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，含有大约10 ppb(10^lt；-8 g/g)的硼。这些浓度水平可以通过我们报告的方法来确定。然而，在半导体领域，它被要求在10ppt(10^lt；-12g/g)的水平。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。在pH为6.0的水介质中，通过荧光检测/流动注射分析，确定了变色酸与硼酸的络合物。通过测量荧光强度(λ_&lt；ex&gt；=313 nm，λ_<em>=360 nm)来检测该络合物。采用EDTA作为缓冲成分，对金属离子起掩蔽剂的作用。变色酸与0.1M氨水形成络合物后，背景荧光减弱，基线稳定。校正曲线的线性范围为10×10~(-9)~10~(-6)~(-3)，检出限为5×10~(-9)~10~(-5)M(S/N=3)。重现性为3.61%(n=10，峰高)，样品通过量为40h。在河水、离子交换水和蒸馏水中的应用无需任何前处理。对于超纯水的分析，由于浓度在LOD以下，没有可作为载体溶液或试剂溶液制备的参照水，因此采用蒸发/预富集的方法进行分析。其次，我合成了几种带有二(甲苯-4-磺酰氨基)或二(三氟甲磺酰氨基)基团的新型荧光试剂。这些试剂可以与硼发生反应。

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.