Optical oxygen sensors based on platinum porphyrin dyes encapsulated in ORMOSILS
Optical oxygen sensors based on platinum porphyrin dyes encapsulated in ORMOSILS
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DOI：
10.1016/j.snb.2010.04.020
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发表时间：
2010-06-03
影响因子：
8.4
通讯作者：
Nogami, Masayuki
中科院分区：
文献类型：
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作者：
Tripathi, Vijay S.;Lakshminarayana, G.;Nogami, Masayuki
提出了一种开发“理想”传感器平台的战略方法。开发了具有100倍可调灵敏度(I-N_2/I-O_2从3到300以上)、反向和快速响应(1 S)、线性校准和长期稳定性的新型猝灭测量O_2传感材料。这些材料是旋转浇注的有机硅酸盐(ORMOSILs)复合干凝胶薄膜，与发光体铂(II)八乙基卟啉(PtOEP)和铂(II)中位四(N-甲基-4-吡啶)四苯基卟啉(PtTMP)隔离。所研究的复合干凝胶为五氟苯丙基三甲氧基硅烷(PFTMOS)/正丙基三甲氧基硅烷(C8TMOS)/四甲氧基硅烷(TMOS)和3，3，3-三氟丙基三甲氧基硅烷(TFTMOS)/正丙基三甲氧基硅烷(C3TMOS)。发光光谱(稳态和时间分辨)已被用来研究它们对气体O2传感的分析优值系数，并确定观察到的性能的根本原因。结果表明，除了PtTMP掺杂的PFTMOS/C8TMOS/TMOS外，其余的干凝胶复合材料均表现出线性的Stern-Volmer关系和单次指数的时间分辨强度衰减，表明发光体的环境是均匀的。对于PtTMP掺杂的PFTMOS/C8TMOS/TMOS干凝胶，Stern-Volmer曲线是非线性的，时间分辨的强度衰减曲线最好地符合双指数衰减模型，这是由于发光体的非均匀环境造成的。可以通过调整干凝胶组成和发光团来调节敏感材料的灵敏度。对于PtOEP掺杂的PFTMOS/C8TMOS/TMOS，当C8TMOS和TMOS的摩尔比保持不变时，当PFTMOS%从0增加到30%时，灵敏度(I-N_2/I-O_2)从333降到246，这是由于双分子猝灭常数(Kg)减小所致。而在PtTMP掺杂的PFTMOS/C8TMOS/TMOS中，I-N_2/I-O_2=3。对于PtTMP掺杂的TFTMOS/C3TMOS，灵敏度随TFT-MOS%从0增加到50%而增加，随着TFTMOS%从50%增加到100%而降低，这主要是由于k(Q)的相应增加和减少所致。在10PFTMOS/45C8TM05/45C8TMOS，I-N_2/I-O_2=330的条件下，得到了具有较高灵敏度的优化配方。(C)2010爱思唯尔B.V.保留所有权利。
A strategic approach to develop an "ideal" sensor platform is addressed. Novel quenchometric O-2 sensing materials with 100-fold adjustable sensitivity (I-N2/I-O2 from 3 to over 300), reverse and fast response (1 s), linear calibration, and long-term stability are developed. These materials are spin-casted composite ORMOSILs (organically modified silicates) xerogel films sequestered with luminophore Pt(II) octaethylporphine (PtOEP) and Pt(II) meso-tetra(N-methyl-4-pyridyl)porphyrin tetrachloride (PtTMP). The composite xerogels studied are pentafluorophenylpropyltrimethoxysilane (PFTMOS)/noctyltrimethoxysilane (C8TMOS)/tetramethoxysilane (TMOS) and 3,3,3-trifluoropropyltrimethoxysilane (TFTMOS)/n-propyltrimethoxysilane (C3TMOS). Luminescence spectroscopy (steady state and time resolved) have been used to investigate their analytical figures of merit for gaseous 02 sensing and to determine the underlying reasons for the observed performance. Results show that, except for PtTMP-doped PFTMOS/C8TMOS/TMOS, all other xerogel composites show linear Stern-Volmer relationship and the single exponential time-resolved intensity decay, which indicate the homogeneous environment of the luminophore. For PtTMP-doped PFTMOS/C8TMOS/TMOS xerogels, the Stern-Volmer plots are non-linear and the time-resolved intensity decay profiles are best fitted by double exponential decay model, which are resulted from the heterogeneous environment of the luminophore. The sensitivity of the sensing materials can be tuned by adjusting the xerogel composition and luminophore. For PtOEP-doped PFTMOS/C8TMOS/TmOS, while keeping C8TMOS and TMOS at the same mol ratio, sensitivity (I-N2/I-O2) decreases from 333 to 246 with increased PFTMOS% from 0 to 30%, which is due to the decreased bimolecular quenching constant (kg). However, I-N2/I-O2 = 3 was observed from PtTMP-doped PFTMOS/C8TMOS/TMOS. For PtTMP-doped TFTMOS/C3TMOS, sensitivity increases with increased TFT-MOS% from 0 to 50% and decreases with further increased TFTMOS% from 50 to 100%, which is mainly due to corresponding increase and decrease of k(q). An optimized composition with high sensitivity is observed at 10 PFTMOS/45C8TM05/45 C8TMOS with I-N2/I-O2 = 330. (C) 2010 Elsevier B.V. All rights reserved.