齐齐哈尔工业区春季大气中PBDEs的污染及气粒分配

齐齐哈尔富拉尔基区为典型的国家重工业集中区域,为研究其大气中多溴联苯醚(PBDEs)的质量浓度水平、污染特征和气/粒分配规律,分别在其下风向和上风向采集大气颗粒相和气相样品,对PBDEs的质量浓度进行测定.结果表明,大气中PBDEs总质量浓度为13.9~102 pg·m-3,平均值为53.6 pg·m-3,BDE-209是质量浓度最高的同系物.来源分析表明,PBDEs主要来源于商用五溴联苯醚和十溴联苯醚的使用.由log KP和log poL线性回归得到的斜率均高于平衡状态理论值-1,说明大气中的PBDEs气粒分配未达到平衡状态.采用Junge-Pankow吸附模型和Harner-Bidleman吸收模型对PBDEs颗粒态百分比(φ)进行了模拟,结果均高于实际值.     

Polybrominated Diphenyl Ethers in Surface Sediment from Songhua River Basin, Northeast of China

Sixty sediment samples were collected from the main Songhua River in three years. Twelve polybrominated diphenyl ether ( PBDE) congeners ( BDE17, 28, 47, 66, 99, 100, 153, 154, 138, 183, and BDE?209) w...     

高铁酸钠对生活污水中阴离子合成洗涤剂的去除研究

通过自制的高铁酸钠对生活污水中的阴离子合成洗涤剂进行去除实验研究。采用国标方法亚甲蓝分光光度法进行测定,结果发现:高铁酸钠对生活污水中的阴离子合成洗涤剂有较好的去除作用,每100 m L生活污水中,加入10 m L浓度为1.41 g/L的高铁酸钠,水样中阴离子合成洗涤剂的去除率为69.28%。     

MoO3/SO4^2- —TiO2 catalyst for transesterification of dimethyl cabonate with phenol

A new MoO3/SO4^2- -TiO2 catalyst was prepared by a conventional impregnation of SO42-/TiO2 as carrier with an aqueous solution of ammonium molybdate and used for the synthesis of transesterification of dimethyl carbonate （DMC） with phenol.A series of MoO3/SO42--TiO2 catalysts with different MoO3 loadings were investigated and characterized using X-ray diffraction （XRD）,Fourier transform infrared spectrometer （FTIR）,NH3-temperature programmed desorption （NH3-TPD） and X-ray photoelectron spectroscopy （XPS）.The results show that MoO3 loading is related to the activity of transesterification reaction.With the increase of MoO3 loading,the activity of transesterification reaction increases.The sulfur species in the catalyst have an influence on the molybdenum species,and lead to an increase in the electropositive of molybdenum,which promotes the catalytic activity of MoO3/SO42--TiO2.Among the series of catalysts prepared,MoO3/SO42--TiO2 with 10% MoO3 and 823 K calcinated is found to be the most active catalyst for transesterification reaction.Under the reaction conditions of 453 K and 12 h,the conversion of DMC is 30.5 %,and the yields of MPC and DPC reach 21.2 % and 8.7 %,respectively.     

4,4’-二氨基二苯砜固化环氧树脂/蒙脱土纳米复合材料反应动力学的研究

选择4,4’-二氨基二苯砜（DDS）作为固化剂,采用非等温DSC法研究了双酚A缩水甘油醚型环氧树脂（E-51）/有机蒙脱土（MMT）纳米复合材料的固化反应动力学,根据Kissinger方程计算出该反应的表观活化能（ΔE）为59.91 kJ/mol,基于Crane方程计算得到该反应的反应级数为0.89,表明该反应为一复杂反应,根据固化反应动力学测试结果确定了E-51/DDS/MMT体系固化成型工艺.     

Ti(OC4H9)4-PbO均相催化反应蒸馏合成碳酸二苯酯

通过对碳酸二甲酯与苯酚酯交换法反应蒸馏合成碳酸二苯酯的研究,筛选合适的催化剂和寻找最佳的工艺条件,为将来碳酸二苯酯的工业化打下基础.实验结果表明在常压下,温度132℃,原料中苯酚与碳酸二甲酯的摩尔配比为21,苯酚与催化剂的摩尔配比为10.012,钛酸四丁酯与氧化铅的摩尔配比为11,反应时间12 h,碳酸二甲酯总转化率为45.43%,碳酸二苯酯产率为26.33%,碳酸苯甲酯产率为19.10%,碳酸二苯酯的选择性为57.96%,且无苯甲醚和CO2生成.所选催化剂Ti(OC4H2)4-PbO的催化性能明显优于二丁基二月桂酸锡和PbO.     

Modified hydrothermal fabrication of a CoS2–graphene hybrid with improved photocatalytic performance

CoS₂ and a CoS₂–graphene composite were synthesized via a facile sonochemical and hydrothermal method. As-prepared samples were characterized by X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray analysis, transmission electron microscopy, and UV-vis diffuse reflectance spectroscopy. The CoS₂–graphene composites exhibited high dye adsorption, extended light absorption, and efficient charge separation properties. Hence, for photodegradation of methylene blue (MB), significant enhancement of the reaction rate was observed for CoS₂–graphene compared to pure CoS₂. The high activity can be attributed to positive synergetic effects between CoS₂ and graphene. The excellent photoinduced charge separation and observed red shift make these hybrid materials potential candidates for the development of high-performance next-generation photocatalyst materials.     

Levels of polybrominated diphenyl ethers in house dust in Central Poland

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in numerous products, from which they are emitted to the environment, including house dust. House dust is a source of human exposure to these compounds by ingestion. The aim of this article was to determine the levels of selected PBDEs in the house dust and indicate their potential sources of origin. PBDE congeners: BDE‐47, BDE‐99, BDE‐153 and BDE‐209, were analyzed in 129 samples. The geometric mean levels (and 95% CIs) of the aforementioned congeners amounted to 3.8 (3.1–4.7) ng/g, 4.5 (3.5–5.6) ng/g, 2.2 (2.1–2.4) ng/g and 345 (269–442) ng/g respectively. BDE‐209 was the dominant congener in the majority of tested samples. We found a statistically significant correlation between the concentrations of BDE‐47 and the computer operating time per day (r_s – 0.18) and the living area (r_s – 0.20). Statistically significant higher levels of BDE‐99 were found in homes where the floor was not replaced during the last 2 years.     

2种二芳醚农药中间体的合成

[目的]二芳醚是重要的农药中间体,用于合成多种重要的杀虫剂,如一些拟除虫菊酯、杀菌剂如醚唑等农药。3,4’-二氯二苯醚和3-甲基二苯醚分别是醚唑和戊菊酯的关键中间体,传统上采用铜粉为催化剂合成效率和选择性欠佳,为此,对2种二芳醚中间体合成进行优化和改进。[方法]采用商用铜粉和自制高分散铜为催化剂,分别对溶剂、反应摩尔比、反应温度、反应时间进行优化合成2种二芳醚中间体。[结果]3,4’-二氯二苯醚的选择性达86.7%,收率为82.2%;3-甲基二苯醚的收率为96.8%。[结论]实验结果显示高分散铜的催化活性和选择性都好于传统Ullmann反应催化剂。     

Well‐defined,environment‐friendly synthesis of polypeptides based on phosgene‐free transformation of amino acids into urethane derivatives and their applications

In this study, both naturally occurring and artificial amino acids were successfully transformed into the corresponding urethane derivatives using diphenyl carbonate. The urethanes thus prepared could be efficiently cyclized into amino acid N‐carboxyanhydrides (NCAs) without the requirement of phosgene. In addition, the presence of primary amines converted the urethane derivatives into NCAs and initiated the ring‐opening polymerization of the in situ formed NCAs, allowing for the well‐defined synthesis of polypeptides. These polypeptides contained initiating ends functionalized by an amine‐derived residue and propagating ends bearing the reactive amino group. By precise control of the structures of the polypeptides, various polypeptide conjugates such as block copolymers and graft copolymers were successfully synthesized as designed, and their applications in antifouling coatings against proteins, drug delivery systems and biosensors were demonstrated. © 2019 Society of Chemical Industry