尿中MDMA和MDA的三氟乙酰化-GC/MS/MS分析法

建立了尿中MDMA和MDA的、用环己烷提取的、三氟乙酸酐衍生化的、GC/MS/MS检测的分析方法。方法操作简便快速,检测MDMA最灵敏的检出限为4ng/mL,检测MDA最灵敏的检出限为2.0ng/mL。方法的回收率为73%—94%,具有较好的线性关系。     

固相萃取GC-MS/MS法检验家兔尿液中氯胺酮

研究了家兔尿中氯胺酮的检验方法.用1mol/L氢氧化钠溶液调正检尿液pH为9-10,上GDX-403柱,以氯仿洗脱.选取209m/Z离子碎片为母离子,进行GC-MS/MS分析,通过与氯胺酮标准品的保留时间及二级质谱图比对定性,外标定量.结果显示氯胺酮在0.02-40μg/mL范围内线性关系良好,所得校准曲线的回归方程为:y=3990.31 47045.2x,r2=0.9995.检出限为20ng/mL.平均回收率为89.36%.     

HPLC-MS/MS检测人血浆中多潘立酮

用HPLC-MS/MS测定人血浆中多潘立酮的浓度。采用Luna C18色谱柱（150mm×2mm,5μm）,流动相为甲醇∶水（0.04%醋酸铵）=85∶15（V∶V）,采用选择反应监测（SRM）模式。多潘立酮在0.5—100ng/mL浓度范围内有良好的线性关系,日内、日间相对标准偏差（RSD）和准确度误差（RE）均小于10%。该方法灵敏、准确、快速,已用于人血浆中多潘立酮浓度的检测。     

Luminol-Cu(Ⅱ)体系流动注射化学发光法测定乙酰半胱氨酸

发现了Luminol-Cu(Ⅱ)-乙酰半胱氨酸化学发光体系,探讨了影响化学发光反应的各个因素,建立了测定乙酰半胱氨酸的流动注射化学发光新方法。该方法的线性范围为7.0×10-10—1.0×10-7g/mL,检出限为2.0×10-11g/mL,相对标准偏差为1.0%(1.0×10-8g/mL,n=11)。该方法已用于药物制剂中乙酰半胱氨酸含量的测定。     

超声萃取-C_(18)柱净化-GC/MS法测定土壤中邻苯二甲酸酯类污染物

采用超声波辅助萃取-非极性C18固相萃取小柱净化-GC/MS技术,测定了土壤样品中6种邻苯二甲酸酯类污染物;对最佳溶剂萃取条件和最佳净化条件进行了优化;在最佳实验条件下,方法的相对标准偏差在6.5%—10.6%之间,最低检出限在0.005—0.049mg/kg之间,实际土样加标回收率在73.9%—105.4%之间。     

SPME/GC/MS分析小一点红挥发性化学成分

利用固相微萃取/气相色谱/质谱(SPME/GC/MS)联用技术对小一点红挥发性成分进行研究。共鉴定出25种化学成分,占挥发性总成分的91.99%。小一点红主要挥发性化学成分是β-月桂烯(51.18%),3,7,11,15-四甲基-2-十六烯-1-醇(21.55%),β-水芹烯(8.42%),n-十六酸(2.48%)等。     

SPME/GC/MS分析荷花玉兰挥发性成分

利用固相微萃取/气相色谱/质谱(SPME/GC/MS)联用技术对荷花玉兰挥发性成分进行研究。共鉴定出48个化学成分,占挥发性总成分的85.76%。荷花玉兰主要挥发性化学成分是反式-香叶醇(38.11%),苯甲醇(4.99%),3,7-二甲基-1,6-辛二烯-3-醇(4.33%),松香芹酮(3.24%)等。     

化学发光法快速检测海洛因

酯酶为脱乙酰剂 ,促使海洛因分子水解生成吗啡。在 5 0 μmol/ L鲁米诺 ,2 .4 μmol/ L H2 O2 及 0 .4 mol/ LNa2 CO3 (p H9— 11)条件下 ,吗啡 -鲁米诺 -过氧化体系具有较高的发光强度。 EDTA作为掩蔽剂可对部分阳离子的干扰予以掩蔽 ,化学发光法快速检测海洛因 ,该法检测速度快、灵敏度高 ,检出限为3× 10 -9mol/ L。     

HS-SPME-GC/MS测定饮用水中三卤甲烷分析条件的优化

对顶空固相微萃取 -气相色谱 /质谱联用测定饮用水中三卤甲烷的分析条件如固相微萃取的萃取时间、萃取温度、溶液的离子强度及 p H值等进行了优化。该方法的线性范围为 5— 15 0 μg/ L,相对标准偏差为 5 .4 %— 8.2 %。     

电感耦合等离子体-串联质谱(ICP-MS/MS)法测定道路尘土中的铂族元素(PGEs)含量

建立了道路尘土中的铂族元素(platinum group elements,PGEs)含量测定的分析方法。道路尘土以王水(2mL HNO_3+6mL HCl)为混合消解试剂经微波消解后直接测定。在MS/MS模式下向碰撞反应池中通入氧气或氨气,分别利用氧气质量转移、氧气原位质量和氨气原位质量法消除多原子离子质谱干扰。在MS/MS模式下,分别向碰撞/反应池(CRC)中加入O_2和NH_3-He(1∶9,V/V),消除质谱干扰,采用O_2质量转移法对铑进行测定,O_2原位质量法和高氦(HeHe)法对钯进行测定,NH_3原位质量法对铑和铂进行测定。通过分析国际标准参考物质(BCR-723)验证方法的准确性和精密度,所测定结果与参考值基本一致,RSD≤7.8%,表明本方法具有良好的准确性和精密度。本方法具有前处理简单、高灵敏度、无干扰、稳定性好等优势,可用于道路尘土样品中超痕量铂、铑,钯含量的测定。     

Fragmentation Study of Globularin Through Positive and Negative ESI/MS,CID/MS,and Tandem MS/MS

Abstract

The structure of globularin was studied by a mass spectrometric methodology based on the combined use of positive and negative electrospray ionization, collision‐induced dissociation (CID), and tandem mass spectrometry. The mass spectrometry investigation was achieved through in‐source fragmentation of the deprotonated [M?H]^?, protonated [M+H]⁺, lithiated [M+Li]⁺, sodiated [M+Na]⁺, and potassium‐cationized [M+K]⁺ ions. This allowed collision‐induced dissociation spectra of the ionized molecular ions to be obtained to give valuable structural information regarding the nature of both the glycoside and the aglycone moieties and the effect of metal cationization on the CID spectra. Glycosidic fission and ring cleavages of both aglycone and sugar moieties were the major fragmentation pathways observed during collision‐induced dissociation, where the losses of small molecules, the cinnamoyl and the cinnamate parts were also observed. Alkali metal cationization offers additional fragmentation pathways involving cross rings cleavage under CID conditions. Unlike the dissociation of protonated molecular ions, that of metal‐cationized molecules also provides sugar fragments where the C₀ ⁺ fragment corresponding with the glucose ion was obtained as a major daughter peak for all the studied compounds. Even with low abundance, fragment ions coordinated to K⁺ were also observed from [M+K]⁺.     

糖脂化合物的激光解吸质谱研究

应用激光解吸电离飞行时间质谱（MALDI-TOF-MS）技术对糖脂化合物进行了质谱研究。结果表明,MALDI-TOF-MS作为一种快速而有效的分析方法,是分析天然产物和生物榈不可缺少的手段之一。     

Quantitation of melatonin and n-acetylserotonin in human plasma by nanoflow LC-MS/MS and electrospray LC-MS/MS

Melatonin (MEL) and its chemical precursor N-acetylserotonin (NAS) are believed to be potential biomarkers for sleep-related disorders. Measurement of these compounds, however, has proven to be difficult due to their low circulating levels, especially that of NAS. Few methods offer the sensitivity, specificity and dynamic range needed to monitor MEL and its precursors and metabolites in small blood samples, such as those obtained from pediatric patients. In support of our ongoing study to determine the safety, tolerability and PK dosing strategies for MEL in treating insomnia in children with autism spectrum disorder, two highly sensitive LC-MS/MS assays were developed for the quantitation of MEL and precursor NAS at pg/mL levels in small volumes of human plasma. A validated electrospray ionization (ESI) method was used to quantitate high levels of MEL in PK studies, and a validated nanospray (nESI) method was developed for quantitation of MEL and NAS at endogenous levels. In both assays, plasma samples were processed by centrifugal membrane dialysis after addition of stable isotopic internal standards, and the components were separated by either conventional LC using a Waters SymmetryShield RP18 column (2.1?×?100 mm, 3.5?μm) or on a polyimide-coated, fused-silica capillary self-packed with 17?cm AquaC18 (3?μm, 125??). Quantitation was done using the SRM transitions m/z 233?→?174 and m/z 219?→?160 for MEL and NAS, respectively. The analytical response ratio versus concentration curves were linear for MEL (nanoflow LC: 11.7-1165 pg/mL, LC: 1165-116,500 pg/mL) and for NAS (nanoflow LC: 11.0-1095 pg/mL).     

芦苇秆粉末的热脱附-气相色谱/质谱分析

采用热脱附-气相色谱/质谱联机技术（TD-GC/MS）分析了芦苇杆粉末在不同环境温度下的挥发物释放行为。结果表明：芦苇杆粉末在40℃及160℃的挥发物中,主要有益成分分别为主要有害成分的4.43倍和5.13倍,环境友好性良好;在60℃及90℃的挥发物中,主要有益成分比例也比主要有害成分高,90℃时的有益成分为有害成分的2.45倍,环境友好性较好。以芦苇杆粉末为基材,在木质素软化温度点和木质材料碳化温度点之间（150—180℃）实施高压无胶模塑成形工艺制备木质粉末基复合材料必将体现出良好的环境友好性。     

固相微萃取/气相色谱/质谱法分析金钱蒲挥发性化学成分

分析金钱蒲挥发性化学成分。利用固相微萃取/气相色谱/质谱联用技术对金钱蒲挥发性成分进行研究。共鉴定出47个化学成分,占挥发性总成分的95.64%。金钱蒲主要挥发性化学成分是爱草脑(66.9%),桉叶素(6.19%),α-石竹烯(4.01%),γ-萜品烯(2.79%),β-榄香烯(2.58%),β-水芹烯(2.22%)等。     

精油中挥发性成分GC/FTIR与GC/MS联合分析

采用同时蒸馏萃取(SDE)法获得了香紫苏(Salvia sclarea L.)精油,利用气相色谱/傅里叶变换红外光谱联用(GC/FTIR)和气相色谱/质谱联用(GC/MS)相结合的手段,对其挥发成分进行了定性和定量分析,着重讨论了GC/FTIR在精油分析中的应用研究。通过不同波数官能团(Gram-Schmidt)重建红外光谱图、红外光谱差谱技术及质谱等相互验证的方法,大大提高了香紫苏油挥发成分的定性分析准确性。     

磷酸苯基二乙基酯的合成及NMR和ESI-MS/MS测定

在冰盐浴条件下,将DEPH和CCl₄混合液滴加到由苯酚、三乙胺、二氧六环组成的混合液中或由水杨酸乙酯, 三乙胺、二氧六环组成的混合液中. 分别用二乙基亚磷酸酯（DEPH)对苯酚和水杨酸乙酯进行磷酰化. 经电喷雾质谱（ESI-MS)及核磁共振检测,目标产物存在, 其分别为磷酸苯基二乙基酯和o-(邻乙氧甲酰（基）苯基)磷酸二乙酯.