Bingcheng Yang

Graphene nanoplatelets as a highly efficient solid-phase extraction sorbent for determination of phthalate esters in aqueous solution

Graphene nanoplatelet (GN) as a solid-phase extraction (SPE) sorbent in combination with high performance liquid chromatography has been used for the determination of five phthalate esters (PAEs) in aqueous solution. The operation parameters affecting the extraction efficiency were optimized. Comparative studies showed that GN was superior to other common SPE sorbents in terms of recovery and adsorption capacity. Under optimization conditions, detection limits of 0.09-0.33 ng mL(-1) were achieved for five PAEs and enrichment factors of 402-711 for the analytes were obtained. The proposed method was successfully applied for the determination of PAEs in tap water and drink samples with recoveries ranging from 87.7% to 100.9%.

Silica based click amino stationary phase for ion chromatography and hydrophilic interaction liquid chromatography

A silica based amino stationary phase was prepared by immobilization of propargylamine on azide-silica via click chemistry. This readily prepared click amino stationary phase demonstrated good selectivity in separation of common inorganic anions under ion chromatography (IC) mode, and the triazole ring in combination with free amino group was observed to play a major role for separation of the anions examined. On the other hand, the stationary phase also showed good hydrophilic interaction liquid chromatography (HILIC) properties in the separation of polar compounds including nucleosides, organic acids and bases. The retention mechanism was found to match well the typical HILIC retention.

A new reversed-phase/strong anion-exchange mixed-mode stationary phase based on polar-copolymerized approach and its application in the enrichment of aristolochic acids.

A novel silica-based reversed-phase/strong anion-exchange mixed-mode stationary phase named C18SAX was synthesized based on the polar-copolymerized approach. C18SAX stationary phase showed excellent compatibility with 100% aqueous mobile phase and comparable performance with commercial SunFire™ C18 column in terms of column efficiency and methylene selectivity. And the results indicated that hydrophobic interaction and anion-exchange mechanism dominate the separation process of aristolochic acids. The utility of C18SAX material-based SPE was demonstrated for the enrichment of aristolochic acids extracted from Caulis Aristochiae Manshuriensis. The SPE method was developed rapidly and simply by HPLC evaluation. Under the optimized SPE conditions, the average recoveries of aristolochic acid I and aristolochic acid II in crude sample were 72.36% and 105.59%, with RSDs of 5.77% and 1.13%, respectively. The complexity of sample matrices was significantly simplified after the SPE procedure and further preparation and purification of target compounds was performed on a preparative C18TDE column. Four aristolochic acids, including aristolochic acid I (31.8 mg), II (8.9 mg), IIIa (6.1 mg) and IVa (4.3 mg) were purified with HPLC purities all above 93%. The results proved that the aristolochic acids could be efficiently enriched by C18SAX material and easily eluted in acidic conditions, indicating its great potential in the enrichment of acidic compounds from complex matrices.

A novel click lysine zwitterionic stationary phase for hydrophilic interaction liquid chromatography

A novel type of zwitterionic HILIC stationary phase was prepared by covalently bonding the l-azido lysine on silica gel via click chemistry. The key intermediate azido lysine was synthesized by transformation the amino group in l-Boc-lysine to corresponding azido group and subsequent removal of the N-protected group (Boc). Finally, the azido lysine was covalently bonded to silica beads by click chemistry to get click lysine. Its structure was confirmed by FT-IR and elemental analysis. The new stationary phase showed good HILIC characteristics, when it was applied to separate polar and hydrophilic compounds, such as organic acids, cephalosporins and carbapenems. Compared with the commercial stationary phases, such as Atlantics HILIC and ZIC-HILIC, click lysine displayed better or similar chromatographic behaviors.

Synthesis of molecularly imprinted polymer sorbents and application for the determination of aminoglycosides antibiotics in honey.

Aminoglycoside antibiotic (AA)-selective molecularly imprinted polymer (MIP) sorbent was synthesized by polymerization of methacrylic acid and ethylene glycol dimethacrylate in the presence of streptomycin as template molecule. The MIP sorbent was in detail characterized and its performance was evaluated by selecting four model AAs including streptomycin, gentamicin, spectinomycin and dihydrostreptomycin. Relative to non-imprinted polymer (NIP), the MIPs exhibited much higher recognizable capacity and specificity to the AAs and negligible adsorption for non-AAs as well. In combination of hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS), the MIP sorbent-based solid phase extraction (SPE) was able to effectively determine the residue of four model AAs in honey samples with recovery ranging from 90% to 110%. The limit of detection (and the limit of quantitation) of streptomycin, gentamicin, spectinomycin and dihydrostreptomycin was 4.5 (15.0), 2.4 (8.0), 6.0 (20.0) and 1.8 (6.0) μg/kg, respectively. Relative standard deviations of intraday and inter-day assay under three spiked levels were 4.4-12.0% and 6.8-14.6%, respectively.

Use of a capacitance measurement device for surrogate noncontact conductance measurement

A capacitance to digital converter (AD7746) is used in the same mode as noncontact conductance detectors. The detector output is linearly proportional to specific conductance (sigma) at low sigma values but becomes nonlinear and reaches a plateau value at sigma approximately >0.75 mS/cm, regardless of the nature of the electrolyte. For all applications at sub- to low-mM concentrations, the device, available as an evaluation board, provides a very affordable nothing-else-required means of contactless surrogate conductivity detection from capillary scale to larger bore conduits. For the same measurement cell volume, the detector provides virtually the same limits of detection (LODs) as a standard galvanic contact conductivity detector in conventional scale suppressed conductometric ion chromatography. The detection limits deteriorate as the conduit inner diameter decreases.

A novel amide stationary phase for hydrophilic interaction liquid chromatography and ion chromatography.

A novel amide stationary phase (ASP) for hydrophilic interaction liquid chromatography (HILIC) has been prepared via the Click chemistry method. It was based on the strategy that the amino group of Asparagine was easily transferred to the corresponding azido group and then clicked onto terminal alkyne-silica gel in the presence of Cu(I)-based catalyst. For the tested polar compounds including nucleosides and nucleic acid bases, ASP-based column has demonstrated good performance in terms of separation efficiency and column stability, and the retention mechanism was found to match well the typical HILIC retention. In addition, the ASP described here showed much better selectivity in separation of inorganic anions under ion chromatography mode relative to other kinds of commercial ASP.

Study of matrix effects for liquid chromatography–electrospray ionization tandem mass spectrometric analysis of 4 aminoglycosides residues in milk

Matrix effect (ME) is always a major issue for the development of LC-MS/MS method. ME resulting from co-eluting residual matrix components can affect the ionization efficiency of target analytes, leading to quantification errors of the analytes of interest. The present work evaluates MEs of milk samples on simultaneous analysis of four aminoglycosides residues via LC-ESI/MS/MS including streptomycin, dihydrostreptomycin, spectinomycin and kanamycin. Approaches to reduce MEs were examined: optimization of the sample preparation, sample dilution and lower flow rate used. Three commercial sorbents were tested including Oasis MCX, Oasis HLB and Oasis WCX. WCX behaved better for all analytes, but high MEs (80.8-134.9%) were obtained. Therefore, a consecutive SPE of tC18-WCX was found to effectively reduce ME. Milk samples from different manufacturers were analyzed and low MEs (85.6-112.9%) were obtained.

Charge detector for the measurement of ionic solutes

We describe a flow-through ionic charge detector in the form of a three-compartmented system. A central water channel is separated from two outer channels bearing water (or a dilute electrolyte) by a cation-exchange membrane (CEM) and an anion-exchange membrane (AEM). Independent fluid input/output ports address all channels. One platinum electrode is put in each outer channel. When the AEM-side electrode is positive with respect to the CEM-side electrode and voltage (approximately 1-10 V) is applied, the observed background current is from the transport of H(+)/OH(-) through the CEM/AEM to the negative/positive electrodes, respectively. The H(+) and OH(-) are generated by the ionization of water, in part aided by the electric field. If an electrolyte (X(+)Y(-)) is injected in to the central channel, X(+) and Y(-) migrate through the CEM and AEM to the negative and positive electrodes, respectively, and generate a current pulse. The integrated area of the current signal (coulombs) elicited by this electrolyte injection is dependent on a number of variables, the most important being the central channel residence time and the applied voltage (V(app)); these govern the transport of the injected electrolyte to/through the membranes. Other parameters include electrode placement, fluid composition, and outer channel flow rates. For strong electrolytes, depending on the operating conditions, the current peak area (hereinafter called the measured charge signal, Q(m)) can both be less or more than the charge represented by the electrolyte injected (Q(i)). Q(m) is less than Q(i) if transport to/through the membranes is subquantitative. Q(m) can be greater than Q(i) at higher V(app). At constant V(app) more voltage is dropped across the membranes as the central channel becomes more conductive and water dissociation at the membrane surface is enhanced. Effectively, the membranes experience a greater applied voltage as the central channel becomes more conductive. The resulting additional current accompanying analyte introduction to the detector can substantially augment Q(m). Thus, the device is not an absolute coulometer although V(app) can be deliberately chosen to have Q(m) = Q(i) over at least a 10-fold concentration range. Importantly, equivalent amounts of diverse strong electrolytes (with substantially different conductivities) injected into the central channel produce the same charge signals. In ion chromatography, this results in identical calibration curves for all strong acid anions, obviating individual calibrations. Whereas with a conductivity detector (CD) only the ionized portion of a weak electrolyte responds, in the present charge detector (ChD), ions are actually removed, leading to further ionization and the detection of a proportionately greater analyte amount.

A multifunctional dual membrane electrodialytic eluent generator for capillary ion chromatography

A multifunctional electrodialytic generator (EDG) for capillary ion chromatography (CIC) is described. The same device can generate acidic, basic or saline eluents. Two oppositely charged ion exchange beads are used to fabricate the EDG; the dual ion exchanger configuration ensures the production of gas-free eluent, obviating the need of a gas removal device used with single ion exchanger EDGs. The ability of the same EDG to produce different eluents is governed solely by the choice of the respective feed solutions; this is presently demonstrated by generation of diverse eluents such as Na(2)CO(3)/NaHCO(3), CH(3)SO(3)H, and KNO(3). The EDG is implemented simply in a commercial cross fitting and has been tested up pressures to 2000psi. Under typical operating conditions, the zero current concentration (open circuit penetration, OCP) is negligible. The generated eluent concentration linearly increases with applied current with a slope that is essentially Faradaic. The device permits both isocratic and gradient operation with good reproducibility, as demonstrated by the analysis of anions using HCO(3)(-)/CO(3)(2-) EDG.