基于吩嗪衍生物的荧光增强型氰离子探针

针对氰根离子的强亲核反应性,设计并合成了一种以吩嗪为荧光团,吲哚磺酸作为吸电子基团和识别基团的反应型化学传感器PDSI。研究表明,具有强给电子能力的吩嗪和带正电荷的拉电子吲哚双键表现出很强的分子内电荷转移(ICT),当加入氰根离子后,由于双键被破坏,吲哚基团上氮原子的正电荷被中和,吸电子能力迅速降低,750nm处的ICT吸收带吸光度相应下降,肉眼可明显观察到溶液体系的颜色由绿色逐渐变为淡黄色,实现了对氰根离子直观的颜色响应;同时吩嗪荧光团荧光恢复,在580nm左右表现出20倍荧光增强;此外,化合物PDSI具有良好的选择性,其它阴离子对体系的吸收和荧光没有明显影响。PDSI对氰根离子的检出限达到0.02μmol/L,低于世界卫生组织及美国环保局规定的饮用水中氰化物含量上限0.02ppm。     

香豆素类氰离子荧光探针研究进展

氰离子有很大毒性,在自然环境及人类社会中广泛存在,开发灵敏、快速的氰离子荧光检测技术对环境及人类健康有重要意义。香豆素染料具有优良的光学物理性质,近年来越来越多科学家设计合成带有香豆素基团的荧光探针分子,用以检测环境及动物组织中的痕量氰离子。基于氰离子自身独特的化学物理性质,本文从氢键、加成反应、取代反应三个方面对近几年的香豆素类氰离子荧光探针进行了分类总结,并进行了展望。     

离子色谱法同时测定化妆品中氟离子、碘离子、溴酸根和氰根

采用离子色谱法同时测定化妆品中氟离子、碘离子、溴酸根和氰根。对化妆品样品的前处理方法和仪器条件进行了优化,以氢氧化钠溶液进行梯度淋洗,阴离子分析柱(IonPacAS11-HC,250 mm×4 mm)分离,氰根采用电化学检测器进行定量,氟离子、碘离子和溴酸根采用电导检测器进行定量。结果表明,氟离子、溴酸根、碘离子和氰根的检出限分别为2.0,10.0,10.0和1.0 mg·kg-1。各离子的回收率为78.5%~110.6%,相对标准偏差为1.9%~6.9%。对实际样品进行检测,满足化妆品中多离子的检测要求。     

合成二硫氰基甲烷母液中硫氰根与氯根共存时氯离子的测定

合成二硫氰基甲烷(即7012)的母液中含有硫氰根、氯根、及极少量的二硫氰基甲烷。通过测定硫氰根、氯根这两种离子的浓度变化来了解整个反映情况。硫氰根和氯根共存时,氯离子的化学测定法,由于两种离子性质相近,关健在于如何排除前者的干扰。一般可用某些氧化剂如高锰酸钾、二氧化铅,硝酸等把硫氰根破坏后测定氯根;也可先以银盐沉淀这种离子后再分离测定。据 Nordman报导用高锰酸钾溶液,能氧化大多数硫氰根,但同样氧化了少量氯根,带来误差。浓硝酸氧化的产物是硫酸根及残存的氰酸,均能与银盐反应,虽然硫酸银和氰酸银溶解于浓硝酸,但始终难以全部除尽硫酸银。在部分卤素离子存在时测定氯离子可使用 Feigle 氧化剂,对溴离子的分离是满意     

β-环糊精包裹的方酸类化合物在纯水体系中对CN-的选择性识别

利用β-环糊精包裹方酸类化合物（SQ）,很好地改善了SQ在纯水体系中的溶解度.包合物中SQ的两个苯环分别嵌入到两个不同的β-环糊精的空腔内,而中间的四元环裸露在外边.方酸类化合物在近红外区强而窄的吸收以及它们对氰化物特有的敏感性使它们成为理想的氰根离子的传感器.β-环糊精的包裹作用使不溶入水的SQ能够直接在纯水体系中选择性识别氰根离子而不需要任何化学修饰.     

有机改性膨润土对水中硫氰根离子吸附性能和机理研究

研究了以阳离子表面活性剂十六烷基三甲基溴化铵和四甲基氯化铵共同改性而成的双阳离子有机膨润土对水中硫氰根离子吸附的特征及机理。结果表明,在温度25℃,溶液pH=7,硫氰根离子质量浓度为0.05 g·L-1的100 mL溶液中,加入有机改性膨润土质量1.5 g条件下,振荡吸附60 min,有机改性膨润土对硫氰根离子的吸附率可达97.05%。有机改性膨润土对硫氰根离子的等温吸附符合Langmuir等温吸附模型,吸附动力学更适合准一级动力学吸附模型,热力学参数计算表明,该吸附过程为自发过程,加热不利于反应的进行。     

荧光分光光度法测定配合物中的氰离子

建立了测定配合物中氰离子含量的荧光分光光度法,使用无色荧光素钠在氰离子和铜离子的存在下,能够被氧化成荧光素钠而显现荧光。实验结果表明,在200~800 ng/m L测定范围内,氰化物呈现良好的线性关系,线性方程为y=0.083 34x-3.312 3,相关系数为r=0.999 3,检出限为40 ng/m L,该方法可用于含氰配合物的测定。     

臭氧降解水中CN~-活性的研究

国内每年约有千万吨含氰废水排入水体中,因氰化物属于剧毒物质,故研究臭氧氧化降解含氰废水的活性具有现实意义。研究了温度、臭氧使用量和pH值对含氰废水中氰根离子降解的影响。结果表明:臭氧降解含氰废水的处理效果好;处理质量浓度为150 mg/L的含氰废水,当反应温度为30℃,臭氧投加量为30 mg/min,臭氧浓度为9.4 mg/L,pH=10时,反应30 min后降解率可达99.8%;以臭氧降解氰根离子活性高,需要设备简单。     

氟离子聚合物荧光传感器的研究进展

近年来氟离子荧光传感器的研究受到了极大的关注。许多具有简便易用、反应迅速、准确灵敏等特性的氟离子传感器出现在生物医用、纳米材料科学和环境科学等领域。相比于小分子传感器,聚合物传感器具有多位点识别、传输信号应用及易器件化等优点。本文将对近年来氟离子聚合物荧光传感器的研究进展进行论述。     

化学传感器技术在离子检测中的研究进展

化学传感器技术在离子检测中发挥着重要作用。本文主要从电化学传感器、荧光传感器、生色（紫外）传感器3个方面对传感器技术在离子检测中的应用进行了综述,并对未来离子传感器的发展进行了展望。     

Chemosensors for pyrophosphate

The selective detection of the anion pyrophosphate (PPi) is a major research focus. PPi is a biologically important target because it is the product of ATP hydrolysis under cellular conditions, and because it is involved in DNA replication catalyzed by DNA polymerase, its detection is being investigated as a real-time DNA sequencing method. In addition, within the past decade, the ability to detect PPi has become important in cancer research. In general, the sensing of anions in aqueous solution requires a strong affinity for anions in water as well as the ability to convert anion recognition into a fluorescent or colorimetric signal. Among the variety of methods for detecting PPi, fluorescent chemosensors and colorimetric sensors for PPi have attracted considerable attention during the past 10 years. Compared with the recognition of metal ions, it is much more challenging to selectively recognize anions in an aqueous system due to the strong hydration effects of anions. Consequently, the design of PPi sensors requires the following: an understanding of the molecular recognition between PPi and the binding sites, the desired solubility in aqueous solutions, the communicating and signaling mechanism, and most importantly, selectivity for PPi over other anions such as AMP and ADP, and particularly phosphate and ATP. This Account classifies chemosensors for PPi according to topological and structural characteristics. Types of chemosensors investigated and reported in this study include those that contain metal ion complexes, metal complexes combined with excimers, those that function with a displacement approach, and those based on hydrogen-bonding interaction. Thus far, the utilization of a metal ion complex as a binding site for PPi has been the most successful strategy. The strong binding affinity between metal ions and PPi allows the detection of PPi in a 100% aqueous solution. We have demonstrated that carefully designed receptors can distinguish between PPi and ATP based on their different total anionic charge densities. We have also demonstrated that a PPi metal ion complex sensor has a bioanalytical application. This sensor can be used in a simple and quick, one-step, homogeneous phase detection method in order to confirm DNA amplification after polymerase chain reaction (PCR).     

基于杯芳烃识别金属离子的荧光化学传感器研究进展

杯芳烃荧光传感器以杯芳烃衍生物为识别主体,以荧光为信号传感手段,通过主体和客体间的选择性结合,实现对客体分子的定性和定量检测。由于荧光传感器具有高度灵敏性、良好选择性和易于操作等优点,研究能选择性识别金属离子的荧光化学传感器对生命化学和环境化学都具有非常重要的意义。文章就基于杯芳烃识别金属离子（碱金属离子、碱土金属离子、重金属离子、过渡金属离子）的荧光化学传感器研究进展进行了综述。     

光学活性1,1'-联-2-萘酚类合成受体的应用研究新进展

具有光学活性的1,1'-联-2-萘酚及其衍生物由于其本身具有C2对称轴而具有独特的化学性质和手性诱导功能,且在适合结构基团修饰下能产生很强的荧光,在不对称催化和手性客体的荧光识别等方面得到了广泛的应用.在与手性胺、手性醇、糖类、手性阴离子、手性氨基醇和手性氨基酸等手性化合物作用时,该类受体在不同位点接受客体分子,通过光...     

罗丹明类荧光探针研究进展

文章主要介绍近年来罗丹明衍生物在分子探针方面研究的一些新进展,系统阐述了该类探针分子在离子和小分予检测方面的应用.     

Simultaneous removal and recovery of cadmium and cyanide ions in synthetic wastewater by ion exchange

Simultaneous removal and recovery of cyanide and cadmium ions using a strong-base anion exchange resin was studied on the basis of formation of Cd-CN complexes at high pH in synthetic wastewater containing cyanide and cadmium ions. Strong-base anion exchange resin particles, of Dowex1X8-50, were contacted with synthetic aqueous solutions. For different molar ratios between cyanide and cadmium, ion exchange characteristics of cadmium-cyanide complexes were studied experimentally in a batch reactor. Treatment efficiencies of packed and fluidized beds were compared under various conditions. Several regenerants, NaSCN, NaCN, and NaOH, were used to regenerate the exhausted resin. The rates of regeneration and recovery for the various regenerants were estimated and discussed. The resin used in this work, Dowex1X8-50, can exchange about 6.6 CIST meq./g resin and 3.2 Cd²⁺ meq./g resin of cyanide and cadmium ions as complexes, respectively. Free cyanide ion has a lower selectivity than Cd-CN complexes on the anion exchange resin. The degree of treatment efficiency applied in this study was greater in the fluidized bed than packed bed. NaSCN was the best regenerant among regenerants used for regeneration of resin saturated with Cd-CN complexes.     

Über die Reaktion von Chloranil mit Cyanidionen – eine ESR-Studie

On the Reaction of Chloranil with Cyanide Ions – an ESR Study The reaction of chloranil 1 with cyanide ions in acetonitrile and methanol solutions has been studied. The ESR Spectra revealed the formation of semiquinone anion radicals 7,8 , and 9 . The latter has been found as its protonated form in methanol only. In addition, both 1 and 2,3-dicyano-5,6-dichloro-1,4-benzoquinone 4 gave tetracyanoethylene anion radicals 6 upon reaction with cyanide ions in acetonitrile. Using ¹³C-labelled cyanide 6 was shown to originate from the fragmentation of the cyanide addition product to 4 . Using the spin trapping technique it was found that no cyanyl free radicals are formed during the thermal reaction of either 1 or 4 with cyanide ions.     

Fluorescence sensors for lithium ions and small peptides

Simple but powerful chemosensors were developed by taking advantage of self-assembly processes. First, we will describe a turn-on fluorescent sensor for the pharmacologically important lithium ion. The sensor can be used in purely aqueous solution, and it displays a very high selectivity for lithium over sodium and magnesium ions. It is based on a metallacrown receptor unit, which can be assembled in situ from simple building blocks. Furthermore, we will describe a cross-reactive sensor array for the detection of small peptides. The individual sensors of the array are formed by mixing metal complexes with fluorescent dyes.     

Removal of heavy metal-cyanide complexes by ion exchange

Simultaneous removal of heavy metal and cyanide ions in an ion exchange column is studied on the basis of formation of metal-cyanide complexes at high pH range. Strong base anion exchange resin beads were contacted with water containing heavy metal (Cu, Cd, Zn) and cyanide ions in semi-fluidized and fluidized beds. Compositions of the heavy metal-cyanide complexes formed for different heavy metal and cyanide concentrations are used to explain the ion exchange behavior. Ion exchange equilibrium data of this study were fitted well with the Langmuir isotherm. The ion exchange capacity of CNas metal complexes increased to about three times that of free cyanide due to higher selectivity of metal complexes on the anion exchange resin. The ion exchange efficiency of the three heavy metalcyanide systems decreases as the concentration ratio of cyanide and heavy metal increases. The regeneration rates of the regenerants used was in the order of NaSCN>NaCN>NaOH, and the regeneration rate of NaOH was substantially lower than other two. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Transport of zinc complexes through an anion exchange membrane

The transport of zinc complexes ions through an anion exchange membrane was evaluated by the treatment of solutions with and without cyanide. The ionic transport was analyzed as a function of the applied current density and of the cyanide and hydroxyl concentration. Experimental results showed that the ionic transfer in electrodialysis was mainly affected by concentration. There is an ideal molar relationship among the concentration of the cyanide ions, hydroxyl and zinc ions, in solution, in which the zinc transport is maximized. For values above or below this, the transport decreases. Zinc extraction from solution containing CN⁻ was more effective when the current density of 29 mA.cm⁻² was applied. The current–voltage curves (CVC) of the anion exchange membrane show that the electrical resistance of the AMV membrane increases with the presence of the zinc–cyanide complex in the solution.     

Anodic oxidation of potassium cyanide on the graphite electrode

The mechanism of anodic oxidation of cyanide on the graphite electrode was investigated by voltammetry, controlled potential coulometry, constant potential electrolysis and colorimetry. Cyanide was oxidized at the first order with respect to cyanide ion and at the zero order with respect to hydroxyl ion on the rate determining step. On the other hand, the result of controlled potential coulometry indicated that n_app was 2 at high OH? concentration, but approached unity at low OH? concentration. When constant potential electrolyses were carried out using electrolytes containing concentrated OH? and diluted OH?, the presence of cyanate was confirmed in both products. In addition to this, since oxalate anion was detected in the product at low OH? concentration, cyanogen, (CN)₂ was considerable to form an intermediate. Based on these results, two probable mechanisms were proposed. The discharge of cyanide ion is considerable to determine the overall rate in both mechanisms. Furthermore, it is informed that the side reaction forming oxalate anion proceeds at low OH? concentration.