CN1235185A - 用于荧光熄灭氧传感器的高灵敏度氧敏感发光材料 - Google Patents

用于荧光熄灭氧传感器的高灵敏度氧敏感发光材料 Download PDF

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CN1235185A
CN1235185A CN 98112477 CN98112477A CN1235185A CN 1235185 A CN1235185 A CN 1235185A CN 98112477 CN98112477 CN 98112477 CN 98112477 A CN98112477 A CN 98112477A CN 1235185 A CN1235185 A CN 1235185A
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oxygen
highly sensitive
metal
complex
responsive
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肖丹
蔡明发
王柯敏
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Hunan University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence

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Abstract

本发明公开了一种用于荧光熄灭氧传感器的高灵敏度氧敏感发光材料。它由高灵敏度氧敏感发光物质经常规的固定化技术固定在一定的无机或有机固体材料表面而获得。所述高灵敏度氧敏感发光物质包括金属钌络合物、金属锇络合物、金属铅络合物、金属铂和钯络合物、金属金络合物、金属铼络合物、过渡金属卟啉络合物,所述一定的无机或有机固体材料是指硅胶、离子交换树脂、难溶金属氧化物、陶瓷材料、多孔硅、玻璃以及可以吸附或键合这些物质的有机或无机高聚物。

Description

用于荧光熄灭氧传感器的高灵敏度氧敏感发光材料
本发明涉及光化学氧传感器的氧敏感发光材料，进一步是指用于荧光熄灭氧传感器的高灵敏度氧敏感发光材料。
氧是许多化学反应和化学物质的主要成份，是生命体赖以存在的的基础物质。氧传感器的研究和应用于氧含量及其变化的测定在生物、临床医学、轻工、化工、环境科学等科学研究与工业领域具有重要作用。
氧传感器检测氧的含量和变化通常有克拉克(Clark)型极谱氧传感器、氧化物陶瓷传感器、光化学氧传感器三种类型。其中光化学氧传感器是八十年代中期逐渐发展起来的传感技术，这类传感器在常温常压下可正常工作，根据不同发光材料的特性也可以在极低或较高温度下工作；由于是采用氧作用荧光熄灭的原理来测定氧，不涉及氧的质量消耗，因此与被测样品极易达到平衡。但到目前为止，已有技术的氧敏感发光材料灵敏度均较低，在无氧气体和纯氧中的发光强度信号比(I无氧/Io2)仅10倍左右，因而使其应用受到了限制。
本发明的目的是，研制出高灵敏度氧敏感发光材料，它有高倍数的发光强度信号比，因而采用它做成的氧传感器具有极高的灵敏度，其应用范围因此得到显著拓展。
本发明的技术方案是，用高灵敏度氧敏感发光物质经常规的固定化技术固定在一定的无机或有机固体材料表面而制得高灵敏度氧敏感发光材料，所述高灵敏度氧敏感发光物质包括金属钌络合物〔如Ru(ph)3 2+,Ru(by)3 2+,Ru(dpp)3 2+〕、金属锇络合物、金属铅络合物、金属铂和钯络合物、金属金络合物、金属铼络合物、过渡金属卟啉络合物，所述常规的固定化技术是指相应的吸附、化学键合、化学交联；所述一定的无机或有机固体材料是指硅胶、离子交换树脂、难溶金属氧化物、陶瓷材料、多孔硅、玻璃以及可以吸附或键合这些物质的有机或无机高聚物，且其形状为粉末或颗粒状、或块状。
以下对本发明做出进一步说明：
采用本发明所述的高灵敏度发光材料可制造高灵敏荧光熄灭氧传感器。例如，以硅胶吸附钌化合物〔Ru(dpp)3(p-clph4B)2〕所成的高灵敏度发光材料在无氧状态下发射粉红色荧光，在低浓度氧(如氧气浓度低至0.5％)存在时也会因熄灭作用而使荧光强度显著减弱，变成淡黄色。这一变化可用肉眼观察到。用该发光材料制成的传感器不仅灵敏度高，还具有良好的稳定性和重现性，在纯Ar中所测得的信号和在纯O2中所测得的信号比为120倍以上。作为比较，已有技术至今所采用过的发光材料如PVC膜、Sol-gel膜、硅橡胶膜、Gelatin膜、纤维素膜和沸石上所制成的氧传感器在纯Ar气或纯N2气中的信号和纯O2中所测得的信号比均在4-10之间；采用卟啉化合物作发光物质的Sol-gel敏感材料的信号比也不足30倍。由此表明本发明的高灵敏发光材料制成的氧传感器具有极高的灵敏度。
由附图可知本发明的工作原理及实际应用。
附图说明：图1和图2分别是应用本发明材料制成的隔离型荧光熄灭氧传感器的两种实施例基本结构图，图3和图4分别是应用本发明制成的流通型荧光熄灭氧传感器的两种实施例基本结构，图5是简便高灵敏氧测量仪结构原理图。在图中：
1-高灵敏度氧敏感发光材料       2-光源                   3-光检测器
4-透光材料或透气透光材料       5-固体材料或固体透气材料
6-光敏检测电路                 7-透光材料               8-气体进口
9-气体出口                    10-高灵敏度氧传感器       A-入射光
B-发射光
图1和图2表示了隔离型氧传感器的基本结构，入射光A可以不同的方位或角度射入。发射光B可以通过不同方位或角度收集。气体或液体流经透气膜后，氧经透气膜接触高灵敏发光材料后使得发射的荧光熄灭而减弱。
图3和图4表示了流通型氧传感器的基本结构，入射光A和发射光B可以通过不同的方位和角度射入或发射，气体或液体直接流经高灵敏度发光材料。
图5是采用本发明的高灵敏度发光材料，通过简易的发光和光敏元件制成的简便的便携式高灵敏氧测量仪的结构原理图。
采用本发明所述发光材料制成的氧传感器可以测定大气中的氧压缩体，室内空气、稀薄空气，特殊环境中的氧和特殊气体(如CO2、N2、Ar、H2等气体)中的氧含量。例如，利用本发明做成的氧传感器可以测定氮气、Ar气中低于1ppm(v/v)的氧气。
采用本发明所述的发光材料，可以通过光导纤维传输入射光和发射光，从而完成远距离检测，或制备成微型探头(例如可用于临床人体内实时测量等)。
实施例：
(1)将金属钌络合物〔如Ru(dpp)3(p-clph4B)2〕溶于有机溶剂(如丙酮)中，然后经化学吸附固定到硅胶(粒度可选用100目左右)表面，即可获得硅胶基体高灵敏发光材料。
(2)将金属锇络合物〔Os(dpp)3 2+〕与离子交换树脂(732型聚苯乙烯强酸型树脂)通过离子对键合结合到离子交换树脂上，即获得离子交换树脂基体高灵敏发光材料。
(3)将过渡金属卟啉络合物通过化学取代结合到有机高聚物膜(Polystyrene)或颗粒表面即可获得有机高聚物基高灵敏发光材料。

Claims (2)

1、用于荧光熄灭氧传感器的高灵敏度氧敏感发光材料，其特征是，所述材料用高灵敏度氧敏感发光物质经常规的固定化技术固定在一定的元机或有机固体材料表面而获得，所述高灵敏度氧敏感发光物质包括金属钌络合物、金属锇络合物、金属铅络合物、金属铂和钯络合物、金属金络合物、金属铼络合物、过渡金属卟啉络合物，所述常规的固定化技术是指相应的吸附、化学键合、化学交联；所述一定的无机或有机固体材料是指硅胶、离子交换树脂、难溶金属氧化物、陶瓷材料、多孔硅、玻璃以及可以吸附或键合这些物质的有机或无机高聚物。
2、根据权利要求1所述的高灵敏度氧敏感发光材料，其特征是，所述一定的无机或有机固体材料的形状为粉末或颗粒状、或块状。
CN 98112477 1998-05-12 1998-05-12 用于荧光熄灭氧传感器的高灵敏度氧敏感发光材料 Pending CN1235185A (zh)

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CN 98112477 CN1235185A (zh) 1998-05-12 1998-05-12 用于荧光熄灭氧传感器的高灵敏度氧敏感发光材料
PCT/CN1999/000067 WO1999058960A1 (fr) 1998-05-12 1999-05-11 Materiau luminescent de refroidissement sensible a l'oxygene et a forte sensibilite

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CN 98112477 CN1235185A (zh) 1998-05-12 1998-05-12 用于荧光熄灭氧传感器的高灵敏度氧敏感发光材料

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004029597A1 (en) * 2002-09-30 2004-04-08 The University Of Hong Kong Sensitive single-layer sensing device of covalently attached luminescent indicator on glass surface for measuring the concentration of analytes
CN102516836A (zh) * 2011-12-03 2012-06-27 东南大学 噻吩-共-噁二唑作为氧猝灭物质的应用
CN102888217A (zh) * 2011-07-21 2013-01-23 陈文通 一种卟啉铁荧光材料
CN102947692A (zh) * 2010-06-16 2013-02-27 英派尔科技开发有限公司 使用金属卟啉的氧检测
CN112656399A (zh) * 2021-01-10 2021-04-16 复旦大学 一种用于呼吸实时监控的传感膜及其制备方法

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* Cited by examiner, † Cited by third party
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GB2470757B (en) * 2009-06-04 2013-11-06 Haemaflow Ltd Non invasive gas analysis

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1261717A (en) * 1982-12-23 1989-09-26 John R. Bacon Method and apparatus for oxygen determination
JPS6312942A (ja) * 1986-07-03 1988-01-20 Rikagaku Kenkyusho 酸素濃度測定用素子
JPH01280242A (ja) * 1988-05-06 1989-11-10 Rikagaku Kenkyusho 酸素濃度測定装置及び酸素濃度測定法
ES2061387B1 (es) * 1992-12-30 1995-07-01 Univ Oviedo Sensor optico de oxigeno basado en complejos fosforescentes metal-ferron.

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004029597A1 (en) * 2002-09-30 2004-04-08 The University Of Hong Kong Sensitive single-layer sensing device of covalently attached luminescent indicator on glass surface for measuring the concentration of analytes
CN1701228B (zh) * 2002-09-30 2010-05-26 香港大学 用于测量氧浓度的单层敏感元件和系统
CN102947692A (zh) * 2010-06-16 2013-02-27 英派尔科技开发有限公司 使用金属卟啉的氧检测
CN102947692B (zh) * 2010-06-16 2015-09-09 英派尔科技开发有限公司 使用金属卟啉的氧检测
CN102888217A (zh) * 2011-07-21 2013-01-23 陈文通 一种卟啉铁荧光材料
CN102516836A (zh) * 2011-12-03 2012-06-27 东南大学 噻吩-共-噁二唑作为氧猝灭物质的应用
CN112656399A (zh) * 2021-01-10 2021-04-16 复旦大学 一种用于呼吸实时监控的传感膜及其制备方法

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