CN111303455A - 一种两性离子聚合物水凝胶及其制备方法和应用方法 - Google Patents
一种两性离子聚合物水凝胶及其制备方法和应用方法 Download PDFInfo
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Abstract
本发明属于聚合物水凝胶制备技术领域,具体为一种两性离子聚合物水凝胶的制备方法及其在生物传感器中的应用。本发明提供的两性离子聚合物水凝胶,包括如下组分:两性离子聚合物、碳量子点和葡萄糖氧化酶,这种两性离子聚合物水凝胶,制备方法简单,有利于水凝胶在生物传感器领域的应用;进一步通过氢键键合将碳量子点和葡萄糖氧化酶封装在两性离子聚合物水凝胶中,制备出pH敏感型含酶水凝胶,可有效地避免干扰酶的疏水活性位点,构建的生物传感器可以对pH和葡萄糖同时响应与检测,响应范围宽,灵敏度高。
Description
技术领域
本发明属于聚合物水凝胶制备技术领域,具体涉及一种两性离子聚合物水凝胶及其制备方法和应用方法。
背景技术
目前在生物传感器开发中,传感器在体内或体外使用的长期稳定性是最重要的性能指标。经过几十年的研究,传感器的灵敏度、线性区间、准确性等指标己经得到很大程度地提高,但是如何实现无创血糖检测已成为研究人员为之努力的方向。为了改变这一局面,近年来正在积极研究血糖浓度的非损伤性测定方法,包括使用近红外光谱、拉曼光谱、荧光等光学手段进行血糖监测。这些方法光谱信噪比低,因而利用其测定的血糖值的准确性低。
有鉴于上述现有的血糖检测手段存在的缺陷,本发明人基于从事此类产品设计制造多年丰富的实务经验及专业知识,并配合学理的运用,积极加以研究创新,以期创设一种两性离子聚合物水凝胶及其制备方法和应用方法,以提高测定的血糖值的准确性,使其更具有实用性。经过不断的研究、设计,并经反复试作样品及改进后,终于创设出确具实用价值的本发明。
发明内容
本发明两性离子聚合物水凝胶检测利用的主要原理如下:
将碳量子点和葡萄糖氧化酶封装在两性离子聚合物水凝胶中,形成pH敏感型含酶水凝胶,应用在生物传感器中可以同时检测pH和葡萄糖;其作用机理是:碳量子点与聚合物形成的复合材料与pH溶液反应时,在电极pH溶液之间的界面处会形成双电层(edl),edl的形成影响电化学测量,并随溶液的pH值而变化,从而导致电极的表面电势发生变化;在水凝胶与葡萄糖溶液反应时,水凝胶中的葡萄糖氧化酶会将葡萄糖氧化成酸和过氧化氢,而过氧化氢在电极上被还原成O2释放出电子,从而导致电极的表面电流发生变化;并通过检测得出,本发明设计的生物传感器对pH响应范围为5-9,颜色的显色范围为橙色至绿色,对pH的电位响应范围为40-50mV,对葡萄糖的电流响应范围为25-300μM,灵敏度为20-48μA/mM。
本发明的第一目的在于,克服现有的血糖检测技术存在的测量准确度低的缺陷,而提供一种两性离子聚合物水凝胶,将碳量子点和葡萄糖氧化酶有效固定在水凝胶中,制备出的水凝胶实现可对pH和葡萄糖同时响应与检测,提高血糖检测准确性,从而更加适于实用,且具有产业上的利用价值。
本发明的上述技术目的是通过以下技术方案得以实现的:
本发明提出的两性离子聚合物水凝胶,包括如下组分:两性离子聚合物、碳量子点和葡萄糖氧化酶,其中两性离子聚合物的结构式如下:
结构中的R1由亚甲基、乙烯基、羰基、磺酸酯基、磷酸酯基中的任意一种或多种基团组成;R2由亚甲基、羰基、磺酸酯基、磷酸酯基中的任意一种或多种基团组成;R3为:氢或烷基;m为1000-17000,n为2000-20000。
本发明提供的两性离子聚合物,由于在分子内部同时含有具有亲水的阴、阳离子基团,具有高电荷平衡,能够高度水化从而具有独特的抗生物污染性能,即能够阻抗非特异性蛋白质的吸附、细菌黏附和生物膜的形成。同时由于具有超亲水性,两性离子聚合物可避免干扰酶的疏水活性位点。本发明制备的两性离子聚合物是采用两种带有阴阳离子基团的烯类单体反应制取单体离子对,然后聚合交联而成;两性离子聚合物具有高电荷且平衡,调节单体用量和反应参数,可以使聚合物在宏观上保持电中性,并且可以通过离子溶剂化牢固结合水分子;蛋白质类酶的构像维持靠疏水作用力,而疏水氨基酸所构成的活性中心的作用力也大。因此,活性中心并不是由于反应的需求而呈现出疏水,而是因为结构维系而疏水。由于本发明提供的两性离子聚合物的水凝胶具有超亲水性,通过其众亲水基团之间的氢键结合大量水的能力而获得了无污染的表面特性。将酶固定在水凝胶中后,能够破坏蛋白质类酶内核的物质阻挡在水凝胶表面,防止了酶被污染而降低酶的活性;从而在水凝胶与葡萄糖溶液反应时,避免了酶的疏水活性位点受到干扰而进一步影响酶的催化反应,进而降低对血糖监测的误差影响,提高监测的灵敏度。
进一步的,碳量子点是1,2,4-三氨基苯二盐酸盐和尿素通过水热合成法制备而成。在本申请中,以1,2,4-三氨基苯和尿素为原料,采用微波辅助水热法合成了一种新型的不依赖于激发的发光碳量子点(O-CDs)。在制备出的碳量子点中,可以发生由pH引起的醌结构与偶氮形式的转变。偶氮化合物即AZO,偶氮基─N=N─与两个烃基相连接而生成的化合物,偶氮基能吸收一定波长的可见光,是一个显色基团。在pH可以诱导下O-CDs可能发生醌型结构和偶氮形式之间的转化。因此本申请中的O-CDs水溶液不仅在光致发光强度方面表现出出色的pH敏感性质,而且在可见光下对pH从5变为9表现出独特的比色响应。
本发明的第二个目的在于,提供一种两性离子聚合物水凝胶的制备方法。
本发明的上述技术目的是通过以下技术方案得以实现的:
更进一步的,一种两性离子聚合物水凝胶的制备方法,包括如下操作步骤:
S1.将1,2,4-三氨基苯二盐酸盐和尿素溶解于超纯水中,充分搅拌后,将混合物溶液转移至应釜中密封,在180-240℃下反应20-60min,自然冷却至室温,得到溶液A;
S2.将步骤S1中的溶液A过滤,过滤后将所得悬浮液用超纯水进行透析;透析结束后,将溶液置于真空冷冻干燥室中冷冻干燥,即可获得固体的碳量子点,存储备用;
S3.取前驱阴离子单体A溶液、前驱阳离子单体B溶液、N,N'-亚甲基双丙烯酰胺依次添加到四氢呋喃溶剂中,在冰浴中超声处理20-30min后,在混合液中继续加入引发剂、促进剂、1×10-9mol/L葡萄糖氧化酶,搅拌混合均匀后,反应15-35min,得到溶液B;
S4.将步骤S3中的溶液B转移到玻璃表面皿中,置于恒温37℃下进行光聚合反应2-4h,聚合结束,即可获得含葡萄糖氧化酶聚合物水凝胶;
S5.将步骤S2中的碳量子点溶于PBS中,配制成浸泡液;将步骤S4中的含葡萄糖氧化酶聚合物水凝胶完全浸入浸泡液中水合反应,每天更换浸泡液,持续N天;然后将水凝胶冲入直径为D mm的圆盘中,即制得两性离子聚合物水凝胶,其中,N≥3,D≥5。
本发明中将含酶水凝胶在含有碳量子点中的PBS缓冲液中浸泡进行水合反应,通过氢键将碳量子点与水凝胶中的聚合物有效键合;同时,通过长时间的浸泡和每天更换浸泡液,能够除去未反应的化学物质和过量的盐。
更进一步的,其制备方法包括如下操作步骤:
S1将1,2,4-三氨基苯二盐酸盐和尿素溶解于10-20mL超纯水中,充分搅拌后,将混合物溶液转移至聚四氟乙烯反应釜中密封,在180-240℃下反应20-60min,自然冷却至室温,得到溶液A;
S2.将步骤S1中的溶液A通过孔径为0.22μm的PTFE注射过滤器过滤以除去大颗粒;然后,将所得悬浮液用超纯水进行透析24-48h,每6-8小时更换一次超纯水;透析结束后,将溶液置于真空冷冻干燥室中冷冻干燥,即可获得固体碳量子点,存储备用;
S3.取前驱阴离子单体A溶液、前驱阳离子单体B溶液、N,N'-亚甲基双丙烯酰胺依次添加到四氢呋喃溶剂中,在冰浴中超声处理20-30min后,在混合液中继续加入引发剂、促进剂、1×10-9mol/L葡萄糖氧化酶,搅拌混合均匀后,反应15-35min,得到溶液B;
S4.将步骤S3中的溶液B转移到玻璃表面皿中,置于恒温37℃下进行光聚合反应2-4h,聚合结束,即可获得含葡萄糖氧化酶聚合物水凝胶。
S5.将步骤S2中的碳量子点溶于5-15mg/L PBS,配制成三份相同的等体积等浓度浸泡液;将步骤S4中的含葡萄糖氧化酶聚合物水凝胶完全浸入浸泡液中水合反应,每天更换浸泡液,持续3天;然后将水凝胶冲入直径为5mm的圆盘中,即制得两性离子聚合物水凝胶。
进一步的,前驱阴离子单体A溶液是2-甲基丙烯酸-四氢吡喃酯溶液或甲基丙烯磺 酸钠溶液中的任意一种。
进一步的,前驱阳离子单体B溶液是2-(二甲胺基)甲基乙烯磺酸乙酯溶液。
进一步的,步骤S1中的1,2,4-三氨基苯二盐酸盐和尿素的质量比例为1:(1-2)。在该比例条件下,制备出的碳量子点具有尺寸达到1.7-2.3nm,大小均一,同时在pH的响应下具有较宽的显色范围。从而间接地影响了生物传感器同时监测pH和葡萄糖,提高对pH的灵敏度。
进一步的,步骤S2中的碳量子点平均粒度大小为1.7-2.3nm。一般量子点的大小在2-20nm,一定的电场或光压下,它们便会发出特定频率的光,而发出的光的频率会随着这种半导体的尺寸的改变而变化,因而通过调节这种纳米半导体的尺寸就可以控制其发出的光的颜色。在本发明选用的平均粒度大小为1.7-2.3nm碳量子点,其为橙色。在此基础颜色下,pH响应能够具有一个明显的显色变化。
进一步的,步骤S3中的前驱阴离子单体A溶液和前驱阳离子单体B溶液是阴离子单体A和阳离子单体B分别在1M NaCl中配制而成的混合溶液。
进一步的,步骤S3中的N,N'-亚甲基双丙烯酰胺浓度为前驱阴离子单体A溶液和前驱阳离子单体B溶液总浓度的1-2%。本浓度范围条件下,能够制备出的水凝胶极高的亲水性,稳定性较好。若浓度过高或过低主要是会影响聚合物交联不充分,从而影响水凝胶的稳定性,难以成胶固化,进一步影响酶和碳量子点的固定,故而导致pH和葡萄糖响应不灵敏。
进一步的,引发剂为过硫酸铵、过硫酸钾、偶氮二异丁酸二甲酯或二甲基乙烯酮甲基三甲硅氧基缩醛中的任意一种或多种的混合物。
进一步的,引发剂的质量为2-5mg。
进一步的,促进剂为四甲基乙二胺、四丁基二苯甲酸氢铵或N,N’-四甲基二硫双硫羰胺中的任意一种。
进一步的,促进剂的用量为3-5μL。
本发明的第三个目的在于,提供一种两性离子聚合物水凝胶的应用在生物传感器中的方法。
本发明的上述技术目的是通过以下技术方案得以实现的:
更进一步的,一种两性离子聚合物水凝胶的应用方法,利用激光技术处理导电胶带,并设计基于柔性基底PET的导电通路,涂覆上Ag/AgCl浆料用作参比电极,粘合上两性离子聚合物水凝胶的小圆片用作工作电极和对电极,构建出生物传感器系统。
本发明提供的生物传感器,通过比色与荧光的双重响应,检测出对pH响应范围为5-9,颜色的显色范围为橙色-绿色;且对pH的电位响应范围为40-50mV,对葡萄糖的电流响应范围为25-300μM,灵敏度为20-48μA/mM。
综上所述,本发明具有以下有益效果:
本发明利用两性离子聚合物和碳量子点的特异性能,开发出一种由两性离子聚合物制备的pH敏感型含酶水凝胶,由两性离子型单体、引发剂、交联剂、促进剂在有机溶剂中通过聚合反应得到。这种两性离子聚合物水凝胶,制备方法简单,有利于水凝胶在生物传感器领域的应用;进一步通过氢键键合将碳量子点和葡萄糖氧化酶封装在两性离子聚合物水凝胶中,制备出pH敏感型含酶水凝胶,可有效地避免干扰酶的疏水活性位点,构建的生物传感器可以对pH和葡萄糖同时响应与监测,响应范围宽,灵敏度高。
具体实施方式
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效,对依据本发明提出的两性离子聚合物水凝胶及其制备方法和应用方法,其具体实施方式、特征及其功效,详细说明如后。
本发明实施例中采用的原材料的生产厂家如下:
1,2,4-三氨基苯二盐酸盐:上海一基实业有限公司;
尿素:西安天正药有辅料有限公司;
N,N'-亚甲基双丙烯酰胺:上海阿拉丁生化科技股份有限公司;
四氢呋喃溶剂:南京奥普奇医药科技有限公司;
二甲基乙烯酮甲基三甲硅氧基缩醛:上海阿拉丁生化科技股份有限公司;
四丁基二苯甲酸氢铵:常州市华东化工研究所;
葡萄糖氧化酶:上海阿拉丁生化科技股份有限公司;
过硫酸铵:上海阿拉丁生化科技股份有限公司;
四甲基乙二胺:上海阿拉丁生化科技股份有限公司;
过硫酸钾:上海阿拉丁生化科技股份有限公司;
N,N’-四甲基二硫双硫羰胺:上海基免实业有限公司;
水溶性碳量子点:南京捷纳思新材料科技有限公司;
2-甲基丙烯酸-四氢吡喃酯溶液:上海阿拉丁生化科技股份有限公司;
2-(二甲胺基)甲基丙烯酸乙酯溶液:上海阿拉丁生化科技股份有限公司;
甲基丙烯磺酸钠溶液:上海阿拉丁生化科技股份有限公司;
2-(二甲胺基)甲基乙烯磺酸乙酯溶液:上海阿拉丁生化科技股份有限公司;
甲基丙烯磷酸钠溶液:上海阿拉丁生化科技股份有限公司;
2-(二甲胺基)甲基乙烯磷酸乙酯溶液:上海阿拉丁生化科技股份有限公司。
一种两性离子聚合物水凝胶,包括如下组分:两性离子聚合物、碳量子点和葡萄糖氧化酶,其中所述两性离子聚合物的结构式如下:
结构中的R1为亚甲基、乙烯基、羰基、磺酸基、磷酸基中的一种或多种基团组成;R2为:亚甲基、羰基、磺酸基、磷酸基中的一种或多种基团组成;R3为:烷基;m为1000-17000,n为2000-20000。
实施例1
一种两性离子聚合物水凝胶的制备方法,具体制备步骤为:
S1.将1,2,4-三氨基苯二盐酸盐和尿素以1:1的质量比例加入到10mL超纯水中溶解,充分搅拌后,将混合物溶液转移至聚四氟乙烯反应釜中密封,在220℃下反应20min,自然冷却至室温,得到溶液A;
S2.将步骤S1中的溶液A通过孔径为0.22μm的PTFE注射过滤器过滤以除去大颗粒;然后,将所得悬浮液用超纯水进行透析36h,每6小时更换一次超纯水,透析结束后,将溶液置于真空冷冻干燥室中冷冻干燥,即可获得固体碳量子点,存储备用;
S3.取:2-甲基丙烯酸-四氢吡喃酯溶液、2-(二甲胺基)甲基丙烯酸乙酯溶液、N,N'-亚甲基双丙烯酰胺依次添加到四氢呋喃溶剂中,在冰浴中超声处理20min后;在混合液中继续加入2mg二甲基乙烯酮甲基三甲硅氧基缩醛的引发剂、4μL四丁基二苯甲酸氢铵的促进剂、1×10-9mol/L葡萄糖氧化酶,搅拌混合均匀后,反应30min,得到溶液B;其中,N,N'-亚甲基双丙烯酰胺浓度为前驱单体A和B总摩尔浓度的1%。
S4.将步骤S3中的溶液B转移到玻璃表面皿中,置于恒温37℃下进行光聚合反应2h,聚合结束,即可获得含酶水凝胶;
S5.将步骤S2中的碳量子点溶于10mg/L PBS,配制成三份相同的等体积等浓度浸泡液;将步骤S4中的含酶水凝胶完全浸入浸泡液中水合反应,每天更换浸泡液,持续3天;然后将水凝胶冲入直径为5mm的圆盘中,即制得pH敏感型含酶水凝胶。
通过上述制备方法,碳量子点平均粒度大小为1.7nm;通过比色与荧光的双重响应,检测出对pH响应范围为5-9,颜色的显色范围为橙色-绿色;构建的生物传感器对pH的电位响应范围为50mV,对葡萄糖的电流响应线性范围为25-300μM,灵敏度为50μA/mM。
实施例2
一种两性离子聚合物水凝胶的制备方法,具体制备步骤为:
S1.将1,2,4-三氨基苯二盐酸盐和尿素以2:3的质量比例加入到20mL超纯水中溶解,充分搅拌后,将混合物溶液转移至聚四氟乙烯反应釜中密封,在180℃下反应60min,自然冷却至室温,得到溶液A;
S2.将步骤S1中的溶液A通过孔径为0.22μm的PTFE注射过滤器过滤以除去大颗粒;然后,将所得悬浮液用超纯水进行透析24h,每6小时更换一次超纯水;透析结束后,将溶液置于真空冷冻干燥室中冷冻干燥,即可获得固体的碳量子点,存储备用;
S3.取甲基丙烯磺酸钠溶液、2-(二甲胺基)甲基乙烯磺酸乙酯溶液、N,N'-亚甲基双丙烯酰胺依次添加到四氢呋喃溶剂中,在冰浴中超声处理25min后;在混合液中继续加入5mg过硫酸铵的引发剂、3μL四甲基乙二胺的促进剂、1×10-9M葡萄糖氧化酶,搅拌混合均匀后,反应35min,得到溶液B;其中,N,N'-亚甲基双丙烯酰胺浓度为前驱单体A和B总摩尔浓度的1.5%。
S4.将步骤S3中的溶液B转移到玻璃表面皿中,置于恒温37℃下进行光聚合反应4h,聚合结束,即可获得含酶水凝胶;
S5.将步骤S2中的碳量子点溶于5mg/L PBS,配制成三份相同的等体积等浓度浸泡液;将步骤S4中的含酶水凝胶完全浸入浸泡液中水合反应,每天更换浸泡液,持续3天;然后将水凝胶冲入直径为5mm的圆盘中,即制得pH敏感型含酶水凝胶。
通过上述制备方法,碳量子点平均粒度大小为2.3nm;通过将设计出的生物传感器对pH和葡萄糖进行监测,检测出对pH响应范围为5-8,颜色的显色范围为橙色至绿色;构建生物传感器对pH的电位响应范围为40mV,对葡萄糖的电流响应范围为100-200μM,灵敏度为30μA/mM。
实施例3
一种两性离子聚合物水凝胶的制备方法,具体制备步骤为:
S1.将1,2,4-三氨基苯二盐酸盐和尿素以1:2的质量比例加入到15mL超纯水中溶解,充分搅拌后,将混合物溶液转移至聚四氟乙烯反应釜中密封,在240℃下反应40min,自然冷却至室温,得到溶液A;
S2.将步骤S1中的溶液A通过孔径为0.22μm的PTFE注射过滤器过滤以除去大颗粒;然后,将所得悬浮液用超纯水进行透析48h,每8小时更换一次超纯水;透析结束后,将溶液置于真空冷冻干燥室中冷冻干燥,即可获得固体碳量子点,存储备用;
S3.取甲基丙烯磷酸钠溶液、2-(二甲胺基)甲基乙烯磷酸乙酯溶液、N,N'-亚甲基双丙烯酰胺依次添加到四氢呋喃溶剂中,在冰浴中超声处理30min后;在混合液中继续加入3mg过硫酸钾的引发剂、5μL N,N’-四甲基二硫双硫羰胺的促进剂、1×10-9M葡萄糖氧化酶,搅拌混合均匀后,反应15min,得到溶液B;其中,N,N'-亚甲基双丙烯酰胺浓度为前驱单体A和B总摩尔浓度的1.5%;
S4.将步骤S3中的溶液B转移到玻璃表面皿中,置于恒温37℃下进行光聚合反应3h,聚合结束,即可获得含酶水凝胶;
S5.将步骤S2中的碳量子点溶于5mg/L PBS,配制成三份相同的等体积等浓度浸泡液;将步骤S4中的含酶水凝胶完全浸入浸泡液中水合反应,每天更换浸泡液,持续3天;然后将水凝胶冲入直径为5mm的圆盘中,即制得pH敏感型含酶水凝胶。
通过上述制备方法,碳量子点平均粒度大小为2.0nm;通过将设计出的生物传感器对pH和葡萄糖进行监测,检测出对pH响应范围为6-9,颜色的显色范围为橙色至绿色;构建生物传感器对pH的电位响应范围为45mV,对葡萄糖的电流响应范围为25-200μM,灵敏度为20μA/mM。
对比例1
一种两性离子聚合物水凝胶的制备方法,具体制备步骤为:
S1.将1,2,4-三氨基苯二盐酸盐和尿素以2:1的质量比例加入到5mL超纯水中溶解,充分搅拌后,将混合物溶液转移至聚四氟乙烯反应釜中密封,在150℃下反应70min,自然冷却至室温,得到溶液A;
S2.将步骤S1中的溶液A通过孔径为0.22μm的PTFE注射过滤器过滤以除去大颗粒;然后,将所得悬浮液用超纯水进行透析72h,每6小时更换一次超纯水;透析结束后,将溶液置于真空冷冻干燥中干燥,即可获得固体碳量子点,存储备用;
S3.取2-甲基丙烯酸-四氢吡喃酯溶液、2-(二甲胺基)甲基丙烯酸乙酯溶液、N,N'-亚甲基双丙烯酰胺依次添加到四氢呋喃溶剂中,在冰浴中超声处理10min后;在混合液中继续加入7mg二甲基乙烯酮甲基三甲硅氧基缩醛的引发剂、4μL四丁基二苯甲酸氢铵的促进剂、1×10-9mol/L葡萄糖氧化酶,搅拌混合均匀后,反应40min,得到溶液B;其中,N,N'-亚甲基双丙烯酰胺浓度为前驱单体A和B总摩尔浓度的5%;
S4.将步骤S3中的溶液B转移到玻璃表面皿中,置于恒温37℃下进行光聚合反应3h,聚合结束,即可获得含酶水凝胶;
S5.将步骤S2中的碳量子点溶于20mg/L PBS,配制成三份相同的等体积等浓度浸泡液;将步骤S4中的含酶水凝胶完全浸入浸泡液中水合反应,每天更换浸泡液,持续3天;然后将水凝胶冲入直径为5mm的圆盘中,即制得pH敏感型含酶水凝胶。
通过上述制备方法,碳量子点平均粒度大小为500nm;通过将设计出的生物传感器对pH和葡萄糖进行监测,检测出对pH响应范围为7-8,颜色的显色范围为橙色;构建生物传感器对pH的电位响应范围为10mV,对葡萄糖的电流响应范围为244-280μM,灵敏度为5μA/mM。
对比例2
此对比例在实施例1的基础上,将前驱物阴、阳离子单体更换为通过市面购买羧酸甜菜碱作为前驱物,具体实验结果如下:
通过将设计出的生物传感器对pH和葡萄糖进行监测,检测出对pH响应范围为6-9,颜色的显色范围为橙色-绿色;构建生物传感器对pH的电位响应范围为14mV,对葡萄糖的电流响应范围为146-160μM,灵敏度为11μA/mM。
对比例3
此对比例在实施例1的基础上,将碳量子点更换为通过市面购买水溶性碳量子点,具体实验结果如下:
通过将设计出的生物传感器对pH和葡萄糖进行监测,检测出对pH响应范围为6-9,颜色的显色范围为橙色-绿色;构建生物传感器对pH的电位响应范围为30mV,对葡萄糖的电流响应范围为63-260μM,灵敏度为18μA/mM。
测试结果:
由本发明所制备的水凝胶构建的生物传感器在监测pH和葡萄糖响应参数的结果可知,在实施例1-3中,实施例1为最佳实施例;通过对比例1-2可知,在本发明所制备的水凝胶应用在生物传感器上,对pH和葡萄糖响应性能稳定,灵敏度高,在临床医学上是具有潜在的应用价值。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (10)
2.根据权利要求1所述的一种两性离子聚合物水凝胶,其特征在于,所述碳量子点是1,2,4-三氨基苯二盐酸盐和尿素通过水热合成法制备而成。
3.根据权利要求1或2所述的一种两性离子聚合物水凝胶的制备方法,其特征在于,包括如下操作步骤:
S1.将1,2,4-三氨基苯二盐酸盐和尿素溶解于超纯水中,充分搅拌后,将混合物溶液转移至应釜中密封,在180-240℃下反应20-60min,自然冷却至室温,得到溶液A;
S2.将步骤S1中的溶液A过滤,过滤后将所得悬浮液用超纯水进行透析;透析结束后,将溶液置于真空冷冻干燥室中冷冻干燥,即可获得固体的碳量子点,存储备用;
S3.取前驱阴离子单体A溶液、前驱阳离子单体B溶液、N,N'-亚甲基双丙烯酰胺依次添加到四氢呋喃溶剂中,在冰浴中超声处理20-30min后,在混合液中继续加入引发剂、促进剂、1×10-9mol/L葡萄糖氧化酶,搅拌混合均匀后,反应15-35min,得到溶液B;
S4.将步骤S3中的溶液B转移到玻璃表面皿中,置于恒温37℃下进行光聚合反应2-4h,聚合结束,即可获得含葡萄糖氧化酶聚合物水凝胶;
S5.将步骤S2中的碳量子点溶于PBS中,配制成浸泡液;将步骤S4中的含葡萄糖氧化酶聚合物水凝胶完全浸入浸泡液中水合反应,每天更换浸泡液,持续N天;然后将水凝胶冲入直径为D mm的圆盘中,即制得两性离子聚合物水凝胶,其中N≥3,D≥5。
4.根据权利要求3所述的一种两性离子聚合物水凝胶的制备方法,其特征在于:所述步骤S1中的1,2,4-三氨基苯二盐酸盐和尿素的质量比例为1:(1-2)。
5.根据权利要求3所述的一种两性离子聚合物水凝胶的制备方法,其特征在于:所述步骤S2中的碳量子点平均粒度大小为1.7-2.3nm。
6.根据权利要求3所述的一种两性离子聚合物水凝胶的制备方法,其特征在于:所述步骤S3中的前驱阴离子单体A溶液和前驱阳离子单体B溶液是阴离子单体A和阳离子单体B分别在1M NaCl中配制而成的混合溶液。
7.根据权利要求3所述的一种两性离子聚合物水凝胶的制备方法,其特征在于:所述步骤S3中的N,N'-亚甲基双丙烯酰胺浓度为前驱阴离子单体A溶液和前驱阳离子单体B溶液总浓度的1-2%。
8.根据权利要求3所述的一种两性离子聚合物水凝胶的制备方法,其特征在于:所述引发剂为过硫酸铵、过硫酸钾、偶氮二异丁酸二甲酯或二甲基乙烯酮甲基三甲硅氧基缩醛中的任意一种或多种的混合物。
9.根据权利要求3所述的一种两性离子聚合物水凝胶的制备方法,其特征在于:所述促进剂为四甲基乙二胺、四丁基二苯甲酸氢铵或N,N’-四甲基二硫双硫羰胺中的任意一种。
10.一种两性离子聚合物水凝胶的应用方法,其特征在于,利用激光技术处理导电胶带,并设计基于柔性基底PET的导电通路,涂覆上Ag/AgCl浆料用作参比电极,粘合上两性离子聚合物水凝胶的小圆片用作工作电极和对电极,构建出生物传感器系统。
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