Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

内置转盘式PVDF膜生物反应器污水处理的试验研究

对内置转盘式PVDF膜生物反应器(SRMBR)处理污水工艺及膜清洗进行了研究.SRMBR处理污水可以长期稳定运行,在实验模拟污水COD为180～368 mg/L时,出水COD在运行1d后稳定在20 mg/L以内,COD去除率>93%.增大转盘式平板膜组件转速可以增大SRMBR的平衡水通量,转速从15 r/min增大到25 r/min,平衡水通量从42.5 L/(m2·h)增大到47.5L/(m2·h).在一定自吸泵停抽时间内(0～1 min),延长停抽时间有利于减缓膜污染、提高平衡水通量.对污染的膜进行水洗、水洗 碱洗、水洗 碱洗 酸洗,3种清洗方式分别使膜平衡水通量恢复至新膜平衡水通量的48.4%、83.5%、90.2%.     

淀山湖沉水植物死亡分解过程中营养物质的释放

测定了上海淀山湖5种常见沉水植物的营养成分含量及其死亡后在好氧(DO>3.5 mg/L)或低氧(DO<3.5 mg/L)状态下分解释放TN、TP和有机物(以高锰酸盐指数计,下同)等营养物质的动态过程,并对营养物质释放强度与营养成分含量的相关性进行了分析.结果表明, 5种沉水植物中,金鱼藻的TN和TP含量最高,质量分数分别为(4.07±0.22)%和(0.99±0.09)%;好氧状态下TN和有机物的释放强度大于低氧状态,两种状态下TP的释放强度没有显著差异;TP的释放比TN快,一般需10 d左右,而TN和有机物的释放分别需要29 d和20 d左右;在好氧状态下,NO-2-N、NO-3-N和可溶性总磷酸盐的平均释放强度与植物TN含量呈显著正相关(p<0.05),NH 4-N的平均释放强度与植物TP含量呈显著正相关(p<0.05);在低氧状态下,NO-2-N的平均释放强度与植物TN含量、NO-3-N的平均释放强度与植物TP含量分别呈显著正相关(p<0.05);有机物的平均释放强度与植物TP含量呈极显著负相关(p<0.01).     

自动电位滴定法快速检测羟基自由基

利用自动电位滴定仪,建立了羟基自由基浓度检测的一种新方法。对方法的检出限、精确度和精密度进行了全面的分析,并对试验中的主要影响因素进行了必要的讨论。在最佳试验条件下,对羟基自由基的浓度进行了测定,并与常规氧化还原滴定法加以比较。结论:羟基自由基浓度的检出限为5.5×10-6mol/L,相对标准偏差为0.19%,灵敏度为1.7×104。该方法终点判断简单、操作简便、稳定性好、测定快速,可作为一种简便易行的测定羟基自由基浓度的新方法。     

一体式膜生物反应器污水处理工艺研究

在一体式膜生物反应器研制开发实验及反应器各参数运行协调理论分析的基础上,提出了一体式膜生物反应器工艺各参数间的设计原则、方法、步骤及设计实例,对该工艺的运行能耗作了评价.     

MACROPHYTE STANDING CROP AND PRIMARY PRODUCTWITY IN SOME FLORIDA SPRING-RUNS1

ABSTRACT: A survey of 31 Florida spring-runs was conducted to estimate their submerged macrophyte standing crop and primary productivity. The standing crops of submerged vegetation were not significantly (p > 0.05) correlated to either total nitrogen (r = 0) or total phosphorus (r =?0.20) concentrations, but standing crops were significantly (p < 0.01) correlated to the percentage of the spring-run's water surface shaded by marginal vegetation (r =?0.76). Maximum daily rates of primary productivity were positively correlated with average submerged macrophyte standing crops (r = 0.81; p < 0.001) and inversely correlated with the degree of shading by marginal vegetation (r =? 0.43; p < 0.05).     

沉积物再悬浮对沉水植物生长的影响研究

通过室内模拟实验,研究了沉积物再悬浮对苦草(Vallisneria natans)和马来眼子菜(Potomogeton malaianus)2种沉水植物生长的影响.为期10周的实验发现,有沉积物再悬浮的处理组中,苦草的生物量显著低于对照组中(没有沉积物再悬浮)苦草的生物量;同样,沉积物再悬浮对苦草的分蘖和块茎数也产生了明显的影响;马来眼子菜的生物量和分蘖数同样受到了沉积物再悬浮的影响,但影响程度小于苦草.因此,沉积物再悬浮对沉水植物的生长、繁殖具有的抑制作用,但这种作用因种类不同而有所差异.     

用自旋捕集技术研究氟化物刺激人多形核白细胞呼吸爆发产生的活性氧自由基

用ESR波谱研究证明,F~-刺激人多形核白细胞(PMN)呼吸爆发产生活性氧自由基(O_2~-和·OH),同时消耗O_2.用DMPO自旋捕集技术表明,在高浓度F~-刺激下PMN产生DMPO-OOH加合物;在低浓度F~-刺激下则产生DMPO-OH;在适中浓度F~-刺激下PMN先产生DMPO-OOH,随浓度降低变为DMPO-OH.用超氧化物歧化酶和过氧化氢酶的实验确定氧自由基主要来自O_2~-.用CTPO和CrOX的自旋探针测氧法证明,PMN受F~-刺激产生氧自由基时消耗的O_2是细胞外介质中的O_2.     

三氯乙烯和四氯乙烯与羟基自由基加成反应的理论研究

用从头计算法在ＵＨＦ／６－３１Ｇ水平上研究了三氯乙烯和四氯乙烯与羟基自由基的加成反应，通过振动分析确认了过渡态，计算了内禀反应坐标（ＩＲＣ）。研究表明，该反应能生成较稳定的加成中间体，活化势垒分别为５０．８７ｋＪ·ｍｏｌ＾－１和６３．８３ｋＪ·ｍｏｌ＾－１，且二者反应在常温下均为熵减、放热、吉布斯自由能变化小于零，能自发进行的过程。     

水中有机物与羟基自由基反应的QSAR分析

本文利用文献提供的有机物与羟基自由基反应的速率常数,分别分析了羟基自由基与苯甲酸类、酚类、烷烃及其衍生物、以及小分子二元羧酸的反应速率常数与化合物理化参数间的定量关系。