Wenpeng Zhang

Universal multilayer assemblies of graphene in chemically resistant microtubes for microextraction.

Graphene is a new kind of two-dimensional carbon nanomaterial with excellent properties and is promising for solid-phase microextraction (SPME). Plastic microtubes such as poly(tetrafluoroethylene) (PTFE) and poly(ether ether ketone) are ideal substrates for in-tube SPME. However, immobilization of graphene layers onto these materials is still a problem due to their nature of chemical resistance. In order to solve the problem, we proposed a novel method based on universal mussel-inspired polydopamine (PD) and layer-by-layer assembly of graphene in this work. To make a graphene assembly layer inside PTFE, the strategy includes two major steps. First, a PD layer is made on the PTFE surface by noncovalent interaction. Second, multilayer graphene is assembled on the PD layer by covalent interaction. By repeating these two steps, a functional graphene oxide (FGO)-modified PTFE tube with a controllable number of layers can be obtained. Morphology of the multilayer structure of graphene has been confirmed by scanning electronic microscopy. Formation of the covalent layer has also been characterized by Foourier transform infrared and X-ray photoelectron spectroscopy. It is very interesting that (FGO-PD)3-PTFE shows exceptional efficiency for SPME. Enrichment from 1082- to 2331-fold was achieved for six polyaromatic hydrocarbons (PAHs). An online SPME-HPLC-fluorescent detection method has been developed on the basis of (FGO-PD)3-PTFE. For qualitative analysis of PAHs, the method has low limits of detection of 0.05-0.1 pg/mL, which is significantly lower (up to 1000 times) than that reported in literature. The method shows wide linear range (0.3-200 pg/mL), good linearity (R(2) ≥ 0.9968), and good reproducibility (relative standard deviation < 3.4%). The method has been applied to determine PAHs in environmental samples. Good recoveries were obtained, ranging from 85.1% to 96.7%.

Growth of metal–organic framework HKUST-1 in capillary using liquid-phase epitaxy for open-tubular capillary electrochromatography and capillary liquid chromatography

Much attention is being paid to applying metal-organic frameworks (MOFs) as stationary phases in chromatography because of their fascinating properties, such as large surface-to-volume ratios, high levels of porosity, and selective adsorption. HKUST-1 is one of the best-studied face-centered-cubic MOF containing nano-sized channels and side pockets for film growth. However, growth of HKUST-1 framework inside capillary column as stationary phase for capillary electrochromatography is a challenge work. In this work, we carry out the growth of HKUST-1 on the inner wall of capillary by using liquid-phase epitaxy process at room temperature. The fabricated HKUST-1@capillary can be successfully used for the separation of substituted benzene including methylbenzene, ethylbenzene, styrene, chlorobenzene, bromobenzene, o-dichlorobenzene, benzene series, phenolic acids, and benzoic acids derivates. High column efficiency of 1.5×10(5) N/m for methylbenzene was achieved. The formation of HKUST-1 grown in the capillary was confirmed and characterized by scanning electron microscopy images, Fourier transform infrared spectra and X-ray diffraction. The column showed long lifetime and excellent stability. The relative standard deviations for intra-day and inter-day repeatability of the HKUST-1@capillary were lower than 7%.

Adsorptive behavior and solid-phase microextraction of bare stainless steel sample loop in high performance liquid chromatography.

In this work, we interestingly happened to observe the adsorption of stainless steel sample loop of HPLC. The adsorptive behaviors of the stainless steel loop toward different kinds of compounds were studied, including polycyclic aromatic hydrocarbons (PAHs), halogeno benzenes, aniline derivatives, benzoic acid derivatives, phenols, benzoic acid ethyl ester, benzaldehyde, 1-phenyl-ethanone and phenethyl alcohol. The adsorptive mechanism was probably related to hydrophobic interaction, electron-rich element-metal interaction and hydrogen bond. Universal adsorption of stainless steels was also testified. Inspired by its strong adsorptive capability, bare stainless steel loop was developed as a modification-free in-tube device for solid-phase microextraction (SPME), which served as both the substrate and sorbent and possessed ultra-high strength and stability. Great extraction efficiency toward PAHs was obtained by stainless steel loop without any modification, with enrichment factors of 651-834. By connecting the stainless steel loop onto a six-port valve, an online SPME-HPLC system was set up and an SPME-HPLC method has been validated for determination of PAHs. The method has exceptionally low limits of detection of 0.2-2pg/mL, which is significantly lower than that of reported methods with different kinds of sorbents. Wide linear range (0.5-500 and 2-1000pg/mL), good linearity (R(2)≥0.9987) and good reproducibility (RSD≤2.9%) were also obtained. The proposed method has been applied to determine PAHs in environmental samples. Good recoveries were obtained, ranging from 88.5% to 93.8%.

Graphene/polydopamine-modified polytetrafluoroethylene microtube for the sensitive determination of three active components in Fructus Psoraleae by online solid-phase microextraction with high-performance liquid chromatography.

Determination of bioactive compounds in traditional Chinese medicines and biological samples is usually interfered with by coexisting components in matrices. In this work, we prepared novel multilayer functional graphene/polydopamine-modified polytetrafluoroethylene microtube for selective solid-phase microextraction of three bioactive compounds in Fructus Psoraleae. Functional graphene/polydopamine-modified polytetrafluoroethylene microtube showed good extraction efficiency toward bavachin, isobavachalcone, and bavachinin; enrichment from 357- to 737-fold was obtained for these compounds. For qualitative analysis, an online solid-phase microextraction with high-performance liquid chromatography method was developed, which showed low limits of detection of 0.02 ng/mL by using UV detection, which is significantly more sensitive than previously reported methods. The proposed method has been used to determine bavachin, isobavachalcone, and bavachinin in Fructus Psoraleae, the contents of three compounds were quantified to be 64.0, 324.0, and 384.5 μg/g; recoveries were 93.4-101.1%. The proposed method has also been applied to determine bavachin, isobavachalcone, and bavachinin in rat plasma samples after oral administration of Fructus Psoraleae.

Tyrosinase inhibitor screening in traditional Chinese medicines by electrophoretically mediated microanalysis

A capillary-electrophoresis-based method for the screening of tyrosinase inhibitors in traditional Chinese medicines was developed. The method integrated electrophoretically mediated microanalysis with sandwich mode injection, partial filling, and rapid polarity switching techniques, and carried out on-column enzyme reaction and the separation of substrate and product. The conditions were optimized including the background electrolyte, mixing voltage, and the incubation time. Finally, the screening of nine standard natural compounds of traditional Chinese medicines was carried out. The inhibitors can be directly identified from the reduced peak area of the product compared to that obtained without any inhibitor. Chlorogenic acid (100 μM) showed inhibitory activity with the inhibitory percentage of 19.8%, while the other compounds showed no inhibitory activity. This method has great application potential in drug discovery from traditional Chinese medicines.

Layered double hydroxides based ion exchange extraction for high sensitive analysis of non-steroidal anti-inflammatory drugs

Layered double hydroxides (LDHs) are ideal sorbents for solid phase extraction (SPE) because of the excellent ion exchange capacity and high specific surface area. However, difficult elution of the analytes from the LDHs is a problem due to the strong ionic interaction between anions and LDHs. High concentrated NaOH solution is employed to elute the sample, but it not suitable for analyzing by HPLC. To solve this problem, a simple acid-base neutralization method was proposed after elution, and then the neutral samples were directly injected to HPLC for analysis. Nickel-aluminum layered double hydroxides (NiAl-LDHs) were synthesized by co-precipitation method and packed into a micro pipette tip for the extraction of three non-steroidal anti-inflammatory drugs (NSAIDs) including ketoprofen, naproxen and flurbiprofen from aqueous samples. After optimization of the experimental parameters such as the concentration of the NaOH, sample pH, sampling rate and sample volume, excellent extraction efficiency towards three NSAIDs was obtained with high enrichment factors of 28-32. A NiAl-LDHs based SPE-HPLC method was developed for quantitative analysis of NSAIDs, and the method showed low limits of detection (0.002-0.1ng/mL), good linearity (R2≥0.9995) and good reproducibility (intraday RSD≤4.37%). The developed method was also applied to the analysis of three NSAIDs in spiked human plasma and rat plasma after oral administration, which demonstrated the practicality of the proposed method.