CN1069409C - Preparation of metal ion sensor - Google Patents

Preparation of metal ion sensor Download PDF

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Publication number
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
preparation
solution
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CN1186237A (en
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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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Changchun Institute of Applied Chemistry of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors

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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。The invention belongs to a preparation method of a metal ion sensor. In this method, 0.1-1mg/ml phospholipids are deposited on the gold electrode modified by alkylthiol self-assembled monolayer by LB film forming technology, and then the membrane electrode of the modified phospholipid molecules is put into the solution containing bacteriocin and soaked for 5 ~20 hours, after cleaning, a metal ion sensor with Nernstian response to Li, Na, Cs, K, Rb, Mg, Ca ions was prepared. It has the advantages of good biocompatibility, fast response, small size, wide dynamic range and good stability. The Nernst response slope is close to 60mv, the detection range is generally 10 -7 M ~ 1M, and the life span is more than 2 months.

Description

The preparation of metal ion sensor
The invention belongs to the preparation method of metal ion sensor.
The detection of metallic ion has outstanding critical role in the field that environmental monitoring, metal industry, food inspection, clinical assay, medicine analysis etc. involve the interests of the state and the people, closely bound up with the people's life.Therefore, the development of metal ion sensor for many years is the major subjects that people study always, develops many metal ion sensors, particularly ion-selective electrode and has been widely used in commercial production and clinical medicine.But still there is the shortcoming that cannot overcome in traditional ion-selective electrode, the shortcoming such as serious and biocompatibility difference such as poor selectivity, memory effect, and they have seriously restricted its application in life science.
The objective of the invention is phosphatidosis on mercaptan self assembled monolayer modified electrode, in immobilized artificial membrane, embed rhzomorph natural or synthetic, the metal ion sensor of preparation good biocompatibility and good stability again.
The present invention will contain the organic solution that carbon chain length is 10～20 alkyl sulfhydryl through the gold electrode of chemistry and galvanochemistry cleaning treatment and dry mistake, comprise ethanol, methyl alcohol, acetone, tetrahydrofuran, dimethyl formamide, dimethyl acetamide and hexane, in soak the people after 1 minute to 2 days, form alkyl sulfhydryl unimolecular film modified electrode, clean repeatedly and nitrogen drying with absolute ethyl alcohol and high purity water again, with 0.1～1.0mg/ml phosphatide, comprise phosphatid ylcholine, oleic acid lecithin, two bay phatidylcholines, two palmityl choline, phosphatidyl-ethanolamine, phosphatidylserine, the chloroform of phosphatidylinositols and methyl alcohol mixed solution spread on the KSV5000 type LB membrane instrument water, kept static 10～40 minutes, slide sliding the barrier with 5～25mm/s speed again, when the surface pressure of phosphatide unimolecular layer is compressed to 40mN/m, sliding barrier stops to slide and keeping static, above-mentioned modified electrode is seen through the phosphatide unimolecular layer from gas phase to be entered the aqueous solution, with suction pipe phosphatide unnecessary on the water surface is sopped up, the electrode of then this having been modified phospholipid molecule immerses and contains mycin, comprise Nigeria's element, soaked in the solution of gramicidins and coban 5～20 hours, and made the biology sensor that certain metal ion species is had this special response of energy after the cleaning.When the ion in the substrate solution and rhzomorph interact, some electrical quantitys may take place, as the variation of current potential, electric current, resistance etc., produce one can detected conversion signal.
Ion transducer among the present invention is the sensitivity that improve to detect of amplification process internally, good biocompatible is arranged, advantages such as response is fast, size is little, wide dynamic range and good stability.These ion transducers approach 60mV to this special response slope of energy of metallic ion, and sensing range is generally 10 -7M～1M, the life-span period of greater than two months.Than traditional ion-selective electrode bigger superiority is arranged in application aspect medicine and the life science such as clinical.
Embodiment provided by the invention is as follows:
Embodiment 1.Preparation contains the K of valinomycins +Sensor.
At first with chemistry and galvanochemistry cleaning treatment and under the high pure nitrogen atmosphere acetone soln of dry gold electrode immersion 2mM hexadecyl mercaptan, take out after 24 hours, clean repeatedly repeatedly and the high pure nitrogen drying with absolute ethyl alcohol and high purity water, with concentration be the volume ratio of 0.625mg/mL phosphatid ylcholine be 4: 1 chloroform and methyl alcohol mixed solution spread over KSV5000 type membrane instrument tank on the liquid level of redistilled water water, kept static 15 minutes, after treating organic solvent volatilization fully, slide sliding the barrier with 10mm/s speed, when the surface pressure of phosphatid ylcholine unimolecular layer was compressed to 40mN/m, sliding barrier stopped to slide and keeping static.With vertical czochralski method above-mentioned modified electrode being seen through the phosphatide unimolecular layer from gas phase again enters the aqueous solution, keep surface pressure and slide the barrier system being in steady state by computing machine in the process, deviation≤± 0.01mN/m, after electrode immerses solution, with suction pipe phosphatid ylcholine unnecessary on the water surface is sopped up, will modify good phosphatid ylcholine membrane electrode again and put into and contain 10 -3M NaCl and 10 -6Soak more than 6 hours in the solution of M valinomycins, promptly obtain the support phosphatid ylcholine film biology sensor of functionalization after the cleaning.It is as follows to metallic ion response order: Li +＜Na +＜Cs +＜K +＜Rb +, to K +This special response slope of energy approach 60mV, K +To Na +, Li +, Ca 2+And Mg 2+Selectivity factor be respectively 10 -4, 10 -4, 2 * 10 -5With 3 * 10 -5K +Detect the range of linearity from 10 -5M to 10 -1M is limited to 10 under detecting -6M.Life-span period of greater than two months under-10 ℃.
Embodiment 2.Preparation contains the Na of coban +Sensor.
The ethanolic solution of the gold electrode immersion 1.5mM tetradecyl mercaptan that will cross through chemistry and galvanochemistry cleaning treatment and nitrogen drying, take out after 20 hours, clean repeatedly repeatedly and the high pure nitrogen drying with absolute ethyl alcohol and high purity water, with concentration be the volume ratio of 0.75mg/ml lauroyl choline be 3: 1 chloroform and methyl alcohol mixed solution spread over KSV5000 type membrane instrument tank on the liquid level of redistilled water water, kept static 20 minutes, slide sliding the barrier with 12mm/s speed again, when the surface pressure of two bay phatidylcholine unimolecular layers is 45mN/m, sliding barrier stops to slide and keeping static, by vertical czochralski method above-mentioned modified electrode being seen through the phosphatide unimolecular layer from gas phase enters the aqueous solution, after electrode immerses solution, with suction pipe unnecessary two bay phatidylcholines on the water surface are sopped up, will modify two good bay phatidylcholine membrane electrodes again and put into and contain 10 -3M NaCl and 10 -6Soaked 10 hours in the solution of M coban, promptly be prepared into Na +Sensor.This sensor is to Na +This special response slope of energy be 60mV, detect the range of linearity from 10 -1M to 10 -5M is limited to 2 * 10 under detecting -6M.Na +To K +, Rb +And Ag +The selection coefficient be respectively 2 * 10 -2, 6 * 10 -3With 32, through continuous coverage, do not find the existence of memory effect, compare biocompatibility with ion-selective electrode and be improved significantly.This sensor exists, and stores after two months down for-10 ℃, and performance does not change.

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。1. A preparation method of a metal ion sensor, characterized in that chemical and electrochemical cleaning processes and dried gold electrodes are immersed in ethanol or acetone solutions containing carbon chain lengths of 10 to 20 alkyl mercaptans for 1 minute After 2 days, wash repeatedly with absolute ethanol and high-purity water and dry with nitrogen gas, mix 0.1-1.0 mg/mL phospholipids, including phosphatidylcholine and dilauroylcholine in a volume ratio of 4-3:1 in chloroform and methanol Spread the solution on the liquid surface of the double distilled water in the water tank of the KSV5000 LB film stretcher, keep it still for 10 to 40 minutes, and then slide the barrier at a speed of 5 to 25 mm/s. When the surface pressure of the phospholipid monolayer is compressed to At 40mN/m, stop sliding the barrier and keep it still, put the above-mentioned modified electrode from the gas phase through the phospholipid monolayer into the aqueous solution, use a straw to suck off the excess phospholipid on the surface of the aqueous phase, and then, the phospholipid membrane modified electrode Soak in a solution containing 10 -3 M NaCl and 10 -6 M valinomycin or 10 -3 M NaCl and 10 -6 M monensin for 5 to 20 hours. + , Cs + , K + , Rb + , Mg, Ca metal ions have a biosensor with Nernst linear response.
CN 96114793 1996-12-26 1996-12-26 Preparation of metal ion sensor Expired - Fee Related CN1069409C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100522244C (en) * 1995-06-07 2009-08-05 杜雷克特公司 High viscosity liquid controlled delivery system
CN101713770B (en) * 2008-10-06 2013-03-20 索尼株式会社 A sensor for thiol analytes

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102495038B (en) * 2011-12-09 2013-06-12 南京大学 Optical ion sensing film for detecting metal ions, and preparation method and application thereof
CN102539507B (en) * 2011-12-19 2013-12-25 北京农业智能装备技术研究中心 Method for evaluating nitrogen nutrition of paddy by micro dynamic ion flux technique and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100522244C (en) * 1995-06-07 2009-08-05 杜雷克特公司 High viscosity liquid controlled delivery system
CN101713770B (en) * 2008-10-06 2013-03-20 索尼株式会社 A sensor for thiol analytes

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