Enhanced debromination of 2,2’,4,4’-tetrabromodiphenyl ether(BDE-47)by zero-valent zinc with ascorbic acid

A new technique of zero-valent zinc coupled with ascorbic acid(ZVZ/AA)was developed and applied to debrominate the 2,2,,4,4,-Tetrabromodiphenyl ether(BDE-47),which achieved high conversion and rapid debromination of BDE-47 to less-or non-toxic forms.The reaction conditions were optimized by the addition of 100 mg/L Z V Z particles and 3 mmol/L A A at original solution p H=4.00 using the solvent of methanol/H2O(v:v=4:6),which could convert approximately 94%of 5 mg/L BDE-47 into lower-brominated diphenyl ethers within a 90 min at the ZVZ/AA system.The high debromination of BDE-47 was mainly attributed to the effect of A A that inhibits the formation of Zn(Ⅱ)(hydr)oxide passivation layers and promotes the corrosion of ZVZ,which leads to increase the reactivity of ZVZ.Additionally,ion chromatography and gas chromatography mass spectrometry analyses revealed that bromine ion and lower-debromination diphenyl ethers formed during the reduction of BDE-47.Furthermore,based on the generation of the intermediates products,and its concentration changes over time,it was proposed that the dominant pathway for conversion of BDE-47 was sequential debromination and the final products were diphenyl ethers.These results suggested that the ZVZ/AA system has the potential for highly efficient debromination of BDE-47 from wastewater.

2,4-Dinitrophenyl Ether of Polyvinyl Alcohol and Polymer Bound Anionic SIGMA Complexes

A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP polymer was characterized by NMR, IR, and UV-visible spectroscopy. The reaction of PVA-DNP with sodium methoxide was followed by NMR and UV-visible spectroscopy. Evidence of polymer bound spirocyclic SIGMA complex, C-1 and C-3 polymer bound DNP-methoxy SIGMA complexes and the formation and C-1 methoxy complex of 2,4-dinitroanisole was observed.

Response of Vitellogenin in Tilapia Liver to 2,2′,4,4′-Tetrabromodiphenyl Ether Stress

[Objectives]This study was conducted to understand the potential harm of BDE-47 to fish and aquatic ecosystems and obtain relevant toxicological data from the perspective of vitellogenin.[Methods]Adopting the semi-static water exposure method,three exposure concentrations of 5,50,and 500μg/L and five sampling time of 1,3,7,15,and 30 d were set to investigate the effect of BDE-47 on vitellogenin in tilapia liver.[Results]The low concentration of BDE-47(5μg/L)had no effect on the level of vitellogenin in the liver of tilapia.When exposed to high concentrations of BDE-47(50 and 500μg/L),the VTG content of tilapia liver showed a trend of first decreasing,then returning to normal,and then increasing.An abnormal VTG content indicates that the endocrine system of tilapia is disturbed to a certain extent.[Conclusions]This study plays a role in promoting the formulation of relevant water quality standards and the protection of aquatic living resources.

Response of 11-Ketotestosterone in Tilapia Liver to 2,2′,4,4′-Tetrabromodiphenyl Ether Stress

[Objectives]This study was conducted to investigate the effect of tetrabromodiphenyl ether(BDE-47)on the activity of 11-ketotestosterone(11-KT)in tilapia liver,with a view to understanding the potential hazard of BDE-47 on fish and aquatic ecosystems from the perspective of sex steroid hormones.[Methods]Adopting the semi-static water exposure method,3 exposure concentrations of 5,50,and 500μg/L and 5 sampling time of 1,3,7,15,and 30 d were set to investigate the effect of BDE-47 on 11-ketotestosterone in tilapia liver.[Results]The low concentration of BDE-47(5μg/L)had no effect on the 11-KT level of tilapia liver;and when exposed to high concentrations of BDE-47(50 and 500μg/L),11-KT in the liver of tilapia was first suppressed and then returned to the normal level.Because the fish reproductive process is completed under the coordinated regulation of sex steroid hormones,significant changes of 11-KT in the liver of tilapia may cause its reproductive dysfunction to a certain extent.[Conclusions]This study provides relevant toxicological data for promoting the formulation(revision)of relevant water quality standards and the formulation of limit standards,and facilitating the protection of aquatic living resources and aquatic ecosystems.

含喹唑啉-4-酮结构的芳氧苯氧丙酸二苯醚酯衍生物的设计、合成及除草活性研究

为了开发新型芳氧苯氧丙酸酯类除草剂,以前期工作发现的QPP-I为先导化合物,采用活性亚结构拼接法,设计、合成了19个含喹唑啉-4-酮结构的芳氧苯氧丙酸二苯醚酯衍生物,其结构经^(1)H NMR和^(13)C NMR确证。利用小杯平皿法初步测试除草活性发现,目标化合物对单子叶植物稗草具有较高的生长抑制率。其中,化合物QPPD-16在10ug/mL浓度下对稗草的生长抑制率达到81.6%,与商品化除草剂-精喹禾灵的抑制效果相当。利用温室盆栽法进一步测试除草活性发现,在土壤处理、750 g/hm2施药量情况下,化合物QPPD-16对稗草、马唐、狼尾草和狗尾草的生长抑制率分别为79.6%,83.1%,84.0%和70.0%。更重要的是,化合物QPPD-16对农作物大豆和花生具有较高的安全性。该研究结果表明,化合物QPPD-16具有作为芳氧苯氧丙酸酯类除草剂先导化合物的潜力。

Degradation characteristic of 4-bromdiphenyl ether in mixed solutions by electron beam irradiation

The degradation characteristic of 4-bromdiphenyl ether （BDE-4） was investigated in different solutions.The study indicates that the process of direct degradation of this compound is dependent upon the bromine and the ether bond connected to diphenyl by electron beam.laser flash photolysis was employed to determine the degradation of each species （cationic,neutral,and anionic）.From these data,intermediate products of BDE-4 degradation were shown for direct irradiationdegradation.The neutral radical was formed during the photolysis of these compounds.For all the compounds,diphenyl ether and hydroxybiphenyl were observed as common products.Reaction of the BDE-4 under electron beam was debromide.The debromide rate of BDE-4 at pH=5.5 is somewhat lower than that of BDE-4 at pH=10.0.The decomposition rate for BDE-4 is 99.8% at pH=10.0 on the dose of 14 kGy.BDE-4 from its radical could provide bromine ion into water and the cation radical of BDE-4 formed quickly recombine with hydrogen radical and formed phenyl ether.

Synthesis and antibacterial activity of brominated 2′(4′)-nitro-3-hydroxy diphenyl ethers

Eight new brominated 2＇（4＇）-nitro-3-hydroxy diphenyl ethers have been designed and synthesized. The structures of new compounds were confirmed by ^1H NMR, IR and HRMS. The bioactivity tests showed that these compounds possessed antibacterial activities against the tested bacteria. These new compounds cannot be transformed into dioxins when they were manufactured and used.

Molecular Design of Crown Ethers. 19~1. Synthesis of Novel Disulfide and Diselenide-Bridged Bis (benzo-12-crown-4)s and their Ag^+ Selective Electrode Properties

Two novel heteroatom-bridged his (benzo-12-crown-4 ether)s, i.e. his [2-nitro-4,5 (1,4,7,10-tetraoxadecamethylene) disulfide 1 and diselenide 2, have been synthesized. X ray crystallographic structure was obtained for 1. Ion selective electrodes (ISE) for Ag+, containing 1 and 2 in PVC membrane as neutral carriers, were prepared, and their selectivity coefficients for Ag^+ (K_(Ag.M)^(pot)) were determined against other heavy metal ions, alkali and alkaline-earth metal ions. and ammonium ion. These ISEs showed excellent Ag^+ selectivities, log K_(Ag.M)^(pot) ≤ -3.8, against most of the interfering canons examined, except for Hg^+.

Molecular and Crystal Structure of 4-Amino-4'-Nitrodiphenyl Ether

The title compound (C 12 H 10 N 2O 3, M r =230.22) is monoclinic, space group P2 1/c with unit cell of a=7.234 (1), b=8.999 (1), c=16.907(2) ; β=102.47°, V=1099.6(2) 3, Z=4, D c= 1.391g/cm 3; λ (Mo Kα )=0.71073 , μ =0.102mm -1 , F (000)=480, final R=0.0322, wR= 0.0770 for 1937 observed reflections [ I>2σ(I) ]. Structure analyses reveal that the two benzene rings are almost perpendicular and the bond angle between the two benzene rings is 118.44°.

Transcriptome profiling analysis of Mactra veneriformis by deepsequencing after exposure to 2,2′,4,4′-tetrabromodipheny1 ether

Polybrominated diphenyl ethers （PBDEs） are ubiquitous global pollutants, which are known to have immune, development, reproduction, and endocrine toxicity in aquatic organisms, including bivalves. 2,2＇,4,4＇-Tetrabromodiphenyl ether （BDE-47） is the predominant PBDE congener detected in environmental samples and the tissues of organisms. However, the mechanism of its toxicity remains unclear. In this study, high-throughput sequencing was performed using the clam Mactra veneriformis, a good model for toxicological research, to clarify the transcriptomic response to BDE-47 and the mechanism responsible for the toxicity of BDE-47. The clams were exposed to 5 pg/L BDE-47 for 3 days and the digestive glands were sampled for high-throughput sequencing analysis. We obtained 127 648, 154 225, and 124 985 unigenes by de novo assembly of the control group reads （CG）, BDE-47 group reads （BDEG）, and control and BDE-47 reads （CG ＆ BDEG）, respectively. We annotated 32 176 unigenes from the CG ＆ BDEG reads using the NR database. We categorized 24 401 unigenes into 25 functional COG clusters and 21 749 unigenes were assigned to 259 KEGG pathways. Moreover, 17 625 differentially expressed genes （DEGs） were detected, with 10 028 upregulated DEGs and 7 597 downregulated DEGs. Functional enrichment analysis showed that the DEGs were involved with detoxification, antioxidant defense, immune response, apoptosis, and other functions. The mRNA expression levels of 26 DEGs were verified by quantitative real-time PCR, which demonstrated the high agreement between the two methods. These results provide a good basis for future research using the M. veneriformis model into the mechanism of PBDEs toxicity and molecular biomarkers for BDE-47 pollution. The regulation and interaction of the DEGs would be studied in the future for clarifying the mechanism of PBDEs toxicity.

Synthesis and Characterization of a Novel Copoly(aryl ether ketone) Containing 4, 4'-Biphenyl-bis[4-phthalazin-1(2H)-one] Moiety

A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA), 4, 4'-biphenyl-bis-[4-phthalazin-1(2H)-one], 4, 4- difluorodiphenylketone (DFK). The monomer and copolymer were characterized by FT-IR and 1H-NMR. DSC and TGA were used to the novel polymer.

SYNTHESIS OF ASYMMETRIC ETHERS CLEAVAGE OF ACYCLIC ACETALS WITH ZrCl_4-LiAlH_4

In this paper, we investigated the selective cleavage of acyclic acetals with the reagent system, ZrCl_4-LiAlH_4. The results indicate that this system is very useful for the cleavage of acyclic acetals to the corresponding asymmetric ethers.

Synthesis of A Novel UV-curable Oligmer 1,4-cyclohexanedimethanol Glycidyl Ether Acrylate and Study on Its UV-curing Properties

A novel UV-curable oligmer 1,4-cyclohexanedimethanol glycidyl ether acrylate（CHDMGEA） was synthesized by utilizing 1,4-cyclohexanedimethanol glycidyl ether（CHDMGE） and acrylic acid（AA） as starting materials, triphenyl phosphine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthetic conditions were that the concentration of triphenyl phosphine was 0.90% of reactants by weight, the concentration of p-hydroxyanisole was 0.20% of reactants by weight, the reaction temperature was 90-100 ℃, and the molar ratio of CHDMGE to AA was 0.5：1.1. The experimental results show that CHDMGEA is a kind of good UV-curable oligmer. The impact resistance of the UV-cured films with CHDMGEA as oligmer to prepare UV-curing coating was superior to that of the UV-cured films with bisphenol A diglycidyl ether diacrylate（BPGEA） as oligmer to prepare UV-curing coating.

Radiolytic decomposition of 4-bromodiphenyl ether

Polybrominated diphenyl ethers (PBDEs) spread widely in the environment are mainly removed by photochemical and anaerobic microbial degradation. In this paper, the decomposition of 4-bromodiphenyl ether (BDE -3), the PBDEs homologues, is investigated by electron beam irradiation of its ethanol/water solution (reduction system) and acetonitrile/water solution (oxidation system). The radiolytic products were determined by GC coupled with electron capture detector, and the reaction rate constant of esol– in the reduction system was measured at 2.7×1010 L·mol–1·s–1 by pulsed radiolysis. The results show that the BDE-3 concentration affects strongly the decomposition ratio in the alkali solution, and the reduction system has a higher BDE-3 decomposition rate than the oxidation system. This indicates that the BDE-3 was reduced by effectively capturing esol– in radiolytic process.

ABSORPTION SPECTRA OF 4f ELECTRON TRANSITIONS OF NEODYMIUM COMPLEX WITH 8-HYDROXYQUINOLINE AND OCTYLPHENOL POLY(ETHYLENEGLYCOL)ETHER

In this paper the absorption spectra of 4f electron transitions of the neodymlum complex with 8-hydroxyquinoline and octylphenol poly(ethyleneglycol)ether have been studied. The marked intensification of the band at low octylphenol poly(ethyleneglycol)ether concentration is found normally at 575 nm, and its resolution into three sharp bands centering at 572, 580 and 584 nm. The absorbances of the absorption maxima are 3.5 (at 572 nm), 7.2 (at 580 nm) and 10.2 (at 584 nm) times greater than that of the chloride.

STUDIES ON COMPLEXES OF RARE EARTHS WITH CROWN ETHERS(Ⅳ)SYNTHESIS AND CHARACTERIZATION OF THE COMPLEXES OF RARE EARTH NITRATES WITH 4'-BROMO-5'-NITROBENZO-15-CROWN-5

Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.

Formation of Hybrid Ring Structure of Cyanurate/Isocyanurate in the Reaction be-tween 2,4,6-Tris(4-Phenyl-Phenoxy)-1, 3,5-Triazine and Phenyl Glycidyl Ether

Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.

烷基酚聚氧乙烯醚磷酸酯的合成及性能评价

随着人们环保意识的增加,烷基酚聚氧乙烯醚磷酸酯作为一种用途广泛、对环境友好的新型表面活性剂得到了大众的青睐。本文以壬基酚聚氧乙烯醚、多聚磷酸为原料合成烷基酚聚氧乙烯醚磷酸酯APEP-4,用IR光谱对产物的结构进行表征。研究了不同温度、不同原料配比和反应时间对酯化反应的影响,最佳反应条件为:温度90℃、n(聚磷酸)∶n(NP-4)=1.2、反应时间4 h。酯化率位90.1%,单酯含量占比82.7%。并计算了最优实验合成条件下的样品的HLB_(ABC)=8.3,属于亲油性,可用作与润湿剂。对合成产物做耐碱性、漂洗性和气泡性进行了测定。

2,2’,4,4’-四溴二苯醚(BDE-47)对大型溞(Daphnia magna)的毒性效应

2,2’,4,4’-四溴二苯醚(BDE-47)在水体及各种水生生物(鱼类、海洋哺乳动物以及水生无脊椎动物)中被广泛检出,但BDE-47对水生无脊椎动物毒性效应的研究还处于起步阶段。以大型溞(Daphnia magna)为受试生物,通过急性(48h)和慢性(21d)毒性暴露实验,考察了BDE-47对大型溞活动抑制率、心率、产仔情况和酶活性等指标的影响。结果显示,BDE-47对大型溞活动抑制率的48h-EC50为112.5μg.L-1;高浓度(>100μg.L-1)BDE-47显著诱导提高大型溞的心率。21d慢性暴露实验中,8μg.L-1处理组中大型溞全部死亡;其他各浓度处理组(0.5、1、2、4μg.L-1)中,母溞第1胎产仔时间延后,第1胎子代数量减少,总产仔数量大幅减少,这表明大型溞的繁殖能力受到抑制。BDE-47在一定程度上抑制了母溞胆碱酯酶(ChE)和谷胱甘肽硫转移酶(GST)的活性,大型溞体内的代谢机制没有被诱导,神经活性虽被抑制,但抑制率不高。BDE-47大幅诱导过氧化氢酶(CAT)的活性,并呈现一定的剂量效应关系,相对于ChE和GST,CAT对BDE-47暴露更为敏感,可作为BDE-47对大型溞慢性暴露毒性效应的潜在生物标志物。

PBDE-47单独和与PCB153联合染毒对大鼠神经发育的影响

目的探讨2,2’,4,4’-四溴联苯醚(2,2’,4,4’-tetrabromodiphenyl ethers,PBDE-47)单独和与2,2’,4,4’,5,5’六氯联苯(2.2’,4,4’,5,5’-hexachlorobiphenyl,PCB153)联合作用对 SD 大鼠学习记忆能力及海马 CA1区神经元超微结构的影响。方法将出生第10天清洁级 SD 大鼠随机分为1、5、10 mg/kg PBDE-47组、5 mg/kg PCB153组、1 mg/kg PBDE-47+5 mg/kg PCB153组、5 mg/kg PBDE-47+5 mg/kg PCB153组、10 mg/kg PBDE-47+5 mg/kg PCB153组和对照组(大豆油),每组18只,雌雄各半,按10 ml/kg 经口灌胃进行一次性染毒处理。在大鼠2个月龄时,进行 Morris 水迷宫实验和海马 CA1区神经元超微结构观察。结果低剂量组染毒大鼠(1 ms/ks PBDE-47组和1 mg/ks PBDE-47+5 mg/kg PCB153组)内质网和线粒体超微结构基本正常。随着染毒剂量的增加,内质网出现肿胀、扩张、脱颗粒,部分出现溶解、消失(5mg/kg PBDE-47组);线粒体出现肿胀、嵴断裂,严重者空泡化,进而出现神经元细胞浓缩(5 mg/kg PBDE-47+5 mg/kg PCB153组),甚至严重变性(10 mg/kg PBDE-47组和10 mg/kg PBDE-47+5mg/kg PCB153组)。PCB153和 PBDE-47联合染毒对大鼠水迷宫定位航行实验中找到平台的潜伏期和路径的影响存在交互作用(P<0.05),各染毒组的潜伏期和路径均长于对照组(P<0.05)。PCB153和 PBDE-47联合染毒对大鼠水迷宫空间探索实验中游经平台所在象限的路径(时间)与总路径(时间)的比值的影响存在交互作用(P<0.05):与对照组相比,所有染毒组的平台所在象限的路径(时间)与总路径(时间)的比值均下降(P<0.05)。超微病理及水迷宫实验结果均未发现性别差异。结论一定剂量的 PBDE-47对2月龄大鼠学习记忆能力及海马 CA1区神经元超微结构有损伤作用,PBDE-47与 PCB153在大鼠发育神经毒作用中存在交互作用。