目的：建立共振瑞利散射法测定大黄素的含量。方法：在p H 7.3的B-R缓冲溶液中,铁（Ⅱ）与1,10-邻菲啰啉形成稳定的1∶3的配合物,再与大黄素（EMO）结合形成1∶2的离子缔合物。铁（Ⅱ）-1,10-邻菲啰啉溶液：称取0.278 0 g Fe SO4·7...目的：建立共振瑞利散射法测定大黄素的含量。方法：在p H 7.3的B-R缓冲溶液中,铁（Ⅱ）与1,10-邻菲啰啉形成稳定的1∶3的配合物,再与大黄素（EMO）结合形成1∶2的离子缔合物。铁（Ⅱ）-1,10-邻菲啰啉溶液：称取0.278 0 g Fe SO4·7H2O溶于70 m L水中,加入邻菲啰啉（1,10-phen）0.595 0 g,加入适量的抗坏血酸,稀释至100 m L,得到1×10^-2mol·L^-1的储备液,用时稀释成2.0×10^-3mol·L^-1的工作液。室温下,于10 m L比色管中依次加入p H 7.3的B-R缓冲溶液2 m L,适量的EMO标准溶液,以及2.0×10^-3mol·L^-1Fe（phen）2＋3溶液1.2 m L。每加一种试剂后混合均匀,用二次蒸馏水定容至刻度,摇匀,静置10 min后,在荧光分光光度计上以λex=λem方式进行同步扫描,记录共振瑞利散射（RRS）光谱,以λem=2λex和λem=1/2λex进行扫描,分别测量不同入射波长（λex）下的散射强度ISOS和IFDS,然后分别以ISOS和IFDS对应的波长作图,得到二级散射（SOS）光谱和倍频散射（FDS）光谱。分别在各自的最大散射波长处测量样品和试剂空白的散射强度IRRS,ISOS,IFDS及I0RRS,I0SOS,I0FDS,ΔI=I-I0。结果：体系的RRS、SOS和FDS显著增强并出现新的散射峰,相应的最大散射峰分别位于349、684和351 nm。EMO的质量浓度在0.8-10.4μg·m L-1时,与RRS、SOS和FDS的散射强度呈良好的线性关系,其检出限（3σ）依次分别为10.1、32.8、28.6 ng·m L^-1。血样和尿样（各3批）中测定EMO的回收率分别在94.9%-102.4%和99.4%-102.7%之间,RSD分别在1.5%-3.1%和1.1%-3.0%之间。将本法与紫外可见分光光度法比较,结果满意。结论：经方法学验证,体系的共振瑞利散射方法可用于尿样和血清中大黄素的测定。展开更多
A novel ternary solid complex, Yb （C5H8NS2）3 （C12H8N2）, was obtained from treating hydrous ytterbium chloride, ammonium pyrrolidin- edithiocarbamate （ APDC ） and 1, 10-phenanthroline （o-phen· H2O） in abso...A novel ternary solid complex, Yb （C5H8NS2）3 （C12H8N2）, was obtained from treating hydrous ytterbium chloride, ammonium pyrrolidin- edithiocarbamate （ APDC ） and 1, 10-phenanthroline （o-phen· H2O） in absolute ethanol, and characterized by elemental analysis. The enthalpies of solution of hydrous ytterbium chloride, APDC, o-phen·H2O, the mixture of APDC with o-phen· H2O in absolute ethanol at 298. 15 K, and the enthalpy changes of liquid- phase reaction of formation for Yb （ C5H8NS2 ）3 （ C12H8N2） at different temperatures were measured by using a RD496-Ⅲ microcalorimeter. Fundamental paconduction microcalorimeter, determining the specific heat a calculation model for capacity of solid subrameters, the activation enthalpy （ΔH≠^θ）, the activation entropy （ΔS≠^θ）, the activation free energy （ΔG≠^θ）, the apparent reaction rate constant （k）, the apparent activation energy （ E ）, the pre-exponential constant （A） and the reaction order （n）, were obtained by the combination of the thermochemical data of the reaction and kinetic equations with the data of thermokinetic experiments. The enthalpy change of complex formation from the reaction of the regents in solid phase, ΔrH≠^θ（s）, was calculated on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. Based on a RD496-Ⅲ heat stance was developed, and the title complex, c m, were accordingly determined.展开更多
基金National Science Foundation of China(21473078,21346006)Department of scientific research project in Heilongjiang province(B2017015)+1 种基金the national project training project of Jiamusi University(GP2016-004)graduate scientific and technological innovation project of Jiamusi University(LZR2016_092,LZR2016_093)
文摘目的：建立共振瑞利散射法测定大黄素的含量。方法：在p H 7.3的B-R缓冲溶液中,铁（Ⅱ）与1,10-邻菲啰啉形成稳定的1∶3的配合物,再与大黄素（EMO）结合形成1∶2的离子缔合物。铁（Ⅱ）-1,10-邻菲啰啉溶液：称取0.278 0 g Fe SO4·7H2O溶于70 m L水中,加入邻菲啰啉（1,10-phen）0.595 0 g,加入适量的抗坏血酸,稀释至100 m L,得到1×10^-2mol·L^-1的储备液,用时稀释成2.0×10^-3mol·L^-1的工作液。室温下,于10 m L比色管中依次加入p H 7.3的B-R缓冲溶液2 m L,适量的EMO标准溶液,以及2.0×10^-3mol·L^-1Fe（phen）2＋3溶液1.2 m L。每加一种试剂后混合均匀,用二次蒸馏水定容至刻度,摇匀,静置10 min后,在荧光分光光度计上以λex=λem方式进行同步扫描,记录共振瑞利散射（RRS）光谱,以λem=2λex和λem=1/2λex进行扫描,分别测量不同入射波长（λex）下的散射强度ISOS和IFDS,然后分别以ISOS和IFDS对应的波长作图,得到二级散射（SOS）光谱和倍频散射（FDS）光谱。分别在各自的最大散射波长处测量样品和试剂空白的散射强度IRRS,ISOS,IFDS及I0RRS,I0SOS,I0FDS,ΔI=I-I0。结果：体系的RRS、SOS和FDS显著增强并出现新的散射峰,相应的最大散射峰分别位于349、684和351 nm。EMO的质量浓度在0.8-10.4μg·m L-1时,与RRS、SOS和FDS的散射强度呈良好的线性关系,其检出限（3σ）依次分别为10.1、32.8、28.6 ng·m L^-1。血样和尿样（各3批）中测定EMO的回收率分别在94.9%-102.4%和99.4%-102.7%之间,RSD分别在1.5%-3.1%和1.1%-3.0%之间。将本法与紫外可见分光光度法比较,结果满意。结论：经方法学验证,体系的共振瑞利散射方法可用于尿样和血清中大黄素的测定。
文摘A novel ternary solid complex, Yb （C5H8NS2）3 （C12H8N2）, was obtained from treating hydrous ytterbium chloride, ammonium pyrrolidin- edithiocarbamate （ APDC ） and 1, 10-phenanthroline （o-phen· H2O） in absolute ethanol, and characterized by elemental analysis. The enthalpies of solution of hydrous ytterbium chloride, APDC, o-phen·H2O, the mixture of APDC with o-phen· H2O in absolute ethanol at 298. 15 K, and the enthalpy changes of liquid- phase reaction of formation for Yb （ C5H8NS2 ）3 （ C12H8N2） at different temperatures were measured by using a RD496-Ⅲ microcalorimeter. Fundamental paconduction microcalorimeter, determining the specific heat a calculation model for capacity of solid subrameters, the activation enthalpy （ΔH≠^θ）, the activation entropy （ΔS≠^θ）, the activation free energy （ΔG≠^θ）, the apparent reaction rate constant （k）, the apparent activation energy （ E ）, the pre-exponential constant （A） and the reaction order （n）, were obtained by the combination of the thermochemical data of the reaction and kinetic equations with the data of thermokinetic experiments. The enthalpy change of complex formation from the reaction of the regents in solid phase, ΔrH≠^θ（s）, was calculated on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. Based on a RD496-Ⅲ heat stance was developed, and the title complex, c m, were accordingly determined.
