水中微量芘和荧蒽的胶束增敏荧光分析法同时测定

建立了吐温-20(Tween-20,Tw-20)直接荧光法同时测定水中溶解态芘(pyrene,Py)和荧蒽(fluoranthene,FLuA)的方法.该法测定芘和荧蒽的线性范围分别为1.98×10-10 ～9.88×10-8 mol/L和2.00×10-9 ～7.99×10-7 mol/L,检出限分别为9.88×10-11 mol/L和5.99×10-10 mol/L.方法灵敏,用于自来水、江水样的分析,取得了良好的效果,芘的回收率分别为92%～102%和101%～102%,荧蒽的回收率分别为90%～100%和94%～111%.为预测和治理水污染提供了一种灵敏、快速且简便的测试手段.     

同步扫描-化学除氧胶束增稳室温燐光法同时测定痕量菲和荧蒽的研究

本文利用同步扫描-化学除氧胶束增稳室温燐光法研究了痕量菲和荧蒽的同时测定。考察了菲和荧蒽二元混合物中两组分的相互干扰限量。讨论了在胶束体系中菲和荧蒽相互干扰的机理。实验表明,适宜的△λ为186nm。菲和荧蒽的同步峰分别位于480nm和547nm。该法的线性范围为:菲为2.7×10~7～4×10~(-6)mol/L,荧蒽为2.2×10~(7-)～1×10~(-5)mol/L。检出限为:菲为2.7×10~7mol/L,荧蒽为2.2×10~(-7)mol/L。相对标准偏差小于3％。     

胶束增敏同步荧光光谱法测定水中微量芘和蒽

十二烷基苯磺酸钠对芘和蒽的荧光有明显的增敏作用,且其荧光的增强程度与芘和蒽浓度分别在4.9×10-9~5.0×10-8mol.L-1和5.6×10-9~5.6×10-8mol.L-1之间呈线性关系。芘和蒽的检出限(3S/N)分别为7.4×10-10mol.L-1和3.7×10-10mol.L-1。利用此反应作为测定芘和蒽的方法并应用于江水、自来水和湖水的分析,测定所得回收率分别为91.0%~102.0%,90.0%~111.1%。     

三维荧光光谱法连续测定苯胺、二苯胺和N-甲基苯胺

本文比较了苯胺、二苯胺、N-甲基苯胺的二维荧光光谱和三维荧光光谱。提出了同时测定苯胺,二苯胺和N甲基苯胺的分析方法,它们的浓度分别在2.0×10~(-7)～5.0×10~(-6)mol/L,9.0×10~(-8)～7.4×10~(-6)mol/L,1.3×10~(-7)～2.0×10~(-8)mol/L范围内有良好的线性关系,检出限为1.0×10~(-7)mol/L,8.0×10~(-9)mol/L,1.0×10~(-7)mol/L.相对标准偏差分别为5％,7％,7％.此方法用于混合样品和工业废水的分析,获得较满意的结果.     

新吖啶酯发光剂测定过氧化氢的研究

本文报道了新发光剂氟磺酸-10-甲基-9-(对甲酰基苯基)羧酸吖啶酯测定饮用水和降水中H_2O_2的研究。该方法无需任何催化剂,选择性好,灵敏度高,检测限达1.2×10~(-9)mol/L,线性范围宽(3×10~(-9)～1×10~(-2)mol/L),测定5×10~(-9)mol/L和6.6×10~(-7)mol/L H_2O_2时,相对标准偏差分别为3.2％和1.6％。     

无保护流体室温燐光法同时测定α-萘乙酸和吲哚-3-乙酸

利用重原子效应(HAE)的选择性,建立了一种仅用TlNO3和KI为重原子微扰剂(HAP)、Na2SO3为除氧剂的无保护流体室温燐光(NP-RTP)同时测定α-萘乙酸(NAA)和吲哚-3-乙酸(IAA)的方法。吲哚-3-乙酸(KI为HAP)、α-萘乙酸(TlNO3为HAP)和α-萘乙酸(KI为HAP)的最大激发/发射峰分别位于280/448nm、280/490nm和280/490nm,线性范围分别为2.5×10-7~1.0×10-5mol/L、1.0×10-7~6.5×10-6mol/L和6.5×10-7~1.0×10-5mol/L,检出限分别为6.5×10-8mol/L、7.1×10-8mol/L和1.98×10-7mol/L。该方法已用于商品萘-吲可湿性粉剂中α-萘乙酸和吲哚-3-乙酸的同时测定,回收率和相对标准偏差分别为95.3%~104.7%和1.8%~4.6%。     

吸附溶出催化伏安法测定人参中的锗

本文提出了利用吸附溶出催化伏安法测定人参中锗的方法。最佳体系为:2.5×10~(-2)mol/LH_2O_2、2.0×10~(-2)mol/L邻苯二酚、2.0×10~(-3)mol/L H_2SO_4。线性范围为2.0×10~(-9)～2.0×10~(-7)mol/L。当富集时间为4 min时,最低检测浓度为4.0×10~(-10)mol/L。此法己成功地应用于测定人参中的锗。     

溶出伏安法同时测定水中痕量铀和镍

本文报道了同时测定钴和镍的一种方法.在 0.01mol/L NH_3·H_2O-0.01mol/LNH_4Cl-3.0×10~(-5)mol/L安息香缩氨基硫脲(BTSC)溶液中,钴(Ⅱ)和镍(Ⅱ)均产生非常灵敏的还原波,其峰电位分别是:-0.94和-0.75V(vs.SCE),峰电流与钴和镍的浓度分别在2.0×10~(-8)~1.0×10~(-6)和1.0×10~(-8)~8.0×10~(-7)mol/L范围内成直线关系,该方法用于测定水中痕量钴和镍,相对标准偏差分别为1.4~2.0%和2.1~2.5%,回收率分别在98.0%~101.8%和97.9%~102.1%之间.     

还原氧化石墨烯-多壁碳纳米管复合膜负载金纳米粒子修饰玻碳电极检测双酚A

以水合肼为还原剂,采用均相还原法制备还原氧化石墨烯-多壁碳纳米管复合材料(rGO-MWCNTs),通过滴涂法将其修饰到玻碳电极(GCE)表面.以此复合材料为载体,采用电化学方法制备了金纳米粒子-还原氧化石墨烯-多壁碳纳米管复合膜修饰电极(AuNPs-rGO-MWCNTs/GCE).通过扫描电镜(SEM)、EDS能谱技术和电化学方法对此电极进行了表征.研究了双酚A在修饰电极上的电化学行为.结果表明,此电极对双酚A的电极过程具有良好的电化学活性,在0.10 mol/L PBS溶液(pH 7.0)中,微分脉冲伏安法测定双酚A的线性范围为5.0 × 10-9~1.0 × 10-7 mol/L和1.0 × 10-7~2.0 × 10-5 mol/L,检出限为1.0 ×10-9 mol/L(S/N=3). 将此电极用于模拟水样和超市购物小票样品中双酚A含量的测定,加标回收率分别为97%~110%和98%~104%.     

苯巴比妥的二次微分简易示波伏安法测定

利用苯巴比妥的示波特性 ,分别建立了在0.2mol/LKOH和1.0×10-4mol/LCd2 +-0.1mol/L硼砂底液中直接和间接测定苯巴比妥的二次微分简易示波伏安法 ;直接测定和间接测定的线性范围分别为1.0×10 -5mol/L～1.0×10 -4mol/L和4.0×10 -6mol/L～8.0×10 -5mol/L ;检出限分别为8×10 -6mol/L和2×10 -6mol/L;在直接测定中 ,对6.000×10 -5mol/L苯巴比妥进行10次测定的RSD为4.5 % ;间接测定中 ,对2.000×10 -5mol/L苯巴比妥进行10次测定的RSD为2.6 % ;这一研究表明对于一些在示波分析中灵敏度不高或本身没有示波活性的药物 ,可以利用其与金属离子生成沉淀的方法间接测定 ,从而提高药物测定的灵敏度、拓宽示波分析应用领域     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.