A novel approach for LC-MS/MS-based chiral metabolomics fingerprinting and chiral metabolomics extraction using a pair of enantiomers of chiral derivatization reagents

Chiral metabolites are found in a wide variety of living organisms and some of them are understood to be physiologically active compounds and biomarkers. However, the overall analysis of chiral metabolomics is quite difficult due to the high number of metabolites, the significant diversity in their physicochemical properties, and concentration range from metabolite-to-metabolite. To solve this difficulty, we developed a novel approach for chiral metabolomics fingerprinting and chiral metabolomics extraction, which is based on the labeling of a pair of enantiomers of chiral derivatization reagents (i.e., DMT-(S,R)-Pro-OSu and DMT-3(S,R)-Apy) and precursor ion scan chromatography of the derivatives. The multivariate statistics is also required for this strategy. The proposed procedures were evaluated by the detection of a diagnostic marker (i.e., d-lactic acid) using the saliva of diabetic patients. This method was used for the determination of biomarker candidates of chiral amines and carboxyls in Alzheimer's disease (AD) brain homogenates. As the results, l-phenylalanine (L-Phe) and l-lactic acid (L-LA) were identified as the decreased and increased biomarker candidates in the AD brain, respectively. Therefore, the proposed approach seems to be helpful for the determination of non-target chiral metabolomics possessing amines and carboxyls.     

Towards the chiral metabolomics: Liquid chromatography–mass spectrometry based dl-amino acid analysis after labeling with a new chiral reagent, (S)-2,5-dioxopyrrolidin-1-yl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl)pyrrolidine-2-carboxylate,and the application to saliva of healthy volunteers

A novel triazine-type chiral derivatization reagent, i.e., (S)-2,5-dioxopyrrolidin-1-yl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl) pyrrolidine-2-carboxylate (DMT-(S)-Pro-OSu), was developed for the highly sensitive and selective detection of chiral amines and amino acids by UPLC–MS/MS analysis. The enantiomers of amino acids were easily labeled with the reagents at room temperature within 40 min in an alkaline medium containing triethylamine. The diastereomers derived from proteolytic amino acids, except serine, were well separated under isocratic elution conditions by reversed-phase chromatography using an ODS column (R_s = 1.2–9.0). dl-Serine was separated by use of an ADME column which has relatively higher polar surface than the conventional ODS column. The characteristic product ions, i.e., m/z 195.3 and m/z 209.3, were detected from all the diastereomers by the collision-induced dissociation of the protonated molecule. A highly sensitive detection on the amol–fmol level was obtained from the selected reaction monitoring (SRM) chromatogram. The chiral amines (e.g., adrenaline and noradrenaline) labeled with DMT-(S)-Pro-OSu were also well separated and sensitively detected by the present procedure. The method using DMT-(S)-Pro-OSu was used for the determination of dl-amino acids in the human saliva from healthy volunteers. Various l-amino acids were identified in the saliva. Furthermore, d-alanine (d-Ala) and d-proline (d-Pro) were also detected in relatively high concentrations (>5%). The ratio was higher in male saliva than in female saliva. However, the difference in the ratio of d-Ala for one day was not very high and the effect of foods and beverage seemed to be negligible. Based on the results using l-Ala-d₃, the d-Ala in saliva seemed to be produced due to the racemization with some enzymes such as racemase. The racemization reaction was reversible, i.e., d-Ala-d₃ was also racemized to l-Ala-d₃ in saliva. Thus, care should be taken during the analysis of dl-amino acids in saliva. The present method using DMT-(S)-Pro-OSu may be applicable for the determination of chiral amine metabolomics, because the resulting derivatives produce the same product ions without relation to the compounds and show highly sensitive detection in the SRM mode of MS/MS. Consequently, DMT-(S)-Pro-OSu seems to be a useful chiral derivatization reagent for the determination of amines and amino acids in biological samples.     

Carboxylated graphene oxide/polyvinyl chloride as solid-phase extraction sorbent combined with ion chromatography for the determination of sulfonamides in cosmetics

A carboxylated graphene oxide/polyvinyl chloride (CGO/PVC) material was prepared as a sorbent for the selective extraction of sulphonamides from complex sample. After being dispersed in buffer solution, sample was transferred into the prefabricated solid-phase extraction (SPE) column, which integrated extraction and cleanup into one single-step. A multi-response optimization based on the Box-Behnken design was used to optimize factors affecting extraction efficiency. Compared with the commonly commercial sorbents including MCX, WCX and C₁₈, CGO/PVC hybrid material had higher extraction selectivity and capacity to sulphonamides. The limits of detection and quantification for seven target compounds were in the range of 3.4–7.1 μg/L and 11.4–23.7 μg/L, respectively. The self-assembly SPE cartridge was successfully used to enrich seven analytes in anti-acne cosmetics prior to ion chromatography detection with good recoveries of 87.8–102.0% and relative standard deviations of 1.2–6.4%, implying that this method was suitable for routine analysis of cosmetics.     

Microwave-assisted micro-solid-phase extraction for analysis of tetracycline antibiotics in environmental samples

In this study, a novel solid-liquid-solid extraction approach, which was termed ‘microwave-assisted micro-solid-phase extraction’ (MAE-μ-SPE), was developed. Target analytes were extracted from the sample into extraction solvent enhanced by microwave field, following adsorption by the adsorbent in the micro-solid-phase extraction device. Without any clean-up steps, the extracts were analysed by high performance liquid chromatography coupled with ultra-violet detector. The MAE-μ-SPE approach was developed for the extraction of four tetracycline antibiotics residues in environmental soil, sludge and atmospheric particulate matters. Variables affecting extraction procedures were systematically investigated. Low detection limits of 0.1–6.3 ng/g and low quantification limits of 0.33–20.7 ng/g were achieved under optimised conditions. The recoveries of antibiotics ranged from 70.6% to 110.5% with relative standard deviation of less than 15.1%. The predominance was showed when compared to conventional MAE and μ-SPE method. According to the results, MAE-μ-SPE was proved to be a simple and effective sample preparation method for the analysis of trace organic contaminants in environmental samples.     

硅橡胶/氟橡胶并用胶的制备及力学性能

硅橡胶和氟橡胶作为国防、航天等重要领域的耐热材料一直被人们青睐,但其有着各自地优缺点且价格昂贵,本文尝试将这两种橡胶制成并用胶以解决氟橡胶不耐低温和加工性差的问题,以期增大其使用温度范围。采用机械共混法制备硅橡胶/氟橡胶并用胶,研究了硅橡胶和氟橡胶的混炼工艺、并用比、共硫化体系和硫化条件对并用胶力学性能的影响。结果表明,当硅橡胶/氟橡胶的质量比为10∶90,共硫化体系为3~#硫化剂/过氧化二异丙苯(DCP),一段硫化温度为170℃、硫化压力为10MPa、硫化时间为30min,二段硫化温度为200℃、硫化时间为6h时,并用胶的力学性能达到最好。     

极谱法检测水体中的孔雀石绿

基于荧光素(SF)在pH=7.0的B-R缓冲溶液中可以产生一灵敏的还原峰,而孔雀石绿(MG)可以与荧光素络合而抑制荧光素的峰电流,建立了一种检测水体中孔雀石绿含量的极谱新方法。最佳测定体系为:1.2×10-5 mol/L的荧光素-9.0mL B-R缓冲溶液(pH=7.0)。在此体系中,于起始电位-0.40V,峰电位-0.85V,孔雀石绿含量在20~100μg/L范围内与峰电流呈线性关系,检出限为7.5μg/L。该方法用于环境水样中孔雀石绿的检测,回收率为90.5%~105.6%。     

含铵根离子等规聚丙烯离聚体的合成及性能研究

合成了一系列高分子量、窄分子量分布且高等规度,含有不同―NR_3~+X~-离子基团含量的聚丙烯离聚体(iPP-NR_3~+X~-).以PP/IUD共聚物作为反应中间体,与三乙胺或N-甲基咪唑氨化得到聚丙烯离聚体.通过离子交换反应制备不同反离子的N-甲基咪唑聚丙烯离聚体,包括双三氟甲基磺酰亚胺根离子(Tf_2N~-)、四氟硼酸根离子(BF_4~-)和六氟磷酸根离子(PF_6~-).热重分析结果发现N-甲基咪唑聚丙烯离聚体的热稳定性明显优于三乙胺聚丙烯离聚体,表明不含β-H的N-甲基咪唑聚丙烯离聚体具有较高的热稳定性.同时,聚丙烯离聚体的表面亲水性得到明显改善.并且,聚丙烯离聚体的断裂伸长率也得到显著提高,最高达到900%.比较不同反离子聚丙烯离聚体的屈服强度和断裂强度发现I~-聚丙烯离聚体具有最优的力学性能.     

经典N=2李共形超代数的导子和第二上同调群

研究了经典N=2李共形超代数的导子和第二上同调群的结构,并应用第二上同调群的结果确定了该李共形超代数的泛中心扩张.     

FINITE ELEMENTAN ALYSIS FOR THE UNSTEADY NEARSHORECIR CULATION DUE TO WAVE－CURRENT INTER－ACTION（I）──NUMERICAL MODEL

ＦＩＮＩＴＥＥＬＥＭＥＮＴＡＮＡＬＹＳＩＳＦＯＲＴＨＥＵＮＳＴＥＡＤＹＮＥＡＲＳＨＯＲＥＣＩＲＣＵＬＡＴＩＯＮＤＵＥＴＯＷＡＶＥ－ＣＵＲＲＥＮＴＩＮＴＥＲ－ＡＣＴＩＯＮ（Ｉ）——ＮＵＭＥＲＩＣＡＬＭＯＤＥＬＷｕＷｅｉ－ｘｉｏｎｇ（吴伟雄）（Ｔｏｎｇｊ...     

EFFECTS OF FINELY DISPERSED METALLIC PALLADIUM ON MICROSTRUCTURE AND PROPERTIES OF NANOCOMPOSITES PRODUCED BY SOL-GEL TECHNIQUE

Nanosized palladium particles were incorporated into mesoporous silica matrix to obtain nanocomposites using the sol-gel technique. Effects of the finely dispersed metallic palladium on the microstructure and properties of the nanocomposites were investigated. By means of X-ray diffraction and optical absorption, it was found that palladium particles were 5-9 nm in diameter and their uniform dispersion in the mesoporous silica depended on both the content of the palladium and the structural features of the silica matrix. The results showed that the mixing method of preparation led to wider size distribution of the nanosized particles as compared to the immersion method, but dispersed degree was reduced. Although the incorporation of nanosized palladium particles could not substantially induce significant structural changes of the matrix, the apparent red-shifted optical absorptions for the nanocomposites were observed as compared to the parent monolithic silica, particularly with increase in palladium loading and calcination temperature.