混合型固相萃取-高效液相色谱-串联质谱法测定稻米中3种谷维素北大核心CSCD

建立了利用高效液相色谱-串联质谱结合混合型阴离子交换固相萃取柱测定稻米中3种谷维素(环木菠萝烯醇阿魏酸酯(CA-FA)、24-亚甲基环木菠萝烯醇阿魏酸酯(24MCA-FA)和菜油甾醇阿魏酸酯(Camp-FA))含量的分析方法。实验通过优化3种谷维素的多反应监测(MRM)质谱参数,比较了在不同流动相中的分离度以及响应强度,同时考察了不同提取条件、净化条件对3种谷维素提取率和净化效果的影响,再结合外标法定量,实现了对稻米中3种谷维素的定量分析。实验结果表明,采用5 mmol/L乙酸铵水溶液为流动相A,甲醇∶乙腈=1∶1(v/v)为流动相B,梯度洗脱,3种谷维素在Agilent Eclipse XDB-C8色谱柱(150 mm×2.1 mm,3.5μm)上基本分离且响应强度和峰形最佳;提取条件经正交实验优化后可得:料液比为1∶20(g/mL)、提取溶剂为甲醇、浸泡时间为12 h、超声温度为40℃以及超声时间为20 min时,3种谷维素提取率最高;对混合型阴离子交换固相萃取柱的上样溶剂以及洗脱溶剂优化后,样品基质效应为1.6%~10.8%。在各优化条件下,3种谷维素在各自的线性范围内线性良好,相关系数(r2)均≥0.9983,检出限(LOD)为0.5~1.0μg/L,定量限(LOQ)为2.0~3.5μg/L。在稻米样品本底浓度2、5和10倍的加标水平下3种谷维素的平均回收率为86.1%~110.6%,相对标准偏差(RSD)为0.9%~3.2%。该方法可快速准确测定稻米中3种谷维素的含量,为后续稻米中谷维素类化合物测定及鉴定奠定基础。     

Optimization of the extraction and fractionation of corn bran oil using analytical supercritical fluid instrumentation

Supercritical fluid extraction (SFE) is combined with supercritical fluid chromatography (SFC) in an analytical mode to develop a system for fractionating and enriching high value ferulate-phytosterol esters (FPE) contained in corn bran oil. Corn bran is initially extracted with neat supercritical carbon dioxide (SC-CO2) at various pressures (13.8, 34.5, and 69 MPa) and temperatures (40, 60, and 80 degrees C) to see if the FPE can be enriched in the extracts. These initial studies show the greatest percentage of FPE could be extracted under two sets of conditions: 69 MPa at 80 degrees C and 34.5 MPa at 40 degrees C. Both sets of parameters yield an extract containing approximately 1.25% FPE. A stock supply of corn bran oil is then produced by scaled-up SFE at 34.5 MPa and 40 degrees C for subsequent chromatographic fractionation. The SFE-obtained corn bran oil is then applied to the head of a minichromatographic column containing an amino-propyl sorbent. SFC is than commenced using neat SC-CO2 at 69 MPa and 80 degrees C to remove the majority of the triglyceride-based oil. Pressure and temperature are then lowered to 34.5 MPa and 40 degrees C, respectively, and ethanol is added as a modifier. The modifier is added in an increasing stepwise gradient program, and fractions are collected at equal volume intervals. The resultant fractions are analyzed by analytical high-performance liquid chromatography with evaporative light-scattering detection and show that FPE could be enriched to a 14.5% (w) level.     

Comparative studies of volatile oil composition of Rhododendron anthopogon by hydrodistillation, supercritical carbon dioxide extraction and head space analysis

Volatile oil composition of the leaves of Rhododendron anthopogon (Ericaceae) growing wild in alpine Western Himalaya was studied using different extraction techniques including SC-CO(2) extraction and hydrodistillation (HD). Results from different extraction methodologies were compared with headspace analysis (HS) and evaluated for the effectiveness of techniques in characterisation of various terpene categories and to assess their influence on the yield and composition of volatiles. Variability in constituents and in quantitative yields was observed. The results varied with different extraction methods. A total of 27 constituents in SC-CO(2) extraction, 31 in HD and 17 in HS analysis were identified. Constituents in SC-CO(2) and HD oils were identified by gas chromatography mass spectrometry analysis. SC-CO(2) extraction was carried out at 40°C and 140 bar pressure and the oil represented by major constituents as β-caryophyllene (5.96%), α-humulene (4.06%) and p-menthadiene-2,9-diol (7.28%); in HD, oil limonene (11.26%), β-caryophyllene (11.62%), α-humulene (7.22%), and E-nerolidol (5.83%) dominated the oil and in HS analysis, limonene (24.14%), γ-terpinene (40.73%), α-terpinene (4.92%), β-phellandrene (3.44%) and β-ocimene (7.15%) were present as major constituents.     

In vivo antioxidant activity of Pinus koraiensis nut oil obtained by optimised supercritical carbon dioxide extraction

In this study, an orthogonal array design OA? (3?) was employed to optimise the conditions of supercritical carbon dioxide (SC-CO?) extraction of Pinus koraiensis nut oil. The effects of pressure, temperature and extraction time on the oil yield were investigated. Next, the fatty acid composition of the oil was examined by gas chromatography-mass spectrometry (GC-MS). The in vivo antioxidant activity of the oil was determined by estimating the superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px), total antioxidant capacity (T-AOC) and the content of malondialdehyde (MDA) in rats fed with a high-fat diet. The results showed that extraction pressure and time were the main variables that influenced the oil yields. The optimal conditions with which to obtain highest yield of oil were determined to be 5760.83?psi, 50°C and 3.0?h (extraction yield was 458.5?g?kg?1); nine compounds, constituting about 99.98% of the total oil, were identified. The most abundant polyunsaturated fatty acids identified in the oil, linoleic acid and α-linolenic acid, constituted 41.79% and 15.62% of the oil, respectively. Moreover, the results on their antioxidant activities showed that the oil could improve the activities of SOD, GSH-Px and T-AOC, and reduce the content of MDA significantly, in the serum. These results indicate that P. koraiensis nut oil obtained by SC-CO? extraction had excellent antioxidant activities.     

Extractability of metals in municipal solid wastes fly ash using supercritical CO(2) containing Cyanex 302.

The extraction of lead from fly ash produced during the thermal treatment of municipal solid wastes was studied using supercritical carbon dioxide (SC-CO(2)) and Cyanex 302 (bis(2,4,4-trimethylpentyl)monophosphinic acid). The extraction of lead from the fly ash was carried out in a 5 cm(3) internal volume reaction vessel under static extraction conditions at 323 K, and 24 MPa for 1 h. The extraction efficiencies of lead ranged from 4% to the total extraction under the conditions of 0.05 g fly ash with 2 cm(3) Cyanex 302. There was a linear relationship between the extraction efficiencies of lead using the SC-CO(2) + Cyanex 302 and using a water-based method described by JLT13.     

Effect of background derivatization on the signal enhancement of pesticide residues extracted from edible oils

The effect of background derivatization on the signal enhancement of pesticide residues extracted from edible oil samples was studied by GC with negative chemical ionization MS. The analytes were extracted by a solvent extraction process, and the extract was subjected to rapid low‐temperature fat precipitation. The residual fatty acids were silylated by derivatization with N,O‐bis(trimethylsilyl)trifluoroacetamide. The chromatograms obtained from the derivatized samples showed higher signal intensity and lower detection levels when compared to the direct analysis without derivatization. The sensitivity levels of the method are either better or comparable to that of previously reported methodologies. The LODs of the analyzed organochlorine, organophosphorus, and synthetic pyrethroid residues in sunflower, rice bran, and ground oil samples were in the range of 0.02–0.5 ng/g, and the LOQs were in the range of 0.1–2 ng/g. The intraday and interday accuracies were in the range of 81–116% with RSDs less than 14%. The recoveries obtained were in the range of 53–89% with the RSD values less than 13% for all the studied pesticide residues.     

Composition and antimicrobial activity of the essential oil of Heracleum thomsonii (Clarke) from the cold desert of the western Himalayas

Volatile oil composition of hydro-distilled (HD) and supercritical carbon dioxide (SC-CO(2)) essential oil of freshly collected aerial parts of Heracleum thomsonii (Umbeliferae) from the western Himalayas was studied by GC-FID and GC-MS. Results revealed qualitative and quantitative dissimilarity in the composition of hydro-distilled and SC-CO(2) extracted oils. Nineteen constituents, which accounted for 89.32% of total constituents in HD oil, represented by limonene (4.31%), (Z)-β-ocimene (3.69%), terpinolene (22.24%), neryl acetate (36.19%), nerol (9.51%) and p-cymene-8-ol (2.61%) were identified. In SC-CO(2) extracted oil, 24 constituents representing 89.95% of total constituents were identified. Terpinolene (5.08%), germacrene D (2.17%), neryl acetate (51.62%), nerol (9.78%), geranyl acetate (2.06%), α-bisabolol (2.48%) and 1-nonadecanol (4.96%) were the dominating constituents. In?vitro antimicrobial activity of hydro-distilled oil was conducted against microrobial strains including two Gram-positive (Staphylococcus aureus and Bacillus subtilis) and five Gram-negative (Burkholderia cepacia, Escherichia coli, Enterobacter cloacae, Klebseilla pneumoniae and Pseudomonas aeruginosa) bacteria as well as seven fungi (Candida albicans, Issatchenkia orientalis, Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus, Aspergillus sydowii and Trichophyton rubrum) using broth microdilution method. The results of bioassay showed that the oil exhibited moderate to high antimicrobial activity against fungi C. albicans (MIC 625 μg?ml(-1)), A. parasiticus (MIC 312.5 μg?ml(-1)), A. sydowii (MIC 312.5 μg?ml(-1)), T. rubrum (MIC 625 μg?ml(-1)), Gram-positive bacteria B. subtilis (MIC 625?μg?ml(-1)) and Gram-negative bacteria P. aeruginosa (MIC 312.5 μg?ml(-1)).     

栀子花挥发油超临界CO2萃取工艺优选分析

采用超临界CO2萃取法,使用正交试验设计方案,以提取率为指标,对萃取温度、萃取压力、分离压力和分离温度等影响因素进行考察。结果表明,超临界CO2萃取法萃取栀子花挥发油成分的最佳工艺条件为：萃取压力15mPa,萃取温度35℃,分离压力15mPa,分离温度25℃。该方法简便、可靠、选择性高,适于工业化生产。     

Applications of supercritical fluid extraction (SFE) of palm oil and oil from natural sources

Supercritical fluid extraction (SFE), which has received much interest in its use and further development for industrial applications, is a method that offers some advantages over conventional methods, especially for the palm oil industry. SC-CO? refers to supercritical fluid extraction (SFE) that uses carbon dioxide (CO?) as a solvent which is a nontoxic, inexpensive, nonflammable, and nonpolluting supercritical fluid solvent for the extraction of natural products. Almost 100% oil can be extracted and it is regarded as safe, with organic solvent-free extracts having superior organoleptic profiles. The palm oil industry is one of the major industries in Malaysia that provides a major contribution to the national income. Malaysia is the second largest palm oil and palm kernel oil producer in the World. This paper reviews advances in applications of supercritical carbon dioxide (SC-CO?) extraction of oils from natural sources, in particular palm oil, minor constituents in palm oil, producing fractionated, refined, bleached, and deodorized palm oil, palm kernel oil and purified fatty acid fractions commendable for downstream uses as in toiletries and confectionaries.     

A Pilot-Scale Supercritical Carbon Dioxide Extraction to Valorize Colombian Mango Seed Kernel

Colombian mango production, which exceeded 261,000 t in 2020, generates about 40% of the whole fruit as solid waste, of which more than 50% are seed kernels (over 52,000 t solid by-product); though none is currently used for commercial purposes. This study reports the results of the supercritical carbon dioxide (scCO₂) extraction of an oil rich in essential fatty acids (EFAs) from revalorized mango seed kernels and the optimization of the process by the Response Surface Methodology (RSM). In pilot-scale scCO₂ experiments, pressure (23–37 MPa) and temperature (52–73 °C) were varied, using 4.5 kg of CO₂. The highest experimental oil extraction yield was 83 g/kg (37 MPa and 63 °C); while RSM predicted that 84 g/kg would be extracted at 35 MPa and 65 °C. Moreover, by fine-tuning pressure and temperature it was possible to obtain an EFA-rich lipid fraction in linoleic (37 g/kg) and α-linolenic (4 g/kg) acids, along with a high oleic acid content (155 g/kg), by using a relatively low extraction pressure (23 MPa), which makes the process a promising approach for the extraction of oil from mango waste on an industrial scale, based on a circular economy model.     

A new method for simultaneous estimation of unsaponifiable constituents of rice bran oil using HPTLC

Rice bran oil (RBO) is rich in a variety of bioactive phytochemicals otherwise known as unsaponifiable constituents (USC). Oryzanols, phytosterols, tocols, etc. are the major USC in RBO; the methods presently used for their estimation involve different techniques and require pretreatment of the sample. In this paper standardization of a simple method for simultaneous estimation of USC directly from RBO using HPTLC is presented. The method involves a two-stage separation of USC on a precoated silica gel 60 F(254 )TLC plate viz.: TLC-1 to separate sterols, oryzanols and tocols; TLC-2 to separate steryl esters, wax, and squalene. Calibration plots using the respective standards were made to determine LOD, LOQ, and linear regression equations. Recovery studies were also conducted and the values ranged from 93.45 to 101.97%. The LOD and LOQ values showed the sensitivity of the method. The instrumental precision was found to be in the range of 0.30 to 1.18 CV%. Quantitative estimation of USC in crude RBO and refined RBO using this method gave a concentration of 52.80 mg/g of USC in the crude and 33.48 mg/g in the refined oil. The present method for estimation of USC using HPTLC is fast, simple, accurate, precise, and sensitive, as demonstrated here.     

Hollow fiber liquid-phase microextraction coupled with gas chromatography-flame ionization detection for the profiling of fatty acids in vegetable oils

The development of a two phase hollow fiber liquid-phase microextraction technique, followed by gas-chromatography-flame ionization detection (GC-FID) for the profiling of the fatty acids (FAs) (lauric, myristic, palmitic, stearic, palmitoleic, oleic, linoleic, linolenic and arachidic) in vegetable oils is described. Heptadecanoic acid methyl ester was used as the internal standard. The FAs were transesterified to their corresponding methyl esters prior to the extraction. Extraction parameters such as type of extracting solvent, temperature, extraction time, stirring speed and salt addition were studied and optimized. Recommended conditions were extraction solvent, n-tridecane; extraction time, 35 min; extraction temperature, ambient; without addition of salt. Enrichment factors varying from 37 to 115 were achieved. Calibration curves for the nine FAs were well correlated (r(2)>0.994) within the range of 10-5000 μg L(-1). The limit of detection (signal:noise, 3) was 4.73-13.21 ng L(-1). The method was successfully applied to the profiling of the FAs in palm oils (crude, olein, kernel, and carotino cooking oil) and other vegetable oils (soybean, olive, coconut, rice bran and pumpkin). The encouraging enrichments achieved offer an interesting option for the profiling of the minor and major FAs in palm and other vegetable oils.     

超临界流体萃取-GC-MS分析西黄丸中挥发性成分

建立西黄丸中挥发油成分乙酸辛酯的含量测定方法,为西黄丸的质控标准提供依据。方法:超临界CO2萃取西黄丸中挥发油成分,采用气相色谱法测定乙酸辛酯含量;研究压力、温度、时间和粒度因素对挥发油得率与乙酸辛酯含量的影响,并进行了化学计量学分析。采用GC-MS分析了适宜条件的挥发油的成分。综合考虑挥发油得率和乙酸辛酯含量双指标,确定的西黄丸挥发油萃取条件为:粉碎粒度为80目,萃取压力为25 MPa,温度为40℃,时间为2 h。在此条件下,挥发油得率达到7.76%,乙酸辛酯含量达到0.72 mg·g^-1。通过指纹图谱、主成分分析(PCA)、正交偏最小二乘判别分析(OPLS-DA)化学计量学分析可知,不同萃取条件对所提取的挥发油物质组分及其含量没有显著性差异。GC-MS鉴定出的主要成分有(1S-endo)-2-甲基-3-亚甲基-2-(4-甲基-3--3-戊烯基)-二环[2.2.1庚烷、10α-羟基日本刺参萜、(±)-麝香酮、4-亚甲基-2,8,8-三甲基-2-乙烯基-双环[5.2.0]壬烷和2-甲基-4-(2,6,6-三甲基-1-环己烯-1-基)丁醛。结论:西黄丸挥发油成分适宜萃取条件,及建立的乙酸辛酯含量测定方法准确、可靠,为有效控制西黄丸质量,完善其质量标准及进一步的药效成分研究提供了科学依据。     

Selective extraction of uranium from a mixture of metal or metal oxides by a tri-n-butylphosphate complex with HNO(3) and H(2)O in supercritical CO(2).

In order to study the decontamination nature of the reactive extraction of uranium in the presence of some metal chemicals using a single-phase mixture of HNO(3), H(2)O and tri-n-butylphosphate (TBP) in supercritical carbon dioxide (SC-CO(2)), we measured the decontamination factors (DFs) of Sr, Zr, Mo, Ru, Pd, Ce and Nd from their mixture with U. These elements were originally added to U(3)O(8) as SrO, ZrO(2), MoO(3), RuO(2), Pd, CeO(2) and Nd(2)O(3), and the extraction was performed at 18 MPa and 323 K with the single-phase mixture. The DFs for these elements were determined to be greater than 10(3) when the molecular ratio of U to TBP in the extracted complex was greater than 0.3. Dilution by SC-CO(2) effectively increased the DFs.     

Extraction and detection of arsenicals in seaweed via accelerated solvent extraction with ion chromatographic separation and ICP-MS detection

An accelerated solvent extraction (ASE) device was evaluated as a semi-automated means of extracting arsenicals from ribbon kelp. The effect of the experimentally controllable ASE parameters (pressure, temperature, static time, and solvent composition) on the extraction efficiencies of arsenicals from seaweed was investigated. The extraction efficiencies for ribbon kelp (approximately 72.6%) using the ASE were fairly independent (< 7%) of pressure, static time and particle size after 3 ASE extraction cycles. The optimum extraction conditions for the ribbon kelp were obtained by using a 3 mL ASE cell, 30/70 (w/w) MeOH/H2O, 500 psi (1 psi = 7 KPa), ambient temperature, 1 min heat step, 1 min static step, 90% vol. flush, and a 120 s purge. Using these conditions, two other seaweed products produced extraction efficiencies of 25.6% and 50.5%. The inorganic species present in the extract represented 62.5% and 27.8% of the extracted arsenic. The speciation results indicated that both seaweed products contained 4 different arsenosugars, DMA (dimethylarsinic acid), and As(V). One seaweed product also contained As(III). Both of these seaweed products contained an arsenosugar whose molecular weight was determined to be 408 and its structure was tentatively identified using ion chromatography-electrospray ionization-mass spectrometry/mass spectrometry (IC-ESI-MS/MS).     

傅里叶变换红外吸收光谱识别五种植物油的研究

以花生油、大豆油、芝麻油、棉籽油和米糠油为样品,采用傅里叶变换红外光谱仪,采集傅里叶变换红外吸收光谱,对光谱预处理后,提取红外特征信息,以1746cm-1和2855cm-1处的吸收峰面积比值为横坐标,1099cm-1处与1119cm-1处的吸收峰面积比为纵坐标,在Origin6.0上做出二维分布图,对各种油脂进行识别分析。结果显示,大豆油与其它4种油脂之间有明显区分;大豆油、花生油和芝麻油分布效果好,但棉籽油各样品点之间比较分散;能与其它油脂区分开的有以下几种分布花生油明显区别于芝麻油、棉籽油和大豆油;米糠油明显区别于棉籽油和大豆油。分布有交叉的油脂有米糠油与花生油或芝麻油有交叉,棉籽油与芝麻油有交叉。     

超临界流体萃取法对有机锡化合物的选择性萃取

 研究了用超临界流体萃取法直接从脂肪基质的固体样品（大豆粉）中选择性地萃取有机锡化合物的方法。模拟试样萃取结果表明：用较低压力和较高温度的超临界态ＣＯ２作流动相时，有机锡达到最大萃取率，而脂肪类物质仅被少量萃取，从而消除了脂肪类物质对超临界流体色谱法测定有机锡的干扰。     

Extraction and detection of arsenicals in seaweed via accelerated solvent extraction with ion chromatographic separation and ICP-MS detection

An accelerated solvent extraction (ASE) device was evaluated as a semi-automated means of extracting arsenicals from ribbon kelp. The effect of the experimentally controllable ASE parameters (pressure, temperature, static time, and solvent composition) on the extraction efficiencies of arsenicals from seaweed was investigated. The extraction efficiencies for ribbon kelp (approximately 72.6%) using the ASE were fairly independent ¶(< 7%) of pressure, static time and particle size after 3 ASE extraction cycles. The optimum extraction conditions for the ribbon kelp were obtained by using a 3 mL ASE cell, 30/70 (w/w) MeOH/H₂O, 500 psi (1 psi = 7 KPa), ambient temperature, 1 min heat step, 1 min static step, 90% vol. flush, and a 120 s purge. Using these conditions, two other seaweed products produced extraction efficiencies of 25.6% and 50.5%. The inorganic species present in the extract represented 62.5% and 27.8% of the extracted arsenic. The speciation results indicated that both seaweed products contained 4 different arsenosugars, DMA (dimethylarsinic acid), and As(V). One seaweed product also contained As(III). Both of these seaweed products contained an arsenosugar whose molecular weight was determined to be 408 and its structure was tentatively identified using ion chromatography-electrospray ionization-mass spectrometry/mass spectrometry (IC-ESI-MS/MS).     

Reactive Extraction of Citric Acid Using Tri-n-octylamine in Nontoxic Natural Diluents: Part 1—Equilibrium Studies from Aqueous Solutions

Use of cheap, nontoxic, and selective solvents could economically provide a solution to the recovery of carboxylic acids produced by the bioroute. In this regard in the present paper, reactive extraction of citric acid was studied. Problems encompassing the recovery of the acid ([H₃A] _aq ^o ?=?0.1?C0.8) was solved by using tertiary amine (tri-n-octylamine, TOA) in natural diluents (rice bran oil, sunflower oil, soybean oil, and sesame oil). TOA was very effective in removal of acid providing distribution coefficient (D) as high as 18.51 (E%?=?95?%), 12.82 (E%?=?93?%), 15.09 (E%?=?94?%), and 16.28 (E%?=?94?%) when used with rice bran oil, sunflower oil, soybean oil, and sesame oil, respectively. Overall extraction constants and association numbers for TOA + rice bran oil, TOA + sunflower oil, TOA + soybean oil, and TOA + sesame oil were evaluated to be 35.48 (mol/l)^?1.46, 29.79 (mol/l)^?1.30, 33.79 (mol/l)^?1.51, and 37.64 (mol/l)^?1.65 and 1.46, 1.30, 1.51, and 1.65, respectively. Specific equilibrium complexation constants (K _E(n/m)) were also predicted using mathematical modeling.     

紫外分光光度计检测十二烷基苯磺酸钠鉴别潲水油的方法研究

建立了潲水油中十二烷基苯磺酸钠(SDBS)的检测方法,样品经高纯水提取、三氯甲烷萃取、亚甲蓝显色后,以紫外分光光度法进行测定。考察了提取温度、提取时间等因素的影响。实验结果表明,水对食用油中SDBS的最佳提取时间为2 h,温度为50℃,检测波长为645 nm。方法检出限(LOD)为0.1μg/kg。加标量分别为1.0、5.0、10.0、20.0μg/kg时的回收率为94%～96%,相对标准偏差(RSD)均小于5%。5组实际样品的检测结果显示,潲水油中SDBS的残留量平均值为19.19μg/kg,优质食用油中SDBS的平均含量为0.35μg/kg。潲水油中SDBS的含量有很大差别,但总体均高于优质食用油中的含量,方法可用于潲水油和食用植物油的鉴别。