Study on Oleuropein Extraction from Olive Tree (Olea europaea) Leaves by means of SFE: Comparison of Water and Ethanol as Co-Solvent

The present study focuses on developing methods for olive leaf extraction and deals with obtaining extract, rich in oleuropein, which is the most abundant phenolic compound in olive leaves. Supercritical fluid extraction (SFE) was applied to the dried and ground olive leaves by using CO₂ as supercritical (SC) fluid in the presence of water and ethanol as co-solvent. The influences of operating parameters by means of co-solvent content (0-1 mL/min), temperature (50 and 100°C) and pressure (100-300 bar) on both extract and oleuropein yields were investigated. Quantitative analysis was performed by using a liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) technique. The experimental results obtained by using SC-CO₂ alone were not satisfactory, and it was seen that addition of a polar modifier is necessary in order to improve yield and selectivity of the process. It was observed that CO₂ modified by water and ethanol showed nearly the same extract performance, where CO₂ modified by water is better for high oleuropein yield.     

Molecular Imprinted Solid-Phase Extraction System for the Selective Separation of Oleuropein from Olive Leaf

Oleuropein has many antimicrobial, antiviral, and anticancer features found in olive leaf. Therefore, its isolation from olive leaf is very important in such kinds of applications. In this study, a solid-phase extraction system based on the molecularly imprinted polymer (MIP) was proposed for the selective separation of oleuropein from olive leaf. First, oleuropein imprinted polymer has been prepared by the suspension polymerization using methacrylolamidoantiprine–iron (III) metal-chelate monomers. After that, the oleuropein adsorption capacity and selectivity of the prepared imprinted polymer has been determined. The maximum adsorption capacity of oleuropein has found to be 140 mg g^?1. Finally, MIP has been used as a sorbent in the solid-phase extraction for the separation of oleuropein from crude extract of olive leaves. The oleuropein analyses have been realized by high performance liquid chromatography. The obtained results indicated that the prepared molecularly imprinted sorbent could be used for at least 10 times for purification of oleuropein from olive leaf. The application of the proposed system in the real sample showed that 24.2 mg pure oleuropein could be obtained from 1.0 g of crude olive leaf extract. As a result, the low cost, simple, and selective adsorbent has been developed for oleuropein adsorption. Supplemental materials are available for this article. Go to the publisher's online edition of Separation Science & Technology to view the supplemental file.     

香椿叶超临界CO2萃取物在卷烟中的作用研究

利用超临界CO2萃取香椿叶,萃取物产率为0．5％。利用GC—MS对香椿叶萃取物化学成分进行了分析鉴定,鉴定出了33种成分。进行了香椿叶萃取物在参比卷烟中的作用评价,结果表明：香椿叶超临界CO2萃取物在细腻柔和烟香方面有明显作用．在提高香气质、降低刺激方面有作用。     

珊瑚姜的超临界CO2萃取及其提取物GC/MS分析

用超临界CO2萃取技术对珊瑚姜进行提取分离,通过正交试验确定了最佳萃取工艺条件,即萃取时间150 min、萃取温度45℃、萃取流速20 L/h、萃取压力25 MPa。用气相色谱/质谱(GC/MS)联用仪对提取物成分进行了分析,共检测出38种化合物。超临界CO2萃取珊瑚姜方法简便、快速、高效,操作温度低,不破坏热敏性成分,无溶剂残留。     

超临界二氧化碳流体萃取油茶籽油及其GC／MS分析

采用环境友好的超临界二氧化碳流体萃取技术制备油茶籽油,考察了压力、时间、温度和二氧化碳流量等因素对茶籽油萃取率的影响,得到优化的工艺参数：当萃取压力30MPa、萃取温度35℃、CO2流量30L／h、萃取时间为3h时茶籽油萃取率可高达44．4％。根据中华人民共和国国家标准进行检测的结果表明：超临界二氧化碳流体萃取出的茶籽油,无需进一步精制即可达到国家食用植物油卫生标准GB／T2716—2005,而除含皂量、水分及挥发物外的指标均达到国家一级茶油标准GB11765—2003;GC／MS分析结果表明油茶籽油富含73．6％不饱和脂肪酸。实验结果表明：超临界二氧化碳流体技术萃取茶籽油具有操作简便、萃取率高、无溶剂残留、绿色环保等优点,萃取出的茶籽油具有较高的品质和良好的应用前景。     

超临界萃取气-质联用分析虎舌红挥发油化学成分

用超临界流体萃取法对虎舌红挥发油的化学成分进行了分离提取研究,用气相-质谱联机技术,对其中的46种组分进行了鉴定,并测定了相对含量。结果表明,所鉴定出的46个组分中,质量分数在1.0%以上的组分有:石竹烯17.20%、α-石竹烯9.02%、3,7,11-三甲基-1,6,10-十二碳三烯-3-醇7.03%、兰桉醇5.54%、龙脑5.51%、α-萜品醇5.02%、水杨酸甲酯2.23%、芳樟醇2.10%、苯乙醇2.19%、α-杜松醇4.45%、己酸4.55%、α-没药醇2.51%、丁子香基乙醇2.11%、金合欢醇1.78%、β-没药烯1.71%、3-己烯-1-醇1.67%、氧化石竹烯1.62%等,它们占挥发油总质量的87.24%。     

Supercritical fluid extraction to determine the oil content in copra and extracted meal

Supercritical fluid extraction (SFE) was used as a primary method to determine the oil content of copra and its meal. Determination of the oil content of copra takes 9 h, and for meal 6 h are necessary with Soxhlet extraction, whereas SFE determined oil contents in about 10 min. The extremely high oil content of copra makes grinding difficult, as the sample becomes very gummy and it is difficult to remove the entire sample from the grinder. Adding diatomaceous earth to the sample before grinding eliminated the difficulties of cleaning the grinder and also enabled very fast SFE extractions. The variances for Soxhlet and SFE were not significantly different from each other (P>0.10) in both copra and meal oil contents. The 95% confidence interval around the mean differences (SFE-Soxhlet) was (−0.35, 0.90) and (0.08, 0.26) and for copra and meal, respectively. Although the SFE meal oil content (9.81%) was significantly higher than the Soxhlet meal oil content (9.64%), the size of the average difference (0.17%) was relatively small. This small difference was considered acceptable owing to the ability to use SFE in real-time process control. Therefore, SFE can be used to determine the oil content in copra and its meal in less than 10 min.     

超声强化超临界流体萃取薏苡仁油和薏苡仁酯的影响因素及效果

考察了超声强化超临界流体萃取(USFE)薏苡仁中的薏苡仁油和薏苡仁酯的效果。以 CO2作为超临界流体分别研究了萃取过程中萃取温度、萃取压力、原料颗粒大小、超临界流体流量、超声参数、萃取时间等因素对萃取率的影响,并与超临界流体萃取(SFE)进行对比。结果表明,超声强化超临界流体萃取过程,最适宜的萃取温度为 40℃,比超临界流体萃取的最适宜的萃取温度降低了 5℃;最适宜的萃取压力为 20Mpa, 比超临界流体萃取的最适宜的萃取压力降低了 5Mpa;最佳萃取时间为 3.5h,比超临界流体萃取的最佳萃取时间缩短了 0.5h;萃取率提高约 10%左右。若萃取率相同时,流体流量可减少 0.5L·h-1 ,原料粒径的要求可放宽。     

液相色谱串联质谱与通过式固相萃取结合测定人体血液和血清中的伏立康唑和卡马西平

采用通过式固相萃取建立高效液相色谱-串联质谱(HPLC-MS/MS)快速测定人体血液和血清中伏立康唑和卡马西平的方法.样品经蛋白沉淀后过PRiME HLB通过式固相萃取柱净化,以Poroshell 120 EC-C18(4.6 mm×50 mm,2.7μm)为色谱柱,0.01 mol/L醋酸铵水溶液-乙腈(含0.1％甲...     

高效液相色谱-电喷雾串联质谱法测定水产品中14种喹诺酮类与磺胺类药物残留

建立了高效液相色谱-电喷雾串联质谱法测定水产品中恩诺沙星、环丙沙星、双氟沙星、沙拉沙星、氟甲喹、喹酸、磺胺嘧啶、磺胺甲唑、磺胺喹啉、磺胺甲基嘧啶、磺胺二甲氧嘧啶、磺胺二甲基嘧啶、磺胺间二甲氧嘧啶、甲氧苄胺嘧啶共14种常用喹诺酮类与磺胺类兽药的残留检测方法。样品制备后,采用1%乙酸-乙腈提取液提取,用正己烷净化处理后,采用LC/MS/MS电喷雾电离(ESI),多反应监测(MRM)正离子模式检测,外标法定量。在0～100μg/kg范围内14种兽药的线性相关系数均>0.99。在添加浓度5～50μg/kg范围内,14种药物的回收率在70.0%～110%,相对标准偏差(RSD)均在12%以内。方法的检出限为0.1～0.5μg/kg。     

Separation and Purification of Three High-Purity Isoflavonoids from Belamcanda chinensis (L.) DC. by Supercritical Fluid Extraction and High-Speed Counter-Current Chromatography

Supercritical fluid extraction (SFE) was used to extract three isoflavonoids including irigenin, irisfloretin and dichtomitin from Belamcanda chinensis (L.) DC. The parameters including pressure, temperature, sample particle size, and flow rate of CO₂ were optimized with an orthogonal test. Under the optimized conditions of 15 MPa, 55°C, a sample particle size of 20–40 mesh and CO₂ flow rate of 40 L h^?1. The process was then scaled up by 10 times using a preparative SFE system. The yield of the crude extract from SFE was 4.1%, which contained irigenin, irisfloretin, and dichtomitin 0.71%, 0.49%, and 0.05%, respectively. To compare the extraction methods, Soxhlet Extraction (SE) was performed. The results indicated that SFE was better than SE. Irigenin, irisfloretin, and dichtomitin in the SFE extract were then separated and purified by high-speed counter-current chromatography (HSCCC) with a two-phase solvent system composed of petroleum ether–ethyl acetate–methanol–water (2:4:3:3, v/v). From 5.0 g of dry crude extract, 27.8 mg irigenin, 16.4 mg irisfloretin, and 2.1 mg dichtomitin were obtained at purities of 97.1%, 96.4%, and 98.0%, respectively, as determined by HPLC-PDA. These results well indicate that SFE and HSCCC are very powerful techniques for the extraction and purification of irigenin, irisfloretin, and dichtomitin from B. chinensis.     

固相萃取-气质联用测定辣椒油中对位红

研究了固相萃取-气质联用测定辣椒油中对位红的分析方法。用Strata-X小柱进行辣椒油样品的前处理,用气质联用法对对位红进行定性和定量分析。对位红方法的检出限为2．0μg／L,平均回收率为93．8％,RSD为1．3～3．5％。     

固相萃取-超高效液相色谱-串联质谱法测定祛痘化妆品中4种林可胺类化合物

采用固相萃取净化技术和超高效液相色谱-串联质谱方法(UPLC-MS/MS),建立了测定祛痘化妆品中4种林可胺类化合物(林可霉素、克林霉素、克林霉素磷酸酯和吡利霉素)的分析方法。样品用酸化乙腈提取,阳离子交换固相萃取小柱(MCX)净化,以乙腈-10mmoL/L乙酸铵溶液(pH 3.0)为流动相,经C18色谱柱梯度洗脱分离,电喷雾正离子模式电离,多反应监测模式检测,外标法定量。结果表明,4种林可胺类化合物的方法定量限(LOQs)均为10μg/kg;在5~200μg/L范围内线性关系良好,相关系数均大于0.999 0;在祛痘膏、祛痘水样品中进行10、100、1 000μg/kg 3个添加水平试验,平均回收率范围为87%~105%,相对标准偏差(n=6)在3.3%~10.2%之间。采用此方法测定了祛痘化妆品中林可胺类化合物的含量水平,发现存在违规添加现象。     

基于液相色谱-串联质谱法检测多种食品中的16种合成着色剂

针对多种食品基质(葡萄酒、汽水、黄酒、植物蛋白饮料、乳饮料、花生酱、芝麻酱和糕点)建立了同时测定赤藓红、亮蓝、诱惑红、日落黄、靛蓝、柠檬黄、苏丹红Ⅰ、苏丹红Ⅱ、苏丹红Ⅲ、苏丹红Ⅳ、酸性红1、酸性红4、酸性红8、酸性红14、酸性红88和酸性红97这16种合成着色剂的高效液相色谱-质谱联用分析方法.根据样品种类和所含成分的差别,建立了不同的样品预处理方法,并且通过对提取溶剂的讨论,采用混合溶剂V(甲醇)∶V(乙腈)=2∶3作为提取试剂,比单一溶剂的提取效率更高.萃取液经Kromasil 100-5型色谱柱(150 mm×2.1 mm×5.0 μm)分离,外标法定量.结果表明,16种合成着色剂呈现良好的线性关系(r2 =0.998 9～0.9998),方法的检测限为0.10或0.010 mg/kg,进行低、中、高3个浓度水平添加实验的平均回收率为86.5％ ～97.3％,相对标准偏差＜4.9％(n=6).该方法重现性好,适合于多种食品中上述16种合成着色剂的检测.     

Characterisation of end groups in poly(2-hydroxyethyl methacrylate) by means of electrospray ionisation-mass spectrometry/mass spectrometry (ESI-MS/MS)

Poly(2-hydroxyethyl methacrylate) (poly(HEMA)) has been characterised by means of electrospray ionisation-mass spectrometry/mass spectrometry (ESI-MS/MS), in order to evaluate this technique for the generation of end group information. Low energy collision-induced dissociation (CID) data from poly(HEMA) enabled information on both end groups of the polymer chain to be gleaned, in a similar fashion to that proposed previously for other methacrylate polymer systems. Exact-mass CID information was employed to aid the understanding of the dissociation mechanism of the polymer. Some additional fragmentation pathways, compared to other methacrylate polymer systems, are proposed. An example of how software can aid the interpretation of the MS/MS data is also shown.     

固相萃取-超高效液相色谱-三重四级杆质谱联用仪同时测定水中有机磷农药残留

应用固相萃取-超高效液相色谱-三重四级杆质谱联用仪(UPLC-MS/MS)建立了水中26种有机磷农药(OPPs)的分析方法。通过对固相萃取柱、淋洗液、流动相等优化,确定以Oasis HLB固相萃取柱、V(丙酮)∶V(二氯甲烷)=8∶2为淋洗液、V(0.1%甲酸甲醇)∶V(0.1%甲酸乙酸铵)=5∶5为流动相做水样预处理。在最优条件下,目标物在水中回收率为80.5%~119.8%,相对标准偏差(RSDs)为5.9%~11.5%。各目标物的线性范围为1~2 000μg/L,线性相关系数(R2)0.999以上。该方法具有检测限低、回收率高等优点,经实际样品测试,可适用于水中26种OPPs残留的同时检测。     

RRLC—MS—MS对海水养殖水体中磺胺类残留量的检测

建立了快速高分离液相色谱-色谱串联质谱法同时测定海水养殖水体中16种磺胺类抗菌素的方法。水样经固相萃取小柱富集、洗脱、浓缩后用液相色谱串联质谱仪测定,采用多反应监测模式进行测定,内标法定量。方法的检出限在0.467-1.88 ng/L之间,加标回收率在80.1%114%之间,相对标准偏差（RSD）0.731%-8.79%;适用于海水养殖水体中磺胺类残留的定量检测。     

Pharmacokinetics of Dibutyl Phthalate (DBP) in the Rat Determined by UPLC-MS/MS

Dibutyl phthalate (DBP) is commonly used to increase the flexibility of plastics in industrial products. However, several plasticizers have been illegally used as clouding agents to increase dispersion of aqueous matrix in beverages. This study thus develops a rapid and validated analytical method by ultra-performance liquid chromatography with tandem mass spectrometry (UPLC-MS/MS) for the evaluation of pharmacokinetics of DBP in free moving rats. The UPLC-MS/MS system equipped with positive electrospray ionization (ESI) source in multiple reaction monitoring (MRM) mode was used to monitor m/z 279.25→148.93 transitions for DBP. The limit of quantification for DBP in rat plasma and feces was 0.05 μg/mL and 0.125 μg/g, respectively. The pharmacokinetic results demonstrate that DBP appeared to have a two-compartment model in the rats; the area under concentration versus time (AUC) was 57.8 ± 5.93 min μg/mL and the distribution and elimination half-life (t_1/2,α and t_1/2,β) were 5.77 ± 1.14 and 217 ± 131 min, respectively, after DBP administration (30 mg/kg, i.v.). About 0.18% of the administered dose was recovered from the feces within 48 h. The pharmacokinetic behavior demonstrated that DBP was quickly degraded within 2 h, suggesting a rapid metabolism low fecal cumulative excretion in the rat.     

超高效液相色谱-串联质谱法测定化妆品中的9种性激素成分

采用超高效液相色谱-串联质谱（UPLC-MS/MS）检测技术,建立了化妆品中睾酮等9种性激素成分的检测方法。样品经质量分数50%乙腈提取,经流动相（水+乙腈）提取过滤后,采用C18柱（100 mm×2.1 mm×3.0μm）进行分离,用电喷雾离子源、正负离子模式进行扫描,在多反应离子监测模式下检测,基质匹配标准曲线外标法定量。结果表明,9种性激素在5～115 ng/mL范围内线性关系良好,相关系数大于0.999;加标回收率为80%～120%,RSD小于5%(n=3),检出限均低于0.03μg/g。该方法简单、快速、灵敏,能够满足化妆品中睾酮等9种性激素的检测需求。     

DSPE-UPLC-QTOF/MS法测定水中氨基甲酸酯类农药

研究建立分散固相萃取-超高效液相色谱-四极杆串联飞行时间质谱(DSPE-UPLC-QTOF/MS)法测定水环境中3种氨基甲酸酯类农药(残杀威、仲丁威、速灭威)的分析方法。将萃取剂HC-C18颗粒直接投加到水样中,经过振荡后对目标物萃取,用空萃取柱进行过滤回收水样中的HC-C18颗粒,后经洗脱、氮吹浓缩后用UPLC-QTOF/MS检测器测定。实验中对萃取剂的选择、萃取时间、洗脱剂种类以及水样的p H等条件进行了优化,得到了最佳的萃取条件。3种氨基甲酸酯农药在0.5~100μg/L范围内具有良好的线性(R0.993 9),检出限介于6.40~11.3 ng/L之间。空白水样加标为1μg/L时,相对标准偏差(RSD)为3.5%~10.4%,加标回收率为77%~105%。该方法可用于水体中氨基甲酸酯的分析测定。