CN1069409C - 金属离子传感器的制备 - Google Patents

金属离子传感器的制备 Download PDF

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CN1069409C
CN1069409C CN 96114793 CN96114793A CN1069409C CN 1069409 C CN1069409 C CN 1069409C CN 96114793 CN96114793 CN 96114793 CN 96114793 A CN96114793 A CN 96114793A CN 1069409 C CN1069409 C CN 1069409C
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metal ion
ion sensor
phospholipid
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CN1186237A (zh
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李景虹
董绍俊
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Changchun Institute of Applied Chemistry of CAS
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    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
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    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract

本发明属于金属离子传感器的制备方法。该方法用LB成膜技术将0.1~1mg/ml磷脂沉积在烷基硫醇自组装单分子层修饰金电极上,再将修饰了的磷脂分子的膜电极放入含菌素的溶液中浸泡5~20小时,清洗后,制得对Li、Na、Cs、K、Rb、Mg、Ca离子具有能斯特响应的金属离子传感器。它具有生物体相容性好、响应快、尺寸小、动态范围宽和稳定性好的优点。能斯特响应斜率接近60mv,检测范围一般为10-7M~1M,寿命超过2个月。

Description

金属离子传感器的制备
本发明属于金属离子传感器的制备方法。
金属离子的检测在环境监测、金属工业、食品检测、临床化验、医药分析等关系国计民生的领域中具有突出的重要地位,与人民的生活息息相关。因此,多年来金属离子传感器的研制一直是人们研究的主要课题,开发出许多金属离子传感器,特别是离子选择性电极已广泛地应用于工业生产和临床医学。但传统的离子选择性电极仍然存在没法克服的缺点,比如选择性差、记忆效应严重和生物相容性差等缺点,他们严重地制约了其在生命科学中的应用。
本发明的目的是将磷脂沉积在硫醇自组装单分子层修饰电极上,再在磷脂膜中嵌入天然的或人工合成的菌素,制备生物相容性好和稳定性好的金属离子传感器。
本发明将经化学和电化学清洗处理和干燥过的金电极在含碳链长为10~20的烷基硫醇的有机溶液,包括乙醇、甲醇、丙酮、四氢呋喃、二甲基甲酰胺、二甲基乙酰胺和己烷,中浸人1分钟至2天后,形成烷基硫醇单分子膜修饰电极,再用无水乙醇和高纯水反复清洗和氮气干燥,将0.1~1.0mg/ml磷脂,包括磷脂酰胆碱、油酸卵磷脂、二月桂酰胆碱、二棕榈酰胆碱、磷脂酰乙醇胺、磷脂酰丝氨酸、磷脂酰肌醇的氯仿和甲醇混合溶液铺展在KSV5000型LB拉膜仪水相上,保持静止10~40分钟,再以5~25mm/s速度滑动滑障,当磷脂单分子层的表面压压缩到40mN/m时,滑障停止滑动并保持静止,将上述修饰电极从气相透过磷脂单分子层进入水溶液中,用吸管将水相表面上多余的磷脂吸掉,然后将此修饰了磷脂分子的电极浸入含霉素,包括尼日利亚素、短杆菌肽和莫能菌素的溶液中浸泡5~20小时,清洗后制得对某种金属离子具有能斯特响应的生物传感器。当底物溶液中的离子和菌素相互作用时,可能发生一些电参数,如电位、电流、电阻等的变化,产生一个可检测到的转换的信号。
本发明中的离子传感器是从内部放大过程提高检测的灵敏度,有很好的生物体相容性、响应快、尺寸小、动态范围宽和稳定性好等优点。这些离子传感器对金属离子的能斯特响应斜率接近于60mV,检测范围一般为10-7M~1M,寿命超过2个月。在医药和临床等生命科学方面应用比传统的离子选择性电极有更大的优越性。
本发明提供的实施例如下:
实施例1。制备含有缬氨霉素的K+传感器。
首先将化学和电化学清洗处理和在高纯氮气氛下干燥的金电极浸入2mM十六烷基硫醇的丙酮溶液,24小时后取出,用无水乙醇和高纯水反复清洗多次和高纯氮气干燥,将浓度为0.625mg/mL磷脂酰胆碱的体积比为4∶1的氯仿和甲醇混合溶液铺展在KSV5000型拉膜仪的水槽中二次蒸馏水水相的液面上,保持静止15分钟,待有机溶剂挥发完全后,以10mm/s速度滑动滑障,磷脂酰胆碱单分子层的表面压压缩到40mN/m时,滑障停止滑动并保持静止。再以垂直提拉法将上述修饰电极从气相透过磷脂单分子层进入水溶液中,过程中由计算机保持表面压和滑障系统处于恒定状态,偏差≤±0.01mN/m,当电极浸入溶液后,用吸管将水相表面上多余的磷脂酰胆碱吸掉,再将修饰好的磷脂酰胆碱膜电极放入含10-3M NaCl和10-6M缬氨霉素的溶液中浸泡6小时以上,清洗后即获得功能化的支撑磷脂酰胆碱膜生物传感器。它对金属离子响应顺序如下:Li+<Na+<Cs+<K+<Rb+,对K+的能斯特响应斜率接近于60mV,K+对Na+、Li+、Ca2+和Mg2+的选择性系数分别为10-4、10-4、2×10-5和3×10-5。K+检测线性范围从10-5M到10-1M,检测下限为10-6M。在-10℃下的寿命超过2个月。
实施例2。制备含有莫能菌素的Na+传感器。
将经化学和电化学清洗处理和氮气干燥过的金电极浸入1.5mM十四烷基硫醇的乙醇溶液,20小时后取出,用无水乙醇和高纯水反复清洗多次和高纯氮气干燥,将浓度为0.75mg/ml月桂酰胆碱的体积比为3∶1的氯仿和甲醇混合溶液铺展在KSV5000型拉膜仪的水槽中二次蒸馏水水相的液面上,保持静止20分钟,再以12mm/s速度滑动滑障,当二月桂酰胆碱单分子层的表面压为45mN/m时,滑障停止滑动并保持静止,通过垂直提拉法将上述修饰电极从气相透过磷脂单分子层进入水溶液中,电极浸入溶液后,用吸管将水相表面上多余二月桂酰胆碱吸掉,再将修饰好的二月桂酰胆碱膜电极放入含10-3M NaCl和10-6M莫能菌素的溶液中浸泡10小时,即制备成Na+传感器。该传感器对Na+的能斯特响应斜率为60mV,检测线性范围从10-1M到10-5M,检测下限为2×10-6M。Na+对K+、Rb+和Ag+的选择系数分别为2×10-2,6×10-3和32,经过连续测量,没有发现记忆效应的存在,与离子选择性电极相比生物相容性得到明显提高。此传感器在,-10℃下贮存二个月后,性能没有发生变化。

Claims (1)

1.一种金属离子传感器的制备方法,其特征在于将化学和电化学清洗处理和干燥过的金电极浸入在含碳链长为10~20的烷基硫醇的乙醇或丙酮溶液中1分钟至2天后,用无水乙醇和高纯水反复清洗和氮气干燥,将0.1~1.0mg/mL磷脂,包括磷脂酰胆碱和二月桂酰胆碱的氯仿和甲醇体积比为4~3∶1的混合溶液铺展在KSV5000型LB拉膜仪的水槽中二次蒸馏水水相液面上,保持静止10~40分钟,再以5~25mm/s速度滑动滑障,当磷脂单分子层的表面压压缩到40mN/m时,停止滑动滑障并保持静止,将上述修饰电极从气相透过磷脂单分子层进入水溶液中,用吸管将水相表面上多余的磷脂吸掉,接下来,将磷脂膜修饰电极放入含有10-3M NaCl和10-6M缬氨霉素或10-3M NaCl和10-6M莫能菌素的溶液中浸泡5~20小时,清洗后制得对Li+、Na+、Cs+、K+、Rb+、Mg、Ca金属离子具有能斯特线性响应的生物传感器。
CN 96114793 1996-12-26 1996-12-26 金属离子传感器的制备 Expired - Fee Related CN1069409C (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100522244C (zh) * 1995-06-07 2009-08-05 杜雷克特公司 高粘度液体受控输送体系
CN101713770B (zh) * 2008-10-06 2013-03-20 索尼株式会社 用于硫醇分析物的传感器

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102495038B (zh) * 2011-12-09 2013-06-12 南京大学 一种用于检测金属离子的光学离子传感膜及其制备方法与应用
CN102539507B (zh) * 2011-12-19 2013-12-25 北京农业智能装备技术研究中心 利用微观动态离子流技术检测水稻氮素营养的方法及其应用

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100522244C (zh) * 1995-06-07 2009-08-05 杜雷克特公司 高粘度液体受控输送体系
CN101713770B (zh) * 2008-10-06 2013-03-20 索尼株式会社 用于硫醇分析物的传感器

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