Characterisation of Slovenian honeys on the basis of sensory and physicochemical analysis with a chemometric approach

The purpose of this study was sensory and physicochemical characterisation of Slovenian honeys with a chemometric approach. Honey samples were obtained from the beekeepers in different natural geographical macroregions of Slovenia. The sensory characteristics of the seven main types of Slovenian honeys are described, together with the physicochemical analyses. The average results of electrical conductivity (0.19–1.61 mS cm^?1), pH (4.01–5.51), free acidity (13.3–30.9 meq kg^?1), proline content (317–558 mg kg^?1), protein content (1.70–3.53 g kg^?1), optical rotation (–19.6 to 12.6), phenolic content (44.9–232.5 mg GAE kg^?1) and antioxidant activity [69.6–456.4 μm Fe(II)] show wide variability among analysed honey types. Statistically significant differences were obtained among different honey types, generally lower values of the analysed parameters were determined in the light honeys, as the acacia, linden and multifloral honeys, while the higher values are characteristic for darker honeys, as the chestnut, fir, spruce and forest honeys. Linear discriminant analysis was performed to classify the honey samples according to their botanical origin and proved that physicochemical parameters analysed can provide enough information for the classification and distinction of acacia, linden, multifloral and chestnut honeys, and the group of honeydew honeys (fir, spruce and forest honeys).     

Solid-phase microextraction-liquid chromatography-mass spectrometry applied to the analysis of insecticides in honey

An approach based on solid-phase microextraction-liquid chromatography-mass spectrometry (SPME-LC-MS) has been developed for determining 12 insecticides (bromophos ethyl, chlorpyrifos methyl, chlorpyrifos ethyl, diazinon, fenoxycarb, fonofos, phenthoate, phosalone, pirimiphos methyl, profenofos, pyrazophos, and temephos) in honey. The influence of several parameters on the efficiency of the SPME was systematically investigated. Under optimal conditions, the procedure provided excellent linearity (>0.990), detection and quantification limits (between 0.001 and 0.1?µg?g^?1 and between 0.005 and 0.5?µg?g^?1, respectively), and precision (<19% at the quantification limits and from 6 to 14% at ten times higher concentrations). However, recoveries were not so good, ranging from 19 to 92%. Honey samples were found that were contaminated with bromophos ethyl, diazinon, fonofos, pirimiphos ethyl, pyrazophos, and temephos at estimated concentrations from 6.2?±?1.2 to 19?±?3?ng?g^?1.     

Investigation of the aroma impact volatiles in Turkish pine honey samples produced in Marmaris,Datça and Fethiye regions by SPME/GC/MS technique

The aroma impact volatiles of twenty‐four pine honey samples produced in Marmaris, Datça and Fethiye regions of Turkey were evaluated by solid phase micro extraction/gas chromatography/mass spectrometry (MS) technique and the results were evaluated by using the analysis of variance and Duncan tests. A total of eight common volatiles nonanal, nonanol, decanal, octanal, 16‐oxosalutaridine, dodecanal, nonadecane and pentadecane were detected in three regions. The total area of the common volatiles were 73.01%, 78.10% and 73.91% in Marmaris, Datça, and Fethiye regions, respectively. There were not significant differences (P < 0.05) between the common volatiles detected in pine honey samples from three different regions. The major contributers to the pine honey aroma seems to be nonanal (aldehyde, citrus, fatty, floral, green, piny), nonanol (green, sweet, oily), decanal (soap, orange peel, tallow), and octanal (fat, soap, lemon, green). Nonanal seems to be the principal volatile component in all samples having average values of 46.82% in Marmaris, 51.67% in Datça and 48.63% in Fethiye regions.     

Optimisation of ultrasound extraction for flavonoids from semen astragali complanati and its identification by HPLC‐DAD‐MS/MS

The optimisation of ultrasound extraction of semen astragali complanati flavonoids was studied by measuring characteristic absorbance at 266 nm as the response and using response surface methodology (four‐variable, three‐level Box–Behnken design, BBD) in this article. The optimal conditions were obtained as 52 °C, 34 min, 26:1 (mL:g) and 100 mesh (0.120–0.150 mm) for extraction temperature, extraction time, solvent‐to‐sample ratio as well as particle size, respectively. Under these conditions, validation experiments were carried out and the experimental value of A₂₆₆ was 0.9907 ± 0.032 (n = 3), which corresponded to an experimental extraction yield of 7.08%. Compounds in the extracts obtained with the optimum extraction conditions were identified by high‐performance liquid chromatography coupled with diode array and mass spectrometry detectors (HPLC–DAD–MS). Among the 14 compounds that were tentatively identified in the extracts according to their ultraviolet‐visible spectroscopy, mass spectrometry and related literature reports, four were reported for the first time.     

Development of an integrated approach for the stability testing of flavonoids and ascorbic acid in powders

An integrated approach for determining the stability of flavonoids and ascorbic acid in powders was developed. A rapid analyte solubility procedure was used to decide whether HPLC, GLC, or NMR would best serve to measure the stability of each flavonoid. Both the flavonoid under study and ascorbic acid were measured in one analysis with any of the determinative methods. Seventeen flavonoids of differing types, as well as ascorbic acid, were evaluated to establish the approach. The effects of storage relative humidity (RH) on the stability of several flavonoid powders with and without ascorbic acid were then determined. Quercetin, luteolin, taxifolin, naringenin, and naringin were stable for up to 8 weeks in RHs up to 98%, and ascorbic acid was significantly destroyed in the presence of quercetin, luteolin, and taxifolin at 98% RH. Both grape anthocyanins and ascorbic acid were unstable in the presence of each other at 98% RH. The integrated approach could be used for shelf-life testing of powdered flavonoids under a variety of storage conditions.     

Multi-residue method for the determination of 450 pesticide residues in honey, fruit juice and wine by double-cartridge solid-phase extraction/gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry

A multi-residue method was developed for the determination of 450 pesticide residues in honey, fruit juice and wine using double-cartridge solid-phase extraction (SPE), gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS). The method development was based on an appraisal of the characteristics of GC-MS and LC-MS-MS for 654 pesticides as well as the efficiency of extraction and purification from honey, fruit juice and wine. Samples were first diluted with water plus acetone, then extracted with portions of dichloromethane. The extracts were concentrated and cleaned up with graphitized carbon black and aminopropyl cartridges stacked in tandem. Pesticides were eluted with acetonitrile + toluene, and the eluates were concentrated. For 383 pesticides, the eluate was extracted with hexane twice and internal standard solution was added prior to GC-MS determination. For 67 pesticides, extraction was with methanol prior to LC-MS-MS determination. The limit of detection for the method was between 1.0 and 300 ng g^-1 depending on each pesticide analyte. At the three fortification levels of 2.0-3000 ng g^-1, the average recovery rates were between 59 and 123%, among which 413 pesticides (92% of the 450) had recovery rates of 70-120% and 35 pesticides (8% of the 450) had recovery rates of 59-70%. There were 437 pesticides (97% of the 450) with a relative standard deviation below 25%; there were 13 varieties (3% of the 450) between 25.0 and 30.4%.     

Determination of the botanical origin of honey by Fourier-transformed infrared spectroscopy: an approach for routine analysis

Fourier-transformed infrared spectroscopy has been established for analysing most of the physical–chemical parameters of honey. Additionally this technique can be used for determination of the botanical origin of a honey sample by comparison of the mid-infrared spectra. In this study calibrations for authentification of the main regional honey types should be developed to be able to measure simultaneously physical–chemical properties and the botanical origin at a minimum of time and at low costs. Honey samples from local beekeepers were collected and characterized by standard methods. The most common honey types were used for calibration. We recorded the mid infrared spectrum from each honey sample. Classification models were achieved by PCA-calibration and validated with samples from various botanical origins. Honey of Brassica spp., Robinia pseudoacacia, Calluna vulgaris, Trifolium spp., Tilia spp., Helianthus annuus, Centaurea cyanus and honeydew honey was used for calibration. Afterwards the calibration models were improved during routine analysis. Most of the honey samples from rape, false acacia, heather and honeydew can be classified correctly by the FTIR in consideration of the physical–chemical and sensorial properties.     

GC-MS法检测婴儿配方奶粉甘油三酯中Sn-2位棕榈酸

研究建立一种高效、准确测定婴儿配方奶粉甘油三酯中Sn-2位棕榈酸含量的方法。采用国际标准化委员会（ISO）14156的方法提取脂肪,利用猪胰脂酶专一水解甘油三酯Sn-1,3位脂肪酸,通过氨基固相萃取柱法分离水解产物中单甘油酯,甲酯化后用气相色谱-质谱联用仪（GC-MS）检测Sn-2位棕榈酸。结果表明用氨基固相萃取柱法取代传统薄层层析法分离单甘油酯不仅操作简单,分离效果好,而且回收率高,测定结果准确,GC-MS法检测3种婴儿配方奶粉中Sn-2位棕榈酸占总棕榈酸的含量分别为40.5%、40.3%和40.8%,添加回收率范围为91.7%⁹8.5%,RSD为1.56%,重现性良好,完全适用于婴儿配方奶粉甘油三酯Sn-2位棕榈酸含量的检测。      

Optimisation and validation of a new analytical method for the determination of four natural and synthetic hormones using LC-ESI-MS/MS

A rapid liquid chromatographic-tandem mass spectrometric method was developed for the simultaneous determination of four natural and synthetic hormone residues (progesterone, testosterone, trenbolone acetate and zeranol) in animal tissue samples. Sample preparation was optimised to minimise time and solvent consumption. Meat samples were mechanically homogenised and digested in a procedure that gave similar recoveries to those enzymatically hydrolysed by Helix pomatia. Efficient extraction was achieved using acidified acetonitrile (1% acetic acid). Chromatographic conditions were optimised to minimise matrix effects. Analytes were separated using a C18 column with gradient elution using ammonium formate solution in methanol (MeOH)/water (1:9) and MeOH mobile phases. Finally, residues were qualitatively and quantitatively determined by electrospray ionisation tandem mass spectrometry in multiple reaction monitoring mode. Different parameters for LC-MS/MS (e.g., declustering potential and collision energy) were optimised using API 6500QT; all analytes were measured using positive-mode electrospray ionisation (ESI⁺) except zeranol which was measured in negative mode (ESI^–). Due to LC-MS/MS signal enhancement/suppression, the determination of hormones was based on matrix-matched standard calculations. The method was validated for the four hormones on meat samples at different fortification levels and showed accepted performance criteria according to European Commission Decision 2002/657/EC. Decision limits and detection capabilities were estimated for all analytes.     

桃仁油的超声波辅助提取及脂肪酸组成分析

以正己烷为溶剂,利用超声波辅助提取桃仁油,采用二次正交回归旋转组合设计,研究了提取温度、提取时间、料液比、超声波功率对出油率的影响,并通过GC-MS测定了桃仁油的脂肪酸组成。结果表明,各因素对桃仁油出油率的影响顺序为:料液比>提取温度>提取时间>超声波功率,最优提取工艺为:提取时间68min,料液比1∶10(g/mL),提取温度57℃,超声波功率160W。GC-MS结果显示桃仁油中含有8种脂肪酸,其中不饱和脂肪酸占88.48%,主要成分是油酸(57.69%)和亚油酸(30.43%)。     

云南不同产地玛咖挥发油成分的GC-MS检测及多元统计分析

为研究云南玛咖挥发油成分,对云南具有代表性的八个玛咖种植区样品采用同时蒸馏萃取法提取挥发油,利用气相色谱-质谱联用技术对所得挥发油进行分离鉴定,应用相似度评价、聚类分析和主成分分析等多元统计方法进行分析,结果鉴定出挥发油成分59种,其中共有成分39种,这些共有成分总含量在各地玛咖样品挥发油总量中占比都超过99%。含量较高的共有成分有:异硫氰酸苄酯、苯乙腈、4-甲氧基苄基异硫氰酸酯、3-甲氧基苯乙腈、棕榈酸、9,12,15-十八碳三烯酸、苯甲醛、9,12-亚油酸、9,12,15-十八碳三烯酸乙酯、亚油酸乙酯。云南八个玛咖种植区样品挥发油成分相似,但由于含量差别而呈现出具有明显差异的两个类别。      

Quantification of organophosphate insecticides and herbicides in vegetable samples using the “Quick Easy Cheap Effective Rugged and Safe” (QuEChERS) method and a high-performance liquid chromatography-electrospray ionisation-mass spectrometry (LC-MS/MS) technique

A Quick Easy Cheap Effective Rugged and Safe (QuEchERS) extraction was developed and followed by selective analysis using a liquid chromatography-mass spectrometry method for the quantification of eighteen pesticides in vegetable samples. This method was accurate (?99.5%), and it exhibited limits of detection and quantification values in the 0.006-0.091 and 0.020-0.314 μg kg⁻¹ ranges, respectively. Furthermore, the coefficients of variations (?0.9999) were less than 1% at the low μg kg⁻¹ end of the method. Mean recoveries ranged between 94% and 102%, and relative standard deviations were below 10%. Based on these results, the methodology was proven to be highly efficient, robust, and suitable for monitoring the maximum residue limits (MRL) compliance of a wide range of commodity/pesticide combination. This method was successfully applied to the analysis of vegetable samples that were collected from different government farmers’ markets and street shops in urban areas. The presence of target pesticides was found in the range of 0.016 and 50.85 μg kg⁻¹.     

气相色谱-质谱法分析福建地区橄榄中橄榄肉和橄榄仁挥发油成分

采用同时蒸馏萃取装置，对产自福建地区的橄榄中的橄榄肉和橄榄仁中的挥发油进行提取，测得橄榄肉、橄榄仁挥发油含量分别为0.96％、1.57％；并用气相色谱．质谱联用技术进行分析鉴定，结合计算机质谱图库检索技术对分离的化合物进行结构分析，鉴定出橄榄肉中有10种化学组分，占总挥发性物质总含量的66.05％；鉴定出橄榄仁中有32种化学组分，占总挥发性物质总含量的88.94％。应用峰面积归一化法确定了各成分的相对含量。结果表明：橄榄肉中主要含有丁化羟基甲苯（38．09％）、石竹烯（6．82％）等：橄榄仁中主要含有石竹烯（36.25％）、α-石竹烯（8．13％）等。     

唐古特白刺籽油的超临界CO2流体萃取及GC/MS分析

利用超临界CO2萃取唐古特白刺籽油,并对籽油进行了GC/MS分析。实验确定的最佳超临界CO2流体萃取条件是:萃取温度45℃,萃取压力20 MPa,CO2流量为35~40 kg/h,萃取时间120 m in,在此条件下白刺籽油的萃取率为15.11%。利用GC/MS对白刺籽油分析,发现其不饱和脂肪酸的相对含量高达93.37%。比较了超临界CO2萃取白刺籽油油样和石油醚萃取白刺籽油油样的理化性质,发现超临界CO2流体萃取的籽油质量优于传统溶剂萃取的籽油。     

Estimation of the honeydew ratio in honey samples from their physicochemical data and from their volatile composition obtained by SPME and GC‐MS

Differentiation of nectar and honeydew honeys is difficult, not only because of the wide variability in composition and organoleptic properties among samples from the same source, but also because of the frequent existence of honeys resulting from a blend of nectar and honeydew. A mathematical expression to evaluate the relative presence of honeydew in a honey sample (HD) has been developed from relevant physicochemical properties of honey samples selected as highly representative of both honey types on the basis of their physico‐chemical and melissopalynological analysis. As honey aroma depends on its volatiles composition, GC‐MS analysis of the volatile fraction obtained by SPME has been carried out in order to evaluate its usefulness in honey source differentiation. Stepwise regression from multicomponent volatiles data was used for the estimation of HD and for determining which volatile compounds were related to the different honey sources. Copyright © 2004 Society of Chemical Industry     

草果多酚物质提取及LC-MS/MS分析

对提油后的草果粉末进行了多酚提取工艺优化,多酚成分分析及抗氧化活性研究。在单因素实验的基础上,选取提取时间、料液比、乙醇浓度、提取温度进行了四因素三水平的Box-Behnken中心组合研究,运用Design Expert8.06软件对实验数据进行分析;利用LC-MS/MS对多酚物质进行定性;通过DPPH自由基清除法和ABTS自由基清除法检测了草果多酚的抗氧化活性。实验结果表明,草果多酚最佳提取工艺条件为:提取时间150 min、料液比1:30 g/mL、乙醇浓度60%、提取温度67℃、多酚提取得率为9.69%;同时,从草果中检测出6种（原儿茶酸、对羟基苯甲酸、香草酸、芦丁、槲皮素-3-O-β-D-吡喃葡萄糖苷、3,5-二-C-β-D-吡喃葡萄糖基根皮素）文献已报道的多酚类物质和4种（龙胆酸、原花青素B2、金丝桃苷、木樨草素-7-O-β-D-葡萄糖苷）文献未报道的多酚类物质;该草果多酚具有一定的DPPH、ABTS自由基清除能力,IC50值分别为42.46μg/mL和85.47μg/mL,且多酚浓度与其抗氧化活性正相关。      

超高效液相色谱-串联质谱法测定食品包装材料中全氟辛酸及其盐类物质

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)结合加速溶剂萃取测定食品包装材料中全氟辛酸及其盐类物质(PFOA)的方法.采用甲醇作为溶剂,加速溶剂提取法提取食品包装材料中的PFOA,提取液经0.2 μm有机滤膜过滤后,以甲醇、水为流动相,梯度洗脱,经UPLC分离后用多级反应监测(MRM)方式测定.用两个子离子的...     

Rapid multi-class multi-residue method for the confirmation of chloramphenicol and eleven nitroimidazoles in milk and honey by liquid chromatography-tandem mass spectrometry (LC-MS)

A confirmatory method was developed to allow for the analysis of eleven nitroimidazoles and also chloramphenicol in milk and honey samples. These compounds are classified as A6 compounds in Annex IV of Council Regulation 2377/90 (European Commission 1990) and therefore prohibited for use in animal husbandry. Milk samples were extracted by acetonitrile with the addition of NaCl; honey samples were first dissolved in water before a similar extraction. Honey extracts underwent a hexane wash to remove impurities. Both milk and honey extracts were evaporated to dryness and reconstituted in initial mobile phase. These were then injected onto a liquid chromatography-tandem mass spectrometry (LC-MS/MS) system and analysed in less than 9 min. The MS/MS was operated in multiple reaction monitoring (MRM) mode with positive and negative electrospray ionization. The method was validated in accordance with Commission Decision 2002/657/EC and is capable of analysing metronidazole, dimetridazole, ronidazole, ipronidazole and there hydroxy metabolites hydroxymetronidazole, 2-hydroxymethyl-1-methyl-5-nitroimidazole, and hydroxyipronidazole. The method can also analyse for carnidazole, ornidazole, ternidazole, tinidazole, and chloramphenicol. A recommended level of 3 µg l^?1/µg kg^?1 for methods for metronidazole, dimetridazole, and ronidazole has been recommended by the Community Reference Laboratory (CRL) responsible for this substance group, and this method can easily detect all nitroimidazoles at this level. A minimum required performance level of 0.3 µg l^?1/µg kg^?1 is in place for chloramphenicol which the method can also easily detect. For nitroimidazoles, the decision limits (CCα) and detection capabilities (CCβ) ranged from 0.41 to 1.55 µg l^?1 and from 0.70 to 2.64 µg l^?1, respectively, in milk; and from 0.38 to 1.16 µg kg^?1 and from 0.66 to 1.98 µg kg^?1, respectively, in honey. For chloramphenicol, the values are 0.07 and 0.11 µg l^?1 in milk and 0.08 and 0.13 µg kg^?1 in honey. Validation criteria of accuracy, precision, repeatability, and reproducibility along with measurement uncertainty were calculated for all analytes in both matrices.     

A simple method for the analysis of trans fatty acid with GC–MS and AT-Silar-90 capillary column

The study was aimed to evaluate a simplified gas chromatography method based on the AOAC method 996.06 to analyze the trans fat content in food samples. The gas chromatograph was equipped with mass spectrometer and Alltech AT^™-Silar-90 capillary column. Ten kinds of the trans fatty acid standard were separated completely from the cis standard and the chemical composition of the peaks was verified by using the mass spectrum. Under the optimized conditions, the recovery rate for triheptadecanoin was 99.0%, the correlation coefficients of trans fatty acid calibration curve was 0.9998 or higher. It demonstrated that the methylation and hexane extraction procedures used in this method was effective and the result was consistent. The major fatty acids found in the shortening sample were 16:0, 18:0, trans-18:1, cis-18:1, cis-18:2, and cis-18:3. The total trans fat content in the sample was 283.6 ± 18.2 mg/g. The current method was more convenient. It is adequate for the routine analysis of trans fat content in food products with low free fatty acid content.