南充市表层土壤中多环芳烃的源解析研究

运用同分异构体比率、聚类分析法和主成分因子载荷法对南充市表层土壤多环芳烃(PAHs)污染源进行了定性和定量分析。研究表明:同分异构体比率分析揭示表层土壤中PAHs污染来源以燃烧源为主;聚类分析将土壤中13种PAHs组分分成3个主群,3个主群分别指示为交通类PAHs污染、煤燃烧类PAHs污染和混合类PAHs污染。主成分因子/多元线性回归分析显示,PAHs主要来源于3大污染源,并定量计算了3种源的贡献量,其中交通燃油污染的贡献率最大(占42.4%),而燃煤燃烧排放、混合污染所占比例分别为32.4%和25.2%。     

光催化降解土壤中多环芳烃

多环芳烃(PAHs)是一类广泛分布于土壤中的持久性有机污染物,其化学结构稳定,具有高疏水性、难降解性和三致毒性,多产生于交通运输、工业生产、垃圾焚烧等人为活动中。近年来,日益严峻的PAHs污染给土壤生态、食品安全和民众健康带来严重威胁。因此,对土壤PAHs污染的治理具有重要意义且亟待解决。在众多PAHs处理技术中,光催化技术凭借能耗低、操作简便、环境友好等优势,受到了研究者们的广泛关注。本文概述了PAHs的光催化降解机理与途径,综述了光催化修复土壤PAHs领域的研究进展,讨论了不同环境因素对催化剂降解效果的影响,并总结了当前光催化技术应用于土壤PAHs污染修复所面临的挑战。     

土壤样品中多环芳烃的GC-MS快速分析方法

多环芳烃(PAHs)是含有多个苯环并具有致毒、致癌和致突变作用的有机化合物,主要由人类的现代化活动产生,通过大气、水等的传递最终污染土壤,而严重污染的土壤会影响农业耕作,最终危害人类健康.美国环保总署确定了16种PAHs作为优先监测污染物,中国政府列出的"中国环境优先监测黑名单"中包括7种PAHs[1].     

β-环糊精对燃煤焦油和烟气中环芳烃的清除作用

采用三维荧光法测定了7处产地煤样燃烧的焦油和烟气中多环芳烃（PAHs）的含量,焦油中PAHs含量为0.201～0.419 mg/g,烟气中PAHs含量为1.1～3.2 μg/g;测试了β-环糊精（β-CD）溶液对煤烟气中多环芳烃的清除作用,最高去除率可达65.6%。 结果表明：不同产地煤的烟气中PAHs含量不同, 煤焦油中PAHs浓度(mol/L)在10-5数量级,远高于烟气中的浓度(mol/L,10-7数量级)。 用β-CD去除不同产地煤燃烧烟气中多环芳烃的去除率不同。 所选7种煤平均清除率为38.4%。 β-CD溶液有希望成为煤烟气中多环芳烃的清除剂。     

烟气催化脱硝装置对多环芳烃排放特性的影响

通过对装有选择性催化还原(SCR)脱硝装置的燃煤锅炉排放烟气中的多环芳烃(PAHs)进行测试,分析比较了工业锅炉排放的PAHs经过SCR脱硝装置前后的排放特性变化.实验结果表明,烟气催化脱硝装置促进了PAHs含量的增加,特别是低环多环芳烃含量的增加,并提高了其毒性当量,但对PAHs在气相与颗粒相的分布影响不大.     

应用搅拌棒吸附萃取-热脱附-气相色谱/质谱法快速测定滇池水系中的16种多环芳烃

应用搅拌棒吸附萃取(SBSE)-热脱附(TDS)-气相色谱/质谱联用(GC/MS)方法测定了滇池水系(滇池和盘龙江上、中、下游)中16种多环芳烃(PAHs)的含量。方法快速简便,无有机溶剂污染,PAHs的最低检出限为1.0~468.8 pg,理论回收率在90%以上,加标回收率为83.1%~109.4%,相对标准偏差小于10%。测定结果表明,这16种多环芳烃在滇池水样中的含量为89.16 ng/L,在盘龙江上游水样中的含量为65.41 ng/L,在盘龙江中游水样中的含量为339.22 ng/L,而在盘龙江下游水样中的含量为62.25 ng/L,说明滇池水系已经受到一定的PAHs污染,加强对滇池、盘龙江中PAHs有机污染的控制势在必行。     

高效液相色谱-电喷雾银离子诱导电离飞行时间质谱定性分析高沸点多环芳烃

建立了高效液相色谱-电喷雾飞行时间质谱联用技术快速鉴别高沸点多环芳烃的方法。多环芳烃经色谱柱分离后,通过柱后添加AgNO3溶液诱导其在电喷雾离子源中电离,生成多环芳烃[M]+及其复合[M+Ag]+和[2M+Ag]+特征离子,根据所获得的各特征离子的精确分子量和分子式,可实现多环芳烃类化合物的快速鉴别。将本方法用于美国环保局(USEPA)规定的16种优先控制多环芳烃及原油中多环芳烃类化合物的分析鉴别,结果表明,四环以上的PAHs质谱信号良好,说明本方法适用于四环以上的高分子量、高沸点多环芳烃类化合物的分析鉴别。     

外源微生物对PAHs污染土壤细菌群落结构的影响

研究了添加分枝杆菌(Mycobacterium sp.)、假单胞菌(Pseudomonas sp.)和混合菌(分枝杆菌和假单胞菌)对多环芳烃(PAHs)污染土壤中细菌群落结构的影响.采用DGGE研究土壤细菌群落结构及多样性的变化,通过测序鉴定细菌种类.研究结果表明:投加微生物能够改变土壤细菌群落结构的组成,促进或加强了有PAHs降解能力的菌株如假单胞菌、如微杆菌(Micrococcus sp.)的出现;投加微生物改变了土壤中的细菌多样性指数,分枝杆菌处理组的多样性指数变化稍大.研究结果为PAHs污染土壤的修复理论与技术进一步发展奠定理论基础,也为PAHs污染土壤修复中微生物的选择提供依据.     

土壤中多环芳烃修复技术的研究进展

近年来我国的土壤污染问题日益严重,严重危害着人类的生活环境与身体健康,其中主要的有机污染物之一为多环芳烃(PAHs)。PAHs作为一种持久性有机污染物在全球范围内广泛存在,其主要污染来源于人为因素。由于PAHs复杂的杂环芳环结构、较强的疏水性和较高的热稳定性等,使其在土壤中不易自然降解因而具有较高的持久性。本文综述PAHs的主要污染来源、暴露途径及其对人体的危害,并从物理、化学和生物三个方面简要介绍土壤中PAHs的修复方法,并分析每种方法的优势以及面临的挑战。新兴的修复技术结合三种修复技术的优点,具有更好的修复效果和应用前景,但仍存在着一些亟待解决的问题。期望本文能为土壤中PAHs的修复提供借鉴,并为今后的研究方向提供新的思路。     

分散固相萃取-气相色谱-串联质谱法测定蔬菜中多环芳烃及卤代多环芳烃

建立了同时检测蔬菜中16种多环芳烃(PAHs)和11种卤代多环芳烃(X-PAHs)污染水平的分散固相萃取-气相色谱-串联质谱(GC-MS/MS)分析方法。样品中的多环芳烃和卤代多环芳烃经正己烷提取,N-丙基乙二胺吸附剂(PSA)和十八烷基键合硅胶吸附剂(C18)分散固相萃取净化剂净化,气相色谱-串联质谱方法测定,外标法定量。16种PAHs和11种X-PAHs在50,100和200μg/kg添加浓度下的回收率为74.7%～115.1%,相对标准偏差为1.6%～15.3%,方法检出限为0.03～7.4μg/kg。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.