Longxing Wang

New reversed-phase/anion-exchange/hydrophilic interaction mixed-mode stationary phase based on dendritic polymer-modified porous silica.

A novel dendritic polymer-modified silica (DPS) stationary phase was prepared by a divergent synthesis scheme starting from propylamine on silica by consecutive amine-epoxy reactions with 1,4-butanedioldiglycidyl ether and aniline. Both elemental analysis and infrared spectra data shows the successful growth of dendritic polymer on silica particles. The carbon and nitrogen contents increased with an increasing number of reaction cycles and achieved 25.2% and 2.1% (w/w) after 11 reaction cycles. The combination of a phenyl ring with a quaternary ammonium, or a tertiary amine at the branch point along with embedded polar functionalities (including ether and hydroxyl groups) in the branch, generated hydrophobic, electrostatic, as well as hydrophilic interactive domains. Depending on solute structure and mobile phase composition, the DPS stationary phase provided multiple retention mechanisms, including reversed phase (RP), anion-exchange (AEX), and hydrophilic interactions. The RP capability achieved separation of polycyclic aromatic hydrocarbons. Basic, neutral and acidic molecules were well separated under RP/AEX mixed mode. Effective separation of small polar compounds (such as nucleobases and nucleosides) was also obtained under hydrophilic interaction liquid chromatography (HILIC) mode.

Dendrimer-functionalized mesoporous silica as a reversed-phase/anion-exchange mixed-mode sorbent for solid phase extraction of acid drugs in human urine.

A new dendrimer-functionalized mesoporous silica material based on large-pore 3D cubic Korea Advanced Institute of Science and Technology-6 (KIT-6) was synthesized by the growing of dendritic branches inside the mesopores of aminopropyl functionalized KIT-6. Detailed physical characterizations using transmission electron microscopy, nitrogen adsorption-desorption measurements, Fourier transform infrared (FTIR) spectroscopy, and elemental analysis reveal that the multifunctional dendrimers have been grown successfully within the confined spaces of mesopores. Although the 3D ordered mesoporous architecture of KIT-6 was well preserved, there was a significant and continuous decrease in pore size, specific surface area (SBET) and pore volume when increasing dendrimer generation up to six. In order to get a compromise between the SBET, pore size and density of functionalities, the dendrimer-functionalized KIT-6 (DF-KIT-6) for generation 2 (SBET, 314.2 m(2) g(-1); pore size, 7.9 nm; carbon and nitrogen contents, 19.80% and 1.92%) was selected for solid phase extraction (SPE) applications. The DF-KIT-6 was then evaluated as a reversed-phase/anion-exchange mixed-mode sorbent for extraction of the selected acidic drugs (ketoprofen, KEP; naproxen, NAP; and ibuprofen, IBU), since the dendrimers contained both hydrocarbonaceous and amine functionalities. The effective parameters on extraction efficiency such as sample pH and volume, type and volume of eluent and wash solvents were optimized. Under the optimized experimental conditions, the DF-KIT-6 based SPE coupled with HPLC-UV method demonstrated good sensitivity (0.4-4.6 ng mL(-1) detection of limits) and linearity (R(2)>0.990 for 10-2000 ng mL(-1) of KEP and IBU, and 1-200 ng mL(-1) of NAP). The potential use of DF-KIT-6 sorbent for preconcentration and cleanup of acid drugs in human urine samples was also demonstrated. Satisfactory recoveries at two spiking levels (30 and 300 ng mL(-1) for KEP and IBU, 3 and 30 ng mL(-1) for NAP) were obtained in the range of 85.7-113.9% with RSD values below 9.3% (n=3).

Rapid quantification of iridoid glycosides analogues in the formulated Chinese medicine Longdan Xiegan Decoction using high-performance liquid chromatography coupled with mass spectromentry

Longdan Xiegan Decoction (LXD) is a formulated preparation composed of 10 ingredient herbs, with iridoids as the main bioactive components. In this study, a rapid, simple and reliable method of simultaneous determination of four iridoid glycosides in LXD using high-performance liquid chromatography (HPLC) coupled with electrospray ionization mass spectrometry (MS) was first developed and validated. The four iridoid glycosides references were isolated from LXD extract and purified using a preparative HPLC chromatography. The sample preparation for quantification comprised of a simple ultrasonic extraction and the satisfactory chromatographic separation of the four structurally similar iridoid glycosides was effected in less than three minutes on a CAPCELL PAK C(18) MGII column (3 microm, 100 mm x 2.0 mm), using an elution system of 10% methanol and their concentrations in different batches of LXD and ingredient herbs were simultaneously determined by HPLC-MS/MS using a multiple reaction monitoring (MRM) mode. The method was validated with respect to the overall intra- and inter-day variation (RSD less than 8%) and the limits of quantification for the four iridoid glycosides were 35, 20, 37 and 33 ng/mL, respectively.

Bioaccumulation and trophic transfer of polybrominated diphenyl ethers (PBDEs) in a marine food web from Liaodong Bay, North China.

The concentrations of 21 polybrominated diphenyl ethers (PBDEs) congeners were analyzed in organisms within a marine food web collected from the Liaodong Bay, North China. The total concentrations of PBDEs in all samples ranged from 0.87 to 91.4 ng g(-1) lipid weight (lw). BDE-47 was the predominant congener and had a concentration ranging from 0.30 to 36.1 ng g(-1) lw. The trophic magnification factors (TMF) of the PBDEs were calculated using the trophic levels obtained from the stable nitrogen isotope ratios. The TMF value of ∑PBDEs was 3.50 for the entire food web and 2.21 for the food web excluding seabirds. Four concentration ratios, BDE-99/BDE-100, BDE-99/BDE-47, BDE-153/BDE-154 and BDE-183/BDE-154, decreased linearly with the increase of the trophic levels in the invertebrates and the fishes (p<0.01). The results suggested that the PBDEs were steadily metabolized in the trophic transfer process along the food chain.

Design and optimization of coating structure for the thermal barrier coatings fabricated by atmospheric plasma spraying via finite element method

Abstract The first prerequisite for fabricating the thermal barrier coatings (TBCs) with excellent performance is to find an optimized coating structure with high thermal insulation effect and low residual stress. This paper discusses the design and optimization of a suitable coating structure for the TBCs prepared by atmospheric plasma spraying (APS) using the finite element method. The design and optimization processes comply with the rules step by step, as the structure develops from a simple to a complex one. The research results indicate that the suitable thicknesses of the bond-coating and top-coating are 60–120 μm and 300–420 μm, respectively, for the single ceramic layer YSZ/NiCoCrAlY APS-TBC. The embedded interlayer (50 wt.%YSZ + 50 wt.%NiCoCrAlY) will further reduce the residual stress without sacrificing the thermal insulation effect. The double ceramic layer was further considered which was based on the single ceramic layer TBC. The embedded interlayer and the upper additional ceramic layer will have a best match between the low residual stress and high thermal insulation effect. Finally, the optimized coating structure was obtained, i.e., the La2Ce2O7(LC)/YSZ/Interlayer/NiCoCrAlY coating structure with appropriate layer thickness is the best choice. The effective thermal conductivity of this optimized LC/YSZ/IL/BL TBC is 13.2% lower than that of the typical single ceramic layer YSZ/BL TBC.

Investigation of Crack Propagation Behavior of Atmospheric Plasma-Sprayed Thermal Barrier Coatings under Uniaxial Tension Using the Acoustic Emission Technique

Uniaxial tension is a common technique to characterize the adhesive strength of plasma-sprayed thermal barrier coatings (TBCs). In this work, the crack initiation, growth, and propagation behavior of atmospheric plasma-sprayed TBCs during uniaxial tension testing was investigated using the acoustic emission (AE) technique, x-ray diffraction analysis, scanning electron microscopy, and the finite-element method (FEM). The experimental results indicated that the position of crack initiation was usually located within the ceramic layer, and the crack tended to propagate along the tension direction, with some key horizontal cracks reaching the metallic layer/ceramic layer interface, after which vertical cracks initiating at the middle and lower segments of the horizontal cracks propagated along the interface. When some critical cracks were formed at the interface and a series of assembled splats separated from the coating, the coating failed completely. The AE signal could be divided into three typical stages, corresponding to the three stages of the stress–stain curve under uniaxial tension. Detailed analysis of the AE signal associated with the failure behavior was performed. The dynamic propagation patterns of the key cracks in the ceramic layer during the tension process were simulated using the FEM, whose results further confirmed the conclusions drawn from the experimental results.

Hexabromocyclododecane and tetrabromobisphenol A in sediments and paddy soils from Liaohe River Basin, China: Levels, distribution and mass inventory.

Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) are two kinds of brominated flame retardants and widely present in the environment and biota. The levels, spatial distributions and mass inventories of HBCD and TBBPA were investigated in sediments and paddy soils from the Liaohe River Basin in northeast China. The concentrations of ΣHBCD and TBBPA were in the range of not detected (nd) to 4.02ng/g dry weight (dw) and 0.03 to 4.06ng/g dw, respectively. γ-HBCD was dominated in sediments, while the abundance of α-HBCD was relatively high in paddy soils. The spatial distributions of HBCD and TBBPA in surface sediments and paddy soils indicated that the local point-input was their major source. The significant correlation between total organic carbon (TOC) contents and the HBCD levels suggested that TOC content also exerted an influence on the distribution of HBCD in sediments. Meanwhile, it was found that the irrigation with river water was not the major transportation pathway of HBCD and TBBPA in paddy soils. Based on the study, it was estimated that there were about 1.67tons HBCD and 2.20tons TBBPA deposited into sediments of the Liaohe River system every year. The total mass inventories of HBCD and TBBPA in sediments were far higher than that in paddy soils.

[Determination of undecanoic acid and 13-methyl-tetradecanoic acid connected to the glyceride with internal standard method and its application to the identification of adulteration of illegal cooking oil].

On the basis of the source of illegal cooking oil (heated vegetable oil and animal oil) and the important referents reflecting their sources, namely, undecanoic acid and 13-methyl-tetradecanoic acid connected to the glyceride, their corresponding ramifications in edible oil were detected with internal standard method. The sensitivity and selectivity of this method were improved by the on-line cleanup and preconcentration. The detection limits of the method were 0.070 mg/kg for undecanoic acid and 0.006 mg/kg for 13-methyl-tetradecanoic acid. Additionally, most of the normal vegetable oils have lower levels of both fatty acids than illegal cooking oils. It was suggested to evaluate the quality of edible oils to some extent on the basis of the contents of undecanoic acid and 13-methyl-tetradecanoic acid.

A new cleanup method of dioxins in sediment using large volume injection gas chromatography online coupled with liquid chromatography

A new cleanup method was developed and validated for the determination of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in sediment. The sample extract was first treated with sulfuric acid and then cleaned up by a large volume injection gas chromatography online coupled with liquid chromatography (LVI-GC-LC) system. PCDD/Fs in the extract were separated by a GC column (DB-5), selected cut, cool trapped and transferred to a LC column (alumina). The fraction of PCDD/Fs eluted from the alumina column was collected and concentrated for the instrumental analysis. Under the optimized conditions, LVI-GC-LC method achieved the recoveries of 57-102% for 2,3,7,8-substituted PCDD/Fs, which met the requirements of US Environmental Protection Agency (EPA) Method 1613 and were better than those obtained using the conventional multistep column cleanup method. Meanwhile, compared with the conventional method, the limit of detection (LOD) values of 2,3,7,8-substituted PCDD/Fs cleaned up by LVI-GC-LC method were decreased due to the high-efficiency removal of interferents. These results suggested that the LVI-GC-LC cleanup method was a promising alternative to the multistep cleanup procedure for the determination of dioxins in environmental samples.

Simultaneous determination of chlorinated aromatic hydrocarbons in fly ashes discharged from industrial thermal processes

Chlorinated aromatic hydrocarbons (CAHs) have received increasing attention because of their environmental persistence, bioaccumulation potential and high toxicity. In this study, an analytical methodology based on high-resolution gas chromatography/high-resolution mass spectrometry for the simultaneous determination of four typical kinds of CAHs including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and chlorinated polycyclic aromatic hydrocarbons (ClPAHs) in fly ash was developed. Highly effective cleanup and separation procedures combined with optimum instrumental conditions provided a reliable method for the detection and quantification of CAHs. Meanwhile, the spike of 13C-labeled standards and deuterated phenanthrene achieved more accurate measurement. The method detection limits were determined to be in the ranges of 0.1–13.4 pg g−1 for tetra- to octa-CDD/F congeners, 0.04–11.1 pg g−1 for tri- to hepta-CB congeners, 0.2–48.5 pg g−1 for mono- to octa-CN congeners and 3.5–9.5 pg g−1 for mono- and di-chlorinated aromatic hydrocarbons. Good recoveries of CAHs (62–136%) were achieved, except for PCN-2 and PCN-6. The developed analytical methodology was validated and then used to determine the levels of CAHs in fly ashes collected from industrial thermal processes. All the target compounds were detected and the CAH congener concentrations showed a wide variation in different fly ashes.