SENSORS FOR ANIONS OF ENVIRONMENTAL AND BIOMEDICAL RELEVANCE

环境和生物医学相关阴离子传感器

• 批准号: 8166138
• 负责人: Md. Alamgir Hossain
• 金额: $ 9.74万
• 依托单位: JACKSON STATE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-06-01 至 2011-05-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8166138
• 关键词: Affinity; Anions; Binding; Binding Sites; Bromides; Chloride Ion; Chlorides; Complex; Computer Retrieval of Information on Scientific Projects Database; Dimethyl Sulfoxide; Fluorescence; Fluorescence Spectroscopy; Fluorides; Funding; Grant; Hydrobromic Acid; Hydrogen Bonding; Inorganic Sulfates; Institution; Iodides; Ligands; Nitrates; Nitrogen; Perchlorates; Reaction; Research; Research Personnel; Resources; Side; Site; Solutions; Source; Structure; Thiophenes; Titrations; United States National Institutes of Health; Unspecified or Sulfate Ion Sulfates; Vertebral column; Work; X-Ray Crystallography; base; design; inorganic phosphate; sensor; solid state; stoichiometry; tertiary amine

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. The second year's work involves the (i) continuation of the binding studies for anions with the four azamacrocyclces (L1, L2, L4 and L5) in the first year, (ii) synthesizing two new compounds (L3 and L6), (iii) NMR titrations for halides and oxoanions, (iv) determination of structures by X-ray crystallography. The synthesized macrocyclic based compounds with paraxylyl (L1) and thiophene (L2) spacers have been shown to effectively bind toxic perchlorate anion in both solution and solid states. The compounds contain suitable cavity consisting of multiple binding sites in their structural backbone. Studies showed that these macrocycles are capable of binding two perchlorates via multiple hydrogen bonds with protonated nitrogen sites, resulting into ditopic complexes in both cases. A hexaaminomacrocycle L3, containing four secondary and two tertiary amines has been synthesized and crystallized with hydrobromic acid. Structural analysis of the bromide complex suggests that the ligand in its tetrtaprotonated form, is involved in coordinating two bromides from both sides via hydrogen bonding interactions, forming a ditopic complex. A macrocyclic-based fluorescence chemosensor (L6) has been designed and synthesized from the reaction of dansyl chloride and a hexaaminomacrocycle containing four secondary and two tertiary amines. The new chemosensor has been examined for its binding ability toward phosphate, sulfate, nitrate, iodide, bromide, chloride, and fluoride by fluorescence spectroscopy in DMSO. The results indicate that the compound binds each of the anions with a 1:1 stoichiometry, showing high affinity for the oxoanions, chloride and iodide with the binding constants up to four orders of magnitude.

这个子项目是许多研究子项目中的一个 由NIH/NCRR资助的中心赠款提供的资源。子项目和 研究者（PI）可能从另一个NIH来源获得了主要资金， 因此可以在其他CRISP条目中表示。所列机构为 研究中心，而研究中心不一定是研究者所在的机构。 第二年的工作包括（i）继续第一年的四个氮杂大环（L1，L2，L4和L5）的阴离子结合研究，（ii）合成两个新化合物（L3和L 6），（iii）卤化物和含氧阴离子的NMR滴定，（iv）通过X射线晶体学确定结构。 合成的具有对二甲苯基（L1）和噻吩（L2）间隔基的大环化合物已被证明在溶液和固体状态下都能有效地结合有毒的高氯酸根阴离子。所述化合物在其结构骨架中含有由多个结合位点组成的合适空腔。研究表明，这些大环化合物能够通过多个氢键与质子化的氮位点结合两个高氯酸盐，在两种情况下都产生ditopic复合物。合成了一种含四个仲胺和两个叔胺的六氨基大环L_3，并用氢溴酸结晶。溴配合物的结构分析表明，在其四质子化形式的配体，参与协调两个溴化物从两侧通过氢键相互作用，形成一个ditopic复合物。设计并合成了一种基于大环的荧光化学传感器（L 6），该传感器由丹磺酰氯和含有4个仲胺和2个叔胺的六氨基大环反应而成。用荧光光谱法研究了该传感器对磷酸根、硫酸根、硝酸根、碘离子、溴离子、氯离子和氟离子的结合能力。结果表明，该化合物结合的每一个阴离子与1：1的化学计量，显示出高亲和力的含氧阴离子，氯离子和碘离子的结合常数高达四个数量级。