Establishment of a simple and sensitive method for the determination of trace amounts of boron in environmental waters and development of novel spectrofluorometric reagents

环境水，如河水和自来水含有约10 ppb （10^<-8> g/g）的硼。这些浓度水平可以用我们报道的方法来确定。然而，在半导体领域，它需要在10 ppt （10^<-12> g/g）水平。在这次调查中，我可以改进以前的方法来确定这些非常低的浓度水平。采用荧光检测/流动注射分析法，在pH为6.0的水溶液中测定硼作为硼酸与显色酸的配合物。通过荧光强度测定（λ <ex>=313 nm, λ <em>=360 nm）对配合物进行检测。EDTA作为缓冲组分，对金属离子具有掩蔽剂的作用。在络合物形成后，与0.1 M氨水混合，使嗜色酸的背景荧光降低，基线稳定。标定曲线在10^<-9> ~ 10^<-6> mol dm^<-3>范围内呈直线关系，检出限为5 × 10^<-10> M （S/N=3）。在硼浓度为6 × 10^<-9> M时，重现性为3.61% （n=10，峰高），样品通量为40 h^<-1>。适用于河水、离子交换水和蒸馏水，无需任何预处理。对于超纯水的分析，由于浓度在LOD以下，且没有可用于载体溶液或试剂溶液制备的参比水，因此采用蒸发/预浓缩程序。接下来，我用萘二磺酸引入二（甲苯-4-磺酰氨基）基团或二（三氟甲烷磺酰氨基）基团合成了几种新型荧光试剂。这些试剂能与硼反应。

Environmental waters, such as river water, and tap water are contained about 10 ppb (10^<-8> g/g) of boron. These concentration level can be determined by our reported method. However, in the field of semi-conductor it is required at 10 ppt (10^<-12> g/g) level. In this investigation, I could improved previous method to determine these very low concentration level. Boron as boric acid was determined as a complex with chromotropic acid at pH 6.0 in an aqueous medium by fluorescence detection/ flow injection analysis. The complex was detected by measuring fluorescence intensities( λ_<ex>=313 nm, λ_<em>=360 nm). EDTA was used for buffer component with a role of masking agent to metal ions. Background fluorescence of chromo-tropic acid was decreased by mixing with 0.1 M ammonia water after the complex formation, resulting in stable baseline. The calibration graph was rectilinear from 10^<-9> 〜 10^<-6> mol dm^<-3> and the detection limit was 5x10^<-10> M (S/N=3). The reproducibility was 3.61% (n=10, with peak height) at 6x10^<-9> M of boron and sample throughput was 40 h^<-1>. Application to river water, ion exchanged water and distilled water could be done without any pretreatments. For analysis of ultrapurified water, evaporation / preconcentration procedure was carried out, because the concentration was under the LOD and no reference water which could be used for carrier solution or preparation of the reagent solutions.Next, I synthesized few novel fluorescence reagents with naphthalenedisulfonic acid introduced di-(toluene-4-sulfonyl-amino) group or di-(trifluoromethanesulfonylamino) group. These reagents could react with boron.