CN114854407A - 一种l-精氨酸基碳点的制备方法及其在柠檬黄检测中的应用 - Google Patents
一种l-精氨酸基碳点的制备方法及其在柠檬黄检测中的应用 Download PDFInfo
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- CN114854407A CN114854407A CN202210591755.8A CN202210591755A CN114854407A CN 114854407 A CN114854407 A CN 114854407A CN 202210591755 A CN202210591755 A CN 202210591755A CN 114854407 A CN114854407 A CN 114854407A
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
本发明为一种L‑精氨酸基碳点的制备方法及其在柠檬黄检测中的应用,常温下将L‑精氨酸、邻苯二胺按照摩尔比为1:20~1:1溶解于水或甲醇或乙醇或正丙醇或丙酮或N,N‑二甲基甲酰胺中;转移至聚四氟乙烯高温反应釜中在170℃~210℃下反应2~12h;待产物自然冷却后高速离心,用500~5000Da透析袋透析24~72h,干燥得到粗碳点,采用柱层析法分离纯化,以洗脱液梯度洗脱,收集蓝色荧光部分,减压回收溶剂得到较纯碳点;较纯碳点继续采用柱层析法以洗脱液二次梯度洗脱,经薄层色谱检测,获得荧光和紫外的双模检测碳点;本发明制备的L‑Arg‑CDs与柠檬黄的荧光淬灭机理属于内滤效应,线性检测最佳浓度范围为0~55μM,检出限为LOD=42.3nM,远低于国标GB/T5009.35‑2003所提供的检出限187.14μM,可作为柠檬黄快速检测方法。
Description
技术领域
本发明属于荧光碳纳米材料应用技术领域,涉及一种碳量子点的制备方法和应用,具体涉及一种L-精氨酸基碳点的制备方法及其在柠檬黄检测中的应用。
技术背景
柠檬黄(Tartrazine,E102)是应用最广泛的偶氮类合成染料之一,为橙黄色粉末,无臭,易溶于水,微溶于乙醇,不溶于油脂。为适应人们对食品的感官需求,在食品的生产、加工、运输过程中,通常用柠檬黄对食品进行调色。然而,过量食用柠檬黄会严重危害人体健康。研究表明,柠檬黄的过量摄入会引起DNA损伤和干扰DNA合成以致胎儿畸形;甚至会转换为致癌物质,引发皮下肉瘤、肝癌、肠癌等[23]。我国食品安全国家标准规定,柠檬黄在果冻、饮料、糖果、固体复合调味料中的最大使用量分别为0.05、0.1、0.3、0.2g/kg[24]。因此,食品中柠檬黄含量的检测十分重要。
现有的柠檬黄检测技术主要包括电化学分析法、分光光度法、高效液相色谱法、高效薄层色谱法和毛细管电泳法等。这些方法通常存在成本高、耗时长、设备贵、操作繁琐或样品制备过程复杂等不可避免的缺点,限制了它们在常规分析检测中的应用。
碳点(Carbon dots,CDs)是一种尺寸小于10nm的分散的类球形荧光碳纳米颗粒,具有良好的分散性和荧光稳定性。2004年,Scrivens[1]等采用电弧放电法制备单壁碳纳米管时,通过电泳纯化首次得到发光碳点。2006年,Sun等首次采用激光刻蚀法制备出覆盖大范围光谱发光的碳点。2007年,Mao等从烛灰中制备分离得到荧光碳纳米颗粒。与其他碳纳米材料相似,碳点的发现激起了人们广泛的研究兴趣。近十年来,碳点的研究与应用得到了飞速的发展,由于碳点具有荧光活性高、种类多样、生物相容性好、毒性低等优点,在生物检测[4]、基因转运、药物传输、和生物成像等领域得到了广泛应用。
近年来,随着人们对碳点及其优异性能的逐步认识,提出了一系列制备优良碳点的方法。这些方法可以概括为两大类:“自上而下法”和“自下而上法”。
自上而下法包括电弧放电法、激光消融法和电化学氧化法。在提纯由煤烟进行电弧放电法制备单壁碳纳米管的过程中,Xu等人发现了一种未知的荧光碳纳米粒子。电弧放电法制得的碳量子点荧光性能较好,但是产率较低、所得产物杂质较多且纯化过程繁琐、产物收集困难。2006年,SUN等首次用激光销蚀法制备了碳量子点,激光销蚀法主要是在高温高压下利用激光销蚀将得到的碳纳米颗粒,经过表面修饰、官能化等后续处理得到发光的碳量子点。该方法合成过程比较复杂,所需仪器设备昂贵,所得碳点产物纯度较低且粒度不均匀。电化学合成法是将碳源作为工作电极制备碳量子点。Zhou等在对负载多层碳纳米管的电极进行多次充放电后,经过干燥、层析后得到的固体在高倍电镜下拥有清晰的晶格条纹,该方法首次实现了碳量子点的电化学合成。Li等以乙醇作为碳源,制备出的碳量子点荧光寿命较长、对pH敏感,激发后可发射具有上转换特征、波长覆盖整个可见光区域的荧光。电化学合成法制得的碳量子点均匀性较好,碳源利用率较高,可大量制备。但是原料的前期处理工作与后期的纯化工作较为复杂。
自下而上法包括水热法、燃烧热法、微波辅助合成法;水热法是近年来合成碳点最常用的方法之一,该方法是将碳源及水、有机或无机溶剂置于聚四氟乙烯反应釜内,通过高温高压条件进行反应,该方法因为在高温高压下反应,不但传承了传统水相法合成碳点的优点,还缩短了大量的时间,使得到的碳点纯度较高。除此之外,该方法操作简单,成本较低,对环境破坏也比较小;MAO 等首次通过燃烧法制备了碳量子点。该方法利用铝箔收集蜡烛烟灰,并将其与硝酸一起回流进行分离提纯,从而获得碳量子点。RAY等则将通过燃烧法收集的蜡烛烟灰,经过离心、萃取等方式进行纯化,从而获得碳量子点,用此法获得碳量子点虽然产率较低,但产物具有石墨烯的特征。微波合成法是利用微波处理碳的前体,合成碳量子点。ZHU等以葡萄糖为碳源,与聚乙二醇(PEG200) 混合后,进行微波加热制备碳量子点。所获得的碳量子点荧光特性与水溶性较好。微波合成法的合成步骤大大简化,但是制备的碳量子点粒度不均匀。
当前制备碳量子点的原料十分广泛,有乙醇、柠檬酸、乙二胺、木质素、壳聚糖、淀粉、海藻酸钠、香菇、白菜、榴莲、以及凤眼莲、银杏、芦荟、绿茶等,但利用精氨酸制备碳量子点尚未见报道。
发明内容
针对现有的基于CDs的柠檬黄检测中CDs纯度较低,本发明提出了一种使用一步水热法制备,量子产率QY=22.670%的高纯度碳量子点的制备方法。
本发明的目的在于提供一种L-精氨酸基碳点的制备方法,该方法步骤包括:
1)常温下将L-精氨酸、邻苯二胺按照1:20~1:1的摩尔比溶解于水或甲醇或乙醇或正丙醇或丙酮或N,N-二甲基甲酰胺中,混匀;
2)转移至聚四氟乙烯高温反应釜中170℃~210℃下反应2~12h;
3)产物自然冷却后,高速离心,用透析袋在超纯水中透析24~72h,冷冻干燥后得到粗碳点;
4)柱层析法分离纯化粗碳点,以洗脱液梯度洗脱,收集蓝色荧光部分,减压回收溶剂得到较纯碳点;
5)较纯碳点继续用柱层析法以洗脱液进行二次梯度洗脱,经薄层色谱检测,获得荧光和紫外的双模检测碳点。
进一步地,所述透析袋的截流分子量MWCO为500~5000Da。
进一步地,所述洗脱液为V二氯甲烷:V甲醇=10:1-1:1或V石油醚:V丙酮=10:1-1:1 或V氯仿:V甲醇=10:1-1:1或V石油醚:V乙酸乙酯=10:1-1:1。
本发明的另一目的是提供一种L-精氨酸基碳点在柠檬黄快速检测中的应用。
进一步地,所述L-精氨酸基碳点在柠檬黄快速检测中的检测步骤包括:
1)将柠檬黄与L-Arg-CDs溶液混合,分别取得至少两种不同柠檬黄浓度的混合溶液,在λEx为367nm,λEm为441nm下分别测得不同柠檬黄浓度的混合溶液的荧光强度;
2)将待测样品与L-Arg-CDs溶液混合,得到待测样品混合溶液,测得待测样品混合溶液的荧光强度;
3)根据步骤1)中荧光猝灭效率(F0–F)/F0与混合溶液中柠檬黄浓度的线性关系计算出待测样品混合溶液中柠檬黄的浓度;所述线性关系为取得荧光猝灭效率(F0-F)/F0与混合溶液中柠檬黄浓度的线性关系,在0~55μM范围内, L-Arg-CDs荧光淬灭效率与E102浓度呈现较好的线性关系,0~7.5μM其线性方程为(F0-F)/F0=0.7047C(E102)-0.01538,R2=0.9961,20~55μM范围内线性方程为(F0-F)/F0=0.00845C(E102)+0.38448,R2=0.9975。
进一步地,所述步骤2)中L-Arg-CDs在pH=5.0的条件下检测E102。
进一步地,所述柠檬黄浓度的线性检测范围为0~55μM。
进一步地,所述步骤1)柠檬黄与L-Arg-CDs溶液混合后前3min内检测荧光强度。
进一步地,所述步骤2)中柠檬黄与L-Arg-CDs溶液混合后前3min内检测荧光强度。
与现有技术相比,本发明的有益效果是:
(1)首次利用氨基酸制备L-Arg-CDs。原料成本较低且来源广泛、无毒性、制备过程简单高效且可大量制备。
(2)首次建立了利用L-Arg-CDs作为荧光纳米探针检测E102,与传统方法相比,合成简单、响应速度快,且具有高选择性和抗干扰能力。
(3)L-Arg-CDs具有很好的酸碱耐受性和耐盐性。
附图说明
图1为不同因素对L-Arg-CDs量子产率(QY)的影响;
其中a为不同反应温度对L-Arg-CDs QY的影响;b为不同摩尔比对 L-Arg-CDs QY的影响;c为不同反应溶剂对L-Arg-CDs QY的影响;d为不同反应时间对L-Arg-CDs QY的影响;
图2为L-Arg-CDs的TEM及粒径分布图;
图3为L-Arg-CDs的XRD图;
图4为L-Arg-CDs的XPS全谱图(a)和C1s(b)、N1s(c)和O1s(d)的高分辨XPS谱图;
图5为L-Arg CDs的FTIR图;
图6为L-Arg-CDs的荧光性能和荧光淬灭曲线(a)、L-Arg-CDs的荧光淬灭效果图(b);
图7为L-Arg-CDs不同激发波长下荧光发射光谱;
图8为L-Arg-CDs荧光寿命衰减曲线;
图9为pH对L-Arg-CDs荧光强度的影响(a)、pH值对L-Arg-CDs检测 E102荧光淬灭效率的影响(b);
图10为离子强度对L-Arg-CDs荧光强度的影响(a)、过氧化氢对L-Arg-CDs 荧光强度的影响(b)、L-Arg-CDs在自然光下的响应时间(c)、L-Arg-CDs在紫外光下的响应时间(d);
图11为3L-Arg-CDs的选择性;
其中a为对部分金属离子,维生素,有机分子的选择性;b为对部分氨基酸的选择性;
图12为反应时间对L-Arg-CDs检测E102荧光淬灭效率的影响(a)、荧光淬灭效率与E102浓度线性关系(b);
图13为6L-Arg-CDs、E102的UV-Vis(a);L-Arg-CDs及CDs+E102荧光衰减寿命(b);L-Arg-CDs荧光光谱(Ex、Em)及E102的UV-Vis(c)
图14为Park方程验证L-Arg-CDs检测E102。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了,下面结合具体实施方式并参照附图,对本发明进一步详细发明。应该理解,这些描述只是示例性的,而并非要限制本发明的范围。此外,在以下发明中,省略了对公知结构和技术的描述,以避免不必要地混淆本发明的概念。
实施例1:L-Arg-CDs粗碳点的制备
利用一步水热法制备来自精氨酸的CDs。首先称取L-精氨酸0.35g,邻苯二胺0.5g溶解于5mL DMF中,混匀,然后转移至20mL聚四氟乙烯高温反应釜中210℃下反应10h。待产物自然冷却,采用薄层层析法(TLC),将碳点混合浓溶液,在层析硅胶板点画样品,以甲醇和二氯甲烷体积比1:10作洗脱剂,分离出碳点的溶剂,经旋转蒸发除去溶剂后获得紫外光下具有蓝色荧光的碳点,然后4℃储存待用。
考察了溶剂(水、DMF、正丙醇、丙酮、乙醇及甲醇)、摩尔比配比(0.0621、 0.1862、0.3104、0.4345、0.5587)温度(170℃-220℃)、时间(2、4、6、8、 10、12h)、对碳量子点荧光性能的影响。最终结果表明,溶剂为DMF,精氨酸及邻苯二胺摩尔比配比为0.4345,温度为210℃、时间为10h所制备的荧光碳量子点荧光性能最好,所得到的量子产率最大,为14.58%。
实施例2:L-Arg-CDs粗碳点的结构表征
利用透射电镜(TEM)研究L-Arg-CDs的形状特征和粒径分布,如图2所示,结果表明L-Arg-CDs具有规则的形状,呈类球形碳纳米颗粒,平均粒径2.75 nm,晶格间距约0.21nm。具有良好的单分散性且没有出现明显聚集,结构稳定,能在水中自由分散,水溶性好。
碳点的晶体结构是通过图3中所示的X射线粉末衍射(XRD)得出的。 L-Arg-CDs的衍射峰2θ=22.27°,表明合成的荧光碳量子点属于无定形碳结构。
利用XPS(图4)分析L-Arg-CDs的表面功能性官能团和组分。XPS全谱图在284.0eV、398.4eV和531.2eV的特征峰分别对应C1s、N1s和O1s。C1s 高分辨率光谱显示:位于283.eV、283.57eV和286.6eV的吸收峰对应C=C、 C-C和C-N/C-O。N1s谱图分析表明:位于397.6.0eV和398.02eV的吸收峰对应N-H和N-C。分析O1s谱图发现:位于529.3eV、530.2eV和530.7eV的吸收峰对应C=O、O-H和C-O C=O。综上所述,此碳量子点含C、H、N、O等元素,其表面含有C-N/C-O、C=C、C=O、N-H和C-N等基团,具有良好的水溶性。为了进一步分析L-Arg-CDs表面上的官能团结构,对其傅立叶变换红外光谱(FTIR)进行分析,
如图5所示,N-H的伸缩振动峰位于3,413cm-1,C=O的伸缩振动以及C=N 的伸缩振动峰位于1,627cm-1,1,452cm-1为C-H的伸缩振动,1,055cm-1为C-N 伸缩振动的吸收峰,而在716cm-1处则是N-H的弯曲振动峰。FTIR表明合成的 L-Arg-CDs表面含有-CH、-NH、-C=O、-C=N等官能团,这些功能性亲水基团的存在赋予L-Arg-CDs良好的水溶性及稳定性。
L-Arg-CDs的紫外-可见吸收光谱如图13c所示,在280nm处有一个较强的宽吸收峰,是由sp2结构杂化芳香族C=C的π-π*跃迁所致,而在约330nm处出现不明显紫外吸收峰,属于C=O键的n-π*跃迁吸收。
图6显示L-Arg-CDs最佳激发和发射波长分别367nm和441nm,在该激发波长下的发射谱图荧光信息号强,斯托克斯位移(Stoke’s shift)为74nm,可有效避免激发和发射峰的重叠,减小干扰,有利于碳点在分析检测中的应用。
L-Arg-CDs的荧光发射光谱图见图7,当Ex从340~400nm(每次间隔10 nm)进行荧光光谱扫描时,在340~370nm范围内,CDs荧光强度随Ex增大而逐渐增强,在Ex为367nm时达到最大;当Ex大于370nm,其发射光谱随着荧光强度的降低出现红移。因此,L-Arg-CDs的荧光具有激发波长依赖性。
实施例3:L-Arg-CDs粗碳点的纯化
将粗碳点进行二次纯化后测定量子产率QY,粗L-Arg-CDs的QY=14.58%;二次纯化L-Arg-CDs的QY=22.670%。QY提高。测定二次纯化L-Arg-CDs和粗 L-Arg-CDs荧光吸收值,如图6a可见二次纯化L-Arg-CDs荧光性能优于粗 L-Arg-CDs;在两种CDs中都加入1mME102进行荧光淬灭,二次纯化L-Arg-CDs对E102淬灭也优于粗L-Arg-CDs。
实施例4:纯化L-Arg-CDs的分析方法
不同pH值缓冲溶液对L-Arg-CDs荧光强度产生影响,如图9a所示, L-Arg-CDs在pH=7.0~12.0内稳定性较好,但当pH值从2.2增加至5.0,荧光强度随之增加,且pH值5.0时荧光最强,荧光强度在酸性条件下比在碱性条件下更高。但总的来说,L-Arg-CDs在酸性或碱性条件下都能维持较强的荧光,说明L-Arg-CDs的酸碱耐受性好,稳定性高。
离子强度对L-Arg-CDs的荧光强度的影响,如图10a所示,随着NaCl溶液浓度逐渐增加,L-Arg-CDs荧光强度基本没有变化,因此表明L-Arg-CDs在高离子强度环境中稳定性好。
为研究L-Arg-CDs的抗氧化性能,加入了不同浓度的过氧化氢溶液,结果如下图10b所示:加入不同浓度过氧化氢后,L-Arg-CDs的荧光强度基本没有太明显的变化。表明L-Arg-CDs的抗氧化性能较好。
为研究自然光下反应时间对L-Arg-CDs荧光响应的影响,在60min之内对其进行多次时间段的荧光测定如图10c所示,L-Arg-CDs的荧光淬灭效率随着时间的增加无明显变化,说明自然光下反应时间对荧光响应的影响较小, L-Arg-CDs具有较强的光稳定性。
紫外光对L-Arg-CDs的稳定性有一定的影响,为研究紫外光下反应时间对 L-Arg-CDs的影响,60min内对其进行多次时间段的荧光测定如下图10d所示, L-Arg-CDs的荧光淬灭效率在0-3min内无明显变化,后随着时间的增加而减小,说明在0-3min内紫外灯光下反应时间对荧光响应的影响较小,比较稳定。
实施例5:纯化L-Arg-CDs检测E102方法学研究
将实施例3制备的L-Arg-CDs(0.0973mg/mL)溶液取7μL置于10mL的离心管,再加入不同体积(0-200μL)的目标物E102,用最佳pH值等于5稀释至4mL,在最优反应时间下涡旋混匀,在CDs的激发波长367nm,slit分别为20nm和5nm下测定荧光强度。
荧光淬灭的标准曲线绘制:以E102的浓度为横坐标,CDs荧光淬灭效率(F 0-F)/F0为纵坐标,经过线性拟合对其相关系数、检测限范围进行计算。
pH值对荧光响应的影响:如图9b所示,当pH值从7.0增加至12.0 时,E102对L-Arg-CDs的荧光猝灭效果比较稳定。荧光淬灭效率在酸性介质pH 2.2-6.0范围内较高,pH 5.0时荧光响应最强,表明L-Arg-CDs在此弱酸性条件下检测E102效果最佳。
L-Arg-CDs检测E102方法的选择性:相同的实验条件下,在L-Arg-CDs 溶液中分别加入1mM的维生素类、小分子类、金属离子类目标物及E102进行实验。如图11a所示,只有E102可以有效淬灭L-Arg-CDs荧光强度,而其他物质对L-Arg-CDs的荧光猝灭作用很小,表明L-Arg-CDs对E102具有良好的选择性,此方法抗干扰能力强,因此L-Arg-CDs可作为强识别的荧光纳米探针用于E102的分析检测。
以同样的方法加入1mM的色素类对粗L-Arg-CDs和二次纯化L-Arg-CDs 进行检测,观察其荧光淬灭效果(图6b),结果显示其余色素对L-Arg-CDs测定E102无干扰。
以同样的方法加入1mM的氨基酸类对L-Arg-CDs进行检测,观察其荧光淬灭效果(图11b),结果显示氨基酸类对L-Arg-CDs检测E102无干扰。
反应时间对L-Arg-CDs检测E102荧光响应的影响见图12a,L-Arg-CDs检测E102的荧光淬灭效率随着时间的增加无明显变化,说明反应时间对荧光响应的影响较小,L-Arg-CDs检测E102具有较强的光稳定性。
L-Arg-CDs检测E102方法学研究:在最佳条件下,研究L-Arg-CDs荧光淬灭强度与E102浓度的关系,如图12b所示。随着E102浓度(0-55μM)增加,L-Arg-CDs的荧光强度逐渐降低。图12b表明,在0~55μM范围内, L-Arg-CDs荧光淬灭效率与E102浓度呈现较好的线性关系,0~7.5μM其线性方程为(F0-F)/F0=0.7047C(E102)-0.01538,R2=0.9961,20~50μM范围内线性方程为(F0-F)/F0=0.00845C(E102)+0.38448,R2=0.9975。
实施例6:E102猝灭纯化L-Arg-CDs的荧光机理研究
为了进一步探究L-Arg-CDs对E102的荧光猝灭机理,测定了淬灭物E102 存在与否条件下的UV-vis、荧光寿命以及最佳激发波长下的荧光光谱。结果如下:根据L-Arg-CDs、E102紫外-可见吸收光谱,图13(a)所示,发生荧光淬灭反应后L-Arg-CDs+E102的谱线,与L-Arg-CDs、E102的谱线进行比较,未观察到新的吸收峰,结果表明无新的化合物生成,即表明E102对L-Arg-CDs的荧光猝灭不属于SQ过程。利用时间相关单光子计数法(TCSPC),测定L-Arg-CDs 溶液的荧光寿命,通过双指数拟合计算后,荧光衰减寿命图见13(b),L-Arg-CDs的荧光衰减寿命为2.28ns,L-Arg-CDs+E102的荧光衰减寿命2.29ns,两者的荧光衰减寿命基本不变,因此,E102的淬灭机理可能是IFE。
L-Arg-CDs荧光光谱与E102的紫外吸收迭加见图13(c),L-Arg-CDs荧光光谱的Em峰与E102的紫外吸收峰部分重叠。
因此,结合UV-Vis、荧光衰减寿命及荧光光谱结果,推测L-Arg-CDs检测E102的荧光淬灭机理为荧光内滤效应(IFE)所致。
利用Park方程来进一步验证IFE机制:
Fobsd指实际测定的PL强度,Fcor是指校正后的PL强度。Aex和Aem分别表示最大激发和发射波长下的吸光度。s是激发光束的厚度(s=0.10cm),g是指石英比色池底部与激发光束的下边缘之间的距离(g=0.40cm),d则为石英比色池的宽度(d=1.00cm)。
Park方程验证L-Arg-CDs检测E102的结果见图14,E102浓度增加时 (0~25μM),Fcor/Fobsd值由1.349增至3.107,完全符合Park方程。
综上所述,L-Arg-CDs检测E102的荧光淬灭机理属于IFE。
实施例7:实际样品中柠檬黄含量检测
实际样品处理方法:
当地超市购买的某种碳酸饮料:超声30min,0.22um滤膜过滤进样。
当地超市购买的固体样品:糖、小米、玉米面。粉碎后取10.0g(万分之一天平),加超纯水20mL,超声30分钟,离心10min(8000g),取上清液,0.22 um滤膜过滤进样。
四种不同样品中加入标准柠檬黄溶液,进行加标回收实验,结果表明这四种样品中柠檬黄含量符合食品添加剂卫生标准,结果见表1。
表1.实际样品中测试柠檬黄浓度检测结果(n=3)
应当理解的是,本发明的上述具体实施方式仅仅用于示例性发明或解释本发明的原理,而不构成对本发明的限制。因此,在不偏离本发明的精神和范围的情况下所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。此外,本发明所附权利要求旨在涵盖落入所附权利要求范围和边界、或者这种范围和边界的等同形式内的全部变化和修改例。
Claims (9)
1.一种L-精氨酸基碳点的制备方法,其特征在于,制备步骤包括:
1)常温下将L-精氨酸、邻苯二胺按照1:20~1:1的摩尔比溶解于水或甲醇或乙醇或正丙醇或丙酮或N,N-二甲基甲酰胺中,混匀;
2)转移至聚四氟乙烯高温反应釜中170℃~210℃下反应2~12h;
3)产物自然冷却后,高速离心,用透析袋在超纯水中透析24~72h,冷冻干燥后得到粗碳点;
4)柱层析法分离纯化粗碳点,以洗脱液梯度洗脱,收集蓝色荧光部分,减压回收溶剂得到较纯碳点;
5)较纯碳点继续用柱层析法以洗脱液进行二次梯度洗脱,经薄层色谱检测,获得荧光和紫外的双模检测碳点。
2.根据权利要求1所述的一种L-精氨酸基碳点的制备方法,其特征在于,所述透析袋的截流分子量MWCO为500~5000Da。
3.根据权利要求1所述的一种L-精氨酸基碳点的制备方法,其特征在于,所述洗脱液为V二氯甲烷:V甲醇=10:1~1:1或V石油醚:V丙酮=10:1~1:1或V氯仿:V甲醇=10:1~1:1或V石油醚:V乙酸乙酯=10:1~1:1。
4.根据权利要求1-3任意一项所述的制备方法取得的一种L-精氨酸基碳点在柠檬黄快速检测中的应用。
5.根据权利要求4所述的一种L-精氨酸基碳点在柠檬黄快速检测中的应用,其特征在于,检测步骤包括:
1)将柠檬黄与L-Arg-CDs溶液混合,分别取得至少两种不同柠檬黄浓度的混合溶液,在λEx为367nm,λEm为441nm下分别测得不同柠檬黄浓度的混合溶液的荧光强度;
2)将待测样品与L-Arg-CDs溶液混合,得到待测样品混合溶液,测得待测样品混合溶液的荧光强度;
3)根据步骤1)中荧光猝灭效率(F0-F)/F0与混合溶液中柠檬黄浓度的线性关系计算出待测样品混合溶液中柠檬黄的浓度;所述线性关系为取得荧光猝灭效率(F0-F)/F0与混合溶液中柠檬黄浓度的线性关系,在0~55μM范围内,L-Arg-CDs荧光淬灭效率与E102浓度呈现较好的线性关系,0~0.75μM其线性方程为(F0-F)/F0=0.7047C(E102)-0.01538,R2=0.987,20~55μM范围内线性方程为(F0-F)/F0=0.00845C(E102)+0.38448,R2=0.9904。
6.根据权利要求5所述的应用,其特征在于,所述柠檬黄浓度的线性检测范围为0~55μM。
7.根据权利要求5所述的应用,其特征在于,所述步骤2)中L-Arg-CDs在pH=5.0的条件下检测柠檬黄。
8.根据权利要求5所述的应用,其特征在于,所述步骤1)柠檬黄与L-Arg-CDs溶液混合后前3min内检测荧光强度。
9.根据权利要求5所述的应用,其特征在于,所述步骤2)中柠檬黄与L-Arg-CDs溶液混合后前3min内检测荧光强度。
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CN115611266A (zh) * | 2022-10-28 | 2023-01-17 | 河北宝力工程装备股份有限公司 | 氧氮金属掺杂的纳米碳材料的制备方法及在橡胶中的应用 |
CN115820249A (zh) * | 2022-12-19 | 2023-03-21 | 广东药科大学 | 一种氮掺杂碳点及其制备方法与应用 |
CN116218523A (zh) * | 2023-03-08 | 2023-06-06 | 北京师范大学 | 一种胍基功能化荧光碳点及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108659833A (zh) * | 2018-05-25 | 2018-10-16 | 山西大学 | 一种黄色荧光碳点及其制备方法和应用 |
CN111807349A (zh) * | 2020-08-31 | 2020-10-23 | 河南师范大学 | 一种光致发光波长稳定的红光碳点的制备方法 |
-
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- 2022-05-27 CN CN202210591755.8A patent/CN114854407B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108659833A (zh) * | 2018-05-25 | 2018-10-16 | 山西大学 | 一种黄色荧光碳点及其制备方法和应用 |
CN111807349A (zh) * | 2020-08-31 | 2020-10-23 | 河南师范大学 | 一种光致发光波长稳定的红光碳点的制备方法 |
Non-Patent Citations (1)
Title |
---|
董学哲: "邻苯二胺基长波长碳点的制备及其光学调控规律研究", 《中国优秀硕士学位论文全文数据库》 * |
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CN115611266A (zh) * | 2022-10-28 | 2023-01-17 | 河北宝力工程装备股份有限公司 | 氧氮金属掺杂的纳米碳材料的制备方法及在橡胶中的应用 |
CN115611266B (zh) * | 2022-10-28 | 2023-06-23 | 河北宝力工程装备股份有限公司 | 氧氮金属掺杂的纳米碳材料的制备方法及在橡胶中的应用 |
CN115820249A (zh) * | 2022-12-19 | 2023-03-21 | 广东药科大学 | 一种氮掺杂碳点及其制备方法与应用 |
CN115820249B (zh) * | 2022-12-19 | 2023-12-26 | 广东药科大学 | 一种氮掺杂碳点及其制备方法与应用 |
CN116218523A (zh) * | 2023-03-08 | 2023-06-06 | 北京师范大学 | 一种胍基功能化荧光碳点及其制备方法和应用 |
CN116218523B (zh) * | 2023-03-08 | 2024-05-07 | 北京师范大学 | 一种胍基功能化荧光碳点及其制备方法和应用 |
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