磁性壳聚糖微球吸附苹果渣多酚的动力学及热力学分析

为了更好的利用胺基化磁性壳聚糖微球吸附分离苹果渣多酚的工艺,对其反应动力学和热力学进行了研究。主要采用Langmuir准一级动力学模型、Langmuir准二级动力学模型、Elovich方程及内扩散方程对吸附反应动力学过程进行拟合,并利用Langmuir等温吸附模型、Freundlich等温吸附模型及Temkin等温吸附模型对吸附反应热力学特性进行解析。结果表明:吸附动力学过程符合准二级动力学模型的描述,吸附温度越高,吸附速率常数和初始吸附速率越大,且平衡吸附量越高。吸附热力学过程符合Freundlich等温吸附模型,热力学参数ΔG<0,ΔH>0,ΔS>0,表明胺基化磁性壳聚糖微球对苹果渣多酚的吸附过程可以自发进行,并且是伴随着焓变>0的吸热过程。动力学及热力学研究为利用胺基化磁性壳聚糖微球进行苹果渣多酚的提取分离提供了技术依据。     

磁性壳聚糖微球吸附苹果汁有机酸的动力学及热力学特性

为充分利用中国丰富的苹果资源,开发多品类的苹果深加工产品,以磁性壳聚糖微球为吸附剂,通过磁分离技术,吸附获得苹果汁中的天然有机酸,并对其吸附过程进行研究。利用Lagergren准一级动力学方程、准二级动力学方程、Elovich方程及内扩散方程对吸附反应动力学过程进行拟合;利用Langmuir等温吸附模型、Freundlich等温吸附模型及Temkin等温吸附模型对吸附等温数据进行拟合,并对其吸附反应热力学特性进行分析。通过比较线性拟合方程的决定系数,发现磁性壳聚糖微球吸附苹果汁中有机酸的动力学过程更加符合Lagergren准二级动力学模型,吸附温度越高,吸附速率常数和初始吸附速率越大,但平衡吸附量越低。等温吸附过程更加符合Langmuir等温吸附模型,表明该吸附过程更趋向于单分子层的化学吸附。298 K时,有机酸的饱和吸附量可达到188.679 2 mg/g,表明磁性壳聚糖微球是苹果汁中有机酸的1种高效吸附剂。热力学参数ΔG°0,ΔH°0,ΔS°0,表明磁性壳聚糖微球对苹果汁有机酸的吸附过程为熵增加的可自发进行的放热过程。动力学及热力学结果为磁性壳聚糖微球吸附苹果汁有机酸的研究提供了理论基础与技术支持。     

微波辅助提取苹果渣中苹果多酚的工艺研究

为了充分利用农业废弃物苹果渣，进一步提高苹果渣中多酚物质的提取效率，采用二次通用旋转组合设计研究了苹果渣中苹果多酚的微波提取工艺。结果表明：乙醇用量对多酚得率有极显著影响，功率、乙醇浓度以及萃取时间和功率的交互项对多酚得率有显著影响，萃取时间对多酚得率无显著影响。最优工艺是：萃取时间60 s，功率750 W，乙醇浓度60％，乙醇用量25 mL(料液比1∶50)，此条件下苹果多酚理论提取的得率为11.93 mg/g(DW)(验证值为11.41 mg/g)，明显高于回流及超声波提取得率。     

联合提取分离苹果渣果胶和多酚工艺优化

为研究从苹果渣中联合提取和分离果胶和多酚的最优工艺条件,该文利用酸提法从干燥的苹果渣中提取果胶和多酚,并利用疏水性大孔树脂进行分离。结合一种基于区间数多决策属性的评价方法优化提取分离过程。提取参数为果胶的产量和多酚的产量;分离参数包括:多酚吸附率、果胶吸附率和果胶的色泽变化。经优化后,提取的最优性条件为:pH值2.0,温度95℃,提取时间1.5h和料液比1:20(g/mL)。果胶、多酚物质的平均提取得率为196.49和10.98mg/g,分别占单一提取产率的92.28%和85.92%。经优化得出:最佳的大孔树脂是XDA-5。根据最优分离条件可得到提取液中98.32%果胶和92.15%多酚。结果表明,多属性决策理论的评价方法应用在提取分离苹果渣是可行的,可减少试验量。     

苹果渣中不同极性多酚的分离及体外抗氧化活性研究

为了优化苹果多酚提取工艺,进而提高苹果多酚提取物中强效多酚的含量,该文采用液-液萃取方法按极性大小对果渣多酚进行分离,进而采用1,1-二苯基-2-苦苯肼自由基法和铁离子还原/抗氧化力法对不同极性多酚体外抗氧化活性进行评价.结果表明:液-液萃取方法,可以实现不同极性多酚的有效分离,不同极性苹果多酚,其体外抗氧化活性有显著差异,水层多酚活性最强,其次为正丁醇层,乙酸乙酯层相对较弱,即多酚的抗氧化性与其极性呈正相关.因此,工业化提取苹果渣中多酚时,增大提取溶剂的极性有利于强效多酚的获取.     

苹果渣多酚提取工艺的优化

为优化苹果渣中多酚提取工艺,并得到提取工艺和多酚组成之间的关系,利用微波辅助提取法设计了由物料颗粒、液料比、乙醇浓度、微波功率和微波提取时间5个因素构成的多酚提取优化试验流程,构建了涵盖黄酮、原花青素2种典型多酚物质和抗氧化能力的提取工艺评价指标体系。采用证据理论对不同工艺在评价指标下的焦元进行识别,并基于信度函数和似真函数得到了不同提取工艺的效用区间和优化方案。优化结果为：物料颗粒60目,液料比30?mL/g,乙醇体积分数60%,微波功率600?W,提取时间70?s,此条件下苹果渣多酚的提取量为213.83?mg/100g,黄酮提取量为83.21?mg/100g,原花青素提取量为52.79?mg/100g,抗氧化的EC50值为3.71?mg/100mL,验证了采用证据理论进行苹果渣多酚提取工艺优化的有效性。     

大孔吸附树脂分离纯化红小豆多酚工艺及效果

为开发利用红小豆加工副产物中的生理活性物质,该研究采用大孔树脂吸附法对煮制红小豆水的多酚类物质进行分离纯化,比较了5种不同型号大孔树脂对红小豆多酚的吸附分离效果,从中筛选出HPD 600型树脂作为理想的吸附剂;研究了 HPD 600树脂对红小豆多酚的吸附等温线,结果表明,该吸附等温线与 Langmuir、Freundlich函数曲线的拟合程度非常高,且采用Langmuir模型的拟合效果略优于Freundlich模型。静态和动态吸附、洗脱试验结果表明：样品液浓度、温度、pH值、乙醇浓度、上样流速及洗脱流速等因素均对HPD 600树脂吸附分离红小豆多酚有影响。较理想的工艺参数为：30℃是较适宜的静态吸附温度;保持煮制红小豆水本身的多酚浓度0.96 mg/mL和pH值6.8,上样体积200 mL,上样流速1.0 mL/min进行动态吸附;吸附饱和平衡后,采用50 mL 60%乙醇溶液,以1.5 mL/min的流速进行动态洗脱。依此得到的红小豆多酚纯化液,其总酚含量和总抗氧化能力均有显著提高,约为纯化前的2.2倍。     

微波辅助提取中pH值与脱色对苹果果胶的影响

为了得到高得率、高品质的苹果果胶,该文利用不同pH值的盐酸溶液对苹果渣中果胶进行微波辅助提取（Microwave-assisted extraction, MAE）,之后对果胶提取液进行大孔树脂XAD-16HP脱色,研究了pH值与脱色对果胶得率和品质的影响。结果表明：微波辅助提取工艺中随着pH值的升高,果胶得率、半乳糖醛酸质量分数和总离子含量减少,酯化度、黏均分子量和总多酚增加,褐变度无显著变化;大孔树脂吸附脱色后果胶褐变度、总多酚、彩度C*值显著下降,色调角H°值显著增加,半乳糖醛酸质量分数和酯化度没有     

苹果渣固态发酵苹果醋工艺研究

以新鲜苹果渣为主要原料,采用果胶酶法对苹果渣的酒精发酵和醋酸发酵工艺进行优化研究,通过正交试验确定最优酿造工艺参数。初步获得的苹果渣酒精发酵条件是果胶酶添加量0.06%、酵母接种量8%、初始糖度16 °Brix;苹果渣醋酸发酵过程的最优工艺条件是干湿苹果渣的配料比为1 ∶ 10、醋酸菌接种量15%、发酵温度32 ℃,此条件下总酸含量增长到38.267 6 g/L。     

BS-12改性不同磁性黏土矿物对苯酚的吸附

采用共沉淀法制备磁性海泡石(MST)、磁性沸石(MZT)和磁性凹凸棒石(MAT),并以两性表面活性剂十二烷基二甲基甜菜碱(BS-12)对其进行改性,以X射线衍射(XRD)对不同吸附剂材料进行表征分析,通过批处理法比较不同磁性黏土矿物经BS-12改性后对苯酚的吸附特征,同时考察温度、pH和离子强度对BS-12改性磁性黏土矿物吸附苯酚的影响。结果表明,三种黏土矿物原样和磁化样对苯酚的吸附能力分别呈NATNSTNZT、MATMSTMZT的大小顺序,磁化对凹凸棒石的苯酚吸附能力影响最大,这与Fe3O4在凹凸棒石上的覆盖度较高有关。经BS-12改性后,三种改性磁性黏土矿物对苯酚的吸附量均随改性比例的增大而增加,具有一致性;三种磁性黏土矿物中,BS-12改性对磁性海泡石的苯酚吸附能力提升最多,这与BS-12在磁性海泡石的改性率较高有关。温度和溶液初始pH的升高不利于BS-12改性磁化样对苯酚的吸附,但离子强度的增加对BS-12改性磁化样吸附苯酚具有促进作用。BS-12改性磁性黏土矿物对苯酚的吸附以疏水分配作用为主,吸附能力取决于有机碳含量。三种改性磁性黏土矿物中,BS-12改性磁性凹凸棒石上的有机碳含量最高,对苯酚的吸附能力最强,且吸附受温度、pH和离子强度的影响最小。     

Aminoparathion: a highly reactive metabolite of parathion. 1. Reactions with polyphenols and polyphenol oxidase

Spiking of tomato and apple fruits with parathion at different levels of about 1-4 mg/kg irradiation and under simulated sunlight conditions resulted in nearly complete photodegradation within 13 h, but extractable parathion degradation products could not be found in any case. However, after irradiation of an unrealistically spiked apple (134 mg/kg) different photoproducts including aminoparathion (AP) were detectable by HPLC, proving that the hitherto postulated photochemistry of parathion indeed takes place in the fruit cuticle environment. Besides the photoreduction pathway it was shown for the first time that AP is also easily formed by reduction of the primary photoproduct nitrosoparathion with thiols (cysteine, glutathione), while ascorbic acid only leaves hydroxylaminoparathion. In the presence of polyphenols, AP was effectively bound to quinone intermediates formed by both silver oxide and polyphenol oxidases. For pyrocatechol, a disubstituted o-quinone derivative could be isolated as a dark red addition product and structurally be elucidated. However, in the presence of caffeic acid, catechol, naringin, and quercetin, respectively, insoluble dark colored polymers precipitated within 48 h, while in the supernatants AP was not detectable any more. Polymer-bound and nonextractable AP was proven by transesterification with sodium ethoxide releasing O,O,O-triethyl thiophosphate which was determined by GC. Additionally, AP itself was a substrate for polyphenol oxidases, resulting in a quinone imine intermediate which in turn reacted with excessive AP yielding deep red colored di- and trimerization products.     

改性磁性荔枝皮对水及果汁中砷的吸附效果及动力学分析

为探索安全高效实用的果汁类食品砷吸附材料,以天然植物副产物荔枝皮为材料,通过共沉法制备砷吸附材料磁性荔枝皮(magnetic litchi peel,MLP),采用电感耦合等离子体质谱法测定砷含量,以砷清除率为判断指标,研究了MLP对三价砷和五价砷吸附效果及机理。结果表明:改性MLP表面含有粉末状的Fe3O4,与未改性荔枝皮相比部分官能团增加,表面粗糙、更加凹凸不平,结构疏松,微孔数量增加,有利于吸附作用的进行,在砷浓度为0.20 mg/L水溶液中三价砷和五价砷吸附率为88%和90%,对苹果汁中的三价砷和五价砷吸附率为83%和93%;MLP对三价砷和五价砷溶液吸附等温线符合Langmuir等温线模型,拟合决定系数R2均大于0.99,为单分子层吸附,在298 K条件下饱和吸附量三价砷为0.181 mg/g,五价砷为0.225 mg/g;MLP对砷溶液吸附动力学可以通过准二级吸附动力学模型描述,R2均高于0.99;MLP对三价砷和五价砷的吸附过程中吉布斯自由能小于0,吸附反应是自发进行的,焓变小于0,MLP对两种价态砷的吸附都是放热反应。研究结果可为改性荔枝皮在果汁类食品中砷脱除方法和工艺的应用提供理论与数据参考。     

黄花菜多酚类化合物的鉴定及漂烫与贮藏对其稳定性的影响研究

为鉴定黄花菜多酚类化合物的结构并研究漂烫与贮藏对其稳定性的影响,本研究采用响应面和正交试验设计,四极杆飞行时间液质串联系统,以及三重四极杆液质串联系统,研究了超声波辅助提取黄花菜多酚,HPD-600大孔树脂吸附多酚,乙醇解吸附多酚的最佳条件,对多酚类化合物进行分离纯化和结构鉴定,并对新鲜、漂烫与室温贮藏的黄花菜多酚类化合物含量进行分析。结果表明,超声辅助提取黄花菜多酚类化合物的最佳条件为:乙醇浓度66%,时间22 min,温度43℃,料液比1∶12 g·mL^-1, 此条件下多酚得率为2.12%;HPD-600大孔树脂吸附多酚的最佳条件为温度50℃,pH值6,吸附时间3 h,此条件下多酚吸附率为28.76%;无水乙醇解吸附的最佳条件为温度60℃,pH值6,解吸时间3 h,此条件下多酚解吸率为78.94%,纯化的多酚溶液浓度为0.61%;黄花菜多酚类化合物的含量由高到低依次为芦丁、绿原酸和槲皮素,高温漂烫和贮藏极易引起多酚类化合物的损失,导致加工后黄花菜的营养品质下降。本研究结果可为黄花菜多酚类化合物的分离鉴定及漂烫和室温贮藏对其稳定性影响的研究提供参考。     

巯基修饰和胡敏酸包裹纳米Fe3O4颗粒的制备及其对溶液中Pb2＋Cd2＋Cu2＋的吸附效果研究

采用改进的化学共沉淀法制备纳米Fe3O4颗粒,利用3-巯丙基三乙氧基硅烷（MPTES）和胡敏酸（HA）对所制备的纳米Fe3O4进行巯基修饰和胡敏酸包裹,通过红外光谱（IR）、X射线衍射分析（XRD）等方法对上述制备的纳米颗粒的性质进行了表征,同时对上述不同的纳米Fe3O4颗粒在恒温下对水体中金属离子（Pb2＋、Cd2＋、Cu2＋）的吸附进行了研究。结果表明,所制备的功能化前后的纳米Fe3O4纯度较高,平均粒径约为20～30nm,且分布均匀。不同纳米型Fe3O4颗粒对溶液中金属离子具有较好的吸附性能,其吸附等温线均可以用Langmuir方程进行较好的拟合;裸露的纳米Fe3O4颗粒对Pb2＋最大吸附量（b）达到172.4mg·g-1,经过胡敏酸包裹后的纳米Fe3O4颗粒对Cd2＋、Cu2＋的最大吸附量分别增加了75.8%和231.5%;对不同金属离子而言,裸露的和巯基修饰的纳米Fe3O4对3种重金属离子的吸附能力的强弱为Pb2＋〉Cd2＋〉Cu2＋,而经胡敏酸包裹后的顺序则为Pb2＋〉Cu2＋〉Cd2＋;与裸露的和巯基修饰的纳米Fe3O4相比,经HA包裹的纳米Fe3O4对Cd2＋和Cu2＋具有较高的吸附量和吸附亲和力参数,而对Pb2＋的吸附无显著性差异。     

大孔树脂分离纯化玫瑰果多酚及其抗氧化性

为了研究大孔树脂对玫瑰果多酚的纯化效果,该试验以玫瑰果多酚粗提液为原料,利用大孔树脂吸附法对其进行纯化,并对其体外抗氧化活性进行了研究。结果表明,大孔吸附树脂纯化较佳工艺为:在20℃条件下,用质量浓度为0.80 mg/m L的玫瑰果多酚粗提液(p H值5.8)以1 m L/min的流速上样200 m L;吸附平衡后用少量蒸馏水洗至洗脱液无色,后用70 m L体积分数为70%的乙醇溶液,以1.5 m L/min的流速进行动态洗脱,洗脱峰相对集中、对称,无拖尾。纯化后,总酚质量分数由纯化前的122.90 mg/g提高到399.42 mg/g。体外抗氧化活性的研究表明:清除1,1-二苯基-2-苦基肼自由基的作用效果顺序为维生素C纯化多酚2,6-二叔丁基-4-甲基苯酚(Butylated hydroxytoluene,BHT)粗多酚;清除超氧阴离子自由基的作用效果顺序为维生素CBHT纯化多酚粗多酚;清除羟基自由基的作用效果顺序为维生素C纯化多酚BHT粗多酚。研究结果为玫瑰果多酚的进一步利用提供依据。     

Apple and pear peel and pulp and their influence on plasma lipids and antioxidant potentials in rats fed cholesterol-containing diets

The aim of this study was to assess the bioactive compounds of apple and pear peel and pulp in vitro and their influence on plasma lipids and antioxidant potentials in vivo. The antioxidant potentials measured by 1,1-diphenyl-2-picrylhydrazyl (DPPH), beta-carotene bleaching (beta-carotene), and nitric oxide inhibition radical scavenging (NO) tests in apple peel and pulp were significantly higher than in pear peel and pulp, respectively. The ethanol extract of apple peels showed the strongest inhibition of lipid peroxidation as a function of its concentration and was comparable to the antioxidant activity of butylated hydroxyanisole. The pear pulp extract had the weakest antioxidant ability, whereas other extracts such as apple pulp and pear peel were nearly equal. The antioxidant activities comprised contributions from polyphenols, phenolic acids, and flavonoids and correlated well with polyphenols and flavonoids. The correlation coefficients between polyphenols and antioxidant activities by DPPH, beta-carotene, and NO were as follows: 0.9207, 0.9350, and 0.9453. Contrarily, the correlation coefficient between the content of dietary fiber and the antioxidant activities test was low. The content of all studied indices in apple and pear peel was significantly higher than in peeled fruits (p < 0.05). Diets supplemented with fruit peels exercised a significantly higher positive influence on plasma lipid levels and on plasma antioxidant capacity of rats than diets with fruit pulps.     

Oligomeric procyanidins in apple polyphenol are main active components for inhibition of pancreatic lipase and triglyceride absorption

Inhibitory effects of apple polyphenol extract (AP) and procyanidin contained in AP on in vitro pancreatic lipase activity and in vivo triglyceride absorption in mice and humans were examined. AP and procyanidin considerably inhibited in vitro pancreatic lipase activity. However, polyphenols, except for procyanidin, in AP (i.e., catechins, chalcones, and phenol carboxylic acids) showed weak inhibitory activities on pancreatic lipase. Procyanidins separated by normal-phase chromatography according to the degree of polymerization were also examined. Inhibitory effects of procyanidins increased according to the degree of polymerization from dimer to pentamer. On the other hand, pentamer or greater procyanidins showed maximal inhibitory effects on pancreatic lipase. These results suggested that with respect to in vitro pancreatic lipase inhibition, the degree of polymerization was an important factor and oligomeric procyanidin mainly contributed. Next, we performed a triglyceride tolerance test in mice and humans. Simultaneous ingestion of AP and triglyceride significantly inhibited an increase of plasma triglyceride levels in both models. These results suggested that the oligomeric procyanidins contained in AP inhibited triglyceride absorption by inhibiting pancreatic lipase activity in mice and humans.