1,4-二氯苯在褐土中的残留量变化及对几种土壤酶活性的影响

1,4-二氯苯(1,4-DCB)作为农药和化工产品生产的原料和中间体,在环境中的含量越来越多.采用气相色谱法对不同浓度1,4-DCB处理后土壤中药物残留量进行了测定;对1,4-DCB处理后褐土土壤中几种重要的氧化还原酶(多酚氧化酶、过氧化氢酶、脱氢酶)和脲酶活性进行测定,用其改变来反应1,4-DCB残留对土壤生态系统的影响.结果发现:在1,4-DCB处理30 d后,土壤中1,4-DCB残留保持在44%~50%;1,4-DCB处理后土壤中多酚氧化酶活性呈现先升高后降低的现象,酶活性峰值因作用时间和作用浓度不同而不同.与多酚氧化酶活性改变趋势不同,1,4-DCB处理后土壤脱氢酶活性降低.两种酶活性与1,4-DCB处理浓度之间均具有一定的浓度-效应和时间-效应关系.与多酚氧化酶和脱氢酶活性变化结果不同,1,4-DCB处理后土壤脲酶和过氧化氢酶的活性则随着处理浓度升高和处理时间延长而升高.因此,土壤中不同酶活性对1,4-DCB污染产生了不同的响应.     

改性Ti/SnO2-Sb电极催化降解1,4-二氯苯废水试验研究

采用聚合物前驱体法制备了未掺杂、掺杂Cu、掺杂Bi、掺杂Ni的4种Ti/Sn O2-Sb电极,运用SEM和XRD分析电极表面形貌及结构,通过线性极化扫描、循环伏安等测试考察其电化学性能,同时进行1,4二氯苯(p-DCB)降解实验进一步探究电极的电催化氧化特性.SEM和XRD结果表明,掺杂金属可改善电极表面形貌,增大其比表面积;电化学测试表明,Ti/Sn O2-Sb电极的析氧电位并未因金属掺杂而有明显改变,掺杂金属后,Ti/Sn O2-Sb电极具有更优的电催化活性和稳定性.p-DCB降解实验表明,改性Ti/Sn O2-Sb电极对p-DCB的降解效率明显提高,其中Ti/Sn O2-Sb-Cu电极的电催化处理效果最优,电解2 h后p-DCB的去除率即达到87.6%,且p-DCB的降解反应遵循一级反应动力学规律.     

Application of a Second-Order Kinetic Model to a Complex Melt Polymerization Reaction

A novel copolymer system has been synthesized using methyl hydroquinone diacetate (MHQDA), 1,4 naphthalene dicarboxylic acid (1,4 NDCA), and polybutylene terephthalate (PBT) using the melt polymerization technique. The optimum kinetic parameters pertinent to this system are reported in this study. A simple second-order reaction sequence summarizes catalyzed and uncatalyzed reactions between MHQDA, 1,4 NDCA, and PBT. The kinetic parameters for the copolymerization reaction were determined using a new second-order model. This technique was used to compute the moles of acetic acid generated in the polymerization process. The model was compared to that of the experimentally determined data. Close comparison (percentage error of less than 5%) was obtained between the experimental and theoretical data. The kinetic data support block copolyester formation. The thermal data also supports formation of block polymers.     

The use of the tergal gland defensive secretion in male intrasexual aggression of the rove beetle,Aleochara curtula (Coleoptera: Staphylinidae), measured by closed-loop-stripping-analyses and tandem bioassay — mass fragmentography

Summary 2-methyl-1,4-benzoquinone as a target compound of the tergal gland secretion of the rove beetle,Aleochara curtula, was quantified from the reservoirs of individual beetles. Males store less secretion than females, and they evaporate more of the secretion as measured by adsorption from the air (closed-loop-stripping-analysis). The amount of emitted quinone is increased during aggressive interactions of rival males. The pulsed emission of the secretion during aggression is demonstrated by a novel technique combining observation of behavior with the on-line measurement of target fragment ions by mass-spectrometry (tandem bioassay — mass fragmentography). The emission of the secretion is used as a weapon in combats between males and may result in the repulsion of subordinate males from the mating site, but may also serve to mimic females chemically in order to avoid aggressive encounters.     

连续流动分析法测定水中硫化物的显色剂配制方法研究

针对连续流动分析法测定水中硫化物方法中显色剂N,N-二甲基-1,4苯二胺二盐酸盐保质期短的问题,研究了不同体积比盐酸或硫酸介质对延长显色剂保质期的影响,确定了延长保质期的试剂配制方法,并对该方法的适用性进行了检验.结果显示,体积比10％硫酸介质的显色剂优于盐酸介质显色剂,可以存放一周.使用此显色剂进行硫化物分析检出限为0.003 mg/L,线性范围0.000 mg/L ～2.00 mg/L,平行测定相对偏差0.0％ ～11.8％,加标回收率82.0％～102％,可以满足环境样品分析需求.     

固相微萃取-气相色谱法测定洗涤制品中二噁烷

本文采用顶空-固相微萃取-毛细管气相色谱联用技术测定了洗涤制品中二噁烷量,使用50μmPEG/树脂萃取头。顶空平衡温度为80℃,萃取时间为40min。使用石英毛细管柱:30m×0.32mm×0.4μmi.d.内壁涂有5%二苯基(95%)二甲基硅氧烷固定液。外标法定量,二噁烷测定结果的相对标准偏差(RSD)为9.33%;在0.35μg/g～120μg/g范围,色谱峰面积与质量浓度之间呈良好线性关系,线性相关系数(R)为0.9998;回收率为98.7%～102%。     

一株高效1,4-雄烯二酮降解菌的筛选、鉴定及其降解转化特性研究

从养殖场废水中筛选出1株1,4-雄烯二酮（ADD）高效降解菌株ADD3,经过16S rDNA序列同源性分析,鉴定该菌株为芽孢杆菌（Bacillus sp.）.通过单因素实验研究了不同实验条件对菌株ADD3降解特性的影响,采用高效液相色谱与质谱联用技术（UPLC-MS/MS）和高效液相色谱与四级杆飞行时间高分辨率质谱联用技术（UPLC-QTof-MS）鉴定转化产物.结果表明：菌株ADD3通过共代谢方式转化ADD,在MH肉汤培养基中降解500 μg·L^-1 ADD的半衰期为3.6 h;葡萄糖、乙酸钠、蔗糖和淀粉对菌株ADD3降解ADD均有一定的促进作用,其中,最佳碳源为淀粉,最佳浓度为1000 mg·L^-1;最佳pH和温度分别为7和40℃.实验中共鉴定出5种产物,降解机理主要包括加氢还原、脱氢氧化和羟基化,TP1（雄烯二酮）为主要产物.研究结果可为探索微生物转化ADD的机理、优化去除ADD的研究提供参考,并为构造相关工程菌提供一些基础数据.     

Safening activity of natural hydroxamic acids and analogous compounds against herbicide injury to maize

Abstract

Safening activities of natural compounds DIMBOA, DIBOA, and MBOA, as well as synthetic 1,4‐benzoxazin‐3‐ones were tested against acetochlor and EPTC injuries to maize. No safening activities of natural products and from low to moderate activity of synthetic benzoxazinones were observed. In order to explain inefficacy of natural compounds we studied the influence of these molecules on enzymes participating in metabolic detoxication of acetochlor and EPTC. Pretreatment with DIMBOA elevated maize cytochrome P450 levels. Pretreatments with chemicals containing 1,4‐benzoxazin‐3‐one backbone did not alter glutathione S‐transferase enzyme activities. However, all natural products inhibited glutathione S‐transferase activity of roots and shoots in vitro after addition to the enzyme. Safening ineffectiveness of natural hydroxamic acids may be explained by their inhibitory effects on GST enzymes due to their reaction with sulfhydryl groups on the enzyme.     

NO3自由基与3种环醚的大气化学反应动力学研究

在自制的大气反应烟雾箱模拟实验装置中,利用相对速率法研究了3种工业常用溶剂四氢呋喃、1,3-二氧五环、1,4-二氧六环与NO3自由基在298 K±1 K和1.01×105 Pa条件下的反应,目的是通过了解这些挥发性有机化合物（volatile organiccompounds,VOCs）在大气中的降解反应动力学来评估这些化合物对环境可能造成的影响.利用配有氢火焰离子化检测器（FID）的气相色谱（GC）检测反应物浓度变化,测得NO3自由基与四氢呋喃的反应速率常数为（5.36±1.93）×10-15cm3·（molecule·s）-1,与文献报道值在误差范围内非常吻合,验证了实验装置和实验方法的可靠性.实验首次测定了298 K±1K和1.01×105 Pa条件下1,3-二氧五环以及1,4-二氧六环与NO3自由基反应的速率常数,分别为（1.84±0.70）×10-15cm3·（molecule·s）-1和（3.20±0.67）×10-16 cm3.（molecule·s）-1.利用所测反应速率常数估算这些化合物在大气中的平均寿命都在1 d甚至十几d,因此,其排放可能会对区域大气环境产生一定的影响.     

二氯苯醌对斑马鱼胚胎发育及超氧化物歧化酶的影响

2,6-二氯-1,4-苯醌（2,6-dichloro-1,4-benzoquinone,2,6-DCBQ）作为一种新型消毒副产物,因其高检出率及高含量的特点而备受人们关注.本研究以斑马鱼胚胎为实验材料探究了2,6-DCBQ的发育毒性.结果发现：斑马鱼胚胎在8~24 hpf（器官发育形成时期）对2,6-DCBQ暴露最为敏感,死亡率最高;2,6-DCBQ安全浓度为27.15 μg·L^-1,属于极度危险外源化学物.在本实验中,2,6-DCBQ对斑马鱼的生长没有显著影响,但高浓度（100和150 μg·L^-1）2,6-DCBQ会显著增加斑马鱼胚胎及仔鱼的畸形率.在实验过程中还发现,高浓度（≥ 80 μg·L^-1）2,6-DCBQ会明显抑制斑马鱼胚胎的心率.此外,≥ 30 μg·L^-1 2,6-DCBQ可提高超氧化物歧化酶（Superoxide dismutase,SOD）的活性,并影响Cu/ZnSOD和MnSOD的正常转录.本研究较全面地探究了2,6-DCBQ对斑马鱼早期发育阶段的发育毒性,可为2,6-DCBQ的毒性研究提供可靠证据.