Products of Thermal Degradation of the Anthocyanins Cyanidin-3-glucoside,Cyanidin-3-rutinoside and Cyanidin-3-sophoroside

During thermal degradation of anthocyanins, cyanidin-3-glucoside, cyanidin-3-rutinoside, cyanidin-3-sophoroside, at 98 °C in model systems of pH = 1, 2.5 3.5 and 4.5, seven compounds were isolated by means of paper chromatography. Among them quercetin, phloroglucin-aldehyde and protocatechuic acid were identified.     

桑葚花色苷的分离纯化及其热降解动力学研究

通过AB-8大孔树脂、乙酸乙酯萃取和Toyopearl TSK HW-40S凝胶柱层析对桑葚汁中的花色苷进行分离纯化,得到两个单一的化合物组分。经HPLC-MS鉴定这两种花色苷分别为矢车菊素-3-芸香糖苷和矢车菊素-3-葡萄糖苷。在此基础上,研究了不同纯度花色苷的降解动力学,结果表明:桑葚花色苷粗提物中所含的黄酮类化合物对花色苷的热降解有较强的保护作用,含黄酮的花色苷体系对p H值的变化更为敏感。在p H 3.5时,矢车菊素-3-芸香糖苷和矢车菊素-3-葡萄糖苷的热稳定性基本相同;在p H 4.0时,矢车菊素-3-芸香糖苷的热稳定性略好于矢车菊素-3-葡萄糖苷。     

超声辅助酶法提取薰衣草花色苷及其热降解动力学

以新疆伊犁熏衣草为研究对象,通过单因素实验和响应面试验研究超声辅助酶法提取薰衣草花色苷,确定最佳工艺条件为:在果胶酶质量分数为0.10%、pH3、乙醇浓度50%、酶解温度50℃、酶解时间62 min、超声时间25 min,该条件下薰衣草花色苷得率为6.22%,较单一超声提取法相比,超声辅助酶法具有明显的优势。通过对不同pH和温度下薰衣草花色苷稳定性的研究发现,不同pH下薰衣草花色苷热降解符合一级动力学方程;在相同pH下,花色苷降解所需要的能量势垒大小与温度无关;薰衣草花色苷热稳定性较差,当pH6.0时,其对热最为敏感,pH1.0时,其热稳定性最强。     

蔗糖含量对牡丹花色苷热稳定性和降解动力学的影响

研究了蔗糖含量对牡丹花色苷热稳定性和降解动力学的影响。结果表明：牡丹花色苷的热降解符合一级反应动力学模型,花色苷半衰期随加热温度升高而缩短;花色苷样品液所含的4 种花色苷中,降解速率依次为矢车菊-3-O- 二葡萄糖＞芍药-3-O- 葡萄糖苷＞矢车菊-3, 5-O- 二葡萄糖苷＞芍药-3, 5-O- 二葡萄糖苷;花色苷样品液的褐变指数随加热温度的升高和加热时间的延长而增大。蔗糖抑制了花色苷的降解,表现为提高了花色苷样品液的吸光度,降低了褐变指数;抑制程度与蔗糖浓度、加热处理的时间和温度有关;但含糖体系花色苷的热降解不符合一级反应动力学。     

Thermal Degradation of Acylated and Nonacylated Anthocyanins

ABSTRACT:  The thermal degradation pathways of acylated and nonacylated anthocyanins from 3 commercial sources have been investigated. Strawberry, elderberry, and black carrot concentrates were purified on XAD-16-HP and Sephadex-LH-20 columns to remove sugars, amino acids, salts, and phenolic compounds, respectively. The so obtained anthocyanin isolates were heated at 95 °C at pH 1, the optimum stability condition for the flavylium cation. During 7 h of thermal exposure, the samples were monitored by HPLC-DAD-MS³ at 280, 320, and 520 nm, respectively, together with spectrophotometric color and anthocyanin assessment. Total anthocyanin content lightness, and chroma, but not hue angle, were appropriate parameters to monitor anthocyanin loss on a statistically significant level. Anthocyanin glycosides were generally cleaved by successive loss of sugar moieties and pentoses were more readily split off than hexoses. Anthocyanin aglycones were further degraded by scission into phloroglucinaldehyde (cyanidin, pelargonidin), 4-hydroxybenzoic acid (pelargonidin), and protocatechuic acid (cyanidin), the residues of the A- and B-rings, respectively. Most interestingly, acylated cyanidin-triglycosides from black carrot were degraded into their corresponding diglycoside derivatives, which are not genuine carrot pigments. Moreover, hydroxycinnamic acid glycosides were generated. It is therefore assumed that the thermal burden during processing of anthocyanic food can be deduced by monitoring the colored and colorless compound profiles.     

有机酸对桑椹花色苷的辅色作用及其热降解动力学规律

为探究不同结构有机酸对桑椹花色苷的辅色作用及其热稳定性的影响,采用超高效液相色谱-质谱法分析花色苷组成,以对羟基苯甲酸、原儿茶酸、没食子酸、绿原酸、苹果酸为辅色剂,考察pH值、温度、有机酸质量浓度对辅色反应的影响,并分别在60、70、80 ℃水浴中模拟食品中花色苷的热降解过程,探究热降解动力学规律。结果表明,在pH=3.5、20 ℃、960 mg/L质量浓度条件下,“增色效应”和“红移效应”达到最大,辅色效果依次为苹果酸>绿原酸>没食子酸>原儿茶酸>对羟基苯甲酸,苹果酸比空白组Aλmax增加45.04%。反应化学计量比（n）、平衡常数（K）、吉布斯自由能ΔG°显示辅色过程均自发进行,苹果酸的平衡常数（K）最大,吉布斯自由能ΔG°最小,分别为26.85、-8.02 kJ/mol。热降解实验表明添加有机酸能延长花色苷半衰期（T1/2）,减小降解常数（k）,60 ℃时,没食子酸可将花色苷溶液半衰期（T1/2）从17.50 h延长至26.23 h,降解常数（k）从6.6×102 min-1减小至4.4×102 min-1。因此,有机酸辅色作用有助于提高桑椹花色苷的稳定性。     

蛇莓果实花色苷的稳定性及其降解动力学

探究蛇莓果实花色苷在多种条件下的稳定性及降解动力学。采用pH示差法测定不同pH值、温度、光照强度、氧化剂、还原剂、金属离子对花色苷稳定性的影响。研究表明,不同pH条件下蛇莓果实花色苷热降解符合一级动力学模型,花色苷在强酸性条件下的稳定性高于弱酸和中性条件;蛇莓果实花色苷的热稳定性较差,随着环境温度升高,降解速率k增大,半衰期和递减时间D值缩短,pH值2.0时活化能最大为68.65 kJ/mol,pH值5.0时活化能最小为42.35 kJ/mol,其降解为吸热非自发反应;6 000 lx光照和H2O2均会加快蛇莓果实花色苷的降解,且花色苷在光照和H2O2条件下降解均符合一级动力学模型,在光照条件下的降解速率为 0.012 3 d-1,半衰期56.35 d,H2O2条件下降解速率随H2O2体积分数的升高而增大;质量分数0.20%的Na2SO3对蛇莓果实花色苷的降解有抑制作用;Na+、K+对蛇莓果实花色苷无影响,而Al3+、Cu2+、Fe3+可显著破坏蛇莓果实花色苷的稳定性。综上,蛇莓果实花色苷应尽量在酸性、低温、避光且无氧化剂及Fe3+的条件下生产加工,以避免大量降解。     

蓝莓花色苷降解动力学及稳定性

以蓝莓花色苷为原料,采用pH示差法测定了不同pH值、温度、光照强度、氧化剂和还原剂对花色苷稳定 性的影响。结果表明：不同pH值下花色苷热降解符合一级动力学方程,强酸性条件下蓝莓花色苷的热稳定性强于 弱酸和中性;花色苷的热稳定性差,随着温度升高,花色苷的降解速率k明显增大,降解半衰期和递减时间D值明 显减小,pH 6.0时活化能最小,为44.77 kJ/mol,pH 1.0时活化能最大,为83.73 kJ/mol,热降解反应为吸热非自发反 应;光照和H2O2会加快蓝莓花色苷的降解,花色苷在光照和H2O2处理条件下降解均符合一级动力学方程,在光照条 件下的降解速率为0.014 8 d－1,半衰期为47 d,花色苷降解速率随着H2O2体积分数的升高明显增加;此外,质量分 数0.20% Na2SO3对花色苷的降解起到抑制作用,而质量分数0.05%、0.10%、0.15% Na2SO3会促进花色苷降解反应。     

紫甘蓝花色苷稳定性及热降解动力学研究

为有效控制紫甘蓝加工过程中花色苷的降解,研究了 pH、温度、光照、金属离子及外源添加物对花色苷稳定性的影响.实验表明,紫甘蓝花色苷稳定性受pH、温度和光照影响较大,pH2.0左右的花色苷5 h保存率仍有92.92％±0.69％、40℃下避光5 h花色苷保存率有70.50％±0.52％,花色苷稳定性较强;添加不同浓度的金...     

Kinetics of Malvidin-3-Glucoside Condensation in Wine Model Systems

Wine model systems containing equimolar quantities of malvidin-3-glucoside and d-catechin, with and without acetaldehyde, were stored anaerobically at 22, 32, 42, and 52°C. Malvidin-3-glucoside and d-catechin disappearance and polymer appearance were monitored by HPLC and colorimetric methods. Reaction rates and activation energies were calculated. The malvidin-3-glucoside and d-catechin condensation reactions showed pseudo first order kinetics both with and without the presence of acetaldehyde. However, activation energies were not significantly different.     

Degradation Kinetics of Anthocyanins in Sour Cherry Juice and Concentrate

The effects of temperature and soluble solids on degradation of anthocyanins in sour cherry concentrate were determined over temperature ranges (-18 to 37)°and 50 to 80°C. Anthocyanin degradation could be modeled as a first-order rate reaction, with rates of 33.97 × 10^minus;3. hr^minus;1 (15°CBrix), 59.19 × 10^minus;3. hr^minus;1 (45°CBrix) and 97.14 × 10^minus;3. hr^minus;1 (71°CBrix) at 80°C. Temperature dependence of reaction was described by the Arrhenius relationship. Activation energy for a solids content of 15-71°C Brix ranged from 16.37-19.14 kcal.mole^minus;1 with an average of 17.45 kcal.mole^minus;1     

龙葵果花色苷降解动力学

通过研究4种龙葵果花色苷提取物在不同pH值和温度下的降解动力学过程,得出其降解规律。结果显示,龙葵果花色苷的降解符合一级反应动力学模型。相同pH下随着温度的升高,龙葵果花色苷的降解速率常数呈现指数型增长趋势,半衰期呈现指数型下降趋势。60℃和70℃时随着pH的增大,粗提物、一级精制物的降解速率常数呈现对数型增长趋势,而组分1和组分2的降解速率常数则呈现指数型增长趋势,4种提取物的半衰期均呈现指数型下降的趋势。而80℃和90℃时,4种花色苷提取物的降解速率常数和半衰期并未呈现规律性的变化。4种龙葵果花色苷提取物均在60℃、pH 1.0时降解最慢,稳定性最好,其中粗提物的稳定性最强。     

超高压加工过程中花色苷降解动力学研究

为了了解超高压加工过程中花色苷的稳定性,以蓝莓汁和模拟果汁为对象,研究两种体系在200、400和600 MPa超高压处理过程中花色苷降解动力学,并探讨花色苷在超高压加工过程中的降解机理。结果表明:在200 MPa和600 MPa超高压处理过程中蓝莓果汁花色苷含量呈现下降趋势,在600 MPa超高压处理过程中模拟果汁花色苷含量也有所减少;蓝莓果汁和模拟果汁花色苷在超高压加工中的降解符合一级反应动力学。在超高压处理过程中花色苷会发生降解,这种降解不止是酶和热造成的,压力本身也会引起花色苷降解,花色苷在超高压处理过程中的降解机理需要进一步研究。     

Antioxidant and antiinflammatory activities of cyanidin-3-glucoside and cyanidin-3-rutinoside in hydrogen peroxide and lipopolysaccharide-treated RAW264.7 cells

Cyanidin-3-glucoside (C3G) and cyanidin-3-rutinoside (C3R) are 2 major anthocyanins found in Korean Rubus fruits (blackberries, raspberries, and black raspberries). The antioxidant and antiinflammatory effects of C3G and C3R in RAW264.7 murine macrophage cells were determined. Anthocyanins (5, 10, and 20 μg/mL) significantly (p<0.05) reduced H₂O₂-induced cytotoxicity in H₂O₂-stimulated RAW264.7 cells, compared with control cells. Incubation with C3G or C3R significantly (p<0.05) decreased intracellular reactive oxygen species and DNA damage (Hoechst and comet assay), and the cellular ferric reducing antioxidant power also increased, compared with control cells. Nitric oxide production in LPS-stimulated RAW264.7 cells treated with C3G and C3R was reduced by 41.9 and 34.4%, respectively. In addition, LPS-induced prostaglandin E₂ production was significantly (p<0.05) inhibited by C3G (51.7%) and C3R (58.6%), compared with LPS-stimulated control cells. Protein expressions of iNOS and COX-2 decreased in cells treated with anthocyanins. Anthocyanins down-regulated NF-κB expression and up-regulated I-κB expression in LPS-treated macrophages.     

蓝靛果汁花色苷热降解动力学的研究

以新榨蓝靛果汁为试材,采用控制温度、调节pH值、连续充N2等方法,探讨蓝靛果汁花色苷的热降解动力学,为深加工条件的优化控制及保质期的预测提供科学的依据。结果表明:蓝靛果花色苷对热不稳定,花色苷的降解过程符合一级动力学反应。随着pH值和温度的升高,蓝靛果花色苷的热降解半衰期(t1/2)和活化能(Ea)显著下降,研究表明充氮气处理可以提高蓝靛果花色苷的稳定性。     

Thermal Degradation Kinetics of Prickly-Pear-Fruit Red Pigment

The color stability of betacyanine from prickly pear was determined in the fruit juice at temperatures up to 90 °C. The degradation rates were dependent on pigment concentration, being slower for higher concentrations. The lack of a significant oxygen effect or inhibitory action of ascorbic acid did not support autooxidation as the exclusive chemical process responsible for decolorization.     

胭脂萝卜红色素热处理及贮藏过程中降解动力学

本文研究了胭脂萝卜红色素在不同溶液体系(pH=3.0的缓冲溶液和不同Vc添加量的软饮料）中的热降解动力学及储藏动力学。结果表明：对胭脂萝卜红色素进行加热处理(75~95 oC),其降解动力学均符合一级反应动力学,且降解速率与温度呈正比。同时,不同Vc添加量对胭脂萝卜红色素的降解速率有一定影响,软饮料中降解速率依次为120 mg/L<40 mg/L<0 mg/L<360 mg/L。在4 oC及25 oC储藏条件下,胭脂萝卜红色素的降解动力学分别符合零级动力学和一级反应动力学模型。     

Thermal Chlorophyll Degradation Kinetics of Mint Leaves Puree

Thermal degradation kinetics of chlorophyll ‘a’, ‘b’ and total chlorophyll in mint leaves puree were investigated as function of pH (4.5–8.5) and processing temperature (80–145°C), respectively. Mint puree was processed at 80°to 100°C at pH 4.5, while that at pH 5.5 to 8.5 was processed at 105°to 145°C. Chlorophyll degradation followed the first order reaction kinetics. Good agreement was found between estimated and experimental chlorophyll retention in all cases (R² > 0.86; MRQE < 0.27). Activation energies ranged from 6.45 to 47.67 kJ/mol. Reaction rate and activation energy data indicated that chlorophylls were more stable at alkaline pH. Transition state theory was applied to estimate the enthalpy, entropy and Gibbs free energy of activation. Enthalpy (ΔH^#) ranged from 3.14 to 44.66 kJ/mol, while entropy (ΔS^#) ranged from ?0.157 to ?0.266 kJ/(mol K). The overall free energy change was 105.76 kJ/mol. Results indicated that, the compensation effect did not exist for chlorophyll degradation in mint puree during thermal processing.     

热降解动力学研究方法在阻燃皮革上的应用

简单介绍了几种热降解动力学的研究方法及其优缺点，综述了热降解动力学在纺织、塑料等领域的应用情况及其在皮革领域的发展现状，并对热降解动力学研究方法在阻燃皮革研究上的应用前景进行了展望。