Basheer Sabeel M, Muralisankar M, Anjana T V, Aneesrahman K N, Sreekanth Anandaram
Department of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, India.
Department of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, India.
Spectrochim Acta A Mol Biomol Spectrosc. 2017 Jul 5;182:95-104. doi: 10.1016/j.saa.2017.04.002. Epub 2017 Apr 4.
The selective chemosensing behaviour of imidazole bisthiocarbohydrazone (IBTC) towards F and Cu are studied via colorimetric, UV-Visible, fluorescence spectra studies, and binding constants were calculated. The H NMR titration study strongly support that the deprotonation of IBTC followed by the hydrogen bond formation via N1H1 and N2H2 protons with fluoride ion. The fluorescence inactive IBTC-Cu complex became fluorescence active in the presence of perchlorate (ClO) ion. The selective detection of perchlorate ion was also explained. The F sensing mechanism of IBTC has been investigated by Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TDDFT) methods. The theoretical outcomes well reproduce the experimental results. And it concluded the NH protons, nearby the imine group was first captured by the added F ion and then deprotonation happened followed by the formation of hydrogen bond. The IBTC found good reversibility character with the alternative addition of Ca and F. The multi-ion detection of IBTC was used to construct the NOR, OR and INHIBITION molecular logic gates.
通过比色法、紫外可见光谱法和荧光光谱法研究了咪唑双硫代碳腙（IBTC）对氟离子和铜离子的选择性化学传感行为，并计算了结合常数。¹H NMR滴定研究有力地支持了IBTC的去质子化，随后通过N1H1和N2H2质子与氟离子形成氢键。荧光无活性的IBTC-Cu络合物在高氯酸根（ClO₄⁻）离子存在下变得具有荧光活性。还解释了高氯酸根离子的选择性检测。通过密度泛函理论（DFT）和含时密度泛函理论（TDDFT）方法研究了IBTC的氟离子传感机制。理论结果很好地再现了实验结果。结果表明，添加的氟离子首先捕获亚胺基团附近的NH质子，然后发生去质子化，随后形成氢键。发现IBTC在交替添加钙离子和氟离子时具有良好的可逆性。利用IBTC的多离子检测构建了“或非”、“或”和“与非”分子逻辑门。
