Design and synthesis of thiourea based receptor containing naphthalene as oxalate selective sensor

Conspectus Coordination-driven self-assembly utilizes the spontaneous formation of metal-ligand bonds in solution to drive mixtures of molecular building blocks to single, unique 2D metallacycles or 3D metallacages based on the directionality of the precursors used. The supramolecular coordination complexes (SCCs) obtained via this process are characterized by well-defined internal cavities and facile pre- or post-self-assembly functionalizations. These properties augment the modularity of the directional bonding design strategy to afford structures with unprecedented tunability both spatially and electronically. Over the past decades, a number of synthetic design methodologies have become established which has led to a substantial library of complexes supported by numerous structural studies. More recently, there has been an emergence of research centered on the potential applications of SCCs, which has developed rapidly on the foundations provided by the aforementioned synthetic and structural bodies of work. The necessary presence of metal ions as structural elements for the directional bonding approach can be exploited to provide biological activity to an SCC, particularly for Pt and Ru-based structures. Since these two metals are not only among the most commonly used for coordination-driven self-assembly but are also the basis for a number of small molecule anticancer agents, a growing number of SCCs have been evaluated for their antitumor properties. When the internal cavity of a cage is optimized for guest encapsulation, a second vector for biological activity, namely drug delivery, is unlocked. Since cages can offer both inherent activity due to their metal ions, as well as delivery of exogenous drug molecules, such ensembles are particularly promising chemotherapeutic agents. The non-covalent interactions of SCCs with guest molecules oftentimes manifest photophysical changes to the resulting host/guest complex. Since a metallacage or cycle can be readily tuned to match a specific guest, certain SCCs are well-suited to act as fluorescence-based sensors for biologically relevant analytes. These interactions are not limited to small molecule analytes, however, and SCCs are increasingly being studied for their chemistry with macro biomolecules including DNA and proteins. In particular, dinuclear iron and ruthenium-based helicates bind to a variety of DNA constructs through non-covalent mechanisms. Studies concerning these cylindrical SCCs, which have expanded beyond Ru and Fe, often include characterizations of specific interactions with DNA or other biomolecules. Such investigations are not limited to dinuclear M2L3 helicates; Pt-based squares are well-suited to stabilize G-quadruplex DNA and rhomboid metallacycles can unravel supercoiled DNA, further demonstrating the versatility of multinuclear supramolecular architectures. Understanding these interactions in the context of observed cytotoxicities and other biological consequences is critical for developing new chemotherapeutic agents and developing mech...

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“…As oxalate exchange disruption is a marker for a number of diseases, it is an important oxyanion in biology. 29 …”

Section: Metallosupramolecular Sensorsmentioning

confidence: 99%

Biomedical and Biochemical Applications of Self-Assembled Metallacycles and Metallacages

et al. 2013

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“…For example, the oxalate anion plays an important role in the functioning of the human body, as quite a number of diseases are associated with the disruption of oxalate exchange. [3] Citrate and tartrate are key metabolites in cellular intermediary metabolism, such as the Kreb’s cycle, and are also essential sources of fatty acids and cholesterol, which are important for hormone synthesis and tissue regeneration. [4] Citrate can also be used as a biomarker in a reliable screening method for prostate cancer.…”

Section: Introductionmentioning

confidence: 99%

Self‐Assembled Arene–Ruthenium‐Based Rectangles for the Selective Sensing of Multi‐Carboxylate Anions

Vajpayee

Song

Lee

et al. 2011

Chemistry A European J

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Novel arene-ruthenium [2+2] metalla-rectangles, 4 and 5, were synthesized by the self-assembly approach using a dipyridyl amide ligand (3) and arene-ruthenium acceptors (arene: benzoquinone (1); naphthacenedione (2)), and characterized by NMR and ESI-MS. The solid-state structure of 5 determined by X-ray diffraction shows the encapsulated diethyl ether molecules in the rectangular cavity of 5. The luminescent 5 was further utilized for anion sensing where the amidic linkage serves as a hydrogen bond donor site for anions, and the ruthenium moiety serves as a signaling unit. A UV-vis titration study demonstrates that, while 5 interacts very weakly with the common mono anions as well as flexible dicarboxylate anions such as malonate and succinate, it displays significant binding affinity (K > 103 in MeOH) for the rigid multi-carboxylate anions such as oxalate, citrate, and tartrate in a 1:1 fashion. It is suggested that the 1:1 bidentate hydrogen bonding assisted by the proper geometrical complementarities is mainly responsible for the increased affinity of 5 towards such anions. In particular, a fluorescence titration study reveals a large fluorescence enhancement of 5 upon binding with multi-carboxylate anions. This indicates that the fluorescence enhancement is attributed to the blocking of the photo-induced electron transfer process from the arene-Ru moiety to the amidic donor in 5 as a result of hydrogen bonding between the donor and the anion.

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“…It shows the large number of charge transfer between phosphate ion and receptors 1, 2 and 3. As found in the previous reports, the higher charge transfer between anion and receptor is the stronger binding interaction [18,30], then the PO 4 3-complexes, the highest in charge transfer, are the most stable complexes.…”

Section: Thermodynamic Property Changes Of Complexationmentioning

confidence: 62%

“…For example, a number of simple tripodal receptors based on amine [8,9], urea [10,11] and thiourea [12][13][14][15] have been synthesized and their binding ability with various anions has been evaluated. In addition, the theoretical investigation has been reported to be the high potential tool to investigate the interaction between thiourea based receptor and anions [16][17][18].…”

Section: Introductionmentioning

confidence: 99%

A theoretical investigation on structures of tripodal thiourea derivatives and their anion recognition

et al. 2011

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The structural geometries of three tripodal thiourea receptors, i.e. 1,3,5-triethyl-2,4,6-tris[(N 0 -methylthioureido)methyl]benzene (1), tris[N 0 -methyl-N-(2-aminoethyl) thiourea]methane (2), tris[N 0 -methyl-N-(2-aminoethyl)thiourea]amine (3), and their complexes with F -, Cl -, Br -, I -, NO 3 -, CO 3 2-, SO 4 2-, HSO 4 -, PO 4 3-, HPO 4 2-and H 2 PO 4 -were obtained using the density functional theory calculations. Electronic and thermodynamic properties of anion binding complexes of the receptors 1, 2 and 3 were investigated. Recognition abilities of all the receptors in terms of selectivity coefficients are reported. Intermolecular interactions in all the studied complexes occurring via multi-point hydrogen bonding were found. The receptors 1, 2 and 3 were found to be excellent selectivity for phosphate ion and their binding free energy for the phosphate ion are -292.57, -291.77 and -295.01 kcal/mol, respectively.

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Design and synthesis of thiourea based receptor containing naphthalene as oxalate selective sensor

Cited by 22 publications

References 23 publications

Biomedical and Biochemical Applications of Self-Assembled Metallacycles and Metallacages

Biomedical and Biochemical Applications of Self-Assembled Metallacycles and Metallacages

Self‐Assembled Arene–Ruthenium‐Based Rectangles for the Selective Sensing of Multi‐Carboxylate Anions

A theoretical investigation on structures of tripodal thiourea derivatives and their anion recognition

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