Determination of thiabendazole in fruit juices by a new monoclonal enzyme immunoassay

A competitive, indirect enzyme-linked immunosorbent assay (ELISA) for thiabendazole has been developed and applied to the analysis of fruit juices spiked with this fungicide. The immunoassay is based on a new monoclonal antibody derived from a hapten functionalized at the nitrogen atom in the 1-position of the thiabendazole structure. To our knowledge, such a structure has not been previously used to obtain antibodies to thiabendazole. The I50 value and the detection limit of the ELISA for standards were 0.2 and 0.05 ng/mL, respectively. Fruit juices were analyzed by diluting samples in assay buffer, without extraction or cleanup. Samples were not even centrifuged or filtered to remove fruit pulp. Under these conditions, the immunoassay was able to accurately determine thiabendazole down to 1 ng/mL in orange and grapefruit juices, down to 5 ng/mL in banana juice, and down to 20 ng/mL in apple and pear juices. Sensitivity differences of the ELISA were caused by the minimum dilution required by each juice to minimize matrix effects: 1/10 for orange and grapefruit juices, 1/50 for banana juice, and 1/100 for apple and pear juices. In an attempt to further increase the sensitivity of the immunoassay for matrixes showing the strongest interferences, apple and pear juices spiked with thiabendazole at low levels (1-20 ng/mL) were extracted with ethyl acetate before analysis. This simple procedure entailed a significant reduction of matrix effects, which in fact allowed us to determine accurately as low as 5 ng/mL thiabendazole in apple and pear juices. Irrespective of whether samples were analyzed by the direct dilution method or after extraction, the simplicity, sensitivity, and sample throughput of this monoclonal immunoassay makes it a very convenient method for the routine monitoring of thiabendazole residues in fruit juices.     

Determination of phenolic acids and flavonoids of apple and pear by high-performance liquid chromatography

A new HPLC stationary phase has been applied to the analysis of phenolic acids and flavonoids with diode array and mass spectrometric detection. The separation of 26 standard compounds was achieved within 1 h. The stationary phase displayed excellent resolution especially of flavonol glycosides. The analytical system has been used for the determination of phenolic compounds in apple pomace and apple juice, and in extracts of pear fruits of different cultivars. Apple pomace was found to be a promising source of phenolics. However, yields are affected by the drying conditions applied. Furthermore, the applicability of the analytical system for the authenticity control of apple and pear juice was demonstrated by determination of characteristic quercetin and isorhamnetin glycosides, and dihydrochalcones, respectively. Since isorhamnetin-3-glucoside was present in all pear cultivars investigated, the usefulness of arbutin as a specific marker of pear products appears to be doubtful.     

Atmospheric pressure glow discharge desorption mass spectrometry for rapid screening of pesticides in food

Flowing afterglow atmospheric pressure glow discharge tandem mass spectrometry (APGD-MS/MS) is used for the analysis of trace amounts of pesticides in fruit juices and on fruit peel. The APGD source was rebuilt after Andrade et al. (Andrade et al., Anal. Chem. 2008; 80: 2646-2653; 2654-2663) and mounted onto a hybrid quadrupole time-of-flight mass spectrometer. Apple, cranberry, grape and orange juices as well as fruit peel and salad leafs were spiked with aqueous solutions containing trace amounts of the pesticides alachlor, atrazine, carbendazim, carbofuran, dinoseb, isoproturon, metolachlor, metolcarb, propoxur and simazine. Best limits of determination (LODs) of pesticides in the fruit juices were achieved for metolcarb (1 microg/L in apple juice), carbofuran and dinoseb (2 microg/L in apple juice); for the analysis of apple skin best LODs were 10 pg/cm(2) of atrazine, metolcarb and propoxur which corresponds to an estimated concentration of 0.01 microg/kg apple, taking into account the surface area and the weight of the apple. The measured LODs were within or below the allowed maximum residue levels (MRLs) decreed by the European Union (1-500 microg/kg for pesticides in fruit juice and 0.01-5 microg/kg for apple skin). No sample pretreatment (extraction, pre-concentration, chromatographic separation) was necessary to analyze these pesticides by direct desorption/ionization using APGD-MS and to identify them using MS/MS. This makes APGD-MS a powerful high-throughput tool for the investigation of very low amounts of pesticides in fruit juices and on fruit peel/vegetable skin. Copyright (c) 2008 John Wiley & Sons, Ltd.     

Sensory quality, volatile compounds and color of pear juice treated with β-cyclodextrin

The effect of the addition of β-cyclodextrin (β-CD), the most used of natural CDs, on the pear juice quality was studied. Several properties of this fruit juice, such as color, odor and aroma have been evaluated in both the absence and presence of β-CD for the first time. A study of the aroma profile of pear juice showed that esters, aldehydes, alcohols and terpenes are the most important chemical families of volatile compounds present in this fruit juice. Furthermore, a trained sensory panel was used to quantify odor/aroma attributes of pear juices in both the presence and absence of increasing β-CD concentrations. The addition of β-CD at a concentration of 15 mM to pear juice significantly increased its global quality, color intensity and reduced its browning but without any significant decrease in aroma. For this reason, a concentration of 15 mM of this type of natural CD is recommended to be used in pear juice manufacturing.     

高效液相色谱法测定果酸

本文研究了反相高效液相色谱法同时分离和测定6种果酸的色谱条件,提出了有效提取果酸的方法,并对苹果梨、香水梨等样品进行了实际分析。结果表明,该法简更快速,具有较高的准确度和精密度。     

Pesticide residue analysis of fruit juices by LC-MS/MS direct injection. One year pilot survey

For this work, thirteen types of fruit juices (orange, pineapple, peach, apple, multifruit, mango, strawberry, tomato, pear, mandarin, grape, banana and grapefruit) were selected to develop an analytical method for the analysis of 53 pesticides by direct injection in LC-MS/MS. The preparation of the samples was very simple: an aliquot of the juice was centrifuged and it was ten-times diluted prior to analysis, which allowed reducing considerably the time and cost of the analyses. Besides, dilution of the samples permits reducing the amount of matrix going into the system, and thus, decreasing the matrix effects, so common in this type of commodities, opening the possibility to perform quantification with solvent based standards. Validation of the method was carried out in accordance with EU guidelines. Calibration curves covering three orders of magnitude were performed, and they were linear over the concentration range studied for all the matrices (from 0.1 to 100 μg L⁻¹). Practical limits of quantification were in the low μg L⁻¹ range, far below the maximum residue levels (MRLs) of the EU regulations, which do not set specific MRLs for juices, and in this cases of processed food, MRLs of the raw product are applied. Repeatability of the instrumental method was studied in all matrices, obtaining good intra- and inter-day relative standard deviations (RSDs). The proposed method was applied to 106 real fruit juice samples purchased in different local markets during a one-year survey in order to validate the suitability for routine analysis. 43% of the analysed samples gave positive results (higher than the practical limits of quantification).     

微乳液体系中溶剂热合成Co纳米纤维

纳米材料的小尺寸及大的表面积使其在光学、电学、磁学以及化学性质上与体相材料具有显著的差异 ,从而在催化、电子、光学、磁性存储和超导等多方面具有很大的应用前景 [1] .目前 ,已经开发出许多制备纳米颗粒的技术 ,如溅射法、共沉淀法、溶胶 -凝胶法、水热法和微乳液法等 .其中利用微乳液等两亲分子有序组合体进行化学反应制备纳米材料是近十几年发展起来的新方法 ,该方法由于具有实验装置简单、易于操作和粒度可控等优点而引起人们的重视 [2 ] .微乳液是一种高度分散的间隔化液体 ,水 (或油 )相在表面活性剂 (助表面活性剂 )的作用下以…     

SMAI法制备的Co/SiO2催化剂及La3+促进Co/SiO2催化剂的比较

实验证明,钴基催化剂是非常有效的F-T合成催化剂. 由于钴基催化剂对形成长链烷烃具有高活性和高选择性,故它尤其适用于天然气间接转换为液态燃料和蜡的过程[1～5]. F-T合成用钴基催化剂由四个主要成分组成: 主金属(Co)、第二过渡金属、氧化物助剂(碱金属、稀土金属或过渡金属氧化物)及大比表面积氧化物载体(氧化硅或氧化铝)[5]. La对钴基催化剂的促进效果因其被加入到催化剂前体中的方式和顺序以及载体的性质和金属钴的状态等参数的变化而有所不同. 为了评价La对Co/SiO2催化CO加氢作用的促进效果,本文对溶剂化金属原子浸渍法(SMAI)制备的Co/SiO2和Co/La-SiO2进行了对比研究. 在保持某些参数(如载体的性质和金属钴的价态等)不变的情况下,评价了La的助催化效果,取得了一些有益的结果.     

Characterization and comparison of volatile constituents of juice and peel from clementine, mandarin and their hybrids

The volatile compositions of juice and peel of clementine (Citrus reticulata x Citrus sinensis var. Commune), mandarin (Citrus reticulata Blanco var. Willow Leaf) and their hybrids were analyzed by headspace solid-phase extraction (HS-SPME) coupled with gas chromatography and either a flame ionization detector (FID) or a mass spectrometer (MS). The major compounds of the volatile fractions of clementine and mandarin were limonene and limonene/gamma-terpinene, respectively. The volatile compositions of juice and peel of the same fruit showed qualitative and quantitative differences. The data analysis established the existence of three main groups based on volatile compounds that correlated with sample genotypes (clementine and mandarin) and fruit samples (peel and juice).     

High-performance liquid chromatographic determination of furfural and hydroxymethylfurfural in apple juices and concentrates

Summary A rapid and sensitive method for determining 2-furaldehyde (FUR) and 5-hydroxymethyl-2-furaldehyde (HMF) in apple juices and juice concentrates has been developed. The method for FUR and HMF involves the solid-liquid extraction of the juice by using a C-18 cartridge prior to reversed-phase separation with detection at 280 nm. The mobile phase was acetonitrile-water (8/92, v/v) at a flow rate of 1.0 ml/min. Recoveries from apple juices and juice concentrates spiked at different levels ranged from 94.1 to 104.0 (FUR) and 94.5 to 100.5 (HMF). The quantification limit for both, FUR and HMF, was 5 ppb.     

Contactless conductivity detection of sodium monofluoroacetate in fruit juices on a CE microchip

Rapid and quantitative determination of sodium monofluoroacetate in diluted fruit juices (dilution 1:9 v/v in deionized water) and tap water was performed by microchip CE, using contactless conductivity detection. A separation buffer consisting of 20 mM citric acid and histidine at pH 3.5 enabled the detection of the monofluoroacetate (MFA) anion in diluted apple juice, cranberry juice, and orange juice without lengthy sample pretreatments. The analyte was very well separated from interfering anionic species present in juices and tap water. LODs in diluted juices and tap water were determined to be 125, 167, 138, and 173 microg/L for tap water, apple juice, cranberry juice, and orange juice, respectively, based upon an S/N of 3:1. Taking into account the dilution factor, the LODs for juice samples range from 1 to 2 mg/L, which is adequate for monitoring the toxicity of MFA in these juice beverages and tap water. The calibration curves for MFA in diluted fruit juices were linear over the range of 500 microg/L to 80 mg/L. The total analysis time for detecting the MFA anion in fruit juices was less than 5 min, which represents a considerable reduction in analysis time compared to other analytical methods currently used in food analysis.     

Solid-phase extraction method for patulin in apple juice and unfiltered apple juice.

Patulin, a mold metabolite, is commonly found in rotting apples. Some countries regulate patulin at levels ranging from 30 to 50 micrograms/L. Most analytical methods for patulin in apple juice include liquid-liquid partitions. A solid-phase extraction method has been developed for apple juice and unfiltered apple juice in the United States. A portion of the test sample (5 mL) was passed through a macroporous copolymer cartridge and was washed with 1 mL 1% sodium bicarbonate and then with 1 mL 1% acetic acid. Patulin was eluted with 3 mL 2% acetonitrile in anhydrous ethyl ether and was determined by reversed-phase liquid chromatography with UV detection at 276 nm. Recoveries ranged from 93 to 104% in test samples spiked at 20-100 micrograms/L.     

Liquid chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry of the Alternaria mycotoxins alternariol and alternariol monomethyl ether in fruit juices and beverages

Alternariol (AOH) and alternariol monomethyl ether (AME) are among the main mycotoxins formed in apples and other fruits infected by Alternaria alternata. For determination of AOH and AME by LC, apple juice and other fruit beverages were cleaned up on C18 and aminopropyl solid-phase extraction columns. Positive and negative ion mass spectra of AOH and AME under electrospray (ESI) and atmospheric pressure chemical ionization (APCI) conditions were obtained. Collision-induced dissociation of the [M+H]+ and [M-H]- ions for both compounds were also studied. The phenolic anions of both compounds are more stable with less fragmentation. In quantitative analysis, negative ion detection also offers lower background and better sensitivity. Sensitive LC-MS and LC-MS-MS confirmatory procedures based on APCI with negative ion detection were applied to confirm the natural occurrence of AOH in nine samples of apple juice and in single samples of some other clear fruit beverages--grape juice, cranberry nectar, raspberry juice, red wine, and prune nectar (which also contained 1.4 ng AME/ml)--at levels of up to 6 ng AOH/ml. Electrospray LC-MS-MS with negative ion detection and in multiple reaction monitoring mode offers higher sensitivity and specificity. Absolute detection was better than 4 pg per injection for both compounds.     

Proteomic fingerprinting of apple fruit,juice, and cider via combinatorial peptide ligand libraries and MS analysis

Combinatorial peptide ligand libraries coupled to MS was applied to extensively map the proteome of apple fruit, and to detect its presence in commercial apple juice and cider to evaluate their authenticity and genuineness. Using the Uniprot_Malus database, 96 proteins were detected in apples, among which 30 proteins were specifically captured via combinatorial peptide ligand libraries. Next, three proteins, previously recognized in fruits, were found in apple juice, which were involved in cellular metabolism of fruit maturation and in allergenic reactions. On the other hand, only one Malus allergen was identified in cider beads eluate, demonstrating that the industrial processes did not prevent any negative effects in sensitive subjects. Thus, the present study not only increases the knowledge of the apple proteome but also offers a reliable analytical method to assess quality and genuineness of commercial products, which could be also used to inform consumers about the presence of allergens.     

Innovative Freeze-Dried Snacks with Sodium Alginate and Fruit Pomace (Only Apple or Only Chokeberry) Obtained within the Framework of Sustainable Production

The aim of the work has been to develop freeze-dried fruit snacks in the form of bars with the use of by-products derived from fruit processing. In effect 14 product designs of fruit gels based on: apple pulp, apple juice, water, sodium alginate and only apple or only chokeberry pomace were prepared. The snacks were freeze-dried. The dry matter content, water activity, structure, colour, mechanical properties, as well as organoleptic evaluation were determined. Freeze-dried bares were obtained according to sustainability production which in this case was relied on application of fruit pomace. The freeze-drying process ensures the microbiological safety of the product without the need to use chemical preservatives. Freeze-dried samples obtained low water activity in the range of 0.099–0.159. The increase in pomace concentration (3–9%) boosted the dry matter content to above 98%, and decreased the brightness of the freeze-dried bars about 6 to 10 units. Mechanical properties varied depending on the product design. With the increase in the amount of pomace, the shear force increased at 23% to 41%. Based on the results, the best variant, that has the most delicate structure and the best organoleptic properties, has proven to contain 1% sodium alginate and 2% pomace.     

Triton X-100存在下钴与α-(α-噻唑偶氮)-5-二甲氨基苯甲酸的胶束显色反应

本文简化并改进了2-(2-噻唑偶氮)-5-二甲氨基苯甲酸(TAMB)的合成方法. 详细研究了在非离子表面活性剂Triton X-100存在下TAMB与钴的胶束增敏显色反应.     

Analysis and identification of several apple varieties using ISFETs sensors

There are a number of variables that are useful to determine the optimal moment for the fruit collection such as starch content, sugar content, acidity and firmness. Other variables, including calcium and potassium concentrations, may establish better the state of ripeness of fruit and can help to optimise the collection process as well as augmenting the nutritional value of fruits. At present, these novel parameters cannot be used for the control of fruit collection due to the slow standard methods required. The need for in situ and in real-time ion measurements calls for fast response sensors and simpler and portable instrumentation. Solid-state sensors respond to these requirements. This work describes the application of ISFET sensors to analyse calcium, potassium and nitrates in several apple varieties, both in juice and in situ fruit. Results show that the analysis of potassium, calcium and nitrate permits to distinguish among apple varieties and can also be used to determine correctly the concentrations of these ions.     

Determination of patulin in fruit juice and dried fruit samples by in-tube solid-phase microextraction coupled with liquid chromatography–mass spectrometry

A simple and sensitive method for the determination of patulin in fruit juice and dried fruit samples was developed using a fully automated method consisting of in-tube solid-phase microextraction (SPME) coupled with liquid chromatography–mass spectrometry (LC–MS). Patulin was separated within 5 min by high-performance liquid chromatography using a Synergi MAX-RP 80A column and water/acetonitrile (80/20, v/v) as the mobile phase. Electrospray ionization conditions in the negative ion mode were optimized for MS detection of patulin. The pseudo-molecular ion [M−H]⁻ was used to detect patulin in selected ion monitoring (SIM) mode. The optimum in-tube SPME conditions were 25 draw/eject cycles of 40 μL of sample using a Carboxen 1006 PLOT capillary column as an extraction device. The extracted patulin was readily desorbed from the capillary by passage of the mobile phase, and no carry-over was observed. Using the in-tube SPME LC–MS with SIM method, good linearity of the calibration curve (r = 0.9996) was obtained in the concentration range of 0.5–20 ng/mL using ¹³C₃-patulin as an internal standard, and the detection limit (S/N = 3) of patulin was 23.5 pg/mL. The in-tube SPME method showed >83-fold higher sensitivity than the direct injection method (10 μL injection volume). The within-day and between-day precision (relative standard deviations) were below 0.8% and 5.0% (n = 6), respectively. This method was applied successfully for the analysis of fruit juice and dried fruit samples without interference peaks. The recoveries of patulin spiked into apple juice were >92%, and the relative standard deviations were <4.5%. Patulin was detected at ng/mL levels in various commercial apple juice samples.     

原子吸收光谱法测定脐橙和蜜桔中微量元素的含量

采用原子吸收光谱仪(AAS),对脐橙的果皮、肉汁和囊瓣外衣中的10种微量元素进行了测定,同时也选择蜜桔进行了对比测定。结果表明,脐橙和蜜桔的果皮、肉汁和囊瓣外衣中含有比较丰富的人体必需的微量元素,且囊瓣外衣和果皮中的微量元素含量大多高于囊瓣中肉汁的微量元素的含量。这为脐橙和蜜桔药效功能的综合开发利用提供科学依据。     

Liquid chromatographic method for quantitation of patulin at 10 ng/mL in apple-based products intended for infants: interlaboratory study

An interlaboratory trial for the determination of patulin in apple juice and fruit puree was conducted, involving 17 participants representing a cross section of industry, official food control, and research facilities. Mean recoveries reported ranged from 74 (10 ng/g) to 62% (25 ng/g) for apple juice and from 72 (25 ng/g) to 74% (10 ng/g) for fruit puree. Based on results for spiked samples (blind pairs at 2 levels), as well as naturally contaminated samples (blind pairs at 3 levels), the relative standard deviation for repeatability (RSDr) in juice ranged from 8.0 to 14.3% and in puree from 3.5 to 9.3%. The relative standard deviation for reproducibility (RSD(R)) in juice ranged from 19.8 to 39.5% and in puree from 12.5 to 35.2%, reflecting HORRAT values from 0.6 to 1.0 for juice and 0.4 to 0.9 for puree. The method showed acceptable within-laboratory and between-laboratory precision for each matrix, as required by current European legislation.