流动注射化学发光法测定自来水中二氧化氯

在pH12．5的NaOH—KCl缓冲介质中，ClO2直接氧化Luminol能产生很强的化学发光，而且发光强度在一定的范围内与ClO2的浓度呈线性关系，据此建立了流动注射化学发光测定ClO2的新方法。探讨了最佳的发光条件，测定ClO2的线性范围为0．5—200μg／L，检出限为0．3μg／L。本法简便、怏速、灵敏，选择性和重复性较好，应用于自来水中剩余ClO2的测定，结果满意。     

离子色谱法测定饮用水中无机消毒副产物

采用直接进样离子色谱法,对饮用水中无机消毒副产物(DBP):ClOˉ2、BrO、ClOˉ3和Brˉ进行分离检测;研究了分离柱的选择、淋洗液的浓度和流速对分离的影响;在优化的条件下,4种离子的工作曲线范围为1．0～50μg／L;检出限为ClOˉ2 0.3μg／L、BrOˉ3 0.6μg／L、ClOˉ3 0.9μg／L和Brˉ0.6μg／L;4种离子的RSD(n=8)分别为3．8％、3．6％、4．0％和5．0％;本法操作简单、运行费用低、灵敏度高,应用于饮用水的分析。结果令人满意。     

顺序注射-样品预处理模块系统-电热原子吸收法测定海水中痕量铜

将样品预处理模块与自动化顺序注射系统相结合,建立了未经稀释的海水中痕量铜的分离富集方法。铜-PDC螯合物在样品预处理模块中被吸附在聚四氟乙烯微珠填充柱上,用少量甲醇洗脱后,将洗脱液引入电热原子吸收中测定。进样体积为1.0mL时,富集倍率为20,检出限为0.015μg/L,采样频率为26次/h,线性范围为0.05~1.00μg/L,相对标准偏差(RSD)为1.8%(0.50μg/L)。利用本方法分离富集并测定了标准海水样品NASS-5及近海水样中的铜含量,并进行了加标回收实验。     

壳聚糖富集火焰原子吸收法测定水中痕量铜

采用壳聚糖修饰钨丝基质螺旋卷，直接浸入含有痕量铜的pH5．0的Brltton-Robinson缓冲溶液中，经电磁搅拌富集一定时间后，将其转移至空气／乙炔火焰燃烧器上，利用火焰原子吸收光谱法简便快速测定水中痕量铜。方法的线性范围为2—75μg／L；检出限为0．98μg／L。同一支钨丝螺旋卷重复涂敷壳聚糖富集Cu，RSD(n=6)为2．7％。     

毛细管区带电泳的离子交换在柱预富集技术研究

提出了离子交换固相萃取的毛细管区带电泳在柱预富集技术。预富集毛细管和分离毛细管的端面靠紧,二者通过一段带侧孔的聚四氟乙烯（PTFE）套管固定。预富集毛细管内壁键合羧基阳离子交换基团,进样时分析离子被保留在预富集管的固定相上,用2mol／L的氯化铵溶液洗脱,再进行毛细管区带电泳分离。方法成功富集和分离了两种低浓度的药物阳离子,普萘洛尔和美托洛尔的灵敏度比常规电动进样分别提高4200和3400倍,其浓度检出限分别为0．02μg/L和0．14μg/L。     

PTFE-g-GMA-PEI纤维填充微柱/ICP-OES在线预富集测定痕量Cr(Ⅵ)和Cr(Ⅲ)研究

采用自制固相萃取材料聚乙烯亚胺胺化的接枝甲基丙烯酸缩水甘油酯的聚四氟乙烯(PTFE-g-GMA-PEI)纤维填充微柱预富集和流动注射(FI)与电感耦合等离子发射光谱仪(ICP-OES)联用测定样品中痕量Cr(Ⅵ)和Cr(Ⅲ)。对Cr(Ⅵ)和Cr(Ⅲ)的富集与洗脱条件进行优化,并给出Cr(Ⅲ)离子的分析特性。结果表明,该法测定的Cr(Ⅲ)离子富集倍数为30,样品通量为72h-1,检出限为2.2μg/L,RSD为1.2%(50μg/L,n=9),其线性范围为2～500μg/L。该法成功用于环境水样中铬的形态分析,其加标回收率为90～104%。     

流动注射壳聚糖在线微柱预富集火焰原子吸收光谱法测定痕量钯

报道了壳聚糖作在线微柱预富集柱填料,流动注射与火焰原子光谱联用(FI-FAAS)测定痕量Pd的方法。当采样体积13．5mL时,采样频率27／h,富集倍数49倍,线性范围0．01～0．4mg／L,检出限(3s,n=11)1．4μg／L,相对标准偏差1．26％(Cpd=0．2mg／L,n=11)和4．0％(Cpd=0．05mg／L)。初步探讨了该过程的吸附机理。将该方法用于催化剂样品中痕量Pd的测定,结果满意。     

在线还原富集火焰原子吸收光谱法测定环境水样中Cr(Ⅲ)和Cr(Ⅵ)的形态

采用单阀双阳离子交换树脂微柱并联，设计了双路采样逆向洗脱在线分离富集系统，该系统与原子吸收测量技术相结合，实现了在线分离富集-火焰原子吸收光谱法同时测定水中Cr(Ⅲ)和Cr(Ⅵ)，富集1min时，分析速度为60样/h，测定Cr(Ⅲ)和Cr(Ⅵ)的特征浓度分别为6．08μg/L和11．58μg/L(相当于1％吸收)，线性范围分别为0～1．0μg/mL和0～2．0μg/mL，对质量浓度为100μg/L的Cr(Ⅲ)和Cr(Ⅵ)测定的相对标准偏差分别为2．9％和3．0％、检出限分别为8．70和10．8μg/L。该法对实际水样加标回收率在94．5％～104．3％之间。     

负载PAN-S强碱性阴离子交换纤维富集-GFAAS法测定海水中的痕量镉

为了消除石墨炉原子吸收法测定海水中痕量镉所存在的基体效应,采用负载PAN-S强碱性阴离子交换纤维柱吸附海水中的Cd2+实现与海水基体的分离,最后以HNO3附的Cd2+供测定。在p H5时,1000 m L海水样品中的Cd2+离子,可在过柱液流速小于14 m L/min下定量富集在填充有0.5g离子交换纤维的固相萃取柱上,并可被10 m L 0.1 mol/L HNO3完全洗脱。洗脱液中共存离子含量分别为Ca2+(0.034 mg),K+(0.045 mg),Mg2+(0.045 mg),Na+(0.107mg),Ba2+(17.1μg),Al3+(0.586μg)时,对测定无影响。镉的方法检出限为0.008μg/L。用该方法富集和测定了国家标准物质GBW(E)080040和NASS-6中的镉,结果均与标准值吻合。     

在线还原富集-导数火焰原子吸收光谱法测定环境水样中铬(Ⅲ)和铬(Ⅵ)的形态

采用单阀双阳离子交换树脂微柱并联，设计了双路采样逆向洗脱在线分离富集系统，该系统与原子吸收导数测量技术相结合，实现了在线分离富集．导数火焰原子吸收光谱法同时测定水中Cr（Ⅲ）和Cr(Ⅵ），导数仪用2mV／min档位，富集lmin时，分析速度为60样/h，测定Cr（Ⅲ）和Cr(Ⅵ）的特征浓度分别为0．448μg/L和0．793μg/L(相当于1％导数吸收度)，线性范围分别为0-90和0-180μg/L；对浓度分别为10、20μg/LCr（Ⅲ）和Cr(Ⅵ）测定的相对标准偏差分别为2．85％和2．85％；检出限分别为0．855和1．7lμg/L．该法对实际水样加标回收率在94．7％．104％之间。     

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.     

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.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.