Calibration of the complex matrix effects on the sampling of polycyclic aromatic hydrocarbons in milk samples using solid phase microextraction

Solid phase microextraction (SPME), a simple, fast and promising sampling technique, has been widely used for complex sample analysis. However, complex matrices could modify the absorption property of coatings as well as the uptake kinetics of analytes, eventually biasing the quantification results. In the current study, we demonstrated the feasibility of a developed calibration method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in complex milk samples. Effects of the complex matrices on the SPME sampling process and the sampling conditions were investigated. Results showed that short exposure time (pre-equilibrium SPME, PE-SPME) could increase the lifetime of coatings, and the complex matrices in milk samples could significantly influence the sampling kinetics of SPME. In addition, the optimized sampling time, temperature and dilution factor for PAHs were 10 min, 85 °C and 20, respectively. The obtained LODs and LOQs of all the PAHs were 0.1–0.8 ng/mL and 1.4–4.7 ng/mL, respectively. Furthermore, the accuracy of the proposed PE-SPME method for milk sampling was validated by the recoveries of the studied compounds in two concentration levels, which ranged from 75% to 110% for all the compounds. Finally, the proposed method was applied to the screening of PAHs in milk samples.     

Polymorph selection in the crystallization of hard-core Yukawa system

Colloid-colloid interactions in charge-stabilized dispersions can to some extent be represented by the hard-core Yukawa model. The crystallization process and polymorph selection of hard-core Yukawa model are studied by means of smart Monte Carlo simulations in the region of face-centered-cubic (fcc) phase. The contact value of hard-core Yukawa potential and the volume fraction of the colloids are fixed, while the Debye screening length can be varied. In the early stage of the crystallization, the precursors with relatively ordered liquid structure have been observed. Although the crystal structure of thermodynamically stable phase is fcc, the system crystallizes into a mixture of fcc and hexagonal close-packed (hcp) structures under small Debye screening length since the colloidal particles act as effective hard spheres. In the intermediate range of Debye screening length, the system crystallizes into a mixture of fcc, hcp, and body-centered-cubic (bcc). The existence of metastable hcp and bcc structures can be interpreted as a manifestation of the Ostwald’s step rule. Until the Debye screening length is large enough, the crystal structure obtained is almost a complete fcc suggesting the system eventually reaches to a thermodynamically stable state.     

In-situ nanoelectrospray for high-throughput screening of enzymes and real-time monitoring of reactions

The in-situ and high-throughput evaluation of enzymes and real-time monitoring of enzyme catalyzed reactions in liquid phase is quite significant in the catalysis industry. In-situ nanoelectrospray, the direct sampling and ionization method for mass spectrometry, has been applied for high-throughput evaluation of enzymes, as well as the on-line monitoring of reactions. Simply inserting a capillary into a liquid system with high-voltage applied, analytes in liquid reaction system can be directly ionized at the capillary tip with small volume consumption. With no sample pre-treatment or injection procedure, different analytes such as saccharides, amino acids, alkaloids, peptides and proteins can be rapidly and directly extracted from liquid phase and ionized at the capillary tip. Taking irreversible transesterification reaction of vinyl acetate and ethanol as an example, this technique has been used for the high-throughput evaluation of enzymes, fast optimizations, as well as real-time monitoring of reaction catalyzed by different enzymes. In addition, it is even softer than traditional electrospray ionization. The present method can also be used for the monitoring of other homogenous and heterogeneous reactions in liquid phases, which will show potentials in the catalysis industry.     

Direct identification of prohibited substances in cosmetics and foodstuffs using ambient ionization on a miniature mass spectrometry system

Significantly simplified work flows were developed for rapid analysis of various types of cosmetic and foodstuff samples by employing a miniature mass spectrometry system and ambient ionization methods. A desktop Mini 12 ion trap mass spectrometer was coupled with paper spray ionization, extraction spray ionization and slug-flow microextraction for direct analysis of Sudan Reds, parabens, antibiotics, steroids, bisphenol and plasticizer from raw samples with complex matrices. Limits of detection as low as 5 μg/kg were obtained for target analytes. On-line derivatization was also implemented for analysis of steroid in cosmetics. The developed methods provide potential analytical possibility for outside-the-lab screening of cosmetics and foodstuff products for the presence of illegal substances.     

A novel immunochromatographic assay based on a time-resolved chemiluminescence strategy for the multiplexed detection of ractopamine and clenbuterol

A novel multiplexed immunochromatographic assay (ICA) based on a time-resolved chemiluminescence (CL) strategy was developed for quantitative detection of β-agonists, by utilizing ractopamine (RAC) and clenbuterol (CLE) as the models. Different from conventional multiplexed ICA methods which usually require two or more test lines, this strategy was developed for detection of two β-agonists by using only one test line on the nitrocellulose membrane. In this study, horseradish peroxidase and alkaline phosphatase were used as the signal probes to label RAC antibody and CLE antibody, respectively. The two CL reactions with flash type and glow type kinetics characteristics were triggered simultaneously by injecting the coreactants, then the signals for RAC and CLE detections were recorded at 3 s and 300 s after coreactants injection, respectively. Owing to the utilization of CL detection, this protocol showed ideal sensitivity for quantitation. Under the optimal conditions, the detection limits for RAC and CLE were 0.17 ng mL⁻¹ and 0.067 ng mL⁻¹ (S/N = 3), respectively. The whole assay process can be accomplished within 20 min without complicated sample pretreatment. The proposed method was successfully applied for the detection of RAC and CLE in spiked swine urine. It opens up a new pathway for designing a low cost, time-efficiency and multiplexed strategy for rapid screening and field assay.     

Enhancing <Emphasis Type="SmallCaps">l</Emphasis>-Lysine Production of Beet Molasses by Engineered <Emphasis Type="Italic">Escherichia coli</Emphasis> Using an In Situ Pretreatment Method

Reducing the viscosity of molasses environmentally and selectively removing the harmful ingredients for microbes are the keys to promoting the bioavailability of molasses. A simple and environmental in situ pretreatment method integrating surfactants and alkali was developed to reduce the viscosity of molasses prior to l-lysine production using Escherichia coli ZY0217. Adding activated carbon and modified orange peel based on the in situ pretreatment process effectively removed pigments and excessive zinc in the molasses and also significantly increased the cell growth and l-lysine yield from E. coli ZY0217. The experimental results showed that a mixture of secondary alkane sulfonate, an anionic surfactant, and HodagCB-6, a non-ionic surfactant, effectively reduced the viscosity of the molasses more so than any single surfactant. When the surfactant mixture was added at a concentration of 0.04 g/L to the molasses, the ω value was 0.4, and when ammonia was added at 0.6 %, the lowest viscosity of 705 mPa?·?s was obtained. Further, 91.5 % of the color and 86.68 % of the original levels of zinc were removed using an activated carbon and modified orange peel treatment on the molasses with the lowest viscosity, which further promoted cell growth and l-lysine production. In the fed-batch cultivation process, the l-lysine concentration achieved using a constant-speed feeding strategy was 45.89 g/L, with an l-lysine yield of 27.18 %, whereas the l-lysine yield from untreated molasses was only 10.13 %. The increase in l-lysine yield was related to the reduced viscosity and the detoxification of the molasses. Lastly, the pretreatment was found to significantly enhance the conversion of sugars in the molasses to l-lysine.     

Topological evolution of cerium(Ⅲ) molybdate microflake assemblies induced by amino acids

In this work, cerium(Ⅲ) molybdate microspheres configured as microflakes were synthesized in the presence of lysine via a hydrothermal process. We studied the role of lysine and other amino acids on the morphologic control of cerium(Ⅲ) molybdate crystals. First, with the increase of lysine, thinner microflakes and smaller microspheres are obtained. Moreover, a transformation in topology of cerium(Ⅲ) molybdate assemblies from three-dimensional(3D) into two-dimensional(2D) can be ascribed to controlled nucleation and growth of cerium(Ⅲ) molybdate induced by lysine. Second, amino acids with strong hydrophilic ‘‘R' groups tend to induce nucleation and result in spherical assemblies formed by nanoparticles or nanoflakes, while those with weaker hydrophilic ‘‘R' groups tend to induce growth and yield spherical assemblies of microflakes.     

Formation of ring calcium oxalate patterns induced by domains in DPPC Langmuir-Blodgett films

The ring patterns of calcium oxalate crystals were induced by domains in Langmuir-Blodgett （LB） films of dipalmitoylpho- sphatidylcboline （DPPC）. The result was explained by the defects at the ring boundaries of liquid condensed （LC） and liquid expanded （LE） phases of LB film. These boundaries could provide less free energy and much more nucleating sites for COM crystals.     

Study of organohalogen contaminants in yogurt by NAA and GC-ECD

The concentrations and distributions of total halogen (TX), extractable organohalogen (EOX) and extractable persistent organohalogen (EPOX) were determined in 20 kinds of yogurt specimens collected from Chinese supermarkets using neutron activation analysis (NAA) and gas chromatography equipped with a ⁶³Ni electron capture detector (GC-ECD). The results indicated that the halogens in yogurt mainly existed as non-extractable organohalogen compounds. About 25–30% of EOX was EPOX. EOCl and EPOCl were the main organohalogen species in yogurt. The average concentration of the identified organochlorine, such as organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), was below 4% of EPOCl.     

Synthesis and photoluminescence properties of 8-hydroxyquinoline derivatives and their metallic complexes

Three new 8-hydroxyquinoline derivatives, i.e. 5-[(4-styryl-benzylidene)-amino]-quinolin-8-ol (1), 5-[(4-bromo-2-fluoro-benzylidene)-amino]-quinoline-8-ol (2) and 2-[2-(9-ethyl-9H-carbazol-2yl)-vinyl]-quinolin-8-ol (3), and their metallic complexes were synthesized and identified by ultraviolet-visible (UV-Vis), ¹H nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectrometer (FTIR), mass spectrometry (MS) spectra and elemental analyses. Their fluorescence properties were studied by photoluminescence, which indicated that the luminescence wavelength of 5-and 2-substitued-8-hydroxyquinoline derivatives shifted to red in comparison with that of 8-hydroxyquinoline. Meanwhile, the fluorescence lifetime of 2-[2-(9-ethyl-9H-carbazol-2yl)-vinyl]-quinolin-8-ol and its zinc complex showed long lifetime in benzene solution. __________ Translated from Chinese Journal of Organic Chemistry, 2007, 27(3): 402–408 [译自: 有机化学]