杭州湾南岸滩涂沉积物中HCHs与DDTs污染特征分析

摘 要：目的 了解六六六（hexachlorocyclohexanes,HCHs）与滴滴涕(dichloro diphenyl trichloroethanes,DDTs)在杭州湾南岸滩涂沉积物中的污染现状。方法 于2018年4月，采集杭州湾南岸地区4个采样点不同深度（0~80 cm）滩涂沉积物，利用气相色谱-串联质谱法（gas chromatography tandem mass spectrometry, GC-MS/MS）测定了该区域中HCHs与DDTs的含量，对其分布规律进行分析，使用共识沉积物质量基准法对其生态学风险进行了评估。结果 所有样品中均检出，HCHs与DDTs含量分别为4.20~6.24 μg/kg与3.37~4.73 μg/kg，主要以β-HCH、δ-HCH以及DDE为主，其污染主要来源于历史性工业品，整体污染处于较低水平；20.3%的沉积物样品中DDEs含量以及28.1%的样品DDTs总量介于阈值效应浓度(threshold concentration, TECs) 和可能效应浓度(probable effect concentration, PECs)之间。结论 杭州湾南岸沉积物中HCHs与DDTs的污染处于较低水平，具有较小的生态学风险。     

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     

丁基橡胶再生胶硫化体系的选择及其对硫化性能的影响

采用超临界CO2流体作传输介质,二苯基二硫(DD)作脱硫剂,研究了废旧丁基橡胶的脱硫再生。结果表明,所得丁基橡胶再生胶(RIIR)不能被硫黄硫化,但能被树脂硫化。在丁基橡胶(IIR)的硫黄硫化过程中,DD不能用作硫化剂和硫化促进剂,其对硫化过程有明显的抑制作用。采用丙酮抽出残留DD后,RIIR可被硫黄硫化。针对IIR/RIIR并用体系,分别以硫黄和树脂作硫化体系且用量相同时,树脂硫化体系的交联密度明显高于硫黄硫化体系。     

超重力法制备Ce-Mn氧化物载体氧化羰基合成碳酸二苯酯

分别采用溶胶-凝胶法、共沉淀法和超重力反应共沉淀法制备铈锰复合氧化物前驱体,再经过高温焙烧得到氧化羰基化合成碳酸二苯酯的催化剂载体。通过XRD,H2-TPR,BET,TEM等手段对不同方法制备所得载体进行表征,结果表明:采用超重力反应共沉淀法所制备的Ce-Mn复合氧化物载体Mn较多进入CeO2中形成Ce-Mn-O共熔体,由于Mn的掺杂而产生的晶格畸变和由此产生的氧缺陷更多,晶体颗粒较小且分布均匀,比表面积大;当负载质量分数为0.5%Pd后用于苯酚氧化羰基化合成碳酸二苯酯,在反应总压为5 MPa,CO与O2分压比为93∶7、反应时间6 h、反应温度100℃时,碳酸二苯酯单程收率可达21.79%,选择性在99.1%以上。且运用旋转填充床设备实现物料在超重力条件下共沉淀制备Ce-Mn复合氧化物载体的制备过程简单,操作方便可控,载体质量稳定,非常适合批量生产。     

铱催化体系不对称合成手性药物中间体

考察了1,1-二苯基丙酮在手性双胺双膦配体与[IrHCl2(COD)]2组成的催化体系下不对称转移氢化合成(S)-(-)-1,1-二苯基-2-丙醇的反应,通过正交实验了考察了反应温度、n(底物):n(铱络合物)、n(铱络合物):n(手性配体)以及n(底物):n(KOH)对反应的影响。结果表明,在异丙醇中,利用该体系催化1,1-二苯基丙酮反应2小时后,反应产率可达97.85%,对映选择性(ee值)达到99.35%     

Flavonoids from Machilus japonica Stems and Their Inhibitory Effects on LDL Oxidation

Stems of Machilus japonica were extracted with 80% aqueous methanol (MeOH) and the concentrated extract was successively extracted with ethyl acetate (EtOAc), normal butanol (n-BuOH), and water. Six flavonoids were isolated from the EtOAc fraction: (+)-taxifolin, afzelin, (−)-epicatechin, 5,3''-di-O-methyl-(−)-epicatechin, 5,7,3''-tri-O-methyl-(−)-epicatechin, and 5,7-di-O-methyl-3'',4''-methylenedioxyflavan-3-ol. The chemical structures were identified using spectroscopic data including NMR, mass spectrometry and infrared spectroscopy. This is the first report of isolation of these six compounds from M. japonica. The compounds were evaluated for their diphenyl picryl hydrazinyl scavenging activity and inhibitory effects on low-density lipoprotein oxidation. Compounds 1 and 3–6 exhibited DPPH antioxidant activity equivalent with that of ascorbic acid, with half maximal inhibitory concentration (IC₅₀) values of 0.16, 0.21, 0.17, 0.15 and 0.07 mM, respectively. The activity of compound 1 was similar to the positive control butylated hydroxytoluene, which had an IC₅₀ value of 1.9 µM, while compounds 3 and 5 showed little activity. Compounds 1, 3, and 5 exhibited LDL antioxidant activity with IC₅₀ values of 2.8, 7.1, and 4.6 µM, respectively.     

Brominated flame retardants in Belgian home-produced eggs: levels and contamination sources

The extent and the sources of contamination with brominated flame retardants (BFRs), such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD), in home-produced eggs from free-foraging chicken of Belgian private owners were investigated. Various factors, such as seasonal variability, exposure of chickens through diet (kitchen waste) and soil, and elimination of BFRs through eggs and faeces were assessed. PBDEs were more important than HBCD in terms of concentrations and detection frequency. Concentrations of PBDEs and HBCD in Belgian home-produced eggs were relatively low and comparable with reported levels from other European countries and the US. The concentrations of PBDEs (sum of 13 congeners, including BDE 209) ranged between not detected and 32 ng/g lipid weight (lw), with medians of 3.0 and < 2.0 ng/g lw for the autumn 2006 and spring 2007 campaigns, respectively. When present, BDE 209 was the major PBDE congener (45% of sum PBDEs). When BDE 209 was not detected, the PBDE profile was composed of PentaBDE (BDE 99 and BDE 47), with, in some cases, higher contribution of OctaBDE (BDE 183 and BDE 153). HBCD was also detected (< 0.4 and 2.9 ng/g lw for the autumn 2006 and spring 2007 campaigns, respectively), but at lower detection frequency. The highest HBCD value was 62 ng/g lw. The similarity between profiles and seasonal variations in the concentrations of BFRs in soil and eggs indicate that soil is an important source, but not the sole source, for eggs laid by free-foraging chicken. The contamination of eggs with PBDEs and HBCD appears to be of low concern for public health and the contribution of eggs to the total daily intake of PBDEs appears to be limited (10% for chicken owners and 5% for the average Belgian consumer).     

Classic and novel brominated flame retardants (BFRs) in common sole (Solea solea L.) from main nursery zones along the French coasts

Brominated flame retardants (BFRs) were investigated in juvenile common sole from nursery zones situated along the French coast in 2007, 2008 and 2009. Extensive identification was performed with regard to PBDEs, novel BFRs 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), and other non-PBDE BFRs, namely, hexabromobenzene (HBB) and 2,2′,4,4′,5,5′-hexabromobiphenyl (BB-153). Polybrominated diphenyl ether (PBDE) concentrations (Σ 14 congeners) ranged from 0.01 ng/g to 0.16 ng/g wet weight (ww) in muscle, and 0.07 ng/g to 2.8 ng/g ww in liver. Concentrations were in the lower range of those reported in the literature in other European locations. Lower PBDE concentrations, condition indices and lipid contents were observed in the Seine estuary in 2009, possibly in relation to a lower water flow. The PBDE patterns and ratios we observed suggested that juvenile sole have a relative high metabolic degradation capacity. Non-PBDE BFRs were detected at lower levels than PBDEs, i.e., within the < method detection limit - 0.005 ng/g ww range in muscle, and < method detection limit - 0.2 ng/g ww range in liver. The data obtained is of particular interest for the future monitoring of these compounds in the environment.     

Contaminant blubber burdens in Atlantic bottlenose dolphins (Tursiops truncatus) from two southeastern US estuarine areas: Concentrations and patterns of PCBs, pesticides, PBDEs, PFCs, and PAHs

Polychlorinated biphenyls (PCBs), chlorinated pesticides (i.e., dichlorodiphenyltrichloroethane (DDT) and its metabolites, chlordanes (CHLs), dieldrin, hexachlorobenzene (HCB), and mirex), polybrominated diphenyl ethers (PBDEs), perfluorinated chemicals (PFCs), and polyaromatic hydrocarbons (PAHs) were measured in blubber biopsy samples collected from 139 wild bottlenose dolphins (Tursiops truncatus) during 2003-2005 in Charleston (CHS), SC and the Indian River Lagoon (IRL), FL. Dolphins accumulated a similar suite of contaminants with ∑ PCB dominating (CHS 64%, IRL 72%), followed by ∑ DDT (CHS 20%, IRL 17%), ∑ CHLs (CHS 7%; IRL 7%), ∑ PBDE (CHS 4%, IRL 2%), PAH at 2%, and dieldrin, PFCs and mirex each 1% or less. Together ∑ PCB and ∑ DDT concentrations contributed ∼ 87% of the total POCs measured in blubber of adult males. ∑ PCBs in adult male dolphins exceed the established PCB threshold of 17 mg/kg by a 5-fold order of magnitude with a 15-fold increase for many animals; 88% of the dolphins exceed this threshold. For male dolphins, CHS (93,980 ng/g lipid) had a higher ∑ PCBs geomean compared to the IRL (79,752 ng/g lipid) although not statistically different. In adult males, the PBDE geometric mean concentration was significantly higher in CHS (5920 ng/g lipid) than the IRL (1487 ng/g). Blubber ∑ PFCs concentrations were significantly higher in CHS dolphins. In addition to differences in concentration of PCB congeners, ∑ PBDE, TEQ, ∑ CHLs, mirex, dieldrin, and the ratios ∑ DDE/∑DDT and trans-nonachlor/cis-nonachlor were the most informative for discriminating contaminant loads in these two dolphin populations. Collectively, the current ∑ PCB, ∑ DDT, and ∑ PBDEs blubber concentrations found in CHS dolphins are among the highest reported values in marine mammals. Both dolphin populations, particularly those in CHS, carry a suite of organic chemicals at or above the level where adverse effects have been reported in wildlife, humans, and laboratory animals warranting further examination of the potential adverse effects of these exposures.