls in water samples. The novel [Cu3(μ3-O)(μ-OH)(triazolate)2]+-coated fibers achieved large enhancement factors (396–1343), low limits of detection (3.9–21.7 pg L−1), and wide linearity (0.1–500 ng L−1) for detecting polychlorinated biphenyls. Relative standard deviations obtained ranged from 2.12 to 7.22%, and spiked PCBs recoveries (spiking concentrations of 1 and 5 ng L−1) in four environmental water samples ranged from 71.3 to 104%. These findings indicate that [Cu3(μ3-O)(μ-OH)(triazolate)2]+ as a solid-phase microextraction coating material is an excellent alternative for the rapid and sensitive analysis of trace levels of polychlorinated biphenyls in the environment.

Magnetic metal–organic framework–titanium dioxide nanocomposite as adsorbent in the magnetic solid-phase extraction of fungicides from environmental water samples

In this work, a core-shell Fe3O4@SiO2@MOF/TiO2 nanocomposite was synthesized and used to as adsorbent for magnetic solid-phase extraction (MSPE) of triazole fungicides from environmental water samples. Five triazole fungicides, namely, triadimenol, hexaconazole, diniconazole, myclobutanil, and tebuconazole, were selected as target analytes for MSPE. These analytes were quantitatively adsorbed on microspheres, and the sorbents were separated from the solution by using a magnet. The analytes were desorbed by methanol and determined through liquid-chromatography coupled with tandem mass spectrometry. The extraction parameters affecting the extraction efficiency were optimized through response surface methodology. The limits of detection and limits of quantification for the selected fungicides were 0.19-1.20ngL(-1) and 0.61-3.62ngL(-1), respectively. The proposed method was applied to determine the concentration of fungicides in actual environmental water samples. The accuracy of the proposed method was evaluated by measuring the recovery of the spiked samples. The satisfying recoveries of the four water samples ranged from 90.2% to 104.2%. Therefore, the magnetic metal-organic framework/TiO2 nanocomposite based MSPE is a potential approach to analyze fungicides in actual water samples.

Transition metal ions: charge carriers that mediate the electron capture dissociation pathways of peptides.

Electron capture dissociation (ECD) of model peptides adducted with first row divalent transition metal ions, including Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+, were investigated. Model peptides with general sequence of ZGGGXGGGZ were used as probes to unveil the ECD mechanism of metalated peptides, where X is either V or W; and Z is either R or N. Peptides metalated with different divalent transition metal ions were found to generate different ECD tandem mass spectra. ECD spectra of peptides metalated by Mn2+ and Zn2+ were similar to those generated by ECD of peptides adducted with alkaline earth metal ions. Series of c-/z-type fragment ions with and without metal ions were observed. ECD of Fe2+, Co2+, and Ni2+ adducted peptides yielded abundant metalated a-/y-type fragment ions; whereas ECD of Cu2+ adducted peptides generated predominantly metalated b-/y-type fragment ions. From the present experimental results, it was postulated that electronic configuration of metal ions is an important factor in determining the ECD behavior of the metalated peptides. Due presumably to the stability of the electronic configuration, metal ions with fully-filled (i.e., Zn2+) and half filled (i.e., Mn2+) d-orbitals might not capture the incoming electron. Dissociation of the metal ions adducted peptides would proceed through the usual ECD channel(s) via “hot-hydrogen” or “superbase” intermediates, to form series of c-/z•- fragments. For other transition metal ions studied, reduction of the metal ions might occur preferentially. The energy liberated by the metal ion reduction would provide enough internal energy to generate the “slow-heating” type of fragment ions, i.e., metalated a-/y- fragments and metalated b-/y- fragments.

Formation of Peptide Radical Cations (M+·) in Electron Capture Dissociation of Peptides Adducted with Group IIB Metal Ions

Peptides adducted with different divalent Group IIB metal ions (Zn2+, Cd2+, and Hg2+) were found to give very different ECD mass spectra. ECD of Zn2+ adducted peptides gave series of c-/z-type fragment ions with and without metal ions. ECD of Cd2+ and Hg2+ adducted model peptides gave mostly a-type fragment ions with M+• and fragment ions corresponding to losses of neutral side chain from M+•. No detectable a-ions could be observed in ECD spectra of Zn2+ adducted peptides. We rationalized the present findings by invoking both proton-electron recombination and metal-ion reduction processes. As previously postulated, divalent metal-ions adducted peptides could adopt several forms, including (a) [M + Cat]2+, (b) [(M + Cat – H) + H]2+, and (c) [(M + Cat – 2H) + 2H]2+. The relative population of these precursor ions depends largely on the acidity of the metal–ion peptide complexes. Peptides adducted with divalent metal-ions of small ionic radii (i.e., Zn2+) would form predominantly species (b) and (c); whereas peptides adducted with metal ions of larger ionic radii (i.e., Hg2+) would adopt predominantly species (a). Species (b) and (c) are believed to be essential for proton-electron recombination process to give c-/z-type fragments via the labile ketylamino radical intermediates. Species (c) is particularly important for the formation of non-metalated c-/z-type fragments. Without any mobile protons, species (a) are believed to undergo metal ion reduction and subsequently induce spontaneous electron transfer from the peptide moiety to the charge-reduced metal ions. Depending on the exothermicity of the electron transfer reaction, the peptide radical cations might be formed with substantial internal energy and might undergo further dissociation to give structural related fragment ions.

Magnetic porous carbon derived from a bimetallic metal–organic framework for magnetic solid-phase extraction of organochlorine pesticides from drinking and environmental water samples

In this work, magnetic porous carbon material derived from a bimetallic metal-organic framework was explored as an adsorbent for magnetic solid-phase extraction of organochlorine pesticides (OCPs). The synthesized porous carbon possessed a high specific surface area and magnetization saturation. The OCPs in the samples were quantified using gas chromatography coupled with a triple quadrupole mass spectrometer. The experimental parameters, including the desorption solvent and conditions, amount of adsorbent, extraction time, extraction temperature, and ionic strength of the solution, were optimized. Under optimal conditions, the developed method displayed good linearity (r>0.99) within the concentration range of 2-500ngL-1. Low limits of detection (0.39-0.70ngL-1, signal-to-noise ratio=3:1) and limits of quantification (1.45-2.0ngL-1, signal-to-noise ratio=10:1) as well as good precision (relative standard deviation<10%) were also obtained. The developed method was applied in the analysis of OCPs in drinking and environmental water samples.

Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition

PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

Hollow fiber-protected metal–organic framework materials as micro-solid-phase extraction adsorbents for the determination of polychlorinated biphenyls in water samples by gas chromatography-tandem mass spectrometry

A novel modified micro-solid-phase extraction (μ-SPE) device was developed in this study using hollow fiber-protected metal–organic framework (MOF) materials as sorbents. Polychlorinated biphenyls (PCBs) were used as model compounds. Gas chromatography with tandem mass spectrometry (GC-MS/MS) was used for sample quantification and detection. Important factors that affect the extraction were investigated and optimized in detail. The developed μ-SPE-GC-MS/MS method had low limits of detection (0.15 ng L−1 to 0.63 ng L−1, S/N = 3), relatively high precision (relative standard deviation <13.5%), and good linearity in the range of 5–1000 ng L−1 for seven PCBs under optimized conditions. The μ-SPE device was more robust than the traditional “envelope” type device and could be used for more than 80 replicate extractions without performance loss. The proposed method was successfully used for analyzing environmental water samples. The results obtained in this paper demonstrate that the hollow fiber protection of MOF materials is an effective type of μ-SPE for aromatic pollutant extraction in water samples.