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    2017年, 第47卷, 第6期 刊出日期:2017-06-22 上一期    下一期
    基础研究
    一种氧化胺表面活性剂pH响应蠕虫状胶束流变行为研究
    Study on rheological behaviors of pH-responsive wormlike micelles formed by an amine oxide surfactant
    张萌, 齐丽云, 龙宇, 王济远, 齐松竹, 黄媛琳, 方雪瑾
    2017 (6):  301-306.  doi: 10.13218/j.cnki.csdc.2017.06.001
    摘要 ( 281 )   PDF(898KB) ( 426 )  
    利用流变学方法研究了不同pH条件下两性表面活性剂α-羧基十三烷基二甲基氧化胺(CTAO)在水溶液中的聚集行为。实验结果表明,在温度25~60 ℃区间内,浓度范围为55~125 mmol/L,溶液pH=6.0~6.7时,无需任何添加剂CTAO水溶液即可形成蠕虫状胶束,其流变行为符合Maxwell模型,零剪切黏度最高可达26.5 Pa·s。在溶液pH>7的条件下,分子在溶液中的存在形式发生改变,分子间作用的斥力增加,蠕虫状胶束转变为球状胶束,其黏度接近于水,零剪切黏度约是pH=6.2时的1/4 000。该pH响应蠕虫状胶束体系仅由CTAO溶于水形成,其相变pH范围窄,具有制备容易、体系简单、流变性能变化显著的特点。 The aggregation behaviors of an amphoteric surfactant,α-carboxyl tridecyl dimethylamine oxide (CTAO) in aqueous solution at different pH values were examined by rheological method.Results show that wormlike micelles would form in CTAO aqueous solutions within concentration 55-125 mmol/L and pH value 6.0-6.7 at 25-60 ℃ without any additive.Their rheological behaviors comply with Maxwell model and the zero-shear viscosity can achieve 26.5 Pa·s.In case the pH value of the solution is higher than 7,form of the molecules of the surfactant in the solution changes and the repulsion between the molecules increases which results in the transition from wormlike micelles to spherical micelles.Meanwhile,the viscosity of the CTAO solution at pH value 7 is close to that of water and the zero-shear viscosity is about 1/4 000 of the solution with pH value 6.2.The pH-responsive micellar systems is obtained by a single-component surfactant CTAO,while displays distinct advantages of simple,narrow responsive pH value range,easy preparation and remarkable change of rheological properties.
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    科技讲座
    离子液体表面活性剂的合成与应用(Ⅵ) ——离子液体表面活性剂的界面张力
    Synthesis and application of ionic liquid surfactants (Ⅵ)Interfacial tension
    王萍, 杨许召, 徐清杰, 邹文苑, 王军
    2017 (6):  307-311.  doi: 10.13218/j.cnki.csdc.2017.06.002
    摘要 ( 240 )   PDF(1463KB) ( 265 )  
    离子液体表面活性剂在油/水界面吸附,降低界面张力。随着疏水烷基链长的增加,降低表面张力的能力增大。吡啶基表面活性剂比咪唑基表面活性剂具有更高的疏水性和降低界面张力能力。在高浓度无机盐存在下,离子液体表面活性剂降低界面张力的能力提高,界面张力可达10-2 mN/m,优于传统表面活性剂。 The interfacial tension between oil and water decreases due to the adsorption of ionic liquid surfactant at the interface.The more carbon number of the alkyl chain in the surfactant molecule,the higher ability for decreasing the interfacial tension.Pyridine based surfactants show higher hydrophobicity and higher interfacial tension decreasing capacity than that of imidazole based surfactants.Under existence of high concentration of inorganic salts,capacity of ionic liquid surfactants for decreasing the interfacial tension can be upgraded that achieves about 10-2 mN/m,which is better than the traditional surfactants.
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    开发与应用
    茶皂素的纯化及抑制酪氨酸酶活性的研究
    Purification of tea saponin and its inhibition on tyrosinase activity
    孙劲毅, 蔡春辉, 梁蓉, 杨成
    2017 (6):  312-316.  doi: 10.13218/j.cnki.csdc.2017.06.003
    摘要 ( 298 )   PDF(782KB) ( 282 )  
    研究了茶皂素的纯化及纯化产物体外对马铃薯酪氨酸酶催化L-DOPA合成多巴醌的抑制作用及其机理。结果表明质量浓度为100 g/L时,市售茶皂素、经大孔树脂纯化的茶皂素TS及2种层析分离得到的茶皂素TS1和TS2对酪氨酸酶的抑制率分别为51.29%,90.06%,94.13%和82.47%;TS和TS1对酪氨酸酶IC50分别为48和40 g/L,抑制作用表现为可逆竞争性抑制,对酪氨酸酶的抑制常数分别为137和101 g/L。 Purification of tea saponin as well as inhibitory effect and inhibiting mechanism for catalytic synthesis of DOPA quinone from L-DOPA by potato tyrosinase in vitro was examined.The tea saponin product that purchased from market,was treated with macroporous resin to get the preliminarily refined tea saponin product (TS).Then the TS were further purified by chromatographic method and two kinds of purified tea saponin product were produced as TS1 and TS2.Results show that at mass concentration of 100 g/L,the inhibition rate of the market product,the TS,TS1 and TS2 achieves 51.29%,90.06%,94.13% and 82.47% respectively.IC50 of TS and TS1 achieves 48 and 40 g/L respectively.The inhibition kinetics analyzed by Lineweaver-Burk plots show that the action of TS and TS1 express as reversible and competitive inhibition for conversion of L-DOPA.The inhibition constants for the TS and TS1 achieves 137 and 101 g/L respectively.
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    茯苓提取物对酪氨酸酶抑制动力学及刺激性研究
    Tyrosinase activity inhibition kinetics and skin irritation of Poria cocos extract
    陈宇霞, 张凯, 龚盛昭
    2017 (6):  317-321.  doi: 10.13218/j.cnki.csdc.2017.06.004
    摘要 ( 399 )   PDF(767KB) ( 428 )  
    研究了茯苓提取物对酪氨酸酶单酚酶和二酚酶活力的影响及其抑制动力学,测试结果表明:茯苓提取物对酪氨酸酶单酚酶和二酚酶的活力均有抑制作用,单酚酶和二酚酶活力下降50%的茯苓提取物质量浓度(IC50)分别为0.008和0.040 g/L。酪氨酸酶单酚酶的催化反应存在迟滞时间,茯苓提取物对酪氨酸酶二酚酶活力的抑制作用表现为可逆效应。Lineweaver-Burk图显示茯苓提取物对二酚酶的作用表现为非竞争性与竞争性混合的抑制类型。在此基础上采用红细胞溶血实验初步评估茯苓提取物对皮肤的刺激性,结果显示含2.000 g/L茯苓提取物的样品无刺激性,质量浓度远大于单酚酶和二酚酶活力下降50%的茯苓提取物质量浓度IC50,茯苓提取物在0.200~0.800 g/L的质量浓度范围内可保证其安全添加且具有美白功效。 The kinetics of inhibitory effect of Poria cocos extract on monophenolase and diphenolase activity of mushroom tyrosinase was studied.Test results show that Poria cocos extract efficiently inhibits both monophenolase and diphenolase activities of mushroom tyrosinase.Concentrations of Poria cocos extract leading to 50% activity lost (IC50) on monophenolase and diphenolase were calculated to be 0.008 and 0.040 g/L respectively.There is a lag time in the catalytic reaction process of the monophenolase.Inhibition of Poria cocos extract on activity of diphenolase of tyrosinase indicates a reversible effect.Lineweaver-Burk plots indicates that the inhibitor binds the enzyme reversibly other than reacts with it destructively.Lineweaver-Burk plots show that the inhibition type is a composite of competitive and non-competitive inhibition.On this basis,Poria cocos extract stimulus preliminary assessment was conducted with RBC hemolysis test,and results show that Poria cocos extract with a mass concentration of 2.000 g/L is non-stimulus while such concentration is far higher than IC50 of Poria cocos extract on monophenolase and diphenolase activity.It further indicates that Poria cocos extract displays whitening effect under the condition of the security.This suggests that Poria cocos extract with mass concentration range of 0.200~0.800 g/L is safe,for whitening cosmetic use.
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    高保湿有机硅蜡的合成与性能研究
    Study on synthesis and performance of a high moisturizing silicone wax
    宋旻子陌, 郑成, 叶嘉荣, 罗方然
    2017 (6):  322-325.  doi: 10.13218/j.cnki.csdc.2017.06.005
    摘要 ( 325 )   PDF(801KB) ( 271 )  
    通过两步法以端氢硅油和1-十八烯为原料合成高保湿有机硅蜡,通过单因素试验和正交试验探究反应物摩尔比、反应温度和反应时间对转化率的影响。利用红外光谱对产物的结构进行表征,并研究了其保湿性。实验结果表明反应温度对转化率的影响较大,较佳反应条件为:n(端氢含氢硅油)∶n(1-十八烯)=1∶24,反应温度125 ℃,反应时间 5 h,在此条件下转化率达92.87%。由红外光谱图可知合成产物为目标产物。将高保湿有机硅蜡的保湿性与市售有机硅蜡产品进行比较,结果显示高保湿有机硅蜡具有更优良的保湿性。 A high moisturizing silicone wax was synthesized with hydrogen-terminated silicone oil and 1-octadecene as starting materials.Effects of molar ratio of the reactants,reaction temperature and reaction time on conversion were examined by single factor test and orthogonal test.Structure of the product was characterized by infrared spectrum,and its moisturizing capacity were studied.The experimental results show that reaction temperature displays great influence on the reaction conversion,and the optimum reaction conditions are as follows:n(terminal hydrogen containing silicone oil)∶n(1-octadecene)=1∶24;reaction temperature,125 ℃;reaction time,5 h.Under such optimum reaction conditions,the conversion rate reaches 92.87%.Then the infrared spectrum shows that the synthetic compound produced is the targeted product.Comparison with respect to the moisturizing capacity between the targeted product and traditional silicone wax product purchased from the market was made.Result shows that the targeted product displays better moisturizing efficacy.
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    透骨草抑菌活性成分提取及抑菌机理研究
    Extraction for antibacterial active ingredient of Phryma leptostachya L.and its mechanism for bacteria inhibition
    张美龄, 梁蓉, 曹光群, 杨成
    2017 (6):  326-330.  doi: 10.13218/j.cnki.csdc.2017.06.006
    摘要 ( 337 )   PDF(2604KB) ( 298 )  
    通过优化透骨草提取工艺,再经有机溶剂萃取,得到透骨草有效抑菌活性成分(PAI)。结果表明,在乙醇体积分数80%,温度60 ℃,料液比1∶30 (g∶mL),时间4 h的条件下提取效果较优,经氯仿萃取后剩余水相有较强抑菌作用,对金黄色葡萄球菌和大肠杆菌的抑菌圈直径分别为(24.32±0.65)和(25.44±1.10) mm,其最小抑菌浓度(MIC)分别为6.25和3.12 g/L。此外,还通过细菌生长抑制曲线、细胞膜通透性以及细胞形貌观察等手段,研究PAI对细菌的抑制机理。结果表明,PAI在细菌繁殖的对数生长期起主要抑制作用,同时破坏细胞膜的通透性和细胞壁的结构,通过栅栏效应达到抑菌作用。 Technological conditions for extraction of antibacterial active ingredient in Phryma leptostachya L.by ethanol was optimized.Then the extract was further extracted by a water immiscible organic solvent chloroform to enrich the effective antibacterial active ingredient (PAI).Extraction under the condition of ethanol volume fraction 80%,60 ℃,ratio of solid to liquid 1∶30 (g∶mL) and 4 h shows the optimal results,and the remaining aqueous phase raffinate after extraction with chloroform shows strong antibacterial activity.The diameter of inhibition zone for S.aureus and E.coli are (24.32±0.65) and (25.44±1.10) mm respectively,and the minimum inhibition concentration (MIC) are 6.25 and 3.12 g/L respectively.In addition,the bacterial growth curve,cell membrane permeability and cell morphology observation are applied to examine the inhibition mechanism on S.aureus and E.coli.Results show that PAI mainly effects on the logarithmic growth phase and destroys the permeability of the cell membrane as well as the structure of the cell wall;thus the bacteria are inhibited by multiple-hurdle effect.
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    表面活性剂辅助微波提取阳荷黄酮工艺条件的优化
    Optimization of extraction of total flavonoids from Zingiber striolatum Diels assisted by surfactant and microwave
    马明兰, 刘阳, 王园, 蔡依, 张海涛
    2017 (6):  331-335.  doi: 10.13218/j.cnki.csdc.2017.06.007
    摘要 ( 317 )   PDF(755KB) ( 352 )  
    采用表面活性剂辅助微波法提取阳荷中的黄酮。研究了表面活性剂种类及其添加量、微波辐射功率、辐射时间、料液比和pH对黄酮收率的影响。以单因素试验为基础,通过正交试验优化了黄酮的提取工艺。确定较佳工艺条件为:pH=4.0,料液比1∶40 (g∶mL),表面活性剂十二烷基硫酸钠质量分数10.5%,微波辐射时间2.4 min,微波辐射功率550 W。在此条件下,黄酮的收率为12.7%。相比于热回流法、超声提取法和微波提取法,通过表面活性剂辅助微波提取,阳荷中黄酮收率分别提高了41.1%,56.8%和46.0%。该法提取效率高、工艺简单。 Flavonoids was extracted from Zingiber striolatum Diels under assistance of microwave as well as surfactant.The effects of the type and amount of surfactant,microwave irradiation power,irradiation time,base material to liquid ratio and pH value on the yield of flavonoids were examined.On the basis of single factor experiment,the extraction technology of flavonoids was optimized by orthogonal experimental design.The recommended conditions were determined as follows:the mass fraction of surfactant sodium dodecyl sulfonate,10.5%;microwave irradiation power,550 W;microwave irradiation time,2.4 min;based material to liquid ratio,1∶40 (g∶mL);pH=4.0.The average yield of the total flavonoids achieves 12.7%.As comparing with the hot reflux method,ultrasonic extraction method and microwave extraction method,the extraction rate of flavonoids was increased by 41.1%,56.8% and 46.0%,respectively.The method shows high extraction efficiency and simple operation.
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    自交联丙烯酸酯乳液合成及在水性指甲油中的应用
    Preparation and properties of self-crosslinking polyacrylic esteremulsion and its application in water-based nail polish
    陈习惠, 万祥龙, 闵凡飞, 郝国防
    2017 (6):  336-340.  doi: 10.13218/j.cnki.csdc.2017.06.008
    摘要 ( 349 )   PDF(3526KB) ( 336 )  
    采用预乳化乳液聚合法合成了自交联丙烯酸酯乳液,以该乳液为基料制备了水性指甲油。比较了不同指甲油涂层的亲疏水性、硬度和耐磨性等。结果表明,自交联水性指甲油感观与理化性能指标能达到QB/T 2287-2011的要求;相对于非交联水性指甲油涂层表现出较好的疏水性,接触角为64.54°;涂层硬度较高,铅笔硬度达到了HB;耐磨性有所提高,其涂层的100转磨耗量为34.58 mg,附着力好,表现出优异的综合性能。与溶剂型指甲油涂层相比,自交联水性指甲油涂层对指甲无腐蚀作用,具备作为水性指甲油安全应用的条件。 Self-crosslinking polyacrylic ester emulsion was synthesized by pre-emulsification polymerization method and a kind of water-based nail polish was prepared using the emulsion as basic material.Performance indices,such as hydrophilic and hydrophobic property as well as hardness and abrasion-proof etc of the film formed by the emulsion and other nail polish commodities were tested and compared.Results show that the self-crosslinking polyacrylic ester water-based nail polish can meet all the requirements for sensory and physical-chemical indices of QB/T 2287-2011.Its film contact angle reaches to 64.54° that indicating a better hydrophobicity as comparing with other non-crosslinked nail polish films.At the same time,its hardness reaches to HB pencil level,with the abrasion loss (100 r/min) of 34.58 mg and good adhesion level.Its conventional performance is excellent.As comparing with the solvent-based nail polishes,the self-crosslinking nail polish shows no corrosive effect on the nail,and safety in application can be achieved.
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    化妆品用聚丙烯酸类增稠剂的增稠性及耐离子性分析
    Testing for thickening and ion resisting effect of polyacrylic acid type thickeners in cosmetics
    刘晓敏, 龙春霞
    2017 (6):  341-344.  doi: 10.13218/j.cnki.csdc.2017.06.009
    摘要 ( 1141 )   PDF(720KB) ( 478 )  
    以5种化妆品常用的聚丙烯酸类增稠剂作为研究对象,通过测试流变学参数黏度对其增稠性及耐离子性进行分析。考察了5种增稠剂水溶液在不同质量分数和pH下的黏度变化,结果表明,共聚物Carbomer 940的增稠效果最好,但黏度在pH=2~11时变化较大;含金属离子共聚物AVS、EMT-10和HMB增稠效果一般,黏度在pH=5~11时保持稳定;自聚物Zen增稠效果最差,但黏度在pH=2~8时保持稳定。向增稠剂水溶液中加入NaCl和MgCl2,考察化妆品中常见离子对增稠剂水溶液稳定性的影响,结果显示,盐的加入均破坏了5种增稠剂水溶液的稳定性,其中自聚物Zen的耐离子性最好;对增稠性和耐离子性最好的2种增稠剂复配体系进行分析,发现Carbomer 940和Zen的复配体系在增稠性方面起到协同增效的作用,两者复配使用能得到增稠性和耐离子性都较好的增稠剂体系。 The thickening and ion resisting effect of five kinds of polyacrylic acid type common thickeners were tested.Viscosity of their aqueous solutions at different mass fraction were measured,and the variations of viscosity with pH value were examined.Results show that co-polymer Carbomer 940 displays the best thickening performance,but its viscosity varies with pH value 2-11.The thickening effect of co-polymers that contain metal ions AVS,EMT-10 and HMB displays a general state,and their viscosity is stable within pH value 5-11.The thickening effect of bulk-polymer Zen is the lowest,while its viscosity is stable within pH value 2-8.NaCl and MgCl2 were added separately to aqueous solution of the five kinds of thickener to examine the influence of common ions in cosmetics on their viscosity.Addition of the salts declines the stability of the aqueous solution of all the five kinds of thickener.However,bulk-polymer Zen displays the best ion resistance.Blends composed of Carbomer 940 and Zen were tested,and their thickening and ion resistance were measured.Result shows that there is synergic effect for thickening performance of the Carbomer 940-Zen system.Both thickening effect and ion resistance can be improved by blending of Carbomer 940 and Zen.
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    专论与综述
    金属离子对蛋白酶作用的研究进展
    Progress in research work field with respect to effects of metal ions on protease
    李静, 张剑, 赵永祥
    2017 (6):  345-351.  doi: 10.13218/j.cnki.csdc.2017.06.010
    摘要 ( 780 )   PDF(1682KB) ( 542 )  
    简述了蛋白酶的结构及性质,系统地比较了不同金属离子与蛋白酶作用后对其活性、稳定性及结构方面的影响。目前研究表明金属离子对蛋白酶作用的可能机理主要有催化作用、酶结构的形成和调节作用3种。介绍了现代化学技术在揭示蛋白酶结构与功能关系方面的重要意义,对金属离子与蛋白酶相互作用的机理进行了总结和思考,并对蛋白酶的应用前景进行了展望。 Structure and properties of protease were briefed.Effects of separate metal ions on the protease,including activity,stability and structure were compared systematically.Current research work suggests that the possible mechanisms of the effects of metal ions on protease are mainly catalytic action,structure formation and regulation.Modern technology plays an important role in revealing the significance of the relationship between structure and function of protease as well as the mechanism of interactions between metal ions and protease.Mechanism of interactions between metal ions and protease is summarized and pondered.Outlooks for future applications of protease is prospected.
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    洗涤剂和化妆品中烷基酚和烷基酚聚氧乙烯醚的检测进展
    Progress in research work field for detection of alkylphenols and alkylphenol ethoxylates in detergent products and cosmetics
    顾宇翔
    2017 (6):  352-356.  doi: 10.13218/j.cnki.csdc.2017.06.011
    摘要 ( 396 )   PDF(736KB) ( 539 )  
    概述了壬基酚、辛基酚、壬基酚聚氧乙烯醚和辛基酚聚氧乙烯醚的性质、应用情况和安全性评价;简单介绍了国内外与洗涤用品中烷基酚和烷基酚聚氧乙烯醚相关的法规和标准;综述了一些标准和论文中关于洗涤剂和化妆品中壬基酚、辛基酚、壬基酚聚氧乙烯醚和辛基酚聚氧乙烯醚的检测方法,并对一些检测方法所采用的技术和注意事项进行了重点说明。 Properties,applications and safety evaluation of nonylphenol,octylphenol,nonylphenol ethoxylates and octylphenol ethoxylates were described.The regulations and standards for alkylphenols and alkylphenol polyethoxylates related to detergent products in China as well as in foreign countries were briefed.An overview of detection methods for nonylphenol,octylphenol,nonylphenol ethoxylates and octylphenol ethoxylates composed in detergent products and cosmetics was reviewed.Operation technique and attention to be paid in the detection process were emphatically presented.
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    分析与检测
    高效液相色谱法同时测定洗发水中6种去屑剂
    Simultaneous determination of six kinds of anti-dandruff agent in hair shampoo by high performance liquid chromatography
    牛水蛟, 唐子安, 李启艳, 王小兵, 李俊婕, 于海英
    2017 (6):  357-360.  doi: 10.13218/j.cnki.csdc.2017.06.012
    摘要 ( 357 )   PDF(731KB) ( 324 )  
    建立了同时测定洗发水中己脒定二(羟乙基磺酸)盐、水杨酸、吡硫翁锌、酮康唑、氯咪巴唑和吡罗克酮乙醇胺盐6种去屑剂的高效液相色谱法。采用Atlantis T3色谱柱(4.6 mm×250 mm,5 μm),以乙腈-甲醇-0.01 mol/L磷酸二氢钾水溶液(含乙二胺四乙酸二钠0.5 mmol/L)为流动相进行梯度洗脱,流速1.0 mL/min,柱温室温,进样量5 μL。结果表明,己脒定二(羟乙基磺酸)盐、水杨酸、酮康唑和氯咪巴唑的线性范围为4~200 mg/L,吡硫翁锌的线性范围为2~100 mg/L,吡罗克酮乙醇胺盐的线性范围为5~250 mg/L,方法的线性关系良好,相关系数均大于0.999。6种去屑剂的平均回收率为96.2%~102.0%,日间和日内精密度分别为0.17%~0.89%和0.27%~1.30%,方法检出限为5~25 mg/kg,定量限为15~75 mg/kg。 A method for simultaneous determination of six kinds of anti-dandruff agent including hexamidine diisethionate,salicylic acid,pyrithione zinc,ketoconazole,climbazole and octopirox in hair shampoo was established by high performance liquid chromatography with an Atlantis T3 column (4.6 mm×250 mm,5 μm).A mixture of acetonitrile-methanol aqueous solution (0.01 mol/L KH2PO4 and 0.5 mmol/L Na2EDTA) was at a flow rate of 1.0 mL/min used as HPLC mobile phase for gradient elution at room temperature;while 5 μL of which was injected for analysis.Following are the results.The linearity range of hexamidine diisethionate,salicylic acid,ketoconazole and climbazole is 4-200 mg/L,pyrithione zinc is 2-100 mg/L,as well as 5-250 mg/L for octopirox.All of which have a fine linear relation with the correlation coefficients greater than 0.999.The spiked recoveries of six components vary from 96.2% to 102.0%.The relative standard deviations of intra and inter day precision are 0.17%-0.89% and 0.27%-1.30%.The limits of detection range from 5 to 25 mg/kg,also 15-75 mg/kg as the limits of quantification.
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