现代化工

现代化工 ›› 2025, Vol. 45 ›› Issue (2) : 79-83. DOI: 10.16606/j.cnki.issn0253-4320.2025.02.016

科研与开发

羟基氧化钴纳米片的飞秒激光液相烧蚀及其抗氧化剂检测应用研究

袁艳萍 ¹^,²^,^* ,
王文博 ¹ ,
郭筱然 ¹

作者信息 +

Fabrication of CoOOH nanosheet by femtosecond laser liquid phase ablation and its application in antioxidant detection

Yan-ping YUAN ¹^,²^,^* ,
Wen-bo WANG ¹ ,
Xiao-ran GUO ¹

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文章历史 +

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摘要

纳米酶具有比传统酶更高、更广泛的底物适应性以及更好的稳定性,使其成为一种替代传统酶的生物催化剂。然而纳米酶通常需要在高温、高压甚至有毒条件下制备,工序复杂、耗时且能量效率不高。羟基氧化钴纳米片是一种典型的纳米材料,具有出色的氧化酶相似活性。在常温、常压且无需添加任何化学试剂稳定的条件下,利用飞秒激光液相烧蚀技术成功制备了晶面规则完整的羟基氧化钴纳米片,其与四甲基联苯胺在显色反应中更易结合且反应效率更高。通过显色反应检测了多种抗氧化物质,结果表明,该方法成本低、操作简单、灵敏度高、易观察,在生物化学检测和食品安全检测等领域具有极大的应用潜能。

Abstract

Traditional enzymes are often used in biological detection,but nano-enzymes has higher and wider substrate adaptability and better stability than traditional enzymes.These advantages make nano-enzymes become a biocatalyst to replace traditional enzymes.However,nano-enzymes usually need to be prepared under high temperature and pressure,or even toxic conditions,and the process is complicated,long-time required,and inefficient.Hydroxyl cobalt oxide (CoOOH) nanosheet is a typical nanomaterial with excellent oxidase-like activity.In this study,CoOOH nanosheets with regular and complete crystal surface is successfully prepared through femtosecond laser liquid phase ablation technology at room temperature and normal pressure without adding any chemical reagents.The prepared CoOOH nanosheets are easier to bind with tetramethylbenzidine in the color reaction and present higher reaction efficiency.Various antioxidant substances are detected by the prepared CoOOH nanosheets through color reaction.It is verified that this method has advantages of low cost,simple operation,high sensitivity,and easy observation,showing a great application potential in the fields of biochemical detection and food safety detection.

Graphical abstract

关键词

羟基氧化钴纳米片 / 液相 / 纳米酶 / 抗氧化物质 / 液相烧蚀 / 飞秒激光

Key words

CoOOH nanosheet / liquid phase / nanozymes / antioxidant substances / liquid phase ablation / femtosecond laser

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人体内的生理活动中每个细胞都会发生化学反应,包括分子的氧化和还原。在健康细胞中存在适当的促氧化剂和抗氧化剂的平衡,然而当氧化物质的产生大大增加或水平降低时,这种平衡将被打破,对细胞产生影响^[1]。氧化剂和抗氧化剂之间的不平衡状态可能导致细胞受损,被称为“氧化应激”^[2]。所产生的负面影响可能会造成一系列的生理衰退,从而出现疾病或加速衰老等症状^[3],因此,抗氧化剂的检测十分重要。纳米酶因其比表面积更大、热稳定性更高和抗酸碱性是替代传统生物酶进行抗氧化剂检测一种材料^[4]。Zhao等^[5]制备Fe-PorCOF并利用其氧化物酶的特性,在碱性条件下提高鲁米诺与过氧化氢之间的化学发光反应。Mohammadpour等^[6]通过液相剥离法制备了FeOCl纳米材料,其制备所使用系统简单且成本低,更适合快速分析检验抗氧化物质谷胱甘肽。Tripathi等^[7]在高温环境下使用磁力搅拌的方法制备出能快速氧化四甲基联苯胺的过氧化物酶(SnO₂-Cu)纳米复合材料,然而这些方法通过高压、高温、耗时甚至有毒的方法来制备纳米材料,增加了抗氧化物质检测的复杂程度。

羟基氧化钴(CoOOH)纳米片是一种典型的纳米材料,其由非化学计量的羟基氧化物组成,表面具有丰富的羟基,因此具有高度的亲水性,易于在极性溶剂中分散^[8]。羟基氧化钴纳米片还具有良好的荧光淬灭能力和出色的氧化酶相似活性^[9]。羟基氧化钴可以在没有H₂O₂和氧气外源添加的情况下将无色的3,3',5,5'-四甲基联苯胺(TMB)氧化为蓝色产物oxTMB,并在652 nm处产生较强的特征吸收峰^[10],加入抗氧化物质如抗坏血酸(AA)后羟基氧化钴纳米片中的Co³⁺转变为Co²⁺,从而抑制蓝色产物oxTMB的生成使蓝色消退^[11]。因此,通过比较含有不同浓度抗氧化物质溶液的颜色深浅差异来确定待测物质的抗氧化物质含量。该方法具有成本低、操作简单、灵敏度高、易于观察等特点,因此越来越具有吸引力。此外,该方法可以用于现场分析检测而不需要昂贵或复杂的仪器,在生物化学检测和食品安全检测等领域具有广泛应用潜力。

针对目前制备羟基氧化钴纳米片时所需要特定高温、高压环境或使用繁多化学试剂的问题,笔者采用飞秒激光液相烧蚀技术,作为一种“自上而下”绿色合成技术,制备环境简单^[12],能够快速地从大块的“靶材”上加工成所需的羟基氧化钴纳米材料,同时合成过程不需要添加任何化学试剂进行辅助。

1 实验部分

1.1 仪器与试剂

利用钛宝石激光器(Spitfire Ace PA-100,Spectra-Physics,USA)、X射线衍射仪(D8 Advance)、紫外光谱仪-C420(UV 2600)、扫描电子显微镜(SEM,日本电子Jsm7610f)对物质微观形貌进行表征;利用透射电子显微镜(TEM美国FEI talos F200)研究羟基氧化钴的纳米结构;利用选区电子衍射仪(XAED)、Zeta粒度分析仪(英国马尔文ZS90)研究羟基氧化钴的粒度。

多巴胺、抗坏血酸、3,3',5,5'-四甲基联苯胺、尿素、单宁酸、表没食子儿茶素没食子酸酯、谷胱甘肽,阿拉丁公司生产;无水乙醇,国药集团化学试剂生产;醋酸-醋酸钠缓冲液(20 mmol/L,pH 4.5)用于羟基氧化钴纳米片与四甲基联苯胺显色反应;实验中所用其他试剂均为AR,液相体系去离子水,自制。

1.2 飞秒激光羟基氧化钴的制备过程

利用2000^#砂纸抛光钴靶材去除表面氧化层,再用无水乙醇清洗并自然干燥。在去离子水液相体系中对高纯钴靶材进行飞秒激光液相烧蚀,制备获得羟基氧化钴纳米片,其中液相烧蚀时,飞秒激光的重复频率为1 kHz、波长为800 nm、脉冲宽度为 100 fs的飞秒脉冲,加工平台的移动速度为1 mm/s,用平凸透镜聚焦光束,加工功率设置0.5 W,使用线间距为0.5 mm的划线法,扫描方向垂直于激光入射方向,如图1所示,加工时间5 min。

在室温下,将制备好的棕色羟基氧化钴纳米片粉末加入去醋酸-醋酸钠缓冲液中进行稀释,将TMB溶于3,3',5,5'-四甲基联苯胺中后与羟基氧化钴纳米片溶液混合。充分反应10 min形成蓝色CoOOH-TMB体系,作为检测抗氧化物质的蓝色探针。蓝色CoOOH-TMB体系在紫外-可见光光谱检测波长为652 nm处测定其紫外吸光度值,最后加入不同浓度抗氧化物质,所得到的混合溶液,在室温下反应后,用肉眼观察到颜色变化,再用紫外-可见光光谱仪在波长652 nm处测定其紫外吸光度值。

2 结果与讨论

2.1 羟基氧化钴纳米片的合成与表征

高纯度钴靶材被飞秒激光脉冲辐照后,在固-液交界面处材料吸收高能量,随后电子通过热离子发射从原子中被激发出来,在靶材表面形成高强度的电场。在电场和压力的作用下,正离子之间的斥力大于结合力,最终导致靶材表面的物质被剥离出来^[13]。同时钴靶材在飞秒激光脉冲能量的作用下产生高温,结合去离子水中被电离的羟基根与氧离子,随着液体环境的冷却作用以及温度和压力逐渐下降得到纳米尺度的羟基氧化钴纳米片。此外,液相烧蚀导致许多过热气泡垂直于钴靶的表面喷射,其中一些存活到达表面。每个气泡的破裂有效地将溶液中氢氧根与氧离子与Co³⁺结合。围绕纳米片的溶剂还用于保护所形成的羟基氧化钴纳米片免于氧化,从而允许他们长时间保持悬浮在其溶液中。纳米片颗粒分散在液体得到羟基氧化钴纳米片棕色溶液。最后将得到的棕色溶液离心,再用去离子水清洗后真空干燥,称量便于后续使用。

羟基氧化钴纳米片的形貌和性能如图2所示。从图2(a)可知,制备所得厚度尺寸约为200 nm片状纳米结构。从图2(b)中可以看出,纳米片的尺寸大小符合纳米材料规定的尺寸要求,其主要占比为150~200 nm。从图2(c)、图2(d)可知,羟基氧化钴纳米片呈现正六边形,符合羟基氧化钴纳米片的外形,且晶格条纹方向一致晶格间距为0.43 nm,具有高度的结晶性。与标准卡对比,晶格条纹匹配羟基氧化钴纳米片的(003)晶面。

通过C420型紫外-可见光谱仪和X射线衍射仪对羟基氧化钴纳米片进行进一步分析,结果如图3所示。从图3(a)可知,羟基氧化钴纳米片的特征吸收峰在波长409 nm处。从图3(b)可知,在20.239 1、38.887 1°和50.583 1°处出现3个主峰,完全指向正六边形的羟基氧化钴纳米片的(003)、(012)和(015)晶面(JCPDS No.07-0169),没有明显杂质特征峰出现,且衍射峰较尖锐,说明结晶较完整,与文献[14]中的研究相一致。具有高表面积的二维层状结构,极大地方便了抗氧化剂的检测。

在相同的制备条件下,将液相环境更换为无水乙醇,因无去离子水所提供的羟基根与氧离子无法制备羟基氧化钴纳米片。材料的形貌和物相性能证明在去离子水中可成功制备晶面完整的羟基氧化钴纳米片。晶面完整的羟基氧化钴正六边形纳米结构为接下来与TMB反应提供大的面积比,在同一时间有更多的分子或原子接触,从而增加反应速率,提高生物检测的速率和灵敏度。

2.2 抗氧化物质的定量检测

羟基氧化钴纳米片不同于其他纳米材料的氧化酶性质,在不加入H₂O₂和氧气的情况下可以将TMB氧化,通过表面结构完整纳米尺寸的特点更快地将无色TMB氧化成蓝色产物oxTMB。TMB分子本身没有明显的紫外-可见吸收峰,而通过羟基氧化钴纳米酶相互作用后的产物oxTMB可以在652 nm处有特征吸收峰。加入抗氧化物质羟基氧化钴发生氧化还原反应后变为Co²⁺,从而使oxTMB减少蓝色褪去,在波长652 nm处特征吸收峰下降。根据以上的原理建立一种基于羟基氧化钴纳米酶比色法快速检测抗氧化物质。以抗氧化剂AA为例,AA单独存在情况下不与TMB溶液或棕色溶液羟基氧化钴发生显色反应。将干燥的羟基氧化钴纳米片分散到缓冲液中并在超声波作用下形成均匀溶液,与TMB溶液混合后溶液呈蓝色,并且在波长652 nm处有特征吸收峰。加入AA后,蓝色溶液颜色褪去,吸收峰降低。说明抗氧化物质检测原理的合理性。

将10 μL 0.4 mg/mL羟基氧化钴加入到300 μL 0.1 mol/L的醋酸-醋酸钠(pH为4.5)缓冲液中,然后加入40 μL的2 mmol/L TMB溶液,在20℃下反应10 min,待反应结束后分别向体系中加入6种抗氧化物质(尿素、盐酸多巴胺、单宁酸、抗坏血酸、谷胱甘肽、表没食子儿茶素没食子酸酯)进行检测和对比分析。这些抗氧化剂均可以在一定浓度范围内使TMB与羟基氧化钴的体系中蓝色溶液发生不同程度颜色的褪色,在波长652 nm处的吸收峰随着抗氧化剂的加入峰值会不断衰减。以抗坏血酸为例,TMB-CoOOH吸光度测试结果如图4所示。从图4(a)中可以看出,在TMB与羟基氧化钴的体系中加入不同浓度的AA后,3 s内蓝色的溶液发生不同程度的褪色,在652 nm处的吸收峰随着AA浓度的增加不断以一定比例衰减。从图4(b)中可以看出,当AA浓度为0.03 μmol/L时吸收峰就存在衰减,证明极限反应浓度在约为0.01 μmol/L左右。并且在0.01~1 μmol/L范围内具有一定的线性关系(R=0.979),随着AA浓度的增加颜色的损失变得越来越明显。6种抗氧化剂的检测反应时间、检测范围和极限反应浓度如表1所示。

不同纳米材料用于AA光学检测的结果如表2所示。结果表明,在这几种纳米酶中,本方法对抗坏血酸的检测的灵敏度最佳,并且未使用贵金属节约了成本,更适合大量的检测。

3 结论

作为一种典型的纳米材料,羟基氧化钴纳米片具有出色的氧化性,广泛用于抗氧化剂检测。在常温、常压且无需添加任何化学试剂稳定的条件下,首次通过飞秒激光液相烧蚀制备羟基氧化钴纳米片,该方法能够简化步骤、缩短时间、减少化学试剂使用、提高效率和降低环境污染。此外,实验结果表明,钴靶材在水系溶液中与飞秒激光相互作用下钴被还原为+3价,结合去离子水中的羟基得到正六边形且晶面完整的羟基氧化钴纳米片,其形貌特征与其他反应物的结合提供了很大的面积比,增加物质反应的速率。利用其表面积比大的特点,基于羟基氧化钴纳米片类氧化酶活性的性质,成功地检测了多巴胺、抗坏血酸、尿素等抗氧化物质。该检测抗氧化剂的方法成本低、操作简单、灵敏度高、易观察,在生物化学检测和食品安全检测等领域具有极大的应用潜能。

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