高效液相色谱-荧光检测法测定橄榄油中4种多环芳烃

建立了高效液相色谱-荧光检测(HPLC-FLD)测定橄榄油中苯并[a]蒽、屈艹、苯并[b]荧蒽、苯并[a]芘4种多环芳烃(PAHs)的分析方法。橄榄油样品经异丙醇稀释,采用具有π-π特异性作用的固相萃取柱净化,Agilent ZORBAX Eclipse PAH色谱柱(100 m m×2.1 m m,1.8μm)分离,以水-乙腈为流动相,梯度洗脱,实现了4种化合物的基线分离,并用基质匹配校准溶液进行外标法定量。4种多环芳烃的线性范围为2.4~40μg/L,相关系数(r)为0.999 0~0.999 9,方法的定量限为0.147~0.413μg/L,加标回收率为95.5%~103.2%,日内和日间精密度(RSD)分别为0.10%~1.69%和2.48%~2.93%(n=5)。该法具有灵敏度高、检出限低、重复性好等特点,适用于橄榄油中4种PAHs快速、准确的定量检测。     

GC–MS法同时测定聚氨酯塑胶跑道中16种多环芳烃

建立气相色谱–质谱法同时测定聚氨酯塑胶跑道中16种多环芳烃如萘、苊、二氢苊、芴、菲、蒽、荧蒽、苯并[b]荧蒽、芘、苯并[a]蒽、屈、苯并[k]荧蒽、苯并[a]芘、茚并[1,2,3-cd]芘、1-甲基奈、2-甲基萘的检测方法。样品采用甲苯为提取剂,经超声提取和硅胶柱净化后,用气相色谱–质谱法测定16种多环芳烃残留量。16种多环芳烃的质量浓度在0.2~10.0 mg/kg范围内与色谱峰面积呈良好的线性,线性相关系数r20.998,检出限为5.0~60.0μg/kg。回收率为72.4%~101.6%,测定结果的相对标准偏差为0.9%~7.2%(n=6)。该方法准确度高、精密度好,适用于聚氨酯塑胶跑道中多环芳烃多残留检测。     

气相色谱-串联质谱法同时测定卷烟滤嘴中15种多环芳烃

建立了气相色谱-串联质谱同时检测卷烟滤嘴中15种多环芳烃的方法。卷烟滤嘴用二氯甲烷振荡萃取后,经0.22μm有机相滤膜过滤,采用DB-5MS色谱柱(30 m×0.25 mm,0.25μm)进行分离,电子轰击源、正离子模式下以多反应监测模式进行检测,内标法进行定量。15种多环芳烃(苊烯、苊、芴、菲、蒽、荧蒽、芘、苯并[a]蒽、屈、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、二苯并[a,h]蒽、苯并[g,h,i]苝和茚并[1,2,3-c,d]芘)的线性关系良好,相关系数(R~2)为0.991 4~0.999 9。15种多环芳烃在低、中、高3个添加水平下的平均回收率为81.6%~111.2%;除了芴在低添加水平时相对标准偏差为19.2%外,其他相对标准偏差均小于16%。15种多环芳烃的检出限为0.02~0.24 ng/滤嘴,定量限为0.04~0.80 ng/滤嘴。方法前处理简便,具有快速、准确、灵敏度高及重复性好的优点,适用于卷烟滤嘴中多环芳烃的分析。     

高效液相色谱法测定黄浦江表层沉积物中的痕量多环芳烃

建立了高效液相色谱-二极管阵列检测器(PDA)测定上海市黄浦江表层沉积物中16种多环芳烃(PAHs)的方法。在保留时间定性分析的基础上,利用PDA获取的紫外扫描光谱图对目标组分进行了准确的定性,并通过异构体紫外光谱图中特征峰的差异有效地识别了样品中的4种异构体,即苯并［b］荧蒽、 苯并［k］荧蒽、 苯并［a］芘和苯并［e］芘。通过检测波长的优化,减少了干扰物的影响,提高了检测灵敏度;针对分离度较差的两种目标组分(苯并［b］荧蒽和苯并［k］荧蒽)的定量进行了分析讨论。该方法对16种PAHs的检出限(以干基计)介于1.1～18.3 ng/g之间,具有较高的方法灵敏度。黄浦江表层沉积物测定结果表明,除二氢苊外的15种PAHs都被检出,含量为10.1～253.0 ng/g。     

冷冻研磨超声浸提分离-气相色谱-质谱法测定充油丁苯橡胶中8种多环芳烃的含量

为从充油丁苯橡胶样品中分离提取其中所含8种多环芳烃化合物(PAHs,包括苯并[a]蒽、艹屈、苯并[b]荧蒽、苯并[j]荧蒽、苯并[k]荧蒽、苯并[e]芘、苯并[a]芘及二苯并[a,h]蒽),采用了冷冻研磨、超声浸提法。试验选择了5件样品分别将其粉碎至约2mm~3的颗粒,并取一定量的颗粒样品置于研磨仪中进行冷冻研磨至粉末状态。称取加工成粉末状的样品1.00g,加入正己烷-丙酮(1+1)混合溶液10mL,在40℃超声提取35min。将所得提取液氮吹浓缩至近干,用正己烷1mL溶解残渣,所得溶液经滤膜过滤,滤液供气相色谱-质谱分析。采用VB-17MS毛细管色谱柱,在90～300℃温度区间按程序升温模式进行分离。在质谱分析中,用电子轰击离子源和选择离子监测模式。测得8种PAHs的线性范围均在0.05～5.0mg·L~(-1)之间,检出限(3S/N)在0.01～0.02mg·L~(-1)之间。在样品溶液中加入混合标准溶液进行回收试验,测得回收率在84.5%～106%之间,并从测定值计算其相对标准偏差(n=6)在1.6%～4.9%之间。     

高效液相色谱法测定煤沥青中16种多环芳烃

建立了煤沥青中苯并[a]蒽、苯并[a]芘等16种多环芳烃(PAHs)的高效液相色谱分离检测方法。以甲苯为溶剂对煤沥青进行萃取,萃取液处理后经柱层析分离,层析洗脱液分组回收,然后进行液相色谱分析。采用ZORBAX Eclipse PAH柱分离,以乙腈-水为流动相进行梯度洗脱,紫外检测器进行测定。结果表明,16种PAHs的线性范围为0.5~20 mg/L,相关系数(r)均大于0.999,检出限为0.0031~0.035μg/L,方法的回收率为97.2%~108.3%,相对标准偏差(RSD)为0.18%~3.5%。方法用于两种不同煤沥青中16种PAHs含量的测定,两种煤沥青中16种PAHs的含量分别为107.86 g/kg和103.71 g/kg,其中苯并[a]芘的含量分别为11.86 g/kg和13.82 g/kg。     

同步扫描-化学除氧胶束增稳室温燐光法同时测定痕量菲和荧蒽的研究

本文利用同步扫描-化学除氧胶束增稳室温燐光法研究了痕量菲和荧蒽的同时测定。考察了菲和荧蒽二元混合物中两组分的相互干扰限量。讨论了在胶束体系中菲和荧蒽相互干扰的机理。实验表明,适宜的△λ为186nm。菲和荧蒽的同步峰分别位于480nm和547nm。该法的线性范围为:菲为2.7×10~7～4×10~(-6)mol/L,荧蒽为2.2×10~(7-)～1×10~(-5)mol/L。检出限为:菲为2.7×10~7mol/L,荧蒽为2.2×10~(-7)mol/L。相对标准偏差小于3％。     

专一性酶解-高效液相色谱-荧光检测法测定3种食用油中4种多环芳烃

称取食用油(动物油、植物油或经用于煎炸的食用油)2.0g与pH 8.0磷酸盐缓冲溶液5mL和脂肪酶0.2g混匀后,于(37±2)℃振荡酶解2h。加入碳酸钾1.0g皂化样品中的脂肪,以及乙醇5mL使在后续的提取中降低溶液的乳化现象。于此溶液中加入水5mL及正己烷提取4种多环芳烃{PAHs,即苯并[a]蒽(BaA)、苯并[b]荧蒽(BbF)、苯并[k]荧蒽(BkF)和苯并[a]芘(BaP)}2次,每次用正己烷15mL,振荡5min,离心5min,移取上层提取液,合并后于40℃旋蒸至干。用乙腈溶解残渣并定容至1.0mL,此溶液经0.22μm滤膜过滤,取滤液供在仪器工作条件下进行高效液相色谱(HPLC)分离后测定。选择Dikma Plus C18色谱柱为固定相,以不同体积比的(A)水和(B)乙腈的混合液为流动相进行梯度洗脱。上述4种PAHs的保留时间依次为9.3,12.0,12.6,13.9min。用荧光检测器分别测定其发射荧光的强度。在此4种PAHs中,BaA的荧光发射波长(λem)为380nm,BbF、BkF和BaP的λem在406nm波长处。分别取上述3种食用油的空白样品作为基体,加入加4种PAH的混合标准溶液系列制作标准曲线,测得其线性范围在相同的区间(0.1～5.0μg·L~(-1)),其检出限(3S/N)为0.03μg·kg~(-1)。分别以3种食用油样品作为基体,按标准加入法进行回收试验,测得其回收率均在90.0%以上,测定值的相对标准偏差(n=5)均小于9.0%。     

高效液相色谱——荧光分光光度法测定水中超微量多环芳烃

本文介绍了水样中超微量多环芳烃的高效液相色谱—荧光分光光度测定法。工作中选定的分离、检测条件,满足了快速定量的要求,10分钟内可实现七种多环芳烃的分离。定性工作中,除经典的保留值定性之外,还介绍了停流扫描荧光光谱、不同检测条件下的峰高比值,以及同步荧光光谱定性。在定量分析中,此法的最小检出浓度和回收率分别为:蒽0.54ppt(84.4%),荧蒽0.40ppt(100.9%),芘1.10ppt(96.5%),苯并[a]蒽0.03ppt(96.0%),苯并[a]芘0.02ppt(95.1%)。方法的精度及定量线性良好,线性范围达10~3。对实际水样的检验表明。本方法适合水中超微量多环芳烃的定性、定量分析。     

基于共价有机骨架涂层的搅拌棒吸附萃取/高效液相色谱测定环境水样中的多环芳烃

以刻蚀不锈钢丝（ESSW）为搅拌棒基体,用1,3,5-三（4-氨苯基）苯（TPB）和2,5-二乙烯基-1,4-苯二甲醛（DVA）两种单体,制备了一种分散良好的共价有机骨架涂层（TPB-DVA-COF）搅拌棒,结合高效液相色谱-紫外检测器（HPLC-UV）建立了环境水样中6种多环芳烃（PAHs）的分析方法。通过扫描电镜（SEM）、透射电镜（TEM）、傅里叶变换红外光谱（FTIR）等对涂层进行了表征,优化了离子强度、萃取温度、搅拌速率、萃取时间等条件。在优化条件下,菲、荧蒽和芘在0.20～200μg/L,?、苯并[b]荧蒽和苯并[a]芘在0.05～200μg/L范围内与色谱峰面积呈良好的线性关系,相关系数（r）不小于0.998 5,富集倍数最高可达到225倍,检出限（LOD,S/N=3）为0.007～0.150μg/L,同一根搅拌棒的相对标准偏差为3.8%～6.1%,样品加标回收率为87.1%～104%。结果表明,该方法可以成功地应用于实际环境水样中PAHs的准确和高灵敏检测。     

反相高效液相色谱/电喷雾质谱法分析化学合成七肽粗产物

利用RP—HPLC／ESI—MS直接分析用芴甲氧羰基(Fmoc)固相多肽合成方法在PHB树脂上偶联合成的一个七肽(H2N—Tyr—Val—Asn-Thr-Asn—Met—Gly—COOH,Mr797．3)粗产物。RP—HPLC显示合成粗产物含有1个主成分,4个次要成分和多个微量成分;与之联用的电喷雾质谱则同步准确地测定出各成分的分子量(m／z)并自动对各主要成分的化学结构进行了串联质谱分析。结果证明,粗产物中的主成分即为目标七肽,另外几个主要副产物为七肽的氧化产物或残缺肽。     

Formation of multimeric steroid metal adducts and implications for isomer mixture separation by traveling wave ion mobility spectrometry

Steroid analysis is essential to the fields of medicine and forensics, but such analyses can present some complex analytical challenges. While chromatographic methods require long acquisition times and often provide incomplete separation, ion mobility spectrometry (IMS) as coupled to mass spectrometry (MS) has demonstrated significant promise for the separation of steroids, particularly in concert with metal adduction and multimerization. In this study, traveling wave ion mobility spectrometry (TWIMS) was employed to separate multimer steroid metal adducts of isomers in mixtures. The results show the ability to separate steroid isomers with a decrease in resolution compared with single component standards because of the formation of heteromultimers. Additionally, ion‐neutral collision cross sections (CCS) of the species studied were measured in the mixtures and compared with CCSs obtained in single component standards. Good agreement between these values suggests that the CCS may aid in identification of unknowns. Furthermore, a complex mixture composed of five sets of steroid isomers were analyzed, and distinct features for each steroid component were identified. This study further demonstrated the potential of TWIMS‐MS methods for the rapid and isomer‐specific study of steroids in biological samples for use either in tandem with or without chromatographic separation.     

沉香的高效液相色谱-四极杆-飞行时间质谱数字化指纹图谱研究

采用高效液相色谱-四极杆-飞行时间质谱联用(HPLC-Q-TOF-MS)技术,研究构建了一种沉香数字化色谱-质谱指纹图谱的新方法。沉香药材经乙醇提取后,采用HPLC-Q-TOF-MS测定,并同时采集HPLC-Q-TOF-MS及液相色谱-紫外数据,得到液相色谱-紫外检测(HPLC-UV)色谱图和高分辨飞行时间质谱(TOF-MS)总离子流色谱图。对色谱图中的各个色谱峰进行精确质量数识别,建立数字化指纹图谱,以精确质量数结合保留时间表征沉香中的化学成分,即为每个色谱峰给出具有唯一性的数字信息,以数字化的形式反映其化学成分,并根据精确质量及同位素推算出分子式,结合二级质谱及文献资料共鉴定出30个化学成分。该方法对沉香的每种化学成分给出了类似于身份认定的数字化信息,具有唯一性,能全面反映沉香的物质成分,可为沉香的药理、药效及质量标准研究提供科学的数据。     

直接进样电喷雾质谱分析烷基苯磺酸盐

采用直接进样法，电喷雾质谱分析三次采油用烷基苯磺酸盐，可以得到定性结果，定出该表面活性剂中各组分的分子式，操作简单易行．     

嗜酸性氧化亚铁硫杆菌代谢产物的常压化学电离质谱分析

本研究以721矿和745矿嗜酸性氧化亚铁硫杆菌为研究对象,采用常压化学电离质谱直接分析其代谢产物,分别考察了顶空采样( Headspace sampling)、界面采样( Interface sampling)和中性解吸采样( Neutral desorption sampling)3种进样方式对电离效果的影响。在优化条件下,常压化学电离质谱对微生物纯菌种和混合菌种的代谢产物均具有良好的分析能力,可根据获得的代谢产物指纹谱图结合主成分分析( PCA)方法和聚类分析( CA)方法区分2个放射性强弱不同区域共4类嗜酸性微生物样品,并对主要胺类、酯类等代谢成分进行串联质谱鉴定,为耐辐射微生物的相关研究提供了一种可借鉴的分析方法。     

Discrimination and characterization of the volatile organic compounds of Acori tatarinowii rhizoma based on headspace-gas chromatography-ion mobility spectrometry and headspace solid phase microextraction-gas chromatography-mass spectrometry

Acori tatarinowii rhizome (ATR) is a Traditional Chinese Medicine (TCM), which has multiple effects, such as neuroprotective activity, antidepressant and other activity. However, the widespread cultivation of ATR has led to it varying quality. Therefore, it is important to find a method to quickly identify the components of ATR. Headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) and headspace solid phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC–MS) were applied to analyze and characterize the volatile organic compounds (VOCs) of ATR. 33 VOCs were identified by HS-GC-IMS and 95 VOCs were identified by HS-SPME-GC–MS from 15 batches of ATR. Then, quantification of estragole, methyleugenol, γ-asarone, β-asarone and asarone by gas chromatography-mass spectrometry (GC–MS). The fingerprint of HS-GC-IMS and the heatmap of HS-SPME-GC–MS were established. Which compared differential components of ATR. In addition, principal component analysis (PCA) was performed on the results of both instruments. The VOCs in the ATR were significantly correlated with β-asarone and asarone by PatternHunter analysis. It assisted HS-GC-IMS determine ATR quality. It is the first report regarding the method development of HS-GC-IMS and HS-SPME-GC–MS that targets the VOCs characterization of ATR, and the findings obtained would benefit the quality control and distinguish the complex analytical objects of ATR.     

反相高效液相色谱-电喷雾质谱法分析食源血管紧张素转换酶抑制肽

利用反相高效液相色谱/电喷雾离子阱质谱法,直接分析从牦牛乳酪蛋白中酶水解得到的血管紧张素转换酶抑制肽粗产物。RP-HPLC显示具有活性的多肽粗产物含有3个主要成分,质谱同步测定各组分的分子量(m/z)分别为815.2,1680.1,962.2,然后选择[M H] 离子通过串联质谱(MS/MS)得到碎片离子,利用b离子和y离子互补的方法鉴定了多肽序列。三条肽分别为Leu-Pro-Tyr-Tyr,Pro-Leu-Pro-Leu-Leu-Gln,Phe-Leu-Pro-Pro-Tyr-Tyr。结果显示,所获得的多肽序列与牛乳酪蛋白一级结构中相应肽段的序列一致。     

气相色谱-质谱测定樟林番荔枝种子挥发油的脂肪酸组成

用溶剂萃取法提取樟林番荔枝果实种子中的挥发性物质,测定出其挥发油质量分数为13.3%;利用GC-MS方法分离确认出其中的9种化学成分;用面积归一化法得出了9种脂肪酸在挥发油中的质量分数;其中9-十八烯酸占49.42%,十六酸占20.37%,十八酸占14.16%,9,2-十八二烯酸占13.59%;不饱和脂肪酸,占63.01%.该项研究给番荔枝果实的深入开发利用及种质资源的有效保护提供了科学依据.     

Accurate mass measurement and tandem mass spectrometry of intact globin chains identify the low proportion variant hemoglobin Lepore-Boston-Washington from the blood of a heterozygote

Within a mixture of proteins, minor polymorphic components are difficult to identify using a conventional proteomic approach. Their identification generally requires multi-dimensional separation steps, before or after proteolytic cleavage, followed by sequence analysis of the proteolytic products. In this study, we investigated the potential of tandem mass spectrometry for protein characterization by identifying the delta-beta hybrid human hemoglobin variant Lepore-Boston-Washington using electrospray ionization tandem mass spectrometry. Hemoglobin Lepore-Boston-Washington occurs mainly in heterozygotes, where it comprises approximately 10% of the total non-alpha-chains, the dominant non-alpha-chain being the normal beta (approximately 90%). Furthermore, Hemoglobin Lepore-Boston-Washington has an average molecular mass (15,865.23 Da) that is only 2 Da lower than that of the normal beta-chain (15,867.24 Da). Consequently, it cannot be resolved from the normal beta-chain by mass spectrometry. Here we show how Hemoglobin Lepore-Boston-Washington was identified directly from the diluted blood of a heterozygote by analyzing the product ions from the Lepore-Boston-Washington and normal beta-chain ions without prior separation of the individual chains. This study shows the potential of the tandem mass spectrometry for identifying a minor component in an unseparated mixture of proteins.     

Characterisation of archaeological waterlogged wood by pyrolytic and mass spectrometric techniques

Two techniques based on analytical pyrolysis and mass spectrometry, direct exposure-MS (DE-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), were used to characterise waterlogged archaeological wood and to study degradation patterns of wood in aqueous environments. The two techniques were applied to samples from the excavation of the Site of the Ancient Ships of Pisa San Rossore in Pisa (Italy), and data were compared to those relative to native sound wood of the same species (pine, elm, beech). Both the methods result valuable in the analysis of ancient wood artefacts, avoiding the long wet-chemical procedures that are commonly used in wood analysis, and allowing us to use a minimal sample size. DE-MS achieves a global mass spectral fingerprint of lignin and polysaccharides pyrolysis compounds in few minutes, and the results have been interpreted with the support of principal component analysis (PCA) of mass spectra. Py-GC/MS permits detailed molecular analysis of pyrolysis compounds and highlights some chemical modifications of lignin in archaeological samples, as demethylation of both guaiacyl and syringyl lignin units. Both the techniques demonstrate consistent loss of polysaccharides in archaeological wood.