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.

该子项目是利用该技术的众多研究子项目之一 资源由 NIH/NCRR 资助的中心拨款提供。子项目和 研究者 (PI) 可能已从 NIH 的另一个来源获得主要资金， 因此可以在其他 CRISP 条目中表示。列出的机构是 对于中心来说，它不一定是研究者的机构。 第二年的工作包括 (i) 继续第一年的阴离子与四种氮杂大环化合物（L1、L2、L4 和 L5）的结合研究，(ii) 合成两种新化合物（L3 和 L6），(iii)卤化物和含氧阴离子的 NMR 滴定，(iv) 通过 X 射线晶体学测定结构。 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可以在溶液和固态下有效结合有毒的高氯酸根阴离子。该化合物在其结构主链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氮位点结合两个高氯酸盐，从而在两种情况下形成双位复合物。合成了含有四个仲胺和两个叔胺的六氨基大环L3，并用氢溴酸结晶。溴化物络合物的结构分析表明，四质子化形式的配体参与通过氢键相互作用配位两侧的两个溴化物，形成双位络合物。通过丹酰氯和含有四个仲胺和两个叔胺的六氨基大环的反应，设计并合成了基于大环的荧光化学传感器（L6）。通过 DMSO 中的荧光光谱检查了新型化学传感器对磷酸盐、硫酸盐、硝酸盐、碘化物、溴化物、氯化物和氟化物的结合能力。结果表明，该化合物以 1:1 的化学计量与每种阴离子结合，对含氧阴离子、氯离子和碘离子表现出高亲和力，结合常数高达四个数量级。