Apple polyphenoloxidase inactivation during heating in the presence of ascorbic acid and chlorogenic acid

It was recently reported that during osmotic dehydration of ascorbic acid (AA)-treated apple cubes, losses in AA and phenolics could partly arise from enzymatic oxidation, provided polyphenoloxidase (PPO) was still active under the processing conditions. To determine the impact of dehydration temperatures on PPO action, as well as chemical and enzymatic oxidation reactions, apple PPO inactivation alone or with AA (1 mM) and/or chlorogenic acid (CG, 3 mM), as well as AA and CG levels evolution, during heating of the model solutions at 45 and 60 °C were investigated. At pH 3.8, PPO was still functional, keeping 61 and 4% residual activity after 2 h of heating at 45 and 60 °C, respectively. The combined treatment of heating and AA was more effective in reducing PPO activity, while incubation at 60 °C with AA and CG minimised the losses of PPO activity. CG remained stable during heating, even in the presence of AA which, in turn, was more affected by heating. Thus, during heating, provided PPO remained active with enough available O₂ in the model systems, CG oxidation and coupled oxidoreduction with AA could readily develop.     

Comparison of the antioxidative properties of caffeic and chlorogenic acids

The antioxidative properties of caffeic and chlorogenic acids during autoxidation of triacylglycerols of sunflower oil at 100 °C were compared. The effects of the two acids within the concentration range 2.8–56.5 × 10⁻⁴ M (50–2000 ppm) were investigated. The stabilization factor (F) as a measure of the effectiveness of the antioxidants and the oxidation rate ratio (ORR) as a measure of their strength were determined. It was found that at concentration 2.8 × 10⁻⁴ M, the effectiveness and the strength of the two acids were practically the same, while at higher concentrations caffeic acid appeared as a much more effective and stronger inhibitor. The analysis of the kinetic data obtained showed that chlorogenic acid and its radicals participated more readily in side reactions with the hydroperoxides and the lipid substrate than caffeic acid and its radicals did.     

Scavenging and antioxidant properties of compound derived from chlorogenic acid in South-China honeysuckle

Chlorogenic acid (CGA) is a natural antioxidant, and nowadays its application has been distributed in medicine, food processing and cosmetic chemical industry. However, at a certain extent its application was restricted because of its only water solubility but no liposolubility. In this research, CGA is prepared from South-China honeysuckle and modified, undergoing efficient conjugation with lauroyl chloride in the presence of triethylamine (TEA) in non-water phase, to yield the adduct that has been identified as chlorogenic laurate (CGL) from its chromatographic behavior and spectral characteristics. The scavenging and antioxidant properties of CGL were evaluated using different antioxidant tests, including 2, 2′-diphenyl-1-picrylhydrazyl radical scavenging, hydroxyl radical scavenging, superoxide anion radical scavenging, reducing power, inhibition of peroxidation of linoleic acid and ferrous ions chelating activity. In the above six assays, CGL showed antioxidant potential to varying degrees in a concentration-dependent manner, and exhibited more antioxidant potency than CGA. Especially, the EC₅₀ value of CGL in scavenging abilities on DPPH radicals was 70.5 μg/ml. The hydroxyl radicals scavenging compared with α-tocopherol was observed to high value in CGL. The antioxidant activity of CGL is not significantly different from BHT in a linoleic acid system. All the evaluations exhibited appreciable antioxidant potential for CGL. The data suggest that the modified CGA, CGL, may have a preventive effect against oxidation in liposoluble system, and would be a promising antioxidant.     

Changes in fatty acid composition of sunflower (Helianthus annuus) seeds in response to time of nitrogen application,supply rates and defoliation

The fatty acid composition of sunflower (Helianthus annuus L ) seed oil was shown to respond to N supply rates and the time of N application in four glasshouse and two field experiments using five cultivars. Changes in individual fatty acids % total were smaller than those caused by differences in minimum temperatures during seed development but they were statistically significant. N supply rates before floret initiation affected the % fatty acid composition of mature seeds; the percentage of palmitic (16:0) and linoleic (18:2) acids responded positively to increases in N supply whereas % stearic (18:0) and oleic (18:1) acids responded negatively. The only fatty acid to respond to N supply rates between floret initiation and anthesis was 18:0 acid. The percentage of 18:1 responded positively and that of 18:2 acid negatively to high N supply rates after anthesis Responses to single N applications at different stages of plant development in the field confirmed these findings but results were more variable than in the glasshouse. Partial or complete defoliation at anthesis in the field caused the same changes in fatty acid composition as did a low N supply after anthesis. The results are difficult to interpret in terms of our current knowledge of lipid biosynthesis. N supply rates may affect the rate of hydrolysis of fatty acid complexes or their transport from the proplastid to the cytosolic compartment. There was no compelling support for the hypothesis that N supply rates bejore floret initiation were affecting fatty acid composition through their effects on other plant characters such as leaf mass, seed number or single seed weight.     

绿原酸在肝微粒体和肠道菌群中的体外代谢研究

摘 要：目的 研究绿原酸在大鼠肝微粒体和肠道菌群中的代谢产物及代谢途径。方法 运用大鼠肝微粒体体外温孵法和大鼠离体粪便温孵法,采用超高效液相色谱串联四极杆飞行时间质谱(UPLC-Q-TOF/MS),色谱柱为Waters ACQUITY UPLC BEH C18 (1.7 μm, 2.1 mm×100 mm),流动相为乙腈和0.1%甲酸水溶液梯度洗脱系统,流速为0.35 mL/min,离子源为电喷雾离子源(ESI),以负离子模式进行检测。采用Masslynx软件通过保留时间与一、二级质谱信息,进行成分分析。结果 大鼠肝微粒体温孵样品中有绿原酸原型成分和奎宁酸、咖啡酸2个代谢产物;粪便温孵样品中有绿原酸原型成分和奎宁酸、3-羟基苯丙酸、二氢咖啡酸、二氢阿魏酸、咖啡酸、O-甲基绿原酸6种代谢产物。结论 UPLC-Q-TOF/MS技术鉴定绿原酸及其代谢产物,操作便捷高效,结果准确全面,绿原酸在体外代谢的主要途径为氢化、甲基化、水解、去羟基化等。     

Yeast-cell-based microencapsulation of chlorogenic acid as a water-soluble antioxidant

The water-soluble antioxidant, chlorogenic acid, was successfully encapsulated in the low cost-high volume yeast cells for the first time, as characterized by FT-IR spectra and fluorescence micrograph of the yeast cells, chlorogenic acid and microcapsule.

The encapsulation efficiency (EE) of yeast cells could be enhanced significantly (P < 0.001) by the treatment of yeast cells with plasmolyser before encapsulation. Also, the release characteristics of the obtained yeast-encapsulated chlorogenic acid were evaluated, and its storage stability as a powder were investigated at 25 °C/75% relative humidity (RH), 25 °C/90% RH and 60 °C. It could be clearly demonstrated that no chemical changes had taken place during the encapsulation, and the yeast-encapsulated chlorogenic acid exhibited a good stability. This study would be helpful to promote the application of chlorogenic acid. The new yeast-cell-based encapsulation protocol may have some general interests for maintaining the stability of other water-soluble substances.     

Chemiluminescent determination of chlorogenic acid in fruits

Chlorogenic acid has been detected by a new flow injection chemiluminescent (FI-CL) method, based on the CL reaction of the acidic potassium permanganate with chlorogenic acid in the presence of formaldehyde as an enhancer. The CL intensity difference of the acidic potassium permanganate and formaldehyde in the presence of chlorogenic acid from the CL intensity without chlorogenic acid was linear with the concentration of chlorogenic acid in the range from 5.0 × 10⁻⁸ to 5.0 × 10⁻⁵ g ml⁻¹ with a detection limit of 5.7 × 10⁻⁹ g ml⁻¹ when the sampling rate was 150 injections h⁻¹. The method was applied successfully to the determination of chlorogenic acid in fruits with recoveries in the range of 100 ± 6%.     

Relationship between the physical properties of chlorogenic acid esters and their ability to inhibit lipid oxidation in oil-in-water emulsions

In oil-in-water emulsions, the physical location of antioxidants has been postulated to be one of the most important factors impacting activity. The purpose of this research was to examine how the esterification of various hydrocarbon chains (C₄, C₈, or C₁₂) onto chlorogenic acid (CGA) influenced physical properties and antioxidant activity in menhaden oil-in-water emulsions. Both surface activity and partitioning of CGA and its hydrocarbon esters into the lipid phase of oil-in-water emulsions increased with increasing size of the hydrocarbon chain. When CGA and its esters were added to a menhaden oil-in-water emulsion at concentration that resulted in equal free radical scavenging activity, CGA, butyl CGA and octyl CGA had similar antioxidant activity while dodecyl CGA was ineffective. These results suggest that phenolic antioxidants conjugated with hydrocarbon chains are more highly associated with lipid emulsions droplets, but these changes in physical properties did not increase antioxidant activity.     

蒲公英绿原酸固体分散体性能分析与比较

利用固体分散技术增强绿原酸的体外溶出速率,将绿原酸固体分别与PVPK30和PEG4000按照料辅比(质量比)12,14,16,18进行混合,比较4种料辅比所制备的固体分散体成品的体外溶解度、累积溶出度和稳定性,对最佳配料比采用电镜扫描分析。结果表明,以PVPK30为载体,料辅质量比14,制备绿原酸固体分散体,其溶解度、溶出度、稳定性都有所提高;扫描电镜(SEM)下显示固体分散体中绿原酸以非晶体形式存在于PVPK30中,表面许多小孔有利于药物的溶出与吸收。绿原酸-PVPK30固体分散体明显提高了绿原酸的体外溶解度和溶出度,明显优于原料药性能。     

菊芋叶片绿原酸的提取工艺条件优化研究

对菊芋叶片中绿原酸的提取工艺条件进行研究,探讨了提取方法、提取试剂、提取温度、时间、固液比等因素对绿原酸含量的影响。在单因素实验的基础上,采用正交实验法优化了菊芋叶片绿原酸的提取工艺。最佳提取工艺为:回流提取法,提取试剂为70%甲醇,提取温度80℃,提取时间2.5h,固液比1∶25,测得的绿原酸平均含量为1.6375mg/g。研究结果可为利用菊芋叶片工业化生产绿原酸提供科学依据。     

Identification of cyclodextrin inclusion complex of chlorogenic acid and its antimicrobial activity

Chlorogenic acid is an important bioactive compound which is unstable under ambient conditions. In this work, chlorogenic acid was extracted from tobacco leaf and purified by high performance liquid chromatography. β-Cyclodextrin (β-CD) was used to form inclusion complex with chlorogenic acid. Analyses of differential scanning calorimeter (DSC) and ¹H nuclear magnetic resonance (NMR) spectroscopy confirmed the formation of inclusion complex and quinic acid moiety was included within the β-CD cavity. A blue shift of ca. 2 nm for chlorogenic acid was detected after inclusion. The storage stability of chlorogenic acid was apparently improved by measurement of absorbance change during 20 weeks. Through determinations of DPPH radical scavenging and antimicrobial activities, no significant difference was observed between chlorogenic acid and its complex. Therefore, construction of β-CD inclusion complex was helpful for the application of chlorogenic acid.     

绿原酸抑制猪肉肌原纤维蛋白氧化及NDEA生成的作用研究

在羟自由基氧化体系中,研究不同添加量的绿原酸对猪肉肌原纤维蛋白(MP)理化性质和亚硝基二乙胺(NDEA)生成的影响。结果表明,氧化导致羰基含量升高,疏水性增加,蛋白结构展开。添加绿原酸后,0.1~0.5 mmol/L能有效抑制羰基的生成(p<0.05),而0.8~1.0 mmol/L未能抑制羰基的生成。0.1~2.0 mmol/L的绿原酸使肌原纤维蛋白疏水性增加,内源色氨酸荧光强度降低。绿原酸对NDEA的生成具有浓度依赖性,0.1~0.8 mmol/L的绿原酸促进NDEA生成,而0.8~2.0 mmol/L的绿原酸抑制NDEA生成。结论:适量的绿原酸抑制了肌原纤维蛋白的氧化和NDEA的生成。     

Anthocyanins and chlorogenic acid copigmentation - influence on the colour of strawberry and chokeberry juices

The effect of copigmentation of chlorogenic acid with anthocyanins in strawberry and chokeberry juices was investigated. It was found that chlorogenic acid, at concentrations greater than that of anthocyanins, enhanced the colour intensity of these juices. The maximum copigmentation effect in both juices was observed at pH 3.4. In the investigated range of the copigment/pigment ratio, i.e. 11 to 501, absorbance increased (A) linearly with copigment content, A/g chlorogenic acid was greater in chokeberry than in strawberry juices. In solutions of purified pigments of these fruits, smaller copigmentation effects were observed than in juices under the same conditions, which indicates the participation of natural copigments present in fruits in the copigmentation process.     

Distribution of caffeic acid derivatives in Gundelia tournefortii L.

The caffeic acid derivatives including neochlorogenic acid (3-COA), cryptochlorogenic acid (4-CQA), chlorogenic acid (5-CQA) and caffeic acid (CA) have been characterised in Gundelia tournefortii using reference compounds, chemical, spectral evidences and chromatographic data. In addition, the total phenolic content and chlorogenic acid were measured in the leaf, hull-less seed, and skin extracts of this herb by the Folin–Ciocalteu reagent and high performance liquid chromatography (HPLC), respectively. The sample analysis was carried out on a C₁₈ column with 5% (v/v) aqueous acetic acid and methanol as the mobile phase, under gradient elution at ambient temperature, at 325 nm. The amount of chlorogenic acid in the leafs (at the flowering stage and after it) and hull-less seed were 984, 466 and 199 mg per 100 g dry plant sample and the total phenolic content in their dry extract were 128.4, 103.8 and 76.3 μg/mg as CGA equivalent, respectively.     

Non-starch polysaccharides from sunflower (Helianthus annuus) meal and palm kernel (Elaeis guineenis) meal—preparation of cell wall material and extraction of polysaccharide fractions

Two different chemical methods, sequential extraction with alkali and sodium chlorite and treatment with 4-methylmorpholine N-oxide (MMNO), were applied to the extraction of non-starch polysaccharides (NSP) from the enzymically deproteinated, water-insoluble cell wall materials of sunflower (Helianthus annuus L) meal and palm kernel (Elaeis guineensis Jacq) meal. The NSP content accounted for 550 g kg^?1 (sunflower meal) and 750 g kg^?1 (palm kernel meal) of the cell wall materials. Neither of the treatments alone was capable of solubilising more than about half of the original NSP. Combined treatment using alkali/chlorite followed by MMNO completely dissolved cell wall material from palm kernel meal, whereas a small residue (40 g kg^?1 of original NSP) was left in sunflower meal. Loss of NSP occurred with both methods (total NSP recovery ranging from 88% for alkali/chlorite extraction of sunflower to 64% for MMNO extraction of palm kernel). Due to differences in solubility revealed upon acidification and/or dialysis, extracts became subdivided into precipitates and soulble fractions. The sugar composition of the resulting fractions enabled a tentative identification of teh major non-starch polysaccharides; sunflower meal was found to contain cellulose, (acidic) xylans, polyuronide-containing fractions and xyloglucan; palm kernel meal was found to contain mannans, cellulose and xylans, with the major part of the mannans originating from the endosperm and the xylans being almost exclusively located in the endocarp.     

高效液相色谱法测定马铃薯中绿原酸和原儿茶酸

目的:建立高效液相色谱法测定马铃薯块茎中绿原酸和原儿茶酸的含量,并测定了两种马铃薯贮藏期间绿原酸、原儿茶酸含量的变化。方法:采用高效液相色谱法梯度洗脱,使用反相C18色谱柱,以1%甲酸水溶液和100%甲醇为流动相,流速为0.8 m L/min,柱温:40℃,在326、280 nm波长处分别对绿原酸和原儿茶酸进行测定。结果:绿原酸、原儿茶酸分别在50~500、200~1000μg/m L范围内与峰面积线性良好,相关系数分别为0.9999、0.9992;精密度RSD均小于0.35%,稳定性RSD均小于1.68%,绿原酸、原儿茶酸重复性RSD分别为2.07%、3.58%,绿原酸、原儿茶酸平均加样回收率分别为98.29%、97.81%,RSD分别为1.46%、1.31%(n=5)。结论:该方法线性范围宽,分离效果好,快速、准确,可用于马铃薯块茎中绿原酸和原儿茶酸含量的测定。      

Effects of irrigation water quantities and seasonal variation on oil content and fatty acid composition of sunflower (Helianthus annuus L.)

A field experiment was conducted in the North Western Group of the Gezira Scheme (longitude 32°48′ and latitude 15°14′) for four successive seasons, two winter and two summer seasons, during the years 1999–2002, to study the effect of different irrigation water quantities (300, 400, 500, 600 and 700 mm per season) on oil content and oleic acid and linoleic acid percentages in two sunflower cultivars [Rodeo, an open‐pollinated variety, and Hysun33, a hybrid). The experiment was designed in a split plot design, with four replicates. The cultivars were allotted to the sub‐plots while the irrigation treatments were assigned to main plots. The results showed that different irrigation water quantities had significant effects on all parameters studied and the cultivar Hysun33 gave a higher oil content (36.6%) at 700 mm whereas the open‐pollinated variety Rodeo gave 34.1% oil at that level of irrigation. The overall percentages of oleic and linoleic acids were 29.7 and 58.1 in winter and 47.6 and 43.1 in summer, respectively. Copyright © 2007 Society of Chemical Industry