CN1587347A - 可抗生物污染的电化学发光复合材料及其制备方法和应用 - Google Patents
可抗生物污染的电化学发光复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明为一种具有抗生物污染效能的电化学发光复合材料及其制备方法和应用。该复合材料由电化学发光物质固定在含有磷酯基团的聚合物中组成。其中，电化学发光物质包括金属钌络合物、金属锇络合物等，聚合物为2－甲基丙烯酰氧乙基－2’－三甲胺乙基磷酸酯·内盐与其他含有可聚合的单体的共聚物。实验表明，该复合材料具有良好的抗生物污染效能，可用于制备各种生物检测用的传感器。
Description
技术领域
本发明属电化学发光材料技术领域，具体涉及一种具有抗生物污染效能的高灵敏度电化学发光复合材料及其制备方法和应用。
背景技术
电化学发光是由电化学反应激发的化学发光，具有高灵敏度，可用于多种物质的分析检测。如果将这种高灵敏度的电化学发光材料固定到电极或光纤表面，则可以节约大量的昂贵试剂，简化操作和仪器结构，有利于扩大仪器的应用范围。
可以产生电化学发光的物质有许多种，但是报道得最多的是钌的络合物，如三联吡啶钌及其衍生物。已有许多文献报道了固定三联吡啶钌的方法，如将三联吡啶钌的衍生物制备成L-B膜和自组装膜，将三联吡啶钌固定到阳离子交换膜中。但是它们的稳定性都不太好。在溶液中易流失。O.Dvorak and M.K.De Armond(J.Phys.Chem.1993，97：2646)首先用溶胶-凝胶法固定三联吡啶钌；A.N.Khramov等(Anal.Chem.2000，72：32943)将三联吡啶钌通过离子交换法固定到Nafion-二氧化硅复合膜中，所得的修饰电极，其灵敏度和稳定性较纯Nafion膜有了较大的改进，但是其长期稳定性仍然不够。
目前市场上已有利用以上方法制作的商业化仪器出现，如将具有荧光猝灭效应的钌络合物涂在光纤顶端制成的电化学发光高灵敏度氧传感器，已广泛应用于太空，环境检测，土壤监测等。和传统的仪器相比，它具有仪器小巧，使用寿命长，测量范围广，反应迅速，重复性好，性能稳定，可实时检测等优点。
现代医学的发展，特别是临床危重病人的抢救，需要对人体的各种参数，包括血氧浓度、pH值，各种离子浓度等等进行长时间的微创实时检测。目前所使用的方法，都存在着传感器和血液接触一定时间后，表面被血小板等蛋白质粘附而造成失效的问题，在其他领域如生物反应器等应用的传感器也存在着类似的生物污染的难题。
磷酸胆碱是生物细胞膜外层磷脂头部分的主要成分，含有磷酸胆碱基团的聚合物已经被应用于生物医用材料和器械表面，可以有效地降低与体液如血液、泪膜和尿液等接触时产生的异物反应。磷酸胆碱基团是有极性的，其分子内部既有正电荷也带有负电荷，而分子总体上是电中性的。它具有强烈的亲水性，可以有效地降低蛋白质在其表面的可逆粘附。目前所报道的含有磷酸胆碱基团的聚合物主要是由2-甲基丙烯酰氧乙基-2′-三甲胺乙基磷酸酯·内盐(MPC)与其他单体共聚而形成的，MPC共聚物已经被应用于心脏支架、介入导管以及血液透析膜等与人体血液直接接触的医疗器械表面，改善器械的血液相容性，减少凝血和血液中蛋白质的粘附。但目前还没有这类聚合物应用于体内植入式电化学发光材料的报道。
发明内容
本发明的目的在于将磷酸胆碱聚合物的高度生物相容性和抗蛋白质粘附性能与高灵敏度电化学发光物质结合起来，提出一种具有抗生物污染效能的电化学发光复合材料及其制备方法，并提出该复合材料的应用。
本发明提出的电化学发光复合材料，由电化学发光物质固定在含有磷脂基团的聚合物中而组成，其中，按质量百分比计，电化学发光物质的用量为0.05-50％，其余为聚合物。
本发明中所用的电化学发光物质是能在相应溶剂中溶解的材料，包括金属钌络合物，金属锇络合物，金属铅络合物，金属铂和钯络合物，卟啉衍生物，金属铼络合物，过渡金属卟啉络合物，为其中的一种或一种以上的混合物，或者为上述物质与硅溶胶的复合物。其中优选金属钌络合物。
本发明中所用的含有磷脂基团的聚合物为2-甲基丙烯酰氧乙基-2′-三甲胺乙基磷酸酯·内盐(MPC)与其他含有可聚合基团的单体的共聚物。该共聚物可以2-甲基丙烯酰氧乙基-2′-三甲胺乙基磷酸酯·内盐(MPC)与如下单体中的一种或一种以上进行自由基共聚得到：丙烯酸或甲基丙烯酸烷基(如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十六烷基、十八烷基)酯，丙烯酸或甲基丙烯酸羟基乙酯，丙烯酸或甲基丙烯酸羟基丙酯，丙烯酸或甲基丙烯酸乙二醇酯，丙烯酸或甲基丙烯酸乙二醇甲醚酯，丙烯酸或甲基丙烯酸聚乙二醇酯，丙烯酸或甲基丙烯酸聚乙二醇甲醚酯，乙烯基吡咯烷酮，醋酸乙烯酯，含有双键的硅烷偶联剂(如γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷，γ-(甲基丙烯酰氧基)丙基三乙氧基硅烷)等等。
本发明提出的电化学发光复合材料的制备方法如下：1)将所述电化学发光物质在相应的溶剂中溶解；2)在上述溶液中加入含有磷脂基团的聚合物溶液，混合均匀；3)将上述混合溶液中的溶剂除去，即得到具有抗生物污染效能的电化学发光复合材料。
由本发明提出的电化学发光复合材料具有良好的抗生物污染效能，可用于制成各种能抗生物污染的生物检测传感器。
例如，将上述电化学发光复合材料制成薄膜，粘贴于生物检测用光纤端部，或者直接将上述电化学发光复合材料的溶液涂布于生物检测用光纤端部，经烘干(使溶剂挥发)处理，即得到抗生物污染的光纤传感器。
例如按照实施例1所合成的钌复合物明显显示了对氧分压的敏感性和重复性(见图1所示)。可以看出对氧分压敏感，反应迅速(小于1分钟达到平衡)。将此复合物涂于光导纤维末端，连接光源，用荧光滤片，光电管接受装置，可以装配小型的可连续实时测量血液中氧分压的荧光氧分压测定仪。
附图说明
图1为本发明的一种复合物对氧分压的敏感性图示。
具体实施方式
实施例1：
将30克MPC、68克甲基丙烯酸丁酯、2克γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷和0.1克引发剂AIBN溶入无水乙醇中，缓慢通入氩气1小时除氧。然后置于70℃恒温水浴中，搅拌下反应24小时。反应完毕后，将溶液冷却至室温，用大量正己烷沉淀提纯2次；在室温下将收集的沉淀物真空干燥24小时。得到含有磷脂基团的共聚物90克。
将0.1毫克金属钌络合物(英文名：Tris(4，7-diphenyl-1，10-phenanthroline)-ruthenium(II)bis(hexafluorophosphate))溶解在10毫升甲醇中，取0.8克上述含有磷脂基团的共聚物溶于同一溶液中，过滤后，向所得溶液中加入20微升水，搅拌均匀后将溶液涂布在光纤的端部，在70度烘箱中热处理5小时，将溶剂挥发，即得可用于测定血液或富含蛋白质溶液中溶解氧的抗生物污染光纤传感器。其响应迅速，结果重现性好，特别是在生物污染环境中能长时间使用。
实施例2：
将15克MPC、10克甲基丙烯酸聚乙二醇(分子量360)甲醚酯、10克甲基丙烯酸乙二醇甲醚酯、63克甲基丙烯酸十二烷基酯、2克γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷和0.1克引发剂AIBN溶入无水乙醇/四氢呋喃(体积比50/50)溶液中，缓慢通入氩气1小时除氧。然后置于70℃恒温水浴中，搅拌下反应24小时。反应完毕后，将溶液冷却至室温，用大量正己烷沉淀提纯2次；在室温下将收集的沉淀物真空干燥24小时。得到含有磷脂基团的共聚物92克。
将1毫升四乙氧基硅烷，0.2毫升水，0.02毫升浓度为0.1毫摩尔/升的盐酸和1毫升乙醇混合均匀，静置3小时后得到硅溶胶。向上述溶胶中加入0.1克二(2，2’-联吡啶)-二氯-二水合钌与菲罗啉咪唑衍生物，搅拌均匀。
取0.9克上述含有磷脂基团的共聚物溶解在15毫升乙醇/四氢呋喃混合溶液中，与上述含有钌络合物的硅溶胶混合均匀，静置2小时，过滤后，将溶液涂布在硅烷化的光纤的端部，在70度烘箱中热处理5小时，将溶剂挥发，即得可用于测定血液或富含蛋白质溶液pH值的抗生物污染光纤传感器。
实施例3：
将20克MPC、8克乙烯基吡咯烷酮、5克甲基丙烯酸β羟基乙酯、67克丙烯酸丁酯和0.1克引发剂AIBN溶入无水乙醇/四氢呋喃(体积比50/50)溶液中，缓慢通入氮气除氧。然后置于75℃恒温水浴中，搅拌下反应24小时。反应完毕后，将溶液冷却至室温，用大量正己烷沉淀提纯2次；在室温下将收集的沉淀物真空干燥24小时。得到含有磷脂基团的共聚物89克。
将1克上述聚合物溶于10毫升四氢呋喃，再加入80毫克全-(2，6-二-O-异丁基)-β-环糊精，20毫克meso-四-(4-甲氧基苯基)卟啉，搅拌溶解均匀后，在洁净的玻璃板上浇铸成膜，空气中干燥后揭下得到厚度约为5微米的透明薄膜。
剪取一小块上述薄膜，用透明的氰基丙烯酸粘合剂粘在光纤的端部，即得具有抗生物污染效能的对二氧化碳敏感的光纤传感器。其对水中[H2CO3]浓度的响应范围约为4×10-7-4×10-5mol/L，并且相应迅速，重现性好。
本说明书中所说明和讨论的实施方案仅仅是用于向本领域的技术人员演示使用本发明的最佳方式。但不能认为是对本发明范围的限定。可以与以上具体描述不同的方式实施本发明。
Claims (6)
1、一种具有抗生物污染效能的电化学发光复合材料，其特征是：由电化学发光物质固定在含有磷脂基团的聚合物中组成，其中，按质量百分比计，电化学发光物质的用量为0.05-50％。
2、根据权利要求1所述的电化学发光复合材料，其特征是：所述电化学发光物质为金属钌络合物、卟啉衍生物、金属锇络合物、金属铅络合物、金属铂和钯络合物、金属铼络合物或过渡金属卟啉络合物之一种或一种以上的混合物，或者是上述物质与硅溶胶的复合物。
3、根据权利要求1所述的电化学发光复合材料，其特征是：所述的含有磷脂基团的聚合物为2-甲基丙烯酰氧乙基-2′-三甲胺乙基磷酸酯·内盐与其他含有可聚合基团的单体的共聚物。
4、根据权利要求3所述的电化学发光复合材料，其特征是：与2-甲基丙烯酰氧乙基-2′-三甲胺乙基磷酸酯·内盐共聚的单体为丙烯酸或甲基丙烯酸烷基酯、丙烯酸或甲基丙烯酸羟基乙酯、丙烯酸或甲基丙烯酸羟基丙酯、丙烯酸或甲基丙烯酸乙二醇酯、丙烯酸或甲基丙烯酸乙二醇甲醚酯、丙烯酸或甲基丙烯酸聚乙二醇酯、丙烯酸或甲基丙烯酸聚乙二醇甲醚酯、乙烯基吡咯烷酮、醋酸乙烯酯、含有双键的硅烷偶联剂中的一种或一种以上。
5、一种根据权利要求1-4所述的具有抗生物污染效能的电化学发光复合材料的制备方法，其特征是在于具体步骤如下：1)将电化学发光物质在相应的溶剂中溶解；2)在上述溶液中加入含有磷脂基团的聚合物溶液，混合均匀；3)将上述混合溶液中的溶剂除去，即得到具有抗生物污染效能的电化学发光复合材料。
6、一种如根据权利要求1-4所述的电化学发光复合材料在制备抗生物污染的生物检测传感器中的应用。
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| EP3471612B1 (en) * | 2016-06-15 | 2023-12-27 | Sorin Group Italia S.r.l. | Devices for monitoring blood |
| WO2019189608A1 (ja) * | 2018-03-30 | 2019-10-03 | 株式会社コーセー | ホスホリルコリン基及びシリコーン基含有共重合体、当該共重合体で被覆された粉体及びその製造方法、並びに当該共重合体及び当該粉体の化粧料への利用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4752115A (en) * | 1985-02-07 | 1988-06-21 | Spectramed, Inc. | Optical sensor for monitoring the partial pressure of oxygen |
| GB9112267D0 (en) * | 1991-06-07 | 1991-07-24 | Biocompatibles Ltd | Polymeric coating |
| US6258371B1 (en) * | 1998-04-03 | 2001-07-10 | Medtronic Inc | Method for making biocompatible medical article |
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2005
- 2005-08-04 US US11/196,305 patent/US20060029979A1/en not_active Abandoned
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193927A (zh) * | 2013-04-27 | 2013-07-10 | 南京构友生物材料有限公司 | 可键合的血液友好聚合物及其制法与用途 |
| CN103193927B (zh) * | 2013-04-27 | 2016-01-20 | 南京构友生物材料有限公司 | 可键合的血液友好聚合物及其制法与用途 |
| CN105542213A (zh) * | 2015-12-08 | 2016-05-04 | 浙江省医疗器械研究所 | 抗胰岛素粘附的基材表面修饰方法 |
| CN105542213B (zh) * | 2015-12-08 | 2019-04-09 | 浙江省医疗器械研究所 | 抗胰岛素粘附的基材表面修饰方法 |
| CN116284548A (zh) * | 2023-05-24 | 2023-06-23 | 广东工业大学 | 一种具有多重自翻转的磷酸胆碱四元共聚物及其制备方法和应用 |
| CN116284548B (zh) * | 2023-05-24 | 2023-08-11 | 广东工业大学 | 一种具有多重自翻转的磷酸胆碱四元共聚物及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006052400A (ja) | 2006-02-23 |
| US20060029979A1 (en) | 2006-02-09 |
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