Searching for chemiluminescent solid enhancer to peroxalate derived chemiluminescent reagents and the application to analytical chemistry

I.化学发光增敏固体对化学发光试剂的研究在化学发光研究中，我们发现了许多有趣的活性固体，它们增强了化学发光(CL)试剂。已经报道了部分结果。为了扩大增强化学发光强度的材料的可能性，我们尝试使用“溶剂可溶化合物”，尽管只使用了“溶剂不可溶材料”。当使用少量的化学发光试剂时，许多有用的化合物，特别是含碱金属的化合物，被发现使用“溶剂可溶化合物”。结果表明，化合物中Na~+离子越多，同一系列化合物如NaH_2PO_4、Na_2HPO_4和Na_3PO_4的发光强度越高。接下来，我们考察了阴离子物种的影响。对于阴离子组分，发现含官能团的羰基具有较高的化学发光强度增强效应，且…越大分子中阴离子基团的大小越大，强度就越高(待发表)。到目前为止，已经发现了几个关于化学发光强度增强现象的“经验规则”。目前，水杨酸钠(SS)被认为是给出最高强度增强效果的最佳催化剂。我们关于化学发光强度的“经验规则”告诉我们，这些规则的组合将产生比SS更高的强度效应。按照规则合成了预期的化合物。IR、DTA-TG和MS测试结果表明该化合物为目标化合物。使用该化合物重复测量了化学发光强度。利用上述结果，测定了微量(或低浓度)过氧化氢(H_2O_2)。在本工作中，将恒量的CL试剂和不同浓度的过氧化氢(氧化剂)混合，用光功率计(或CL探测器：Lumicounter)测量得到的化学发光强度。通过绘制发光强度与H_2O_2浓度(或摩尔量)的对数对数图，得到校正曲线。获得了满意的校正曲线。不同的溶剂种类、滴样体积和固体介质不同。在溶剂中，乙醇和乙腈表现出较高的强度。灭活固体介质(玻璃板)的最低检出限为1.4×10~(-9)~(-9)mol。而优良的活性固体介质则使其强度提高了100倍。样本量从100μL减少到2μL(100μL→20μL→2μL)。然而，对数-对数标绘的斜率没有改变。使用Lumicounter显示的灵敏度是光功率计的106倍。较少

I.Searching for chemiluminescent enhancing solid to chemiluminescent reagentsWe have found many interesting activated solids that enhance chemiluminescent(CL) reagents during chemiluminescence studies. Parts of the results have been reported. To extend the possibility of materials for enhancing the chemiluminescent intensity, we have tried to use "solvent-soluble compounds", although only "solvent-insoluble materials" had been used. Many useful compounds, especially alkaline metal containing compounds, have been found using "solvent-soluble compounds" when small amount of chemiluminescent reagents were used. We have shown that the more Na^+ ion in the compounds, the higher the luminescent intensities in the same series of compounds such as NaH2PO4,Na2HPO4, and Na3PO4. Next, effects of anionic species have been examined. As for anionic components, it was found that carbonyl group contaning functional group shows the higher chemiluminescence intensity enhancement effects, and the larger … More the size of anionic group in the molecule, the higher the intensity(to be published). Until now, several "empirical rules" for chemiluminescence intensity enhancement phenomena have been found. At the present, sodium salicylate(SS) is thought to be the best catalyst for giving the highest intensity enhancement effects. Our "empirical rules" around chemiluminescent intensity teach us that the combination of those rules will give the higher intensity effect than that of SS. According to the rules, the expected compounds was synthesized. Results of IR, DTA-TG, and MS measurements showed the evidence of the desired compound. Using this compound chemiluminescent intensities were measured repeatedly. The obtained intensity for the compound was 3 times as high as that of SS.II.Application to analysis by use of activated solid enhancer for chemiluminescent reagentsUsing above results, small amounts of (or low concentrations of) hydrogen peroxide(H2O2) were determined. In the present work, constant quantity of CL reagent and varied concentraion of H2O2(oxydizing agent) was mixed and resulting chemiluminescent intensities were measured using a light-power meter (or CL detector : Lumicounter). Calibration curves were obtained by log-log plotting of luminescent intensity vs.H2O2 concentration (or molar quantity). Satisfactory calibration curves were obtained. Kinds of solvents, volumetric amout of dropped samples and solid media were varied. Among solvents, EtOH, and MeCN(acetonitrile) showed the higher intensities. Inactivated solid medium(glass plate) gave the lowest detection limit of 1.4×10^<-9> mol. While, excellent activated solid media gave the ca., 100 times higher intensities. Sample quantities were reduced from 100μL to 2μL (100μL→20μL→2μL). However, slopes of log-log plotting did not change. Use of the Lumicounter showed the 10^6 times of sensitivity than that of the light power meter. Less