涂宁宇,刘洋,刘国光,吕文英,林嘉庆.基于DFT计算和实验研究无机氮对水中萘普生及其产物光解的影响[J].环境科学学报,2019,39(12):4039-4046
基于DFT计算和实验研究无机氮对水中萘普生及其产物光解的影响
- Effects of inorganic nitrogen on photolysis of naproxen and its photoproducts in water based on DFT calculations and experiments
- 基金项目：国家自然科学基金（No.21677040，21377031）
- 涂宁宇
- 1. 广东工业大学环境科学与工程学院, 广州 510006;2. 广东石油化工学院环境工程系, 茂名 525000
- 刘洋
- 广东石油化工学院环境工程系, 茂名 525000
- 刘国光
- 广东工业大学环境科学与工程学院, 广州 510006
- 吕文英
- 广东工业大学环境科学与工程学院, 广州 510006
- 林嘉庆
- 广东工业大学环境科学与工程学院, 广州 510006
- 摘要：萘普生（NP）是一种广泛使用的消炎镇痛类药.本文研究了水中不同形态无机氮对萘普生及其两种重要的光解中间产物NP1和NP2光降解的影响.结果表明，NH4+对于NP及产物的光解几乎没有影响，NO2-和NO3-对NP、NP1和NP2的光解均表现出抑制作用.NO2-和NO3-对NP的影响主要是光屏蔽效应，而对NP1和NP2光解影响的主导因素是由光化学环境中产生的·NO、·NO2同·OH的竞争关系造成的间接抑制.光化学环境中·OH、·NO2、·NO氧化NP1和NP2的化学反应活化能垒呈现上升趋势（NP1：7.0、21.2、54.4 kcal·mol-1；NP2：34.5、47.1、70.3 kcal·mol-1）.活化能垒的差异表明，光化学反应体系中生成的·NO2和·NO将会导致反应速率下降，这也诠释了NO2-和NO3-对NP1和NP2光解抑制的差异性.
- Abstract：Naproxen (NP) is a widely used anti-inflammatory and analgesic drug. The effects of different forms of inorganic nitrogen in water on the photodegradation of naproxen and its two important photolysis intermediates NP1 and NP2 were studied. The experimental results showed that NH4+ had little effect on the photolysis of NP and its photoproducts, while NO2- and NO3- had inhibitory effects on the photodegradation of NP, NP1 and NP2. The influences of NO2- and NO3- on NP were mainly the light shielding effect, while the dominant influence for the photolysis of NP1 and NP2 was the indirect inhibition caused by the competition among·NO,·NO2 and·OH produced in photochemical environment. The free energy barriers of·OH,·NO2 and·NO oxidizing NP1 and NP2 showed an upward trend (NP1:7.0, 21.2 and 54.4 kcal·mol-1; NP2:34.5, 47.1 and 70.3 kcal·mol-1). The differences of free energy barrier indicated that·NO2 and·NO generated in the reaction system would lead to the decrease of reaction rate. This explained well the differences of NO2- and NO3- on the photolysis of NP1 and NP2.
