CN110316757B - 一种氧化钒制备方法及其应用 - Google Patents
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Abstract
本发明属于纳米材料的制备和抗菌及检测传感的领域，涉及一种以乙醇和三氯化钒为原料利用乙醇热合成氧化钒量子点而不加入任何表面活性剂或者模板的方法。其具体工艺包括以下步骤：称取三氯化钒溶于乙醇中，搅拌溶解后制得溶液，将制备的溶液转移入聚四氟乙烯密封罐密封并放入高温反应釜中，在180℃的温度下加热10小时，待加热后的溶液降至室温后，将聚四氟乙烯罐取出，取出溶液至离心管中，以大于12000转/分钟的转速离心10分钟，得到无色的上清液即获得氧化钒量子点溶液。所制备出的氧化钒量子点平均尺寸为3.39±0.57nm，并被证明同时具有两种纳米酶活性，可以基于其双酶协同互作反应应用于抗菌消炎，其总体工艺过程简单，制备效率高，市场前景极为广阔。
Description
技术领域：
本发明属于纳米材料的制备和抗菌及检测传感的领域，涉及一种一步法自下而上的基于乙醇热法制备氧化钒量子点的工艺，特别是涉及一种以乙醇和三氯化钒为原料利用乙醇热合成氧化钒量子点而不加入任何表面活性剂或者模板的方法。同时将氧化钒量子点应用于抗菌消炎及血清葡萄糖检测传感的方法。
背景技术：
目前，氧化钒材料作为一种新型的过渡金属氧化物由于其广泛的应用而引起了世界各地的广泛关注。由于氧化钒独特的晶体结构，因此，氧化钒具有许多优异的性能，并广泛应用于高能金属离子电池，超级电容器，储氢器和纳米酶等许多领域。同时，众所周知的是，材料的性能常常依赖于其聚集态结构，晶态结构，颗粒尺寸。当其尺寸减小到纳米尺寸时(通常<10纳米)，由于独特边缘效应和强大的量子限域效应，从而暴露更多的活性中心和催化位点，其催化能力会得到增强，并且细胞毒性会大大降低，可以制备成体内抗菌材料和纳米传感器，进行抗菌消炎和血清葡萄糖检测。
目前氧化钒量子点现有的制备方式一般以氧化钒或者钒酸盐为钒前驱体，以强氧化剂(双氧水或浓硝酸)存在的情况下合成。合成过程有许多安全隐患且强氧化剂的除去会使制备过程变得复杂。除此之外，电化学沉积法和管式炉煅烧法也被用作制备氧化钒量子点。但也有很多弊端，例如合成周期较长，所需温度较高，成本高，需要进行透析等一些复杂的处理。
相对于以上几种方法，溶剂热法制备过程极为简单而应用最为广泛，前期自上而下的溶剂热剥离技术一般需要对大块氧化钒原材料进行超声粉碎等前期处理步骤，步骤繁琐耗时，且材料转化率和产率都相对较低。因此，为了进一步研究氧化钒纳米材料的应用和发展，需要采用一种简单易行的、高效的氧化钒纳米结构的制备方法，如果可以通过一步法制备得到多种价态的氧化钒纳米材料，将会大大提高氧化钒纳米材料的制备和研究效率，但目前尚未见此类研究报道。因此，本发明寻求设计提供一种新型的氧化钒制备方法，该方法制备出的氧化钒是基于级联纳米酶性质进行抑菌的纳米材料。
发明内容：
本发明的目的在于克服现有技术存在的上述缺陷，设计提供一种氧化钒制备方法，该方法制备出的氧化钒基于双酶协同互作进行抑菌的纳米材料，该方法以三氯化钒为钒前驱体合成氧化钒量子点，通过自下而上乙醇热的作用合成氧化钒量子点。能稳定、可靠地制备氧化钒量子点。
为了实现上述目的，本发明涉及的氧化钒制备方法的具体工艺包括以下步骤：
S1、称取三氯化钒溶于乙醇中，搅拌溶解后制得溶液，将制备的溶液转移入聚四氟乙烯密封罐密封并放入高温反应釜中，在180℃的温度下加热10小时，待加热后的溶液降至室温后，将聚四氟乙烯罐取出，取出溶液至离心管中，以大于12000转/分钟的转速离心10分钟，得到无色的上清液即获得氧化钒量子点溶液。
所制备出的氧化钒量子点平均尺寸为3.39±0.57nm，并被证明同时具有两种纳米酶活性，可以基于其双酶协同互作反应应用于抗菌消炎，该材料的抗菌机理是：基于材料本身的氧化酶活性，可以分解氧气产生超氧阴离子和羟基等自由基，这些自由基具有很强的抗菌能力；同时当外部有过氧化氢加入时，基于材料本身的过氧化物酶活性,会分解过氧化氢产生更多的羟基自由基，抗菌性能大大增强；相比于已报道的氧化钒量子点抗菌，本发明的抗菌效果更加显著，抗菌类型更广，实验结果显示，即使在过氧化氢浓度为50μM条件下，氧化钒量子点也具有极强的抗菌性能，显著抑制大肠杆菌和金黄色葡萄球菌，该过氧化氢浓度远低于金掺杂碳化氮(100μM)、石墨烯量子点掺杂银(1mM)、纳米金(1mM)、银掺杂氧化铁(1mM)、石墨烯量子点(1mM)、二硫化钼(100μM)、卟啉金属有机骨架(100μM)、二氧化硅负载金(1mM)和铂掺杂银(200μM)等材料所需浓度。此外，还对一些耐药性细菌(耐甲氧西林金黄色葡萄球菌，产超广谱β-内酰胺酶的大肠杆菌，抗卡那霉素大肠杆菌)也具有很强的抗菌性能。另外，基于所制备的氧化钒量子点显著的过氧化物酶活性，被证明还可以应用于体内血清的葡萄糖检测传感。该传感器对葡萄糖具有更低的检测限和更宽的检测范围，其检测线为1.7μM，远低于五氧化二钒(10μM),二氧化钒(18μM)和氧化钴(5μM)等材料的葡萄糖检测限。其检测范围是0.005-2mM，远宽于三氧化二钒有序介孔碳复合物(0.01-4mM),五氧化二钒(0.01-2mM),铂掺杂氧化钼(0.005-0.5mM)和四氧化三铁(0.01-0.5mM)。
本发明与现有技术相比，只需采用乙醇作为溶剂，无需使用强氧化剂作为模板，是一种新的氧化钒量子点的制备方法，相对于现有技术来说，此制造工艺简单，这有效的提高了氧化钒的比表面积，从而提高其催化能力。其总体工艺过程简单，制备效率高，产品质量好，稳定性能强，具有环境友好的特性，市场前景极为广阔。
附图说明：
图1为本发明涉及的制备的氧化钒量子点的TEM图及高分辨透射电镜(HRTEM)图(A)、粒子尺寸分布图(B)和原子力显微镜图(C)。
图2为本发明涉及地氧化钒量子点与体外不同浓度的过氧化氢线性关系图(A)及不同浓度葡萄糖的的线性关系图(B)。
图3为本发明涉及的氧化钒量子点体外抗菌实验细菌平板计数的实物照片图(A)、不同处理后的细菌扫描电子显微镜(SEM)图(B)。
图4为本发明涉及的氧化钒量子点对不同耐药性细菌的抗菌效果实物图
具体实施方式：
下面通过实例并结合附图对本发明作进一步说明。
实施例1：
S1、称取0.2g的三氯化钒于20mL乙醇中，充分搅拌溶解；
S2、将步骤S1所制备溶液转移入聚四氟乙烯密封罐并放入水热反应釜中，在180℃的温度下水热10h；
S3、待水热后的溶液降至室温后，将聚四氟乙烯罐取出，取出溶液至离心管中，以12000转/分钟的转速离心10分钟，取上层清液即为制得的氧化钒量子点溶液；
S4、在进行抗菌实验时，需要取适量体积的氧化钒量子点溶液，置于恒温干燥箱中并在50℃下加热直至乙醇完全蒸发，之后加入等体积的蒸馏水得到氧化钒量子点水悬液。
实施例2：
本实施例将实施例1制备的氧化钒量子点溶液应用到过氧化氢检测方面，将10μLTMB(20mM)，30μLVOxQD(10mg mL-1)和各种浓度的H2O2加入到乙酸盐缓冲液(200mM，pH＝3)中以达到混合溶液的总体积为200μL，在40℃条件下反应30分钟后，使用酶标仪测量溶液在652nm处的吸光度，空白对照实验使用PBS(无H2O2)溶液进行，测量结果如图2(A)所示,氧化钒量子点对过氧化氢的检测线性范围为0.5-100μM，回归方程y＝0.00713x+0.18125(R2＝0.9923)。
本实施例将实施例1制备的氧化钒量子点溶液应用到葡萄糖检测方面，将具有不同终浓度(0.005-4mM)的葡萄糖添加到含有葡萄糖氧化酶(2mg mL-1)的PBS(pH 7.4)中，首先将混合溶液(85μL)在37℃下孵育30分钟，然后通过加入75μL乙酸盐缓冲液(270mM，pH 3)终止反应，随后加入10μLTMB(20mM)和30μLVOxQD(10mgmL-1)以达到最终溶液(200μL)，将其在40℃温育30分钟，并准备使用酶标仪测量溶液在652nm处的吸光度，测量结果如图2(B)所示，氧化钒量子点对葡萄糖的检测线性范围为y＝1.72622x+0.28117(R2＝0.991)，，远宽于三氧化二钒有序介孔碳复合物(0.01-4mM),五氧化二钒(0.01-2mM),铂掺杂氧化钼(0.005-0.5mM)和四氧化三铁(0.01-0.5mM)。
实施例3：
本实施例将实施例1制备的氧化钒量子点溶液应用到体外抗菌实验方面，将固体LB培养基上的单菌落非抗药性和抗药性细菌接种到50mL无菌液体LB培养基[含有胰蛋白胨(0.5g)，酵母提取物(0.25g)和NaCl(0.5g)]中，然后将非抗药性和抗药性细菌的悬浮液置于旋转振荡器上以180转/分钟在37℃下培养过夜。随后用无菌PBS将细菌稀释至106CFU mL-1，将获得的细菌溶液(200μL)与1mgmL-1VOxQD和50μM H2O2在37℃下温育30分钟，之后将溶液在37℃的固体培养基上培养24小时，用CFU法计数细菌菌落数，使用PBS作为空白对照，细菌单独与H2O2或VOxQD进行平行对照实验，测量结果如图3(A)所示，同时加入H2O2和VOxQD时，平板中只有很少的细菌菌落，对大肠杆菌和金黄色葡萄球菌的抗菌率分别是99.2％和97％，表明VOxQD在过氧化氢条件下，具有极强的抗菌性能。此外，图4为VOxQD对不同耐药性细菌的抗菌效果实物图，可以看出同时经H2O2和VOxQD处理后，平板中的细菌菌落相比于对照组明显减少，对抗卡那霉素大肠杆菌、产超广谱β-内酰胺酶的大肠杆菌和耐甲氧西林金黄色葡萄球菌的抗菌率分别为99.8％、96.5％和94.3％，表明VOxQD对多种耐药性细菌都具有明显的抗菌性能。
本实施例将实施例1制备的氧化钒量子点溶液应用到细菌扫描电子显微镜成像方面，将细菌分别用PBS，H2O2，VOxQD或H2O2/VOxQD处理后，通过8000rpm离心15分钟收集金黄色葡萄球菌和大肠杆菌，然后将细菌细胞用PBS缓冲液洗涤三次，随后与2.5％戊二醛混合在4℃条件下过夜处理，最后，将细菌细胞分别用30,50,70,90和100％乙醇脱水15分钟，并通过扫描电子显微镜表征。测量结果如图3(B)所示，细菌经H2O2和VOxQD处理后，大肠杆菌和金黄色葡萄球菌都展现出严重的生物膜破坏情况，表明VOxQD的抗菌机理是破坏细菌表面的生物膜。
Claims (3)
1.一种氧化钒制备方法，其特征在于，包括以下步骤：
S1、称取三氯化钒溶于乙醇中，搅拌溶解后制得溶液，将制备的溶液转移入聚四氟乙烯密封罐密封并放入高温反应釜中，在180℃的温度下加热10小时，待加热后的溶液降至室温后，将聚四氟乙烯罐取出，取出溶液至离心管中，以大于12000转/分钟的转速离心10分钟，得到无色的上清液即获得氧化钒量子点溶液；
所制备出的氧化钒量子点平均尺寸为3.39±0.57nm，并同时具有两种纳米酶活性。
2.根据权利要求1所述的氧化钒制备方法得到的氧化钒在检测过氧化氢中的应用，其特征在于，制备的氧化钒量子点溶液能够应用到过氧化氢检测，氧化钒量子点对过氧化氢的检测线性范围为0.5-100μM，回归方程y＝0.00713x+0.18125，其中R2＝0.9923。
3.根据权利要求1所述的氧化钒制备方法得到的氧化钒在检测葡萄糖中的应用，其特征在于，对葡萄糖的检测线性范围为y＝1.72622x+0.28117其中R2＝0.991，其中检测线为1.7μM，检测范围能够达到0.005-2mM。
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