Development of a novel decay odor sensor which is working at normal temperature on the basis of electrochemiluminescence

1. 水溶液中的基本检查。(1)小型化细胞的制备：以三（联吡啶）钌（II）配合物为发光材料制备细胞。对氨基酸和肽的电化学发光（ECL）测定表明，脯氨酸和含有n端脯氨酸残基的肽具有较强的响应。该细胞的使用使我们能够测定浓度范围为10^-6 m的仲胺或叔胺的分析物。(2)具有蛋白质修饰电极的流动检测器的制备：具有溶菌酶修饰的Au电极的检测器对脯氨酸具有高选择性，该检测器适用于脯氨酸传感器。腐味传感器的制备。(1)测量条件；将三（联吡啶）钌络合物、有机电解质、碳酸丙烯酯和阴离子聚合物Nafion混合制备了一种电解聚合物凝胶。流动式气体传感器配有铂网工作电极、铂板反电极和银丝参比电极；凝胶被包裹在工作电极和反电极之间。脉冲电解（El, +1.2V vs Ag; E2, +0.2V； El和E2的间隔时间，每0.1 Hz），传感器对三甲胺气体反应强烈，工作稳定。稳定性可能是由于比直接电解更小的热演化。在10 ~ 310 ppb的浓度范围内建立了线性校准曲线，低检出限为3 ppb (S/N = 3)；其敏感性优于人类的嗅觉。(2)实际样品应用；海产品样品在袋中放置30分钟，通过传感器监测袋中气体的释放情况。鱿鱼的ECL响应曲线与K值的响应曲线吻合较好，说明该传感器也适用于新鲜度传感器。

1. Basic examination in aqueous solution.(1) Preparation of miniaturized cell: The cell was made where tris (bipyridine)ruthenium(II) complex was used as a luminescent. The electrochemiluminescence (ECL) measurement of amino acids and peptides showed that proline and peptides having an N-terminal proline residue gave strong responses. The use of the cell allowed us to determine analytes with a secondary or tertiary amine in the concentration range of 10^-6 M.(2) Preparation of the flow-through detector having protein-modified electrodes : The detector having a lysozyme-modified Au electrode showed the high selectivity for proline and the detector was applicable to a proline sensor.2. Preparation of decay-odor sensor.(1) Measurement conditions ; An electrolytic polymer gel was prepared by mixing tris(bipyridne) ruthenium complex, organic electrolyte, propylene carbonate, and an anionic polymer Nafion. A flow-through gas sensor was equipped with a Pt gauze working electrode, a Pt plate counter electrode, and a Ag wire reference electrode ; the gel was packed between the working and counter electrodes. The sensor strongly responded to trimethylamine gas and the stable work was attained with pulse electrolysis (El, +1.2V vs. Ag ; E2, +0.2V ; interval times of El and E2, each 0.1 Hz). The stability may be due to smaller heat evolution than that at direct electrolysis. A linear calibration curve was obtained in the concentration range from 10 to 310 ppb with low detection limit of 3 ppb (S/N = 3) ; the sensitivity was superior to that of the sense of smell in human.(2) Application to practical samples ; Seafood samples were allowed to stand in bags for 30 min and the gas evolved in bag was monitored by our sensor. The ECL response profile for squid was in good accordance with that obtained by the K value, showing that the sensor is also applicable to freshness sensor.