CN116832862A - 一种超薄金-锰纳米复合材料、制备方法及其在检测领域中的应用 - Google Patents
一种超薄金-锰纳米复合材料、制备方法及其在检测领域中的应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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Abstract
本发明公开了一种超薄金‑锰纳米复合材料、制备方法及其在检测领域中的应用，属于纳米材料科学和检测技术领域。本发明首先通过柠檬酸钠还原法合成出特定尺寸的金纳米球，并将具有还原性的链长较长的PVP接枝到金纳米球表面，进而在水热合成过程中MnO4 ‑能沿着PVP链还原生长，最终形成超薄荷包蛋形态的超薄金‑锰纳米复合材料，合成方法简单，制得的超薄金‑锰纳米复合材料具有的超强催化性能和催化过程无需氧气参与的特性，进一步的，基于该超薄金‑锰纳米复合材料和碱性磷酸酶的双酶级联反应调控的均相电化学方法可用于检测有机磷农药，且检测速度快、灵敏度高、检出限低。
Description
技术领域
本发明属于纳米材料科学和检测技术领域，具体涉及一种超薄金-锰纳米复合材料、制备方法及其在检测领域中的应用。
背景技术
有机磷农药(OPs)因其药效高、广谱、成本低等众多优点，普遍应用于除草、杀虫等农业生产过程中。除此之外，在畜禽养殖业也有相关应用，如作为畜禽体内体表杀虫剂、杀菌药物等。以有机磷农药敌百虫为例，敌百虫作为杀螨剂或杀虫剂防治害虫对农业畜牧养殖生产有巨大的经济效益，但若使用不当，容易通过皮肤渗透或食物链导致急性、慢性中毒。此外，长期暴露于低剂量的OPs，也可引起免疫功能障碍、肿瘤发生、肌肉功能障碍和生殖功能损伤等不良影响。所以，迫切需要制定有效的方法来监测和检测食物中低剂量的OPs，以保证食品安全。
电化学检测具有简单、快速、灵敏、成本低等优点，被广泛应用于快速检测行业。但是传统电化学检测需要修饰电极，存在稳定性差、检测不准确等问题，具有一定的局限性。使用均相电化学传感器取代传统电化学检测方法，省去修饰电极这一繁琐的步骤，可以大大提高检测结果的稳定性和准确性。在众多电化学分析方法中，差分脉冲伏安法(DPV)由于其优异的灵敏度、高分辨率和较低的信噪比，已成为电化学分析方法的优先选项。
在目前已有的报道中，二氧化锰(MnO2)因其原材料廉价易得、无污染等优点在生物成像和治疗、化学传感、光子和光电器件等领域被广泛关注。目前许多二氧化锰纳米材料，如二氧化锰纳米花、二氧化锰纳米片、二氧化锰纳米线等形态已具有较为完善的合成方法，然而单一的二氧化锰纳米材料参与催化时通常需要氧气参与，首先将氧气转化为强氧化性的活性中间物种，再利用中间物种完成对底物的催化氧化。然而，在实际检测应用时，不同检测体系中的溶解氧浓度不可避免存在差异，如果氧气在二氧化锰催化氧化机理中占据重要作用，会严重影响检测结果的准确性。
公开号为CN113155816A的中国专利文献公开了一种基于金纳米簇-二氧化锰纳米片的甲基对氧磷荧光-比色分析方法，该方法首先制备牛血清白蛋白功能化的金纳米簇(AuNCs)，再以AuNCs和MnCl2·4H2O为原料制备AuNCs-MnO2，进一步利用AuNCs-MnO2，将其用于甲基对氧磷的荧光检测方法中，但是上述方法的准确性有待进一步提高。
目前为止，并没有一种能够实现不受氧气浓度影响的二氧化锰催化材料合成方法。因此构建一种不受氧气影响的高灵敏度、高准确性的均相电化学传感方法用于日常生活中的食品安全检测具有非常高价值的研究和应用意义。
发明内容
本发明提供了一种超薄金-锰纳米复合材料的制备方法，步骤简单，易于合成，制得的超薄金-锰纳米复合材料具有氧化性，是一种类氧化物酶，具有的超强催化性能和催化过程无需氧气参与的特性，可用于差分脉冲伏安法检测有机磷农药。
具体采用的技术方案如下：
一种超薄金-锰纳米复合材料的制备方法，包括以下步骤：
(1)以氯金酸为原料，采用柠檬酸钠还原法制备金纳米球溶液；进一步利用聚乙烯吡咯烷酮修饰金纳米球，得到接枝PVP的金纳米球溶液；所述的金纳米球的粒径为15～20nm；
(2)利用水热合成法，将接枝PVP的金纳米球溶液分散在去离子水中，加入高锰酸钾80～90℃反应30～45min后，再加入高锰酸钾70～80℃反应8-10h得到所述的超薄金-锰纳米复合材料。
本发明通过柠檬酸钠还原法合成出特定尺寸的金纳米球，并将具有还原性的链长较长的PVP接枝到金纳米球表面，进而在水热合成过程中MnO4 -能沿着PVP链还原生长，并控制水热条件和投料顺序，使MnO2层更均匀的成长，最终形成超薄荷包蛋形态的超薄金-锰纳米复合材料。
优选的，利用聚乙烯吡咯烷酮修饰金纳米球的过程为：将金纳米球溶液与聚乙烯吡咯烷酮溶液混合，70～90℃修饰30～45min后，离心除去多余的聚乙烯吡咯烷酮，得到接枝PVP的金纳米球溶液。
进一步优选的，所述的聚乙烯吡咯烷酮的分子量为8000～40000；聚乙烯吡咯烷酮溶液的浓度为0.02～0.04g/mL。
优选的，步骤(2)中，接枝PVP的金纳米球溶液、第一次投料的高锰酸钾溶液、第二次投料的高锰酸钾溶液的体积比为1:0.08～0.1:0.02～0.04，高锰酸钾溶液的浓度为10～15mM。
本发明还提供了所述的超薄金-锰纳米复合材料的制备方法制得的超薄金-锰纳米复合材料。
优选的，该超薄金-锰纳米复合材料中的Au@MnO2的直径为120～200nm，厚度为1.1～1.9nm。Au@MnO2具有氧化性，是一种类氧化物酶，具有的超强催化性能和催化过程无需氧气参与的特性，用于DPV检测OPs时检测效果好，LOD最低检测限比二氧化锰纳米花低。
本发明还提供了一种双酶级联反应调控均相电化学检测有机磷农药的方法，具体包括以下步骤：
(1)在36～37℃下，将待测样品与碱性磷酸酶孵育10～30min，再加入L-抗坏血酸-2-磷酸孵育3～5min，得到混合溶液，在混合溶液中依次加入PB缓冲液、所述的超薄金-锰纳米复合材料和3,3',5,5'-四甲基联苯胺，得到待测溶液；
(2)用氧化铝粉末对玻碳电极进行抛光打磨，清洗，将清洗好的玻碳电极在K3Fe(CN)6溶液中进行循环伏安法活化；
(3)以活化后的玻碳电极为工作电极，铂电极为对电极，氯化银电极为参比电极，构建三电极体系；将活化后的玻碳电极置于待测溶液中，在电位0.1～0.6V的区间内利用差分脉冲伏安法检测待测溶液的DPV峰值电流信号，将DPV峰值电流信号代入到相应的标准曲线中得到待测样品中有机磷农药含量。
有机磷农药对碱性磷酸酶(ALP)具有特异性抑制作用，当无有机磷农药存在时，ALP催化L-抗坏血酸-2-磷酸(AAP)脱去磷酸基团生成抗坏血酸(AA)，AA具有强还原性，优先与Au@MnO2中的MnO2反应并将其还原成二价锰离子，使3,3',5,5'-四甲基联苯胺(TMB)保持还原状态，此时，检测到较高的DPV电流信号；当有机磷农药存在时，ALP的酶活性被抑制，与AAP作用生成的AA减少，对Au@MnO2的分解作用减弱，未分解的Au@MnO2完成对TMB氧化，还原态的TMB减少，检测到较低的DPV电流信号；本发明方法通过建立有机磷农药与TMB的DPV峰值电流信号动态关系，达到检测有机磷农药的目的。
优选的，待测样品、碱性磷酸酶、L-抗坏血酸-2-磷酸的体积比为1:2～2.5:0.8～1；碱性磷酸酶和L-抗坏血酸-2-磷酸的浓度比为100～150U:1mM。
优选的，在混合溶液中加入PB缓冲液后，再加入所述的超薄金-锰纳米复合材料反应3～5min，再加入3,3',5,5'-四甲基联苯胺反应3～5min后，得到待测溶液；
进一步优选的，混合溶液、PB缓冲液、所述的超薄金-锰纳米复合材料和3,3',5,5'-四甲基联苯胺的体积比为4～5:545～546:8～10:1；其中，PB缓冲液的pH为6～8，浓度为0.01～0.1M；3,3',5,5'-四甲基联苯胺的浓度为10～15mM。
所述的标准曲线建立方法包括：将浓度为1～50ng/mL的有机磷农药的标准溶液进行上述检测，再以DPV峰值电流信号为纵坐标、以浓度为横坐标绘制标准曲线，优选的，所述的有机磷农药为敌百虫。
与现有技术相比，本发明的有益效果在于：
(1)本发明提供的超薄金-锰纳米复合材料的合成方法简单，金纳米球大小、PVP的链长以及复合材料的大小易于调节，制得的超薄金-锰纳米复合材料(Au@MnO2)是一种类氧化物酶，具有超强催化性能和催化过程无需氧气参与的特性，可基于差分脉冲伏安法用于检测有机磷农药。
(2)本发明提供的检测有机磷农药的方法快速简便，普适性好，不受检测样品和纳米酶本身的颜色以及环境中O2的干扰，灵敏度高，检出限低至0.039ng/mL。
附图说明
图1为基于Au@MnO2和ALP的双酶级联反应调控的均相电化学检测有机磷农药的方法的原理流程图。
图2为实施例1制得的Au@MnO2溶液的TEM图片，其中，A图中的标尺为1μm，B图中的标尺为200nm。
图3为实施例1制得的Au@MnO2溶液的紫外光谱图。
图4中的A为应用例1中不同浓度的敌百虫与DPV电流信号变化之间的关系图，B为对应的线性拟合图。
具体实施方式
下面结合实施例与附图，进一步阐明本发明。应理解，这些实施例仅用于说明本发明，而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法，通常按照常规条件，或按照制造厂商所建议的条件。
实施例1
(1)柠檬酸钠还原法制备金纳米球的步骤包括：
在三口烧瓶中加入97.5mL去离子水与2.5mL的氯金酸(10mM)。剧烈搅拌，加热至120℃，一次性加入875μL的100mM的柠檬酸钠溶液；在120℃保持温度30min后自然冷却，得到纳米金球溶液，金纳米球的粒径为15nm。
(2)接枝PVP的金纳米球溶液：
待金纳米球溶液冷却至70℃后，加入0.02g/mL聚乙烯吡咯烷酮(分子量为8000)，金纳米球溶液与聚乙烯吡咯烷酮溶液的体积比为1：0.1，冷凝回流30min后，离心除去多余的PVP，制备得到接枝PVP的金纳米球溶液。
(3)Au@MnO2的合成：
取10mL步骤(2)制得的接枝PVP的金纳米球溶液，重新分散在去离子水中，加入800μL 10mM的KMnO4溶液90℃反应30min，再加入200μL 10mM的KMnO4 80℃反应8h；得到尺寸为120～200nm的Au@MnO2。
该Au@MnO2的TEM图如图2中的A和B所示，Au@MnO2呈均匀分散的状态，直径在120～200nm，紫外吸收峰光谱图如图3所示，在377nm处呈现MnO2的特征吸收峰。
实施例2
本实施例中Au@MnO2的制备方法与实施例1的区别仅在于，聚乙烯吡咯烷酮的分子量为20000；接枝PVP的金纳米球溶液、第一次投料的高锰酸钾溶液、第二次投料的高锰酸钾溶液的体积比为1:0.1:0.04，高锰酸钾溶液的浓度为15mM。
实施例3
本实施例中Au@MnO2的制备方法与实施例1的区别仅在于，水热合成Au@MnO2的过程中，先加入高锰酸钾80℃反应45min后，再加入高锰酸钾75℃反应8h。
应用例1
基于Au@MnO2和ALP的双酶级联反应调控的均相电化学检测有机磷农药的方法的原理流程图如图1所示。
本应用例中，有机磷农药选用高毒性、用量大的敌百虫。
配制1ng/mL、5ng/mL、15ng/mL、25ng/mL、50ng/mL的敌百虫溶液，利用其进行标准曲线的测定；将上述10μL敌百虫溶液与1000U碱性磷酸酶25μL 37℃孵育15min，使敌百虫能有效抑制碱性磷酸酶活性。加入10mM AAP 10μL 37℃孵育3min，使AAP在ALP的作用下分解为AA，得到混合溶液；在混合溶液中加入PB缓冲液(pH为6～8，浓度为0.1M)使溶液总体积到5.5mL。加入80μL实施例1制得的Au@MnO2溶液于37℃反应3min，加入10μL 10mM的TMB反应3min；得到标准溶液；
用氧化铝粉末对玻碳电极进行抛光打磨，清洗，将清洗好的玻碳电极在K3Fe(CN)6溶液中进行循环伏安法活化；
以活化后的玻碳电极为工作电极，铂电极为对电极，氯化银电极为参比电极，构建三电极体系；将活化后的玻碳电极分别置于标准溶液中，在电位0.1～0.6V的区间内利用差分脉冲伏安法检测标准溶液的DPV峰值电流信号，以DPV峰值电流信号为纵坐标、以标准溶液的浓度为横坐标绘制标准曲线。不同浓度的敌百虫与DPV电流信号变化之间的关系图如图4中的A所示，线性拟合图如图4中的B所示，由图中可知，敌百虫在1～50ng/mL范围内呈现良好的线性，说明本发明方法具有较好的适用性，可以用于检测0.1～50ng/mL范围内的OPs敌百虫，检测限为0.039ng/mL。
在3种不同的实际样品(小白菜、牛肉、猪肝)中检测了3种浓度(0.1ng mL-1、1ngmL-1和10ng mL-1)的敌百虫的回收率；首先，将敌百虫添加到小白菜、牛肉和猪肝中，将小白菜、牛肉和猪肝打成汁，离心除去沉淀后作为待测样品；按照上述测标准曲线的标准步骤将待测样品制成待测溶液，测量待测溶液的DPV，并重复3个样品以获得数据，测得最终加标回收率在95～105％之间。
以上所述的实施例对本发明的技术方案进行了详细说明，应理解的是以上所述的仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等，均应包含在本发明的保护范围之内。
Claims (9)
1.一种超薄金-锰纳米复合材料的制备方法，其特征在于，包括以下步骤：
(1)以氯金酸为原料，采用柠檬酸钠还原法制备金纳米球溶液；进一步利用聚乙烯吡咯烷酮修饰金纳米球，得到接枝PVP的金纳米球溶液；所述的金纳米球的粒径为15～20nm；
(2)利用水热合成法，将接枝PVP的金纳米球溶液分散在去离子水中，加入高锰酸钾80～90℃反应30～45min后，再加入高锰酸钾70～80℃反应8～10h得到所述的超薄金-锰纳米复合材料。
2.根据权利要求1所述的超薄金-锰纳米复合材料的制备方法，其特征在于，利用聚乙烯吡咯烷酮修饰金纳米球的过程为：将金纳米球溶液与聚乙烯吡咯烷酮溶液混合，70～90℃修饰30～45min后，离心除去多余的聚乙烯吡咯烷酮，得到接枝PVP的金纳米球溶液。
3.根据权利要求2所述的超薄金-锰纳米复合材料的制备方法，其特征在于，所述的聚乙烯吡咯烷酮的分子量为8000～40000；聚乙烯吡咯烷酮溶液的浓度为0.02～0.04g/mL。
4.根据权利要求1所述的超薄金-锰纳米复合材料的制备方法，其特征在于，步骤(2)中，接枝PVP的金纳米球溶液、第一次投料的高锰酸钾溶液、第二次投料的高锰酸钾溶液的体积比为1:0.08～0.1:0.02～0.04，高锰酸钾溶液的浓度为10～15mM。
5.根据权利要求1-4任一所述的超薄金-锰纳米复合材料的制备方法制得的超薄金-锰纳米复合材料。
6.一种双酶级联反应调控均相电化学检测有机磷农药的方法，其特征在于，具体包括以下步骤：
(1)在36～37℃下，将待测样品与碱性磷酸酶孵育10～30min，再加入L-抗坏血酸-2-磷酸孵育3～5min，得到混合溶液，在混合溶液中依次加入PB缓冲液、权利要求5所述的超薄金-锰纳米复合材料和3,3',5,5'-四甲基联苯胺，得到待测溶液；
(2)用氧化铝粉末对玻碳电极进行抛光打磨，清洗，将清洗好的玻碳电极在K3Fe(CN)6溶液中进行循环伏安法活化；
(3)以活化后的玻碳电极为工作电极，铂电极为对电极，氯化银电极为参比电极，构建三电极体系；将活化后的玻碳电极置于待测溶液中，在电位0.1～0.6V的区间内利用差分脉冲伏安法检测待测溶液的DPV峰值电流信号，将DPV峰值电流信号代入到相应的标准曲线中得到待测样品中有机磷农药含量。
7.根据权利要求6所述的双酶级联反应调控均相电化学检测有机磷农药的方法，其特征在于，待测样品、碱性磷酸酶、L-抗坏血酸-2-磷酸的体积比为1:2～2.5:0.8～1；碱性磷酸酶和L-抗坏血酸-2-磷酸的浓度比为100～150U:1mM。
8.根据权利要求6所述的双酶级联反应调控均相电化学检测有机磷农药的方法，其特征在于，在混合溶液中加入PB缓冲液后，再加入所述的超薄金-锰纳米复合材料反应3～5min，再加入3,3',5,5'-四甲基联苯胺反应3～5min后，得到待测溶液。
9.根据权利要求6所述的双酶级联反应调控均相电化学检测有机磷农药的方法，其特征在于，混合溶液、PB缓冲液、所述的超薄金-锰纳米复合材料和3,3',5,5'-四甲基联苯胺的体积比为4～5:545～546:8～10:1；其中，PB缓冲液的pH为6～8，浓度为0.01～0.1M；3,3',5,5'-四甲基联苯胺的浓度为10～15mM。
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987006706A1 (en) * | 1986-04-30 | 1987-11-05 | Igen, Inc. | Electrochemiluminescent assays |
| US20020127734A1 (en) * | 2000-11-08 | 2002-09-12 | Huebner Jay S. | Sensing device and method using photo-induced charge movements |
| EP1258533A1 (en) * | 2001-05-11 | 2002-11-20 | Tecnav S.N.C. di Marco Antonio Stracuzzi E C. | Process for detection and determination of toxic agents and related biosensor |
| FR2846338A1 (fr) * | 2002-10-28 | 2004-04-30 | Univ Claude Bernard Lyon | Biocapteur electrochimique multi-enzymatique a algues unicellulaires, procede et utilisation mettant en oeuvre un tel biocapteur |
| WO2006109311A2 (en) * | 2005-04-15 | 2006-10-19 | Ramot At Tel Aviv University Ltd. | Enzyme-channeling based electrochemical biosensors |
| CN105717179A (zh) * | 2016-02-25 | 2016-06-29 | 济南大学 | 一种光电化学有机氯农药生物传感器的制备方法及应用 |
| CN108872209A (zh) * | 2018-08-08 | 2018-11-23 | 福建医科大学 | 基于纳米金簇电致化学发光探针的碱性磷酸酶测定方法 |
| CN113155816A (zh) * | 2021-03-14 | 2021-07-23 | 吉林大学 | 一种基于金纳米簇-二氧化锰纳米片的甲基对氧磷荧光-比色分析方法 |
| CN115598082A (zh) * | 2022-10-25 | 2023-01-13 | 杭州师范大学（Cn） | 基于二氧化锰纳米花和碱性磷酸酶的双酶级联反应调控金纳米棒刻蚀检测有机磷农药的方法 |
-
2023
- 2023-05-23 CN CN202310584754.5A patent/CN116832862B/zh active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987006706A1 (en) * | 1986-04-30 | 1987-11-05 | Igen, Inc. | Electrochemiluminescent assays |
| US20020127734A1 (en) * | 2000-11-08 | 2002-09-12 | Huebner Jay S. | Sensing device and method using photo-induced charge movements |
| EP1258533A1 (en) * | 2001-05-11 | 2002-11-20 | Tecnav S.N.C. di Marco Antonio Stracuzzi E C. | Process for detection and determination of toxic agents and related biosensor |
| FR2846338A1 (fr) * | 2002-10-28 | 2004-04-30 | Univ Claude Bernard Lyon | Biocapteur electrochimique multi-enzymatique a algues unicellulaires, procede et utilisation mettant en oeuvre un tel biocapteur |
| WO2006109311A2 (en) * | 2005-04-15 | 2006-10-19 | Ramot At Tel Aviv University Ltd. | Enzyme-channeling based electrochemical biosensors |
| CN105717179A (zh) * | 2016-02-25 | 2016-06-29 | 济南大学 | 一种光电化学有机氯农药生物传感器的制备方法及应用 |
| CN108872209A (zh) * | 2018-08-08 | 2018-11-23 | 福建医科大学 | 基于纳米金簇电致化学发光探针的碱性磷酸酶测定方法 |
| CN113155816A (zh) * | 2021-03-14 | 2021-07-23 | 吉林大学 | 一种基于金纳米簇-二氧化锰纳米片的甲基对氧磷荧光-比色分析方法 |
| CN115598082A (zh) * | 2022-10-25 | 2023-01-13 | 杭州师范大学（Cn） | 基于二氧化锰纳米花和碱性磷酸酶的双酶级联反应调控金纳米棒刻蚀检测有机磷农药的方法 |
Non-Patent Citations (7)
| Title |
|---|
| HUANG L等: "Dual signal AA detection based on fluorescence and local surface plasmon resonance absorption technology", SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, vol. 306, 25 October 2023 (2023-10-25), pages 123570 * |
| JUNLIANG ZHANG等: "Au Nanocrystals@Defective Amorphous MnO2 Nanosheets Core/Shell Nanostructure with Effective CO2 Adsorption and Activation toward CO2 Electroreduction to CO", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 9, no. 14, 29 March 2021 (2021-03-29), pages 5230 - 5239 * |
| WU JH等: "Two-Dimensional MnO2 Nanozyme-Mediated Homogeneous Electrochemical Detection of Organophosphate Pesticides without the Interference of H2O2 and Color", ANALYTICAL CHEMISTRY, vol. 93, no. 8, 2 March 2021 (2021-03-02), pages 4084 - 4091 * |
| ZENG HL等: "Highly-oxidizing Au@MnO2_X nanozymes mediated homogeneous electrochemical detection of organophosphorus independent of dissolved oxygen", JOURNAL OF HAZARDOUS MATERIALS, vol. 459, 22 July 2023 (2023-07-22), pages 132116, XP087381758, DOI: 10.1016/j.jhazmat.2023.132116 * |
| 杨清如;李琳;刘续威;曹正强;马冰倩;: "新鲜果蔬有机磷农药快速检测技术研究进展", 当代化工, no. 12, 28 December 2019 (2019-12-28), pages 217 - 222 * |
| 林楠: "过渡金属钒酸盐纳米带、纳米棒的合成、电化学及光催化特性", 中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑), no. 3, 15 March 2017 (2017-03-15), pages 020 - 893 * |
| 黄梦娜: "功能化金纳米颗粒的暗场显微成像研究", 中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑), no. 4, 15 April 2022 (2022-04-15), pages 014 - 10 * |
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