聚乙烯醇存在下孔雀绿与[PtX_2(SnX_3)_2]~(2-)缔合显色反应的研究与应用

碱性染料阳离子与铂族金属络阴离子形成显色离子缔合物的反应,应用于铂族金属的萃取光度和浮选光度法测定已有一些文献报导。文献的研究表明,在过量卤离子(X~-)存在下的氢卤酸介质中,卤化亚锡与铂形成〔PtX_2(SnX_3)_2〕~(2-)络阴离子,Marczenko采用结晶紫(CV~+)阳离子与〔PtCl_2(SnCl_3)2〕~(2-)络阴离子形成离子缔合物用苯浮选,沉淀溶于乙醇后作光度测定铂,摩尔吸光系数可达2×10~5l·mol~(-1)·cm~(-1)。文献采用明胶使此类难溶于水的离子缔合物胶束增溶,在溶液中直接光度测定铂族     

溶剂浮选缔合物光度法测定痕量硒

根据亚硒酸 ( H2 Se O3)氧化 I-生成 I2 ,I2 与 I-配阴离子 ,I-3 ,配阴离子I-3 与孔雀绿阳离子 ( MG+ )发生离子缔合反应 ,用 N2 气将此缔合物浮选的三元缔合物用光度法测定硒。方法的 ε为 2 .2× 1 0 6L· mol-1· cm-1,RSD为2 .7% ,检出限为 4.7× 1 0 -10 g· m L-1     

氮气-苯浮选光度法测定痕量锰

提出了根据 Mn( )氧化 I-生成 I2 ,I2 与 I-反应生成 I-3 配阴离子 ,I-3 配阴离子与孔雀绿阳离子发生离子缔合反应 ,用苯和 N2 将此缔合物浮选 ,以光度法测定此缔合物间接测量锰新方法。表观摩尔吸光系数为(ε=5.0 4× 1 0 5 L· mol-1· cm-1) ,测定 5.0μg/2 0 0 m L的锰 ( n=6 ) RSD为 1 .8%。已用于水中锰的测定。     

溶剂浮选三元缔合物光度法测定痕量锰的研究

在 p H=9.5碱性条件下 Mn( )能与 1 ,1 0 -二氮杂菲 ( Phen)形成配位阳离子 [Mn( Phen) 3 ]2 + ,该阳离子易与四碘荧光素 ( TIF)形成缔合物。缔合物在苯中稳定 ,据此建立了用 N2 浮选三元缔合物于苯中的光度法测定锰的新体系 ,本法灵敏度高 ( ε=9.6× 1 0 5L·mol- 1·cm- 1)。实测了天然水和酒中 Mn( ) ,结果令人满意     

银与碘化物和罗丹明B在水溶液中显色反应的研究

基于(AgIs)~2-络阴离子在聚乙烯醇存在下的水溶液中,与罗丹明 B 产生的离子缔合反应,提出了一个高灵敏度分光光度法测定银的方法.形成离子缔合物的适宜酸度范围是0～0.04N 硝酸(pH7～1.4).以连续变化法和平衡移动法确定离子缔合物的组成是[RB]_2[AgI_s].离子缔合物溶液的最大吸收位=j=600nm处,摩尔吸光系数为1.65×10~5·mol·~(-1)cm~(-1).方法有较好的选择性.在某些掩蔽剂存在下可用于钢中微量银的测定.     

聚氯乙烯(PVC)膜固相光度法测定废水中汞

采用一种新型的、高灵敏度且简便易行的聚氯乙烯(PVC)膜固相光度法测定废水中汞含量。此方法基于Hg2+与Br-生成络阴离子HgBr-3,再与碱性染料罗丹明B(RB+)大阳离子形成有色缔合物(RB+·HgBr-3)。此缔合物被PVC膜吸附、富集后,于560nm波长下测定膜的吸光度。此方法线性范围为0.05～1.0μg·ml-1,检出限为0.01μg·ml-1,相对标准偏差小于5%。     

分光光度法测定高纯氧化铝中的二氧化硅

在含有明胶聚乙烯醇 (PVA)和草酸的 0 .0 1 2～ 0 .0 60 mol/L 盐酸介质中 ,罗丹明 B(RB)与硅钼杂多酸能形成离子缔合物 ,发生高灵敏显色反应 ,缔合物在 585nm处的表观摩尔吸光系数ε=1 .8× 1 0 5L· mol-1· cm-1,缔合物可稳定 2 4 h以上 ,此法已用于测定高纯氧化铝中的二氧化硅     

水中阴离子表面活性剂的吸附分光光度法测定

研究萘基二苯甲烷与阴离子表面活性剂的缔合反应及缔合物在聚合物颗粒表面的吸附及洗脱 ,提出了碱性艳蓝BO分光光度法测定河水中的阴离子表面活性剂 ;碱性艳蓝BO与十二烷基苯磺酸钠、十二烷基硫酸钠、十二烷基磺酸钠的缔合物的表观摩尔吸光系数分别为3.76×104、3.63×104、2.15×104L·mol -1·cm -1 ,方法的线性范围为0.0～2.0mg/L,相对标准偏差3.8% (n=8);应用该法测定河水中阴离子表面活性剂含量 ,结果令人满意     

硫酸铵-碘化钾-溴化十六烷基吡啶体系浮选分离铅

研究了硫酸铵 碘化钾 溴化十六烷基吡啶体系浮选分离铅的行为及其与常见离子的分离条件。实验表明 :Pb2 + 与I- 形成的PbI2 -4能与溴化十六烷基吡啶 (CPB+ )形成浮于盐水相上层且不溶于水的三元缔合物 (PbI2 -4)·(CPB+ ) 2 。当碘化钾 (0 .5 0mol L)和CPB+ (1.0× 10 - 2 mol L)溶液的用量分别为 1.5 0mL和 2 .0 0mL时 ,Pb 可被完全浮选 ,控制pH =4 .0 ,该浮选体系能使Pb 与Zn 、Fe(Ⅲ )、Co 、Ni 、Mn 、Al(Ⅲ )等常见离子分离     

铁(Ⅲ)与硫氰酸盐和碱性呫吨染料在水溶液中显色反应及其应用

在酸性溶液中,铁(Ⅲ)与较高浓度的硫氰酸盐形成Fe(SCN)_6~(3-)配阴离子,配阴离子在阿拉伯树胶等增溶剂存在下的水溶液中能与罗丹明B、罗丹明6G、乙基罗丹明B、丁基罗丹明B等碱性呫吨染料形成离子缔合物[BXD]_3[Fe(SCN)_6]并产生高灵敏显色反应。不同显色体系的ε值在1.85×10~5～6.14×10~5L·mol~(-1)·cm~(-1)之间,其中以罗丹明6G和罗丹明B体系最灵敏,可用于某些样品中痕量铁的吸光光度测定。     

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.     

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.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Catalyst free,visible-light promoted photoaddition reactions between C60 and N-trimethylsilylmethyl-substituted tertiary amines for synthesis of aminomethyl-1,2-dihydrofullerenes

An efficient and benign method for the preparation of aminomethyl-substituted fullerenes has been developed. The process, involving catalyst free, visible-light irradiation of 10% EtOH-toluene solutions containing fullerene C₆₀ and N-trimethylsilylmethyl-substituted amines by using a 20 W compact fluorescent lamp, leads to formation of aminomethyl-substituted fullerene adducts in a highly efficient manner. The photoaddition reaction takes place via a pathway initiated by visible light absorption by C₆₀, followed by SET from the amine to the triplet excited state of C₆₀. Ethanol-promoted desilylation of the resulting a minimum radical then generates the corresponding α-amino radical which couples with the C₆₀ radical anion to form the anion precursor of the fullerene adducts. The new approach using visible-light takes place under mild conditions and it does not require the use of photocatalysts. Thus, the method developed in this effort could broadens the range of functionalized fullerene derivatives that can be readily prepared.     

Highly efficient and stereoselective cycloaddition of nitrones to indolyl- and pyrrolylacrylates

The reactions of various nitrones with indolyl- and pyrrolylacrylates proceeds regioselectively with high diastereoselectivity in the case of aldonitrones, and represents an effective method for obtaining new indolyl- and pyrrolyl-substituted isoxazolidine carboxylates stabilized by weak (CH?O) and moderate (NH?N) strength intramolecular hydrogen bonding. The resulting cycloadducts exhibit promising in vitro anti-influenza activities.     

Transition metal-free direct amination of benzoxazoles using formamides as nitrogen sources

A transition metal-free method for the direct amination of benzoxazoles using formamides as nitrogen sources is reported, which was mediated by an inexpensive and environmentally friendly tetrabutylammonium iodide/tert-butyl hydroperoxide system and gave the 2-aminobenzoxazole derivatives with moderate to good yields.     

l-Proline-catalyzed five-component domino reaction leading to multifunctionalized 1,2,3,4-tetrahydropyridines

Multifunctionalized 1,2,3,4-tetrahydropyridines are concisely synthesized in good yields via l-proline-catalyzed or l-proline/FeCl₃-cocatalyzed one-pot multicomponent reactions (MCRs). The MCRs involve a domino hydroamination/prins reaction/Mannich-type reaction/intramolecular dehydration-cyclization process. The molecular structure of 5baa, one of multifunctionalized 1,2,3,4-tetrahydropyridines, was confirmed by single-crystal X-ray diffraction.     

Exploring the scope of the Gewald reaction: Expansion to a four-component process

An efficient four-component reaction was developed to take advantage of the reactivity of the 2-aminothiophene-3-carbonitrile functionality, which is obtained during the classical three-component Gewald reaction. Various α-methylene bearing ketones were reacted with malononitrile, elemental sulfur, and aryl/heteroarylnitrile derivatives in t-BuOH/NaOH to afford 2-arylthieno[2,3-d]pyrimidin-4-amines in high yields. Preliminary studies revealed the photophysical properties of the products and their potential for use as metal sensors.