近年来,31P-NMR(nuclear magnetic resonance)已成为研究环境有机磷的有力武器,然而此方法在湿地学研究中的应用却很少,关于湿地沉积物样品制备方法的研究更缺乏。本研究通过改变提取剂组成、提取剂比例、离心条件、检测扫描时间等因素...近年来,31P-NMR(nuclear magnetic resonance)已成为研究环境有机磷的有力武器,然而此方法在湿地学研究中的应用却很少,关于湿地沉积物样品制备方法的研究更缺乏。本研究通过改变提取剂组成、提取剂比例、离心条件、检测扫描时间等因素设计实验,寻找最佳的湿地沉积物样品处理及检测方法,以期为31P-NMR技术在湿地沉积物样品有机磷研究中的应用提供科学依据。结果表明采用:1mol·L-1 HCl预提取,0.25mol·L-1 NaOH+0.05mol·L-1 EDTA主提取,沉积物与提取剂比例为1∶8的提取方法,可获得更好的提取效果。提取完成后,采用冷冻高速离心可更好地分离提取液、避免某些磷组分的水解。此外,NMR扫描分析时间设为14~16h(约扫描25 000次)可获得更完整的图谱。相较于传统的化学分析法,31P-NMR法的样品前处理相对简单、分析时破坏性小且组分分辨完全,该技术的运用,有望获得湿地磷循环,特别是对有机磷认知的新突破。展开更多
The substituent effects on ^(31)P-NMR chemical shifts, are determined by five empirical rules. The proposed rules are based on that the shielding (upfield shift) of resonance nucleus is governed by the spherical symme...The substituent effects on ^(31)P-NMR chemical shifts, are determined by five empirical rules. The proposed rules are based on that the shielding (upfield shift) of resonance nucleus is governed by the spherical symmetry of the electron cloud.展开更多
The thermolysis of (EtO)_2P(O)SCF_3 was measured by ^(31)P-NMR with external standard method. Kinetic parameters of the reaction, i.e., order, rate constant, pre-exponential, activation energy were obtained. For const...The thermolysis of (EtO)_2P(O)SCF_3 was measured by ^(31)P-NMR with external standard method. Kinetic parameters of the reaction, i.e., order, rate constant, pre-exponential, activation energy were obtained. For constant external-standard method, It is better to choose the value of ^(31)P peak area of standard substance slightly greater than the middle value of the area of the measured compounds.展开更多
Solution ^（31）P nuclear magnetic resonance spectroscopy（ ^（31）P-NMR） is a useful method to analyze organic phosphorus（Po）, but a general procedure for the analysis method is lacking.The authors used solution ^...Solution ^（31）P nuclear magnetic resonance spectroscopy（ ^（31）P-NMR） is a useful method to analyze organic phosphorus（Po）, but a general procedure for the analysis method is lacking.The authors used solution ^（31）P-NMR, which was found to be an effective method for analysis of Po in Haihe River sediment, to analyze the Po in the surface sediment in Eastern China at the regional scale, and found that the Na OH-ethylenediaminetetraacetic acid（EDTA）extraction rate was affected by environmental factors. At the regional scale, the extraction rate showed a positive relationship with loss on ignition, when the extraction rate was lower than 60%. The extraction rate had no relationship with the loss on ignition when the extraction rate was higher than 60%. The extraction rate showed a negative relationship with p H, which means that the extraction rate was higher in acidic sediment and lower in alkaline sediment. The ratio of TC/TN（the ratio of total carbon to total nitrogen） was considered to represent the origin of organic matter in the sediment. The extraction rate was high when the TC/TN ratio was lower than 20, meanwhile the extraction rate decreased as the TC/TN ratio increased. The results show that the origin of organic matter in sediment significantly affects the Na OH-EDTA extraction rate. This study will give theoretical support for building an effective and general solution ^（31）P-NMR analysis method.展开更多
文摘农田生态系统中土壤磷形态转化,影响土壤磷对作物的有效供应。土壤磷分为无机磷和有机磷两大部分。化学连续提取法(chemical sequential fractionation,CSF)研究土壤磷形态分级,采用不同的化学提取剂,分级提取土壤中组成或分解能力接近的有机无机含磷化合物,是目前表征土壤磷素形态的重要方法。但该方法虽历经改进,仍难以确切反映土壤磷的实际组成,提取的不同磷形态间存在重叠,有机磷和无机磷组分分级存在一定的误差;不同分级磷组分对作物的有效性,需谨慎评估。核磁共振波谱技术(nuclear magnetic resonance,NMR)根据核磁共振波谱图上共振峰的位置、强度和精细结构来研究土壤中含磷化合物的分子结构。液相31PNMR可以同吋检测出土壤中多种磷组分,如正磷酸盐、磷酸单酯、磷酸二酯、膦酸脂、焦磷酸盐和多聚磷酸盐,识别土壤提取物磷形态,可将有机磷与无机磷分开。本文综述了应用31P-NMR技术研究土壤磷形态组分的一些进展,总结了样品制备过程、NMR测试参数及在土壤磷形态转化研究中的应用。二维31P-NMR技术发展为鉴定分析土壤中更多种类的含磷化合物提供了契机。
文摘The substituent effects on ^(31)P-NMR chemical shifts, are determined by five empirical rules. The proposed rules are based on that the shielding (upfield shift) of resonance nucleus is governed by the spherical symmetry of the electron cloud.
文摘The thermolysis of (EtO)_2P(O)SCF_3 was measured by ^(31)P-NMR with external standard method. Kinetic parameters of the reaction, i.e., order, rate constant, pre-exponential, activation energy were obtained. For constant external-standard method, It is better to choose the value of ^(31)P peak area of standard substance slightly greater than the middle value of the area of the measured compounds.
基金supported by the National Natural Science Foundation of China (No. 21507146)the special fund from the State Key Joint Laboratory of Environment Simulation and Pollution Control (Research Center for Eco-environmental Sciences, Chinese Academy of Sciences) (No. 15Z01ESPCR)
文摘Solution ^（31）P nuclear magnetic resonance spectroscopy（ ^（31）P-NMR） is a useful method to analyze organic phosphorus（Po）, but a general procedure for the analysis method is lacking.The authors used solution ^（31）P-NMR, which was found to be an effective method for analysis of Po in Haihe River sediment, to analyze the Po in the surface sediment in Eastern China at the regional scale, and found that the Na OH-ethylenediaminetetraacetic acid（EDTA）extraction rate was affected by environmental factors. At the regional scale, the extraction rate showed a positive relationship with loss on ignition, when the extraction rate was lower than 60%. The extraction rate had no relationship with the loss on ignition when the extraction rate was higher than 60%. The extraction rate showed a negative relationship with p H, which means that the extraction rate was higher in acidic sediment and lower in alkaline sediment. The ratio of TC/TN（the ratio of total carbon to total nitrogen） was considered to represent the origin of organic matter in the sediment. The extraction rate was high when the TC/TN ratio was lower than 20, meanwhile the extraction rate decreased as the TC/TN ratio increased. The results show that the origin of organic matter in sediment significantly affects the Na OH-EDTA extraction rate. This study will give theoretical support for building an effective and general solution ^（31）P-NMR analysis method.
