同一体系中铜(Ⅱ)、铅(Ⅱ)、镉(Ⅱ)、镍(Ⅱ)和钴(Ⅱ)的络合物吸附波及其分析应用

研究了丁二酮肟 氨 氯化铵 柠檬酸钠 明胶 抗坏血酸体系中Cu(Ⅱ )、Pb(Ⅱ )、Cd(Ⅱ )、Ni(Ⅱ )和Co(Ⅱ )的络合物吸附波 ,建立了同时测定水溶液中痕量相应元素的新方法。上述金属络合物分别在 -0 .44、-0 60、-0 .76、-1.0 7和 -1.2 4V左右产生灵敏的极谱波。信噪比为 3时 ,检出限分别为 1.0× 10 - 8、2 .3×10 - 8、1.3× 10 - 8、2 .9× 10 - 1 0 和 3 .6× 10 - 1 1 mol/L。铜、铅、镉、镍和钴的浓度分别为 2 .0× 10 - 8～ 2 .0× 10 - 5,4.8× 10 - 8～ 4.8× 10 - 5,3 .0× 10 - 8～ 3 .0× 10 - 5,5 .4× 10 - 1 0 ～ 5 .4× 10 - 7和 6.8× 10 - 1 1 ～ 6.8× 10 - 8mol/L时 ,与相应峰电流线性关系良好。方法用于同时快速测定实际样品中这些金属离子 ,获得满意结果     

磁性铅(Ⅱ)离子表面印迹聚合物的合成及吸附性能

采用表面离子印迹技术,以磁性Fe_3O_4@SiO_2微球为载体、Pb(Ⅱ)为模板、甲基丙烯酸和水杨醛肟为功能单体、二甲基丙烯酸乙二醇酯为交联剂,合成了磁性铅(Ⅱ)离子表而印迹聚合物,并通过对比证实了印迹聚合物对Pb(Ⅱ)的良好吸附性能和选择识别能力。当温度为277 K~286 K时,在最佳吸附pH 6.0下,可在4 h达到吸附平衡,最大吸附量为81.83 mg/g;当Pb(Ⅱ)浓度为300 mg·L~(-1),2倍的Cu(Ⅱ)、Zn(Ⅱ)或Cd(Ⅱ)与之共存时,印迹聚合物对Pb(Ⅱ)仍有较高的选择性,相对选择性系数分别为2.79、4.55和4.70。将印迹聚合物重复利用5次后,吸附量的损失约为8%。     

应用内标的PAN-Ni体系快速共沉淀分离富集和火焰原子吸收光谱测定食盐中铅

应用1-(2-吡啶偶氮)-2-萘酚(简写作PAN)-镍(Ⅱ)共沉淀体系,以锰(Ⅱ)为内标,在pH 9的氨性缓冲溶液中对食盐中痕量铅(Ⅱ)进行快速共沉淀富集,并用火焰原子吸收光谱法测定铅的含量,对共沉淀条件作了优选。在优化的条件下,试液中作为内标的锰(Ⅱ)及铅(Ⅲ)离子均定量地与PAN-Ni(Ⅱ)共沉淀析出。锰(Ⅱ)、铅(Ⅱ)及镍(Ⅱ)均匀地存在于沉淀中,而且在铅(Ⅱ)、锰(Ⅱ)之间或镍(Ⅱ)、锰(Ⅱ)之间存在着一定的比例关系。因此,根据共沉淀中铅(Pb1)及锰(Mn1)的吸光度APb1,AMn1的比值即可求得铅的含量(w%),原试样中铅含量(Pb0)可由下式计算:mPb0=APb1/AMn1.mMn0。试验结果表明,经过共沉淀分离,基体干扰已予消除。此方法的检出限为3.18×10-2mg.L-1。应用于3种不同来源的食盐的分析,算得铅含量测定值的RSD(n=6)均小于4.3%,回收率测得值在95.4%至101.6%之间。     

微乳液介质中meso-四(3-羟基苯基)卟啉与铅显色反应的研究

研究了在TritonX 10 0 /正丁醇 /正庚烷 /水组成的非离子型微乳液中Pb(Ⅱ )与meso 四(3 羟基苯基 )卟啉 [T(3 HP)P]的显色反应。结果表明 ,微乳液较TritonX 10 0胶束体系有更好的增溶增敏作用。在混合掩蔽剂氟化钠 柠檬酸 乙二胺及pH 10 .0的硼砂 氢氧化钠缓冲液中 ,经沸水浴加热 3min ,Pb(Ⅱ ) T (3 HP)P在微乳液和少量过氧化氢中形成配合物 ,ε4 6 6 =1.5 0×10 5L·mol- 1·cm- 1,Pb(Ⅱ )在 0～ 11μg/2 5ml内遵守比耳定律 ,对样品中微量铅的测定结果满意。     

一种高选择性汞(Ⅱ) 吸附剂的制备和应用

利用两步反应法制备了溴联苯三酚红功能性硅胶(BPRSG),并通过静态平衡方法研究了该功能性硅胶对多种性质相近的金属离子的选择性吸附性能,考察了溶液pH值和搅拌时间对Hg?吸附率的影响。结果表明,在pH=7.0时,该固相萃取剂对Hg(Ⅱ)有特异的选择性吸附,可以实现与Pb(Ⅱ),Co(Ⅱ),Mn(Ⅱ),Zn(Ⅱ),Cu(Ⅱ),Cd(Ⅱ),Ni(Ⅱ)等金属离子的选择性分离,对Hg?的吸附平衡时间为30 min;最大吸附容量为4.80 mg/g。将该吸附剂制成微型固相萃取柱,用动态平衡法研究了柱流速、洗脱剂种类、洗脱速度和各种干扰离子对分离富集Hg(Ⅱ)的影响。在优化条件下,微柱对Hg?的最低富集浓度为10μg/L,富集倍率为170倍,柱容量为0.65 mg/g。20种常见离子不干扰Hg?的吸附,用1.0 mol/L醋酸即可洗脱Hg(Ⅱ),柱子可重复使用。将微柱用于环境水样中Hg?的固相萃取,回收率在95.5%～98.0%之间。     

硒代胱氨酸修饰银电极及应用研究

介绍了硒代胱氨酸修饰银电极的制备及其电化学特性 ,并将该修饰电极用于痕量金属离子的分析。研究结果表明 ,此修饰电极具有良好的电化学性质和化学、机械和电化学的稳定性 ,在测定Pb2 + 时 ,检出限可达到 1.0× 10 - 11mol·L- 1,线性范围在 2 .0× 10 - 10 ～ 4 .0× 10 - 11mol·L- 1,同时对于其他金属离子 (Cd2 + ,Cu2 + ,Zn2 + )的分析中也获得较满意的结果     

胞外生物高聚物的制备及其对铅离子的吸附性能研究

采用Pseudomonas sp.的胞外生物高聚物对Pb(Ⅱ)进行吸附试验。分别用扫描电子显微镜、X射线能谱仪(SEM-EDX)和傅里叶变换红外光谱(FTIR)对吸附铅前后的胞外生物高聚物进行表征分析,研究了Pb(Ⅱ)在胞外生物高聚物上的吸附行为。结果表明,Pb(Ⅱ)的最佳吸附pH值为6.0,其吸附行为符合Langmuir吸附等温模型,最大单分子层吸附容量为34.48mg/g。FTIR及EDX实验结果表明,胞外生物高聚物对Pb(Ⅱ)的吸附被认为是高聚物表面的活性基团对Pb(Ⅱ)的络合作用和离子交换机制共同发挥作用。被吸附的Pb(Ⅱ)可用1mol/L的硝酸定量洗脱。方法检出限为3.6ng/mL,相对标准偏差为2.7%[Pb(II):0.05μg/mL,n=9]。在优化的实验条件下,实测了环境水样中痕量Pb的含量,结果满意。     

改性纳米二氧化钛对Pb(Ⅱ)的吸附行为研究

利用浸渍法对纳米二氧化钛进行表面改性, 制备出改性纳米二氧化钛, 用扫描电镜(SEM)对其进行了表征, 并以其为吸附剂, 以火焰原子吸收光谱法(FAAS)为分析手段, 探讨了改性纳米二氧化钛在静态吸附条件下对Pb(Ⅱ)的吸附性能, 考察了影响其吸附和解脱的主要因素及优化条件下Pb(Ⅱ)的吸附容量, 考察了常见共存离子的影响. 结果表明: 在pH 5.0下, 改性纳米二氧化钛能定量吸附Pb(Ⅱ); 1.0 mol/L HNO3作为解脱剂可使Pb(Ⅱ)定量解脱; 优化条件下Pb(Ⅱ)的静态饱和吸附容量为32.88 mg/g.     

枯草杆菌中性蛋白酶与Cu(Ⅱ)相互作用的EPR研究

利用电子顺磁共振（EPR）研究了枯草杆菌中性蛋白酶（B.S.N.P)与无机Cu(Ⅱ）离子的相互作用,结果发现：枯草杆中性蛋白酶活性中心Zn(Ⅱ）与外加的Cu(Ⅱ)存在着直接相互作用,Cu(Ⅱ)可部分置换原酶活性中心Zn(Ⅱ),而进入酶的活性中心Zn(Ⅱ)位,形成“Cu-N.P”酶衍生物,影响了酶的催化活性。此外还发现溶液的pH对相互作用后形成酶衍生物的结构有较大的影响,并得到了“Cu-N.P”酶衍生物及随pH变化的EPR谱图。     

聚苯乙烯系席夫碱螯合树脂的制备及其对Hg(Ⅱ)的吸附性能研究

通过大孔氯甲基化聚苯乙烯树脂的化学改性,制得了与金属离子具有良好配位性能的聚苯乙烯系席夫碱螯合树脂PSCS,借助红外光谱、扫描电镜和元素分析等方法对PSCS进行了表征。采用静态吸附的方法,研究了PSCS树脂对水体中Hg(Ⅱ)的吸附性能,分别考察了介质pH、接触时间、金属离子初始浓度等因素对PSCS吸附Hg(Ⅱ)的影响。结果表明,当Hg(Ⅱ)溶液初始浓度在10~200mg/L范围内,PSCS对Hg(Ⅱ)的去除率均可保持在97%以上,显示了良好的Hg(Ⅱ)去除能力。PSCS对Hg(Ⅱ)的吸附过程符合准二级动力学模型和Freundlich等温吸附模型,说明该螯合树脂对Hg(Ⅱ)的吸附是化学吸附和物理吸附的共同结果。     

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.