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

一、寻找化学发光增强固体对化学发光试剂的增强作用在化学发光研究中，我们发现了许多有趣的增强化学发光（CL）试剂的活化固体。部分结果已报告。为了扩展材料用于增强荧光强度的可能性，我们已经尝试使用“溶剂可溶性化合物”，尽管仅使用了“溶剂不溶性材料”。当使用少量荧光试剂时，已经发现许多有用的化合物，特别是含碱金属的化合物使用“溶剂可溶性化合物”。我们已经证明，在NaH 2 PO 4、Na 2 HPO 4和Na 3 PO 4等同一系列化合物中，Na^+离子越多，发光强度越高。接下来，已经检查了阴离子物种的影响。对于阴离子组分，含羰基官能团的化学发光增强效果更强， ...更多信息 分子中阴离子基团的大小，强度越高（待发表）。迄今为止，化学发光强度增强现象的“经验规则”已被发现，水杨酸钠（SS）被认为是最能产生最强增强效应的催化剂。我们的“经验规则”周围的发光强度告诉我们，这些规则的组合将给出更高的强度效果比SS。按照设计原则合成了预期的化合物。IR、DTA-TG和MS分析结果证实了目标化合物的存在。使用该化合物，重复测量荧光强度。Ⅱ.活化固体荧光增强剂在分析中的应用利用上述结果，测定了少量（或低浓度）过氧化氢（H_2O_2）。本工作中，将恒定量的CL试剂和不同浓度的H_2O_2（氧化剂）混合，并用光功率计（或CL检测器：Lumicounter）测量所产生的荧光强度。通过发光强度与H2 O2浓度（或摩尔量）的对数-对数作图获得校准曲线。获得了满意的校准曲线。溶剂种类、滴样量和固体介质不同。在溶剂中，EtOH和MeCN（乙腈）显示出较高的强度。在灭活的固体介质（玻璃板）中，最低检测限为1.4×10 ~（-1）<-9>mol.而优良的活化固体培养基，100倍的强度。样品量从100μL减少至2μL（100μL→20μL→2μL）。然而，双对数曲线的斜率没有变化。使用光度计的灵敏度是光功率计的10^6倍。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