Total Amount Control of Air Pollutant in Building Industrial Area

该文论述了在工业区建设环境管理中实施大气污染物总量控制的必要性,阐述了区域实施大气污染物总量控制的基本条件,提出在工业区建设环境管理中实施大气污染物总量控制的步骤和方法。The paper points out it is necessary that total amount control of air pollutant should be implemented in build ing industrial area.sets forth its basic conditions ,then puts forward its steps and methods

Neurotoxic Effects of Co-exposure to Lead and Dechlorane Plus on Zebrafish (Danio rerio) Embryos

以斑马鱼(Danio rerio)为研究对象,探讨铅(Pb); 、得克隆(DP)及二者联合急性暴露对斑马鱼胚胎的神经毒性作用。结果表明,Pb(5、20 mug·L~(-1))和DP(15、60; mug·L~(-1))单独暴露均会引起斑马鱼自主运动频率增加,触摸反应能力和自由游泳活力下降,并且抑制初级运动神经元的生长,加剧尾部细胞凋亡。但; 与20 mug·L~(-1) Pb单独暴露相比,高剂量联合暴露(20 mug·L~(-1) Pb + 60 mug·L~(-1); DP)使斑马鱼的自主运动频率显著降低(P < 0.05),触摸反应能力和自由游泳活力显著增强(P <; 0.05),初级运动神经元轴突长度显著增加(P < 0.05),尾部细胞凋亡减少。与5 mug·L~(-1); Pb单独暴露相比,低剂量联合暴露(5 mug·L~(-1) Pb + 15 mug·L~(-1) DP)也显著减少斑马鱼尾部的细胞凋亡(P <; 0.05); 。上述结果表明,Pb或DP单独暴露对斑马鱼均可引起神经毒性作用;但二者联合暴露对斑马鱼自主运动、触摸反应以及自由游泳活力的影响则表现为拮抗作用。Neurotoxic effects of acute exposure to lead (Pb) or Dechlorane Plus; (DP),or both were investigated using zebrafish (Danio rerio) embryos.; Results showed that exposure to Pb (5,20 mug·L~(-1)) or DP (15,60 mug·; L-1) alone increased spontaneous movement,decreased touch response and; free-swimming activity,inhibited axonal growth of primary motoneuron and; induced cell apoptosis in zebrafish embryos. Co-exposure to 20; mug·L~(-1) Pb and 60 mug·L~(-1) DP significantly decreased spontaneous; movement (P < 0.05),enhanced touch response and free-swimming activity; (P < 0.05),increased axonal length of primary motoneuron (P < 0.05) and; reduced cell apoptosis in zebrafish when compared to 20 mug·L~(-1) Pb; exposure alone. Co-exposure to 5 mug·L~(-1) Pb and 15 mug·L~(-1) DP also; significantly decreased cell apoptosis on the tail region when compared; to 5 mug·L~(-1) Pb exposure alone (P < 0.05). These results demonstrated; that Pb or DP exposure alone could induce neurobehavioral toxicity in; zebrafish, but Pb and DP co-exposure had antagonistic effects on; spontaneous movements,touch response and free swimming activity.国家自然科学基金项目; 高等学校博士学科点专项科研基

Advances for the Ruthenium Complexes-Based Homogeneous Catalytic Hydrogenation of Oxalates to Ethylene Glycol

草酸酯加氢是重要的有机化学反应,在工业制乙二醇生产中有着重要的应用.对钌金属配合物均相催化反应的研究进行了综述.以催化反应体系为焦点,探讨了多种; 因素如温度、氢气压力、催化剂浓度、反应时间、添加剂等对底物转化率以及产物选择性的影响,并讨论了催化反应机理,其中金属-配体协同促进的H_2分子异; 裂,进而完成对底物分子中酯基依次加氢的反应机理是探讨的重点,这为新型催化剂的设计和应用提供参考.Hydrogenation of oxalates is one of the important organic reactions, which has an ultimate use for the industrial production of ethylene glycol. The studies on the ruthenium complexes-based homogeneous catalytic reaction systems are herein summarized. With the focus on the catalytic reaction systems, the important factors with significant influences on the oxalate transformation efficiency as well as the product selectivity are discussed, including temperature, H-2 pressure, catalyst concentration, reaction duration, additives, and so on. The catalytic reaction mechanisms are also discussed in detail, where the mechanism for the H-2-heterolysis promoted under the metal-ligand cooperation for the oxalate hydrogenation to ethylene glycol is enhanced. This study would be useful for designing the new catalyst applicable in industry.National Natural Science Foundation of China [21473142, 91545115,; 21473145]; Innovative Research Team of China [IRT_14R31, J1310024

Selective activation of the C–O bonds in lignocellulosic biomass for the efficient production of chemicals

高效转化来源丰富且可再生的木质纤维素制备化学品和燃料对建立可持续发展社会具有重要意义.木质纤维素利用的一条理想途径是将其主要成分纤维素、半纤维素和木质素在温和条件下高选择性地催化转化为关键平台化学品.本文综述了近年报道的有关纤维素、半纤维素和木质素或其模型分子中C–O键选择性活化生成葡萄糖、葡萄糖衍生物(包括葡萄糖苷、六元醇和葡萄糖酸)、木糖、阿拉伯糖和芳香化合物的新催化剂和新策略,阐述了决定催化性能的关键因素.本文还讨论了相关反应机理以深入理解C–O键选择性活化.纤维素由葡萄糖单元通过β-1,4-糖苷键连接而成,通过水解反应,选择性切断这些糖苷键可以获得葡萄糖或其低聚物.鉴于葡萄糖在水热条件下不稳定,发展纤维素温和条件下水解的酸催化剂至关重要.众多研究表明,均相酸催化剂(如无机酸,杂多酸等)具有强br？nSTEd酸,在该水解反应中显示高的催化活性.另一方面,拥有强酸性基团-SO3H的固体酸也表现出优异的水解糖苷键性能,但是-SO3H官能团易于流失,限制了这类固体酸催化剂的循环使用.最近研究显示,一些催化剂尤其是碳材料上引入能够与纤维素形成氢键的官能团时,其催化纤维素水解性能显著增强.设计合成这类具备酸性位和氢键位协同效应的稳定固体酸催化剂是纤维素水解转化的一个颇具前景的研究方向.以醇替代水为溶剂实施纤维素醇解制葡萄糖苷是高效活化糖苷键的有效策略.杂多酸被证实为该醇解反应的高性能催化剂.在相同反应条件下,醇解产物葡萄糖苷较水解产物葡萄糖更为稳定,因此可以获得高的葡萄糖苷收率.开发稳定可重复利用的固体酸催化剂是纤维素醇解的关键.耦合水解与加氢或氧化反应可以直接将纤维素转化为相对稳定且具有广泛用途的多元醇或有机酸.目前已有一系列双功能催化剂被报道,这些催化剂通常组合了具备水解功能的液体酸或固体酸和具备加氢或氧化功能的贵金属或过渡金属(譬如ru,PT,nI和Au).其中杂多酸盐或含有磺酸官能团的固体酸负载ru或Au双功能催化剂显示出优异的生成六元醇或葡萄糖酸的催化性能.半纤维素由葡萄糖、甘露糖、木糖、阿拉伯糖、半乳糖等单糖单元通过糖苷键连接而成,糖苷键选择性活化可生成各种单糖混合物.硫酸可以有效水解半纤维素,但是同时也易于催化所生成的单糖深度转化为呋喃及其衍生物.较之硫酸,酸性较弱的有机酸特别是二元羧酸(例如马来酸、草酸等)具有较高的单糖选择性.固体酸如酸性树脂,分子筛等亦可催化半纤维素水解反应,但树脂类催化剂中官能团的流失问题有待解决.木质素是由含甲氧基等取代基的苯丙烷单元通过一系列化学键连接而成的复杂大分子,其芳香单元间包括β-O-4,α-O-4和4-O-5等三种主要连接方式,选择性切断这些C–O键可获得高附加值的芳香化合物.水解和氢解是两类普遍用以活化木质素及其模型化合物C–O键的反应.酸和碱均可催化木质素及其模型化合物水解,但是通常需要苛刻条件获取高转化率.近期研究显示,通过对木质素Cα-OH预氧化,再以HCOOH/HCOOnA实施水解反应,可以成功实现温和条件下有机溶剂提取木质素及其模型化合物的高效转化.另一方面,均相金属络合物(如nI,fE和ru)或多相负载型金属催化剂(如nI,Cu,MO,PT,ru,Pd或ru等)均可有效催化木质素及其模型化合物中C–O键氢解,获得芳烃化合物.在部分多相催化剂体系中,除C–O键活化断裂外,还伴随芳环深度加氢反应,产生较多环己烷衍生物.因此,设计合成具备氢解功能同时抑制过度加氢功能的催化剂是获得芳烃化合物的关键.The efficient transformation of abundant and renewable lignocellulosic biomass for the production of chemicals and fuels is of considerable importance for establishing a sustainable society.The selective catalytic conversion of the major components of lignocellulosic biomass, including cellulose, hemicellulose and lignin, into key platform chemicals under mild conditions represents an ideal route for the utilization of this abundant resource.Cellulose is composed of multiple glucose units, which are linked together through β-1,4-glycosidic bonds, and the selective cleavage of these glycosidic bonds would therefore provide access to glucose and glucose derivatives.Hemicellulose is a heteropolysaccharide composed of different sugar units such as glucose, mannose, xylose, arabinose and galactose.The selective cleavage of the glycosidic bonds in hemicelluloses would therefore provide a mixture of different sugars.In contrast to cellulose and hemicellulose, lignin is a complex macropolymer consisting of methoxylated phenylpropane structures.Furthermore, lignin contains a variety of different C–O bond types, including β-O-4, α-O-4 and 4-O-5 bonds, which connect the primary aromatic units in lignin.The selective cleavage of these C–O bonds would therefore lead to the formation of high-value aromatic compounds.In this review article, we have provided a detailed summary of recent advances towards the development of new catalysts and novel strategies for the selective cleavage of the C–O bonds in cellulose, hemicellulose and lignin, as well as closely related model systems, for the production of glucose, glucose derivatives(including alkyl glucosides, hexitols and gluconic acid), xylose, arabinose and aromatic compounds.The key factors determining catalytic performances have been described in detail.The reaction mechanisms have also been discussed to provide the reader with a deeper understanding of the processes involved in the selective activation of C–O bonds.supportedbyNationalNaturalScienceFoundationofChina(21173172;21473141); theResearchFundfortheDoctorialProgramofHigherEducation(20130121130001); theProgramforInnovativeResearchTeaminUniversity(IRT_14R31)~

Hydrogenation of carbon dioxide to light olefins over non-supported iron catalyst

研究了非负载型铁催化剂上CO2加氢制低碳烯烃反应.结果显示,添加碱金属可显著提高铁催化剂上的CO2转化率和烯烃选择性.在经k和rb修饰的fE催化剂上,CO2转化率可达约40%,烯烃选择性达到50%以上,其中C2~C4烯烃收率超过10%.催化剂表征结果表明,碱金属促进了催化剂中碳化铁的生成,这可能是催化剂性能提高的一个关键原因.随着k含量由1WT%增加至5WT%,CO2转化率及烯烃选择性均升高.但k含量过高时,催化剂活性降低.这可能是由于催化剂比表面积和CO2化学吸附量降低所致.当k含量为5%~10%时,k-fE催化剂上烯烃收率较高;进一步添加适量的硼可进一步提高烯烃选择性,且CO2转化率下降不大.The hydrogenation of CO2 to light olefins was investigated over non-supported Fe catalysts.It was found that the addition of alkali metal ions to the Fe catalyst led to significant increases in both the CO2 conversion and the selectivity for olefins.Over K-or Rb-modified catalysts, about 40% CO2 conversion and more than 50% olefin selectivity were obtained.The yield of C2–C4 olefins exceeded 10% over these modified catalysts.Catalyst characterization suggested that the formation of iron carbide species was accelerated by the modification of the Fe catalyst with alkali metal ions, and this enhancement may be one of the key reasons for the enhanced catalytic performance.For the K-modified Fe catalysts, K content has a major influence on the catalyst behavior.An increase in the K content from 1 to 5 wt% increased both CO2 conversion and olefin selectivity.However, too high a K content led to a decrease in the activity, probably because of decreases in the surface area and CO2 chemisorption capacity of the catalyst.The presence of an appropriate amount of B in the K-modified Fe catalyst was found to be beneficial to the olefin selectivity, without significantly de-creasing the conversion of CO2 .supportedbytheNationalBasicResearchProgramofChina(973Program;2013CB933100); theNationalNaturalScienceFoundationofChina(21173174;20923004;21033006;and21161130522); theSpecializedResearchFundfortheDoctoralProgramofHigherEducation(20090121110007); thePro

Study on quality standard of Minghuanggao gel

目的:研究明黄膏质量标准。方法:采用薄层色谱(TLC)法对明黄膏中的主要成分大黄、黄连、苦参进行定性鉴别;高效液相色谱(HPLC)法测定明黄膏中大黄酚的含量。结果:TLC色谱中均能明显地检出大黄、黄连、苦参;HPLC法测得本品中大黄酚的含量为0.267~0.308 mg·g-1;在10.02~100.16 mg·L-1的范围内,溶液的浓度与峰面积呈良好线性关系,r=0.999 9;加样平均回收率为98.48% (n=6),RSD为1.20%。结论:本品定性、定量方法简便、准确,专属性强,质量标准能够控制该制剂的内在质量。OBJECTIVE To study the quality standard of Minghuanggao gel. METHODS Radix et Rhizoma Rhei, Rhizoma Coptidis and Radix Sophorae Flavescentis in Minghuanggao gel were identified by TLC. The content of chrysophanol in this preparation was determined by HPLC. RESULTS Radix and Rhizoma Rhei, Rhizoma Coptidis and Radix Sophorae Flavescentis in Minghuang-gao gel could be detected obviously by TLC. The content of chrysophanol in this gel was 0.267 - 0.308 mg·g -1 . The linear ranges were 10.02 - 100.16 mg·L -1 with good positive correlation. The average recovery of chrysophanol was 98.48% ( n =6),RSD= 1.20% . CONCLUSION TLC is a simple, method HPLC is accurate and reliable method. The quality standard can be used for quality control of this product.甘肃省科技厅中青年科技基金资助项目(编号:YS 011 A23 015

Synthesis of Ruthena-polycyclic Complexes by Ruthenium-Vinylcarbene Complex

研究了配位不饱和的钌杂S-顺丁二烯化合物[ru(CHC(PPH3)CH(2-Py))Cl2PPH3]bf4(1)与水、甲醇、苯胺和2-巯基吡啶等亲核试剂的[4+1]关环反应,合成了一系列有趣的钌杂多环化合物[ru(CHC(PPH3)CHr(2-Py))Cl(PPH3)2]bf4[r=OH(2),OME(3),和nHPH(4)]与[ru(CHC(PPH3)CH(S(2-Py))(2-Py))PPH3(S(2-Py)]bf4(5).此外,将配位不饱和的钌配合物1与三苯基膦配体反应,制备了类似于氮杂金属萘的配位饱和化合物[ru(CHC(PPH3)CH(2-Py))Cl2(PPH3)2]bf4(6).6与Hbf4反应可生成金属杂环结构类似的分子内含三氯桥的双钌核配合物[{ru(CHC(PPH3)CH(2-Py))PPH3}2(μ-Cl)3](bf4)3(7).以上产物均通过核磁(nMr)与元素分析进行了表征,并解析了部分产物的X射线单晶结构.Treatment of ruthenium-vinylcarbene complex [Ru(CHC(PPh3)CH(2-Py))Cl2 PPh3 ]BF4(1) and PPh3 with nucleophilic reagents H2 O,CH3 OH,NH2 Ph,or 2-mercaptopyridine led to the ruthena-polycyclic complexes [Ru(CHC(PPh3)CHR(2-Py))Cl(PPh3)2 ]BF4 [R = OH(2),R = OCH3(3),R = NHPh(4)] or [Ru(CHC(PPh3)CH(S(2-Py))(2-Py))PPh3(S(2-Py)]BF4(5).They are stable under air at solid state.CH3 OH in the reaction is not only the reagent but also the solvent and the reaction must be heated at 60 ℃ for 6 h.All the other reactions were carried out at room temperature in CH2Cl2.The crystals of 4 and 5 were grown from CH2 Cl2 and CHCl3 solutions layered with diethyl ether,respectively.The structures 4 and 5 were determined by X-ray crystallography.The crystal size of 4 is a=1.29145(3) nm,b=1.37687(5) nm,c= 1.86914(4) nm,α=92.114(2)°,β=106.271(2)°,γ=96.333(3)° and the size of 5 is a=1.15333(18) nm,b=1.20072(19) nm,c=1.9081(3) nm,α=88.466(3)°,β=87.918(3)°,γ=79.521(3)°.In addition,refluxing 1 with PPh3 in CHCl3 for 6 h to produce red solid [Ru(CHC(PPh3)CH(2-Py))Cl2(PPh3)2 ]BF4(6).The reaction of complex 6 with HBF4 at room temperature for 3 h afforded the(μ-Cl)3-bridged bisruthenium-vinylcarbene complex [{Ru(CHC(PPh3)CH(2-Py))PPh3 }2(μ-Cl)3 ](BF4)3(7) in 87% yield.The crystal of 6 was grown from CH3 COCH3 solution layered with diethyl ether,and the crystal of 7 was grown from CHCl3 solution layered with diethyl ether.The structures of 6 and 7 were also determined by X-ray crystallography.The crystal size of 6 and 7 are a=1.13777(3) nm,b=1.56466(7) nm,c=1.79541(7) nm,α=75.822(3)°,β=79.502(2)°,γ= 79.259(3)°,a=1.68830(3) nm,b=2.33421(4) nm,c=2.48603(4) nm,α=90°,β=96.5530(10)°,γ=90°,respectively.The CCDC number for 3,5,6,and 7 are 945539(3),945538(5),945541(6),and 945542(7).All these complexes were fully characterized by elemental analysis and NMR spectroscopy.国家重点基础研究发展计划(No.2012CB821600); 国家自然科学基金(Nos.20925208;21174115;21272193); 长江学者和创新团队发展计划资助~

Treatment characteristics of marine microalgae hydroxyl radicals in ship′s ballast water

鉴于当前尚无一种有效治理压载水中外来有害生物入侵的方法,为解决这一难题,本文采用高级氧化技术,即生成高浓度羟基溶液的方法治理船舶压载水中的海洋微生物.研究主要是利用介质阻挡强电离放电的方法,将空气中的O2和海水中H2O电离离解成.OH等氧化自由基,溶于海水中形成高浓度羟基溶液.同时,实验以羟基致死压载水中的湛江等鞭金藻、牟氏角毛藻和大肠杆菌为例进行了研究.结果表明:羟基致死微生物的阈值为0.6 Mg·l-1,主要是破坏了藻类体内的叶绿素,进而导致藻类的死亡.Currently,there is no effective method to treat the introduced algaes and bacteria in the ship′s ballast water.To solve this problem,the method of advanced oxidation technology producing high-concentration hydroxyl radical solution was used to treat marine microorganisms.With strong ionization discharge,O2 in air and H2O in seawater could be ionized and dissociated into a number of activate particles such as hydroxyl radicals(· OH),which can dissolve into seawater(a part of ballast water) to form the high concentration · OH solution.With the high reaction rate and broad-spectrum lethal characteristic,· OH radicals could kill the introduced microorganisms through dissociative radical reactions in the course of both discharging and inputting the ballast water,without the pollution by medicament.In this study,Isochrysis zhanjiangensis,Chaetoceros muelleri and Escherichia coli in ballast water were killed by · OH radicals.Results indicated that the threshold lethal concentration of · OH radicals for microorganisms in ballast water was 0.6 mg · L-1.A-chlorophyll was damaged by · OH radicals during the treatment,which resulted in the death of algaes.国家自然科学基金项目(No.50877005); 国家杰出青年科学基金项目(No.61025001); 国际科技合作项目(No.2010DFA61470); 国家高技术研究发展(863)计划(No.2012AA062609); 中央高校基本科研业务费(No.2011QN63;2012QN067)~

Catalytic conversion of methyl chloride to lower olefins over modified H-ZSM-34

比较了几种典型的沸石分子筛在氯甲烷转化制乙烯、丙烯和丁烯等低碳烯烃反应中的催化性能,发现H-zSM-34具有较佳的催化活性和选择性.经乙二胺四乙酸二钠(nA2H2EdTA)水溶液处理,并经离子交换及焙烧后,H-zSM-34上氯甲烷转化制低碳烯烃的催化性能显著改善.当nA2H2EdTA浓度为0.1 MOl/l,反应温度为673 k,CH3Cl分压9.2 kPA时,C2–C4烯烃选择性和收率分别达82%和61%.研究还发现,CE修饰H-zSM-34催化剂同样可改善氯甲烷制低碳烯烃的选择性和收率.表征结果表明,nA2H2EdTA处理和CE修饰均降低了H-zSM-34的酸性.酸性的降低可抑制低碳烯烃的氢转移反应,继而避免了其进一步转化为低碳烷烃.Among several typical zeolites,H-ZSM-34 was found to be an efficient catalyst for the conversion of methyl chloride to lower olefins,i.e.,ethylene,propylene,and butenes.Treatment of H-ZSM-34 with a Na2 H2 EDTA(EDTA = ethylenediaminetetraacetate) aqueous solution followed by ion exchange and calcination enhanced the catalytic performance significantly.The selectivity to lower olefins increased significantly for certain Na2 H2 EDTA aqueous solution concentrations;when the H-ZSM-34 catalyst was treated with a 0.1 mol/L Na2 H2 EDTA solution,the selectivity and yield of C2 –C4 olefins reached 82% and 61%,respectively,at 673 K and a CH3 Cl partial pressure of 9.2 kPa.The modifica- tion of H-ZSM-34 with Ce ions improved C2 –C4 olefin selectivity and yield.Catalyst characterization suggests that treatment with Na2 H2 EDTA or modification by Ce decreases the acidity of H-ZSM-34.The weakened acidity of the treated or modified H-ZSM-34 may suppress the hydrogen transfer reaction and prevent lower olefins from further transformation to paraffins.supportedbytheNationalBasicResearchProgramofChina(2010CB732303); theNationalNaturalScienceFoundationofChina(21173174;20923004;21033006;and21161130522); theProgramforChangjiangScholarsandInnovativeResearchTeaminUniversity(IRT1036)~