赖氨酸/葡萄糖美拉德反应产物对丙烯酰胺生成的抑制作用

建立天冬酰胺/葡萄糖模式反应体系,运用高效液相色谱法、自由基清除法等手段研究赖氨酸/葡萄糖美拉德反应产物对该模式体系中丙烯酰胺生成量及体系抗氧化性的影响。结果显示:高、低分子量的赖氨酸/葡萄糖美拉德反应产物(H-LGP和L-LGP)均能显著降低模式反应体系中的丙烯酰胺生成量,其中H-LGP和L-LGP的添加量为10 mg/mL时,对丙烯酰胺生成的抑制率最大,分别为32.0%和31.4%。H-LGP和L-LGP(均为10mg/mL)的添加还可显著提高反应体系清除自由基DPPH和ABTS的能力。结论:赖氨酸/葡萄糖美拉德反应产物(LGP)能够显著抑制天冬酰胺/葡萄糖模式反应体系中丙烯酰胺的生成,且高浓度的LGP能够显著提高反应体系的抗氧化性。     

添加甘氨酸对天冬酰胺/葡萄糖模拟体系中丙烯酰胺形成的抑制作用

美拉德反应目前被认为是形成丙烯酰胺的重要途径,极探讨了甘氨酸在葡萄糖/天冬酰胺模拟体系中抑制丙烯酰胺形成的规律。模拟体系分别在90、100、110、120℃下反应4h,丙烯酰胺的生成、褐变度的增加、产物的减少以及对天冬酰胺和甘氨酸降解动力学的分析表明,甘氨酸的添加能够显著降低美拉德反应生成的丙烯酰胺,且在该反应体系中甘氨酸与天冬酰胺之间存在竞争关系。     

添加甘氨酸对天冬酰胺/葡萄糖模拟体系中丙烯酰胺形成的抑制作用

美拉德反应目前被认为是形成丙烯酰胺的重要途径,极探讨了甘氨酸在葡萄糖/天冬酰胺模拟体系中抑制丙烯酰胺形成的规律。模拟体系分别在90、100、110、120℃下反应4h,丙烯酰胺的生成、褐变度的增加、产物的减少以及对天冬酰胺和甘氨酸降解动力学的分析表明,甘氨酸的添加能够显著降低美拉德反应生成的丙烯酰胺,且在该反应体系中甘氨酸与天冬酰胺之间存在竞争关系。      

食品中丙烯酰胺形成机理的研究进展

综述了当前研究富含淀粉的食品在油炸、煎炸和焙烤等高温加工工艺形成丙烯酰胺的几种可能的反应机理.目前获得的公认研究结果是:天冬酰胺酸与还原糖发生美拉德反应,是大量的丙烯酰胺形成的主要途径;另外食品中的油脂、蛋白质和碳水化合物等成分在高温下条件下反应,生成丙烯醛,进而形成丙烯酰胺,是其在食物中存在的另一原因.本文希望通过揭示高温食品中丙烯酰胺形成的机理,能促进关于食品中有效地抑制/消除丙烯酰胺形成研究的进一步开展.     

氨基酸对葡萄糖-天冬酰胺模拟体系中丙烯酰胺形成的抑制作用研究

目的 研究4种氨基酸对已建立的葡萄糖-天冬酰胺模拟体系中丙烯酰胺生成的影响。方法 以葡萄糖-天冬酰胺组为对照组,在此基础上分别加入半胱氨酸、甘氨酸、赖氨酸和谷氨酸4种氨基酸为实验组,于140℃反应5～30min,测定反应后模拟体系的褐变程度、色差值、生成丙烯酰胺含量和剩余葡萄糖含量。结果 4种氨基酸中,半胱氨酸和谷氨酸对模拟体系中的褐变度和色差值的抑制作用较好;半胱氨酸和赖氨酸对底物葡萄糖的消耗作用较快;半胱氨酸对丙烯酰胺的抑制效果最好,抑制率为(76.00±0.73)%,其他氨基酸的抑制率分别为甘氨酸(38.39±0.44)%、赖氨酸(51.03±3.09)%和谷氨酸(28.76±2.43)%;进一步研究发现,当添加4.2mmol半胱氨酸时,丙烯酰胺抑制率达(95.32±0.47)%。结论 4种氨基酸相比,半胱氨酸对丙烯酰胺形成的抑制效果最好,且对于降低葡萄糖-天冬酰胺模拟体系的褐变度、色差值、葡萄糖含量有较好的效果。     

3-氨基丙酰胺在丙烯酰胺形成和消减中的作用

3-氨基丙酰胺是天冬酰胺与还原糖发生美拉德反应的中间产物,同时也是丙烯酰胺的直接前体,它在高温下脱氨形成丙烯酰胺。研究发现：3-氨基丙酰胺在转化为丙烯酰胺的同时,可与丙烯酰胺形成加合物,降低丙烯酰胺的暴露水平。为此,本研究在鉴定3-氨基丙酰胺与丙烯酰胺形成加合物的基础上,研究了不同反应条件对加合物形成的影响。研究结果表明：反应温度、时间和反应物的浓度比显著影响加合物的形成,当丙烯酰胺与3-氨基丙酰胺浓度比例为3︰5,在160 ℃下反应20 min,有47.29%的丙烯酰胺通过形成加合物被消除。     

丙烯酰胺天冬酰胺/葡萄糖低湿模式反应体系条件优化

试验主要研究了天冬酰胺/葡萄糖低湿模拟体系中丙烯酰胺生成及提取条件,对影响体系丙烯酰胺生成的反应条件和丙烯酰胺提取条件进行了优化。结果表明,天冬酰胺/葡萄糖低湿模拟反应体系中丙烯酰胺最佳反应条件为:40μL葡萄糖(0.25 mol/L)和40μL天冬酰胺(0.25 mol/L)加入40μL蒸馏水在160℃反应20 min,反应结束后向体系中加入1 mL蒸馏水超声重复提取2次,每次5 min,提取温度30℃。在上述条件下体系中生成和提取的丙烯酰胺量达到最大。     

Glu-Asn食品模拟体系中丙烯酰胺的形成规律

以葡萄糖和天冬酰胺为主要反应物,建立美拉德模拟体系,研究不同的反应条件和不同种类的糖对模拟体系中丙烯酰胺生成的作用规律。结果表明:温度是丙烯酰胺形成的重要因素。在120~180℃条件下丙烯酰胺含量与温度呈正相关的趋势,200℃时丙烯酰胺含量呈先上升后下降的趋势;模拟体系的初始p H值小于8时,丙烯酰胺含量随p H值升高而增加,当p H=8时其达到最大值,继续升高p H值,丙烯酰胺含量开始下降,说明高p H值条件不利于丙烯酰胺的生成;Glc/Asn物质的量比接近1∶1时反应生成的丙烯酰胺最多,且天冬酰胺过量引起的影响要小于葡萄糖过量引起的影响;半乳糖、果糖和蔗糖对丙烯酰胺的生成起促进作用,甘露醇、赤藓糖醇、山梨醇、β-环糊精对丙烯酰胺的抑制作用较为明显,前三者均有各自的最佳抑制浓度。丙烯酰胺抑制率与β-环糊精加入量呈正相关趋势。β-葡聚糖的浓度对丙烯酰胺最终形成几乎没有影响。     

葡萄糖/天冬酰胺模拟体系中丙烯酰胺的产生及其机理研究

油炸食品中丙烯酰胺的发现引起了科学家们的广泛重视。美拉德反应是形成丙烯酰胺的重要途径。为了进一步证实其形成机理,进行了葡萄糖和天冬酰胺模拟体系的研究。采用高效液相色谱-紫外检测器分析模拟体系中的丙烯酰胺,结果表明:不同的加热温度和加热时间对丙烯酰胺的产生量影响显著,且随着反应温度的升高和反应时间的延长,整个反应体系的颜色逐渐加深,丙烯酰胺的产生量也逐渐增多。     

辐照预处理对天冬酰胺-葡萄糖模拟体系中丙烯酰胺生成的影响

采用60Co-γ分别对天冬酰胺、葡萄糖进行辐照处理后,将其混合得到天冬酰胺-葡萄糖模拟体系,分别在不同的油浴温度和时间下使其发生反应,研究辐照剂量对模拟体系中丙烯酰胺的生成量和褐变程度的影响,并建立褐变程度与丙烯酰胺生成量的相关性。结果表明:随辐照剂量的增大,丙烯酰胺的生成量呈现先减小后增大的趋势;60Co-γ不同剂量预处理后的天冬酰胺-葡萄糖的模拟体系在高温油浴中反应后,褐变程度与丙烯酰胺的生成量之间有一定的相关性。      

Acrylamide–taurine adducts formation as a key mechanism for taurine’s inhibitory effect on acrylamide formation

Amino acids have attracted increasing attention in developing effective inhibitors on acrylamide (AA) formation during food processing. The main purpose of this study was to evaluate the inhibitory effect and mechanism of taurine (Tau) on AA formation. In the presence of Tau, AA formation was effectively inhibited in asparagine/glucose (Asn/Glc) model system. Results also showed that Glc content was decreased as Glc–Tau solution was heated, which indicated that Tau could react directly with Glc in the Maillard reaction. LC‐QTOF MS revealed two peaks in extracted ion chromatograms [M + H] ⁺ at m/z 197 and m/z 268 during the thermal treatment, which were identified as AA–Tau and AA dimmer–Tau adducts, respectively. Our results demonstrated that inhibitory effect of Tau on AA formation was not only mediated through contesting consumption of Glc with Asn, but also directly reacting with AA to promote formation of AA–Tau and AA dimer–Tau adducts.     

Impact of selected additives on acrylamide formation in asparagine/sugar Maillard model systems

The main purpose of this paper was to study the effect of selected additives, NaCl, NaHSO₃, ascorbic acid, cysteine and allicin, on acrylamide (AA) formation in asparagine/fructose (Asn/Fru) and asparagine/glucose (Asn/Glc) by microwave processing. Our results showed that NaHSO₃ and cysteine had the best reduction rate on AA formation, but the browning would be influenced by the addition of these additives. Ascorbic acid is another good inhibitor for AA formation both in Asn/Fru and Asn/Glc model systems, but the browning would be inhibited by the high concentration of ascorbic acid. Natural antioxidants are attractive candidates for the development of effective inhibitors for AA formation. In the present study, allicin effectively reduced AA formation and achieved a maximum reduction rate of > 50% for the use of allicin at a concentration of 0.0375% in Asn/Fru model system. While in Asn/Glc model system, allicin did not show good reduction rate. Through RSM study, the lowest AA content was 0.181 ??g/mL by the addition of allicin in Asn/Fru and 0.029 ??g/mL by the addition of ascorbic acid in Asn/Glc model system, respectively. The study could be regarded as a pioneer contribution on AA reduction in Maillard model system by the addition of allicin.     

High correlation of methylglyoxal with acrylamide formation in glucose/asparagine Maillard reaction model

α-Dicarbonyl compounds were highly reactive intermediates formed in Maillard reaction (MR), and o-phenylenediamine (OPD) was widely used as a trapping agent for α-dicarbonyl compounds. Both aqueous glucose/asparagine (Glc/Asn) and glucose/asparagine/o-phenylenediamine (Glc/Asn/OPD) model systems were heated at 150 °C for up to 30 min. The α-dicarbonyl compounds formed in MR were identified by HPLC/MS in our particular model system, indicating that 3-deoxy-2-hexosulose, 2,3-butanedione and methylglyoxal (MG) were three main α-dicarbonyl compounds. In this work, MG was chosen as a representative of α-dicarbonyl compound in MR to investigate the influence on the formation of acrylamide (AA). The concentrations of AA, MG and Asn were detected during MR by HPLC method. The results indicated that the formation of AA increased with the heating time, and nearly 80% of AA formed through participation of α-dicarbonyl compounds. These results were consistent with the changes of amounts of MG. The amounts of formation and consumption of MG increased with heating time, and from 9 min of reaction, the consumed amounts of MG accounted for 73–88% on basis of total amounts of MG formed in MR, suggesting that most of MG take part in the next reaction steps. Meanwhile, the Asn concentration decreased with heating time in both models. The formation of AA and consumption of Asn were highly correlated with MG. Indeed, as MG concentration in MG/Asn model system decreased during heating at 150 °C, the concentration of AA significantly increased. The coefficient of correlation between consumed amounts of MG and the formed amounts of AA is 0.931, again demonstrating that MG does play a role in AA formation.     

Study of acrylamide mitigation in model systems and potato crisps: effect of rosmarinic acid

In the current study, rosmarinic acid (RosA) played a critical role in inhibiting acrylamide (AA) formation in Maillard system and potato chips. Compared to the control group, AA formation was markedly inhibited by RosA of 10⁻⁴ and 10⁻¹ mm in asparagine (Asn)-glucose (Glc) system, and 10⁻⁵−1.0 mm in Asn-fructose (Fru) system. The kinetic study indicated that with heating time ranging from 30 to 60 min, RosA had a significant inhibition effect on AA formation. Mechanism study showed the addition reaction between RosA and AA was the primary pathway to inhibit AA formation. In potato crisps, response surface methodology showed that frying temperature of 140.11 °C, frying time of 6.02 min and RosA concentration of 0.012 μm had the lowest AA formation. In conclusion, RosA inhibited AA formation in both the model systems and potato crisps, and its application in food industry is well expected.     

Determination of acrylamide in processed foods by LC/MS using column switching

An LC/MS method was developed for the determination of acrylamide (AA) in processed or cooked foods. AA was extracted with a mixture of water and acetone from homogenized food samples after the addition of 13C-labeled acrylamide (AA-1-(13)C) as an internal standard. The extract was concentrated, washed with dichloromethane for defatting, and cleaned up on Bond Elut C18, PSA and ACCUCAT cartridge-columns, and then AA was determined by LC/MS in the selected ion recording (SIR) mode. For the LC/MS analysis, four LC columns were connected in-line and the flow of the mobile phase was switched according to a time-program. Monitoring ions for AA were m/z 72 and 55, and those for AA-1-(13)C were m/z 73 and 56. AA and AA-1-(13)C were determined without interference from the matrices in all samples. The recoveries of AA from potato chips, corn snack, pretzel and roasted tea spiked at the level of 500 ng/g of AA were 99.5-101.0% with standard deviations (SD) in the range from 0.3 to 1.6%. The limits of detection and quantification of the developed method were 9 and 30 ng/g for AA in samples, respectively. The method was applied to the analysis of AA in various processed or cooked food samples purchased from retail markets. High levels of AA were found in potato chips and French-fried potato (467-3,544 ng/g). Fried and sugar-coated dough cakes (karinto) contained 374 and 1,895 ng/g. Corn snacks contained 117-535 ng/g of AA. Roasted foods (such as roasted sesame seed, roasted barley (mugi-cha), roasted tea (hoji-cha), coffee beans and curry powder) contained 116-567 ng/g of AA. Foods made from fish, egg and meat contained lower levels of AA than the plant-based foods. Foods containing much water showed a tendency to have low levels of AA compared with dry foods. The proposed method was applicable to the analysis of AA in variety of processed foods.     

Application of ion-trap LC/MS/MS for determination of acrylamide in processed foods

Ion-trap LC/MS/MS was evaluated for use in the determination of acrylamide (AA) in processed foods. Multiple reaction monitoring (MRM) analysis of a series of AA standard solutions containing deuterium-labeled acrylamide (AA-d3) as an internal standard was performed. A linear relationship between the concentration of AA and the ratio of peak area (AA/AA-d3) in the extracted ion chromatogram (m/z 55, 58 derived from m/z 72, 75, respectively) was obtained over a wide range of 2-20,000 ng/mL. The quantification limit of AA was 2 ng/mL. In analyses of 37 commercial foods, AA was detected in a potato snack at the maximum value of 3,570 ng/g and found in 23 foods prepared or cooked at high temperature. The samples were analyzed in triplicate and the relative standard deviations (RSD) were less than 15% in many processed foods.     

The influence of variety, agronomical factors and storage on the potential for acrylamide formation in potatoes grown in Norway

Freeze-dried potato samples were obtained from the varieties Saturna and Peik that had been subjected to different agronomic conditions and storage. Powdered samples originating from the same growth year were mixed with oil and heated simultaneously in a stone oven in order to study the potential for acrylamide (AA) formation in a fixed time and temperature situation. For baked samples originating from unstored potato a linear relationship was found between asparagine (Asn) and reducing sugar (RS) content and AA formation. For these samples the AA content varied linearly with a* except from samples that originally were high or low in Asn. Upon storage the correlation between the quantity of the common precursors, Asn and RS, and AA were smaller. Results of the baking experiments suggest that the AA potential for stored potato cannot be predicted from RSs and Asn alone, and that other factors that might change during storage are of importance. Due to north European conditions the RSs might not always be the limiting substrate for AA formation. Additional information for the precursor content in 2004 and 2005 are included. No systematic effect on precursor contents related to chemical vine killing was observed. Precursor contents varied among and between varieties, different cultivation years and growth sites.     

A comparative study of acrylamide formation induced by microwave and conventional heating methods

ABSTRACT:  In this study, the formation of acrylamide upon treatment with microwave and conventional heating, boiling, or frying was investigated in both Asn/Fru and Asn/Glc model systems and in potato chips. Acrylamide levels were analyzed by HPLC method, which was confirmed by HPLC-MS/MS. Present results in model systems showed that pH value had a complex influence on the formation of acrylamide in the 2 systems during both microwaving (600 W) and boiling (120 ± 1 ^oC). At pH < 8.0, acrylamide content increased with increasing the pH value, reaching the maximum at pH 8.0 whereas acrylamide content decreased with the increase of pH. Regardless of pH and heating methods, acrylamide content generally increased with increasing treatment time. Surprisingly, all present results showed that microwave heating not only induced acrylamide formation in the 2 model systems but also facilitated more acrylamide to be formed as compared to the boiling method at identical pH and treatment time. At pH 4.0, 8.0, and 10.0, the larger the microwave power, the more the acrylamide content. Consistent with the above observation, treatment of potato chips with microwave heating for 2.5 to 3.5 min in the range 550 to 750 W similarly resulted in acrylamide formation. The highest acrylamide content was formed by 750 W microwave treatment as 0.897 ± 0.099 mg/kg, which was significantly higher than that produced by traditional frying (180 ± 1^oC), 0.645 ± 0.035 mg/kg ( P < 0.05).     

Correlation of methylglyoxal with acrylamide formation in fructose/asparagine Maillard reaction model system

α-Dicarbonyl compounds were highly reactive intermediates formed in Maillard reaction (MR), and o-phenylenediamine (OPD) was widely used as a trapping agent for α-dicarbonyl compounds. Both aqueous fructose/asparagine (Fru/Asn) and fructose/asparagine/o-phenylenediamine (Fru/Asn/OPD) model systems were heated at 150 °C for up to 30 min. Methylglyoxal (MG) was the main α-dicarbonyl compounds formed in MR, which was chosen as a representative of α-dicarbonyl compound to investigate the influence on acrylamide (AA) formation. The concentrations of AA, MG and Asn were detected during MR by HPLC method. The results indicated that the formation of AA increased with the heating time, and nearly 75% of AA was formed through the participation of α-dicarbonyl compounds. The amounts of formation and consumption of MG increased with heating time, and from 12 min of reaction, the consumed amounts of MG accounted for 62.1–90.3% on the basis of total amounts of MG formed in MR, suggesting that most of the MG took part in further reactions. Meanwhile, Asn concentration decreased with heating time in both models. The formation of AA and consumption of Asn were highly correlated with MG. Indeed, as MG concentration in MG/Asn model system decreased during heating at 150 °C, the concentration of AA significantly increased. The coefficient of correlation between consumed amounts of MG and the formed amounts of AA was 0.931, demonstrating that MG plays a role in AA formation.     

生物抗氧化剂抑制丙烯酰胺形成的研究进展

丙烯酰胺(acrylamide,AA)是富含碳水化合物的食物经高温加热后产生的对人类具有潜在致癌性的化合物。目前,基于生物抗氧化剂天然、高效、低毒等特点,采用生物抗氧化剂抑制食品中AA的形成已成为新的研究热点。本文主要综述了近年来生物抗氧化剂在加热过程中对美拉德模拟体系或食物中AA形成和消除的影响和机制。目前已经证实了多种生物抗氧化剂的可能作用机制,包括防止脂质氧化、捕获羰基化合物、消除自由基、减少3-氨基丙酰胺(3-APA)转化为AA、与AA前体或其本身反应等。本文同时提出了展望,希望将对于美拉德模拟系统的研究转化为对真正食品基质的研究,尽快将生物抗氧化剂有效、经济、广泛地应用于食品工业,以减少膳食AA对人类健康的危害。