咖啡酰氨基酸乙酯的合成及其抗氧化活性

以L-氨基酸乙酯盐酸盐和咖啡酸为原料,1-(3-二甲基氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)及1-羟基苯并三唑(HOBt)为催化剂,合成咖啡酰缬氨酸乙酯、咖啡酰亮氨酸乙酯、咖啡酰蛋氨酸乙酯、咖啡酰酪氨酸乙酯4种产物。利用~1HNMR、质谱及红外对产物进行了表征;通过清除DPPH自由基、羟基自由基及红细胞溶血等实验分别对咖啡酰氨基酸乙酯类物质的体外抗氧化活性及刺激性进行了初步评价。结果表明,以该法合成4种咖啡酰氨基酸乙酯,收率在75%～82%。咖啡酸与氨基酸结合后,4种产物均呈现较好的抑制DPPH自由基、羟基自由基活性的效果;咖啡酰缬氨酸乙酯(Ⅲa)清除DPPH自由基能力最强,其IC_(50)为(11.23±0.24)μmol/L;咖啡酰蛋氨酸乙酯(Ⅲc)清除羟基自由基能力最强,其IC_(50)为(0.24±0.002)mmol/L;3种咖啡酰氨基酸乙酯相对于咖啡酸单体对于红细胞膜具有更弱的刺激性。咖啡酰氨基酸乙酯类物质抗氧化活性明显强于L-抗坏血酸(VC),可作为潜在的抗氧化剂。     

油酸和十二烷二酸的氨基酸酯的合成及其生物抗菌性

以L-丙氨酸乙酯盐酸盐、甘氨酸乙酯盐酸盐、L-蛋氨酸甲酯盐酸盐、L-亮氨酸乙酯盐酸盐和L-酪氨酸甲酯盐酸盐在1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和1-羟基苯并三唑(HOBt)的作用下分别与油酸进行反应，生成了5种油酸的氨基酸衍生物；将L-丙氨酸乙酯盐酸盐和甘氨酸乙酯盐酸盐分别与十二烷二酸进行反应，生成了两种十二烷二酸的氨基酸衍生物，7种产物的收率均≥75%。利用FTIR、TGA、¹HNMR和LC-MS对产物进行了表征，测试了产物的水油分散性，考察了产物对金黄色葡萄球菌和大肠杆菌的抑菌性。结果表明，所合成的脂肪酰氨基酸酯均能在水油体系中分散，且具有较强的生物抗菌性，其中，0.01 mg油酸酰亮氨酸乙酯能有效地抑制金黄色葡萄球菌(菌数由2.0×10⁹ CFU/mL降至1.4×10⁷ CFU/mL)，而相同质量油酸酰酪氨酸甲酯则能抑制大肠杆菌(菌数由2.0×10⁹ CFU/mL降至1.8×10⁷ CFU/mL)。     

壬二酸的化学改性及产物抑制酪氨酸酶活性的研究

以壬二酰二氯和氨基酸乙酯盐酸盐为原料,采用改进后的肖顿-鲍曼缩合反应首先合成了壬二酸二丙氨酸乙酯、壬二酸二亮氨酸乙酯和壬二酸二缬氨酸乙酯,然后经过氢氧化钠溶液水解最终得到壬二酰二丙氨酸钠、壬二酰二亮氨酸钠和壬二酰二缬氨酸钠;对两步反应的产物结构采用1HNMR和LC-MS进行表征确认;考察了壬二酸化学改性产物对酪氨酸酶活性的抑制率,并与壬二酰二甘氨酸钾进行了比较。结果表明,通过在壬二酸中引入丙氨酸、亮氨酸和缬氨酸后,其水溶性明显增强,壬二酰二丙氨酸钠、壬二酰二亮氨酸钠和壬二酰二缬氨酸钠对酪氨酸酶活性有明显的抑制作用,随着质量浓度的升高抑制率均随之升高;当4种样品对酪氨酸酶活性的抑制率达到50%时,壬二酰二丙氨酸钠和壬二酰二缬氨酸钠的质量浓度(IC50)约为6.5 g·L-1,阳性对照壬二酰二甘氨酸钾的IC50约为15 g·L-1,与阳性对照壬二酰二甘氨酸钾比较,壬二酰二丙氨酸钠和壬二酰二缬氨酸钠在质量浓度较低时对酪氨酸酶活性发挥更强的抑制效果。     

向日葵花提取液的美白、抗氧化功效及刺激性研究

采用醇提法制备向日葵花提取液。采用酪氨酸酶活性抑制试验、DPPH自由基法、羟自由基法以及红细胞溶血试验分别对其美白、抗氧化效果以及刺激性进行体外评估。结果表明,向日葵花提取液对酪氨酸酶活性具有一定的抑制作用,半数抑制浓度IC_(50)为38.4 g/L;对于羟自由基和DPPH自由基具有较好的清除效果,半数清除浓度EC_(50)分别为0.495 g/L、7.4 g/L。根据红细胞溶血试验结果,向日葵花提取液为无刺激性。同时,人体测试结果表明,在化妆品膏霜基质中质量分数为2%时,产品无刺激,连续使用1个月,96%以上受试者认为脸部肌肤状态有改善。     

三白草提取物对自由基的清除作用研究

考察了三白草乙醇提取物经不同溶剂萃取所得的各部分对1,1-二苯基-2-三硝基苯肼(DPPH)自由基、羟基自由基和超氧自由基的清除能力。以2,6-二叔丁基-4-甲基苯酚(BHT)为参考。结果表明,三白草乙醇提取物经不同溶剂萃取所得的各部分对DPPH自由基、羟基自由基和超氧自由基都具有清除能力,且随着提取物浓度的增加,清除能力逐渐增高;其中乙酸乙酯部分对DPPH自由基、羟基自由基和超氧自由基的清除作用最强。     

满山香精油和金橘精油的成分分析及其抗氧化性能研究

采用气相色谱-质谱联用法(GC-MS)对满山香和金橘精油的化学成分进行分析,并采用DPPH自由基(DPPH·)清除法、ABTS自由基阳离子(ABTS~+·)清除法对精油及其主要单体的抗氧化性能进行了研究。结果表明,满山香精油鉴定出49个组分的化学成分,占总含量的70.86%,其主要成分为葎草烯(11.71%)和石竹烯(9.22%);金橘精油经鉴定出28种组分,占总含量的96.31%,其主要成分为柠檬烯(70.15%)。满山香精油和金橘精油对DPPH·和ABTS~+·具有清除活性,其中满山香精油清除DPPH·和ABTS~+·的IC_(50)值分别为12.75 mg/mL和1.30 mg/mL;金橘精油清除DPPH·和ABTS~+·自由基的IC_(50)值分别为22.34 mg/mL和3.33 mg/mL。     

红葡萄酒、桃红葡萄酒和白葡萄酒的抗氧化活性比较

本文比较了红葡萄酒、桃红葡萄酒和白葡萄酒的总酚含量及抗氧化活性差异。通过比较红葡萄酒、桃红葡萄酒和白葡萄酒的总酚含量、1,1-二苯基-2-三硝基苯肼(DPPH)自由基清除能力、Fe~(3+)总抗氧化能力(FRAP)、铁还原能力、清除羟基自由基能力等试验,评价不同种类葡萄酒的抗氧化活性。实验结果表明,红葡萄酒总酚含量最高,达到GAE 2120mg·L~(-1)。其中红葡萄酒的DPPH自由基清除试验、铁还原能力试验、清除羟基自由基能力试验的半数抑制浓度(IC_(50))值所对应的葡萄酒稀释倍数分别为:0.046、0.033和0.13,Fe~(3+)总抗氧化能力(FRAP)试验结果为449.57μmol·L~(-1) Fe SO_4。红葡萄酒、桃红葡萄酒和白葡萄酒均具有一定的抗氧化活性,活性强弱依次为红葡萄酒桃红葡萄酒白葡萄酒。     

羊蹄甲果荚总黄酮提取工艺优化及抗氧化性研究

以羊蹄甲果荚为原料,乙醇为提取溶剂,通过单因素和正交试验对回流提取羊蹄甲果荚总黄酮工艺进行优化;并通过考察羊蹄甲果荚总黄酮对1,1-二苯基-2-三硝基苯肼(DPPH·)和羟基自由基(·OH)的清除能力来评价其抗氧化性。结果表明,羊蹄甲果荚总黄酮的最佳提取工艺参数为:提取时间5 h、料液比1:30(g:mL)、提取温度80℃、乙醇体积分数80%。在此优化工艺条件下,提取液中总黄酮含量为10.837 mg·g~(-1)。羊蹄甲果荚总黄酮对DPPH自由基(IC_(50)=34.511μg·mL~(-1))和羟基自由基(IC_(50)=0.090mg·mL~(-1))具有一定的清除作用,表明其具有一定的体外抗氧化活性。     

篱栏网多糖的提取工艺优化及抗氧化活性

优化了热水浸提法提取篱栏网多糖的工艺,最佳条件为:液料比26 mL/g,温度94.5℃,提取时间3.6 h,提取次数2次,此时多糖提取率为(4.38±0.04)%;该多糖清除DPPH自由基的IC_(50)值为(0.12±0.03)mg/mL,清除羟基自由基的IC_(50)值为(1.21±0.02)mg/mL。     

满山香精油和金橘精油的成分分析及其抗氧化性能研究

采用气相色谱-质谱联用法(GC-MS)对满山香和金橘精油的化学成分进行分析,并采用DPPH自由基(DPPH·)清除法、ABTS自由基阳离子(ABTS⁺·)清除法对精油及其主要单体的抗氧化性能进行了研究。结果表明,满山香精油鉴定出49个组分的化学成分,占总含量的70.86%,其主要成分为葎草烯(11.71%)和石竹烯(9.22%);金橘精油经鉴定出28种组分,占总含量的96.31%,其主要成分为柠檬烯(70.15%)。满山香精油和金橘精油对DPPH·和ABTS+·)清除法对精油及其主要单体的抗氧化性能进行了研究。结果表明,满山香精油鉴定出49个组分的化学成分,占总含量的70.86%,其主要成分为葎草烯(11.71%)和石竹烯(9.22%);金橘精油经鉴定出28种组分,占总含量的96.31%,其主要成分为柠檬烯(70.15%)。满山香精油和金橘精油对DPPH·和ABTS⁺·具有清除活性,其中满山香精油清除DPPH·和ABTS+·具有清除活性,其中满山香精油清除DPPH·和ABTS⁺·的IC_(50)值分别为12.75 mg/mL和1.30 mg/mL;金橘精油清除DPPH·和ABTS+·的IC_(50)值分别为12.75 mg/mL和1.30 mg/mL;金橘精油清除DPPH·和ABTS⁺·自由基的IC_(50)值分别为22.34 mg/mL和3.33 mg/mL。     

咖啡酸苯乙酯的合成

以咖啡酸和β-溴乙基苯为原料合成咖啡酸苯乙酯,研究了溶剂种类、反应时间、反应温度及催化剂种类对反应的影响。结果表明:使用V(PEG):V(H2O)=9:1混合溶剂,磷酸钾为催化剂,反应温度为60℃,反应时间为48h,咖啡酸苯乙酯产率可达60%。     

沙棘口服液中5-羟色胺的电化学检测

采用电化学沉积法制备咖啡酸膜修饰电极,研究了5-羟色胺(5-HT)在该修饰电极上的电化学行为。结果表明,高浓度的抗坏血酸(AA)和肾上腺素(EP)共存不干扰5-HT的检测,5-HT在0.41 V和-0.12 V出现一对灵敏的氧化还原峰,其氧化峰电流与浓度在2.0×10-6～6.0×10-5mol/L范围内呈良好的线性关系,检测下限为8.0×10-7mol/L。该修饰电极制备简单,可准确检测神兴沙棘欣之安口服液中5-HT的含量。     

咖啡酸衍生物的合成方法及其生物活性研究进展

咖啡酸衍生物是近年来新药研发的热点化合物,具有抗肿瘤、抗氧化、抗炎和免疫调节等多方面的药理作用。本文就各类咖啡酸衍生物的合成方法及其生物活性进行综述。     

Effects of three phenolic acids on chlorophyll content and ions uptake in cowpea seedlings

This study was conducted to test the hypothesis that interfering with chlorophyll metabolism and ion uptake may be mechanisms through which some phenolic acids inhibit the growth of cowpea seedlings. Three concentrations (10^–4 M, 5 × 10^–4 M, and 10^–3 M) of each of syringic, caffeic, and protocatechuic acids were used to test their effects using sand-culture medium. It was found that seedling growth, chlorophyll a, total chlorophyll, chlorophyll a/b ratio, and the uptake of N, P, K, Fe, and Mo were significantly reduced by most of the test concentrations of the phenolic acids. However, chlorophyll b content and the Mg uptake were not significantly affected by all the phenolic acid concentrations. Calcium uptake was significantly inhibited by 5 × 10^–4 M and 10^–3 M of caffeic acid and 5 × 10^–4 M of protocatechuic acid. In most cases, the reduction in dry weight was parallel to the reduction in chlorophyll content and ion uptake, and the reduction in chlorophyll was also parallel to the reduction in ion uptake. The relationships among the inhibition of dry weights, chlorophyll content, and ion uptake are briefly discussed.     

荆条蜂胶化学成分的研究

本文对荆条蜂胶乙醇提取物的化学成分进行了研究,为进一步的活性评价及建立标准化模型提供基础数据。蜂胶原胶经65%乙醇溶液80℃加热得到蜂胶提取物,将提取物采用石油醚、乙酸乙酯、正丁醇进行逐级溶剂分配、硅胶色谱柱层析、重结晶、制备液相等方法进行分离和纯化,从乙酸乙酯部分分离得到31个化合物,通过对化学物理性质分析以及红外、紫外、质谱、核磁共振波谱的测定解析,确定了化合物结构。其中黄酮类化合物14个,肉桂酸衍生物7个,咖啡酸酯类化合物6个,其它类4个。     

Zn2+配位双模板印迹聚合物的制备表征及同时萃取升麻中的阿魏酸和咖啡酸

以Zn²⁺-阿魏酸-咖啡酸配合物为模板制备了双分子印迹聚合物,优化了制备条件,用傅里叶红外光谱和扫描电镜对分子印迹聚合物进行结构表征,测试了分子印迹聚合物的吸附特性,探讨了分子印迹聚合物固相萃取应用效能并对萃取条件进行了优化.结果表明,当预反应混合液中金属离子、模板总量(阿魏酸-咖啡酸摩尔比为2:3)、功能单体及交联剂用量比为1:1:3:30(摩尔比)时,所得印迹聚合物对两种模板(阿魏酸和咖啡酸)均具有最好的吸附性能,吸附量分别达51.12mg/g和70.26mg/g.吸附动力学测试表明吸附3h,分子印迹聚合物可达到吸附平衡.用分子印迹聚合物进行固相萃取时,优化的淋洗过程为1.00mL H₂O、1.00mL甲醇-H₂O (3/7,体积比)及1.00mL甲醇-H₂O-ACN (4/4/2,体积比),洗脱溶剂为2.00mL甲醇.在优化条件下,分子印迹聚合物可同时选择富集升麻初提液中的阿魏酸和咖啡酸,二者回收率分别为92.67%和95.42%,而且产品中杂质少于用硅胶萃取所得产品.     

Caffeic Acid Enhances the Anti-Leukemic Effect of Imatinib on Chronic Myeloid Leukemia Cells and Triggers Apoptosis in Cells Sensitive and Resistant to Imatinib

Among the phenolic acids tested on the K562 cell line, a model of chronic myeloid leukemia (CML), caffeic acid (CA) was biologically active on sensitive and imatinib (IM)-resistant cells at micro-molar concentration, either in terms of reduction of cell proliferation or triggering of apoptosis. The CA treatment provoked mitochondrial membrane depolarization, genomic DNA fragmentation and phosphatidylserine exposure, hallmarks of apoptosis. Cell cycle analysis following the treatment with comparable cytotoxic concentrations of IM or CA showed marked differences in the distribution profiles. The reduction of cell proliferation by CA administration was associated with increased expression of two cell cycle repressor genes, CDKN1A and CHES1, while IM at a cytotoxic concentration increased the CHES1 but not the CDKN1A expression. In addition, CA treatment affected the proliferation and triggered the apoptosis in IM-resistant cells. Taken together, these data suggested that CA induced the anti-proliferative effect and triggered apoptosis of CML cells by a different mechanism than IM. Finally, the combined administration of IM and CA at suboptimal concentrations evidenced a synergy of action in determining the anti-proliferative effect and triggering apoptosis. The ability of CA to potentiate the anti-leukemic effect of IM highlighted the nutraceutical potential of CA in CML.     

Reversible adhesives based on acrylate copolymer modified by caffeic acid containing boroxin

4-formyl-phenylboronic acid (FBA) and caffeic acid (CA) can combine to obtain a novel vinyl monomer containing boroxin, which was named as FBCA. Having been reduced the inhibition of phenolic hydroxyl groups, FBCA could directly copolymerize with acrylate (for instance, isobornyl acrylate (IBOA), butyl acrylate (BA), and hydroxypropyl methacrylate (HPMA)) by free-radical polymerization to produce modified acrylate copolymer adhesive (FBCA-IBH). Compared with sole acrylate copolymer adhesive (IBH), the FBCA-IBH adhesive presents a higher thermal stability, cohesive strength, creep resistance, strain recovery, and adhesion strength to different substrate (such as carbon steel, polypropylene (PP), and polytetrafluoroethylene (PTFE)). According to the results of TGA, the initial degradation temperature of FBCA-IBH is increased by 50 °C. The creep resistance of FBCA-IBH is improved and its holding power to carbon steel is increased from 19 min to 3 h. It is eye catching that the shear strength to carbon steel could reach 9.37 MPa. Besides, this shear strength can be maintained even if after 18 cycle times, even the maximum value can achieve 14.36 MPa. The adhesion of thermoplastic adhesives to carbon steel exhibits adhesion strength comparable to that of thermoset adhesives. The reversible adhesive presents bonding strength in macro-field, not just limited in micro-field. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48703.     

A first pilot study to produce a food antioxidant from sunflower seed shells (Helianthus annuus)

This article explains a laboratory procedure to produce an antioxidant from grinded, dehulled and partially defatted sunflower seeds. Initially, a solvent suitable to extract phenols was searched among different solutions of water mixed with ethanol, methanol and acetone at 40% (vol/vol) (each tested at pH 5, 7 and 9). Both the ethanol/water 60:40 (vol/vol) and the acetone/water 60:40 (vol/vol) mixtures proved to be suitable for the dephenolization of sunflower seed shells, but in the next steps of this research, the mixture ethanol/water 60:40 (vol/vol) at pH 5 was used. Secondly, the procedure to obtain the antioxidant product was defined, which consisted in hydrolysis of sunflower seed phenols with 1.25 N NaOH at room temperature for 60 min and finally the recovery of caffeic acid formed from chlorogenic acid with ethyl acetate. From 25 g of partially defatted sunflower shells, around 90 mg of powdery antioxidant product, consisting of 58% caffeic acid, was obtained. The antioxidant product, the caffeic acid standard and propyl gallate were added to different edible fats at the same dose of 240 AU (antioxidant units) per kg fat. A Rancimat test, at 130 °C and an air flow of 20 L h^?1, demonstrated that the effectiveness of the sunflower antioxidant product was essentially similar to that of the caffeic acid standard, but 15–20% lower than that of propyl gallate. In conclusion, dephenolization of sunflower seeds could be economically convenient, not only because a useful antioxidant can be produced, but also because the raw material composition can be improved for other uses.