Sheet Sanjoy Kumar, Sen Bhaskar, Thounaojam Romita, Aguan Kripamoy, Khatua Snehadrinarayan
Centre for Advanced Studies, Department of Chemistry, North Eastern Hill University , Shillong, Meghalaya 793022, India.
Department of Biotechnology and Bioinformatics, North Eastern Hill University , Shillong, Meghalaya 793022, India.
Inorg Chem. 2017 Feb 6;56(3):1249-1263. doi: 10.1021/acs.inorgchem.6b02343. Epub 2017 Jan 18.
A new bis-heteroleptic Ru(II) complex (1) of benzimidazole-substituted 1,2,3-triazole pyridine ligand has been designed and constructed for the photoluminescent detection of cationic and anionic analytes, Ag and phosphate ions. Compound, 1[PF] was fully characterized by various spectroscopic techniques and the solid-state structure was determined via single-crystal X-ray diffraction. The cation and anion sensing properties in 50% aqueous buffer (pH 9.2) and pure acetonitrile were carefully examined in photoluminescence (PL) spectroscopy. The 1[PF] was found to be highly selective to pyrophosphate; PPi/HPO and HPO ions in CHCN. It showed ∼10-fold PL intensity enhancement at 583 nm in the presence of only 1 and 2 equiv of PPi and HPO ions, respectively. The PL titrations of 1[PF] with PPi and HPO in CHCN furnished the association constant (K = 3.3 × 10 M and 6.8 × 10 M) and the detection limit was as low as 5.73 and 5.19 ppb, respectively. The 1[PF] also selectively detected Ag over other competitive cations through the luminescence light up in 50% aqueous buffer (pH 9.2) media. The PL titration of 1[PF] with Ag showed ∼8-fold luminescence enhancement at 591 nm and yielded association constant, K = 3.5 × 10 M and the detection limit was determined to be 5.05 ppb. A new cation sensing mechanism has been established where the Ag ion is detected in photoluminescence spectroscopy through the unique cyclometalated Ag-triazolide complex formation. The high selectivity of 1[PF] for phosphates and Ag was established by PL in the presence of various competing ions. Finally, for biological application, the cytotoxicity study was performed. The probe showed low cytotoxicity and was suitable for intracellular Ag imaging. The cell imaging and in vitro photoluminescence study revealed that the probe stained the cell nucleoli and specifically bind with ribosomal RNA (rRNA) and, therefore, it can also serve as a luminescent probe for rRNA in the presence of Ag.
设计并构建了一种新型的苯并咪唑取代的1,2,3 - 三唑吡啶配体的双异质Ru(II)配合物(1)，用于阳离子和阴离子分析物、Ag和磷酸根离子的光致发光检测。化合物1[PF]通过各种光谱技术进行了全面表征，并通过单晶X射线衍射确定了其固态结构。在光致发光(PL)光谱中仔细研究了其在50%水性缓冲液(pH 9.2)和纯乙腈中的阳离子和阴离子传感特性。发现1[PF]对焦磷酸根具有高度选择性；在CHCN中对PPi/HPO和HPO离子也有选择性。在仅存在1和2当量的PPi和HPO离子时，它在583 nm处的PL强度分别增强了约10倍。1[PF]与CHCN中的PPi和HPO的PL滴定提供了缔合常数(K = 3.3×10 M和6.8×10 M)，检测限分别低至5.73和5.19 ppb。1[PF]还通过在50%水性缓冲液(pH 9.2)介质中的发光增强，选择性地检测Ag而不受其他竞争性阳离子的干扰。1[PF]与Ag的PL滴定在591 nm处显示出约8倍的发光增强，得到缔合常数K = 3.5×10 M，检测限确定为5.05 ppb。建立了一种新的阳离子传感机制，即在光致发光光谱中通过独特的环金属化Ag - 三唑配合物的形成来检测Ag离子。通过在各种竞争性离子存在下的PL确定了1[PF]对磷酸盐和Ag的高选择性。最后，进行了生物应用的细胞毒性研究。该探针显示出低细胞毒性，适用于细胞内Ag成像。细胞成像和体外光致发光研究表明，该探针可对细胞核仁进行染色，并与核糖体RNA(rRNA)特异性结合，因此，在存在Ag的情况下，它也可作为rRNA的发光探针。
