A Luminescence Assay in the Red for the Detection of Hydrogen Peroxide and Glucose Based on Metal Coordination Polyelectrolyte-Induced Supramolecular Self-Assembly of Alkynylplatinum(II) Complexes.

A new sensing strategy towards hydrogen peroxide based on metal coordination polyelectrolyte-driven self-assembly of alkynylplatinum(II) 2,6-bis(benzimidazol-2'-yl)pyridine (bzimpy) complex was demonstrated. The cationic in situ-generated Ag(I)-thiocholine coordination polyelectrolytes were shown to induce the supramolecular self-assembly of anionic low-energy red-emissive alkynylplatinum(II) bzimpy complexes via non-covalent Pt(II)⋅⋅⋅Pt(II), electrostatic and π-π stacking interactions. The presence of hydrogen peroxide was shown to inhibit the formation of coordination polyelectrolytes and the coordination polyelectrolyte-induced self-assembly of platinum(II) complexes. The weakening of Pt(II)⋅⋅⋅Pt(II), electrostatic and π-π stacking interactions was supported by UV-vis absorption, emission, and resonance light scattering (RLS) studies. The present assay was also applied to probe glucose indirectly based on the enzymatic reaction of glucose oxidase on the substrate. Operating in a label-free manner, together with the low-energy red emission and large Stokes shift of alkynylplatinum(II) complexes, these features render the proposed design attractive for biological applications.

Aggregation and Supramolecular Self-Assembly of Low-Energy Red Luminescent Alkynylplatinum(II) Complexes for RNA Detection, Nucleolus Imaging, and RNA Synthesis Inhibitor Screening.

As an important nuclear substructure, the nucleolus has received increasing attention because of its significant functions in the transcription and processing of ribosomal RNA in eukaryotic cells. In this work, we introduce a proof-of-concept luminescence assay to detect RNA and to accomplish nucleolus imaging with the use of the supramolecular self-assembly of platinum(II) complexes. Noncovalent interactions between platinum(II) complexes and RNA can be induced by the introduction of a guanidinium group into the complexes, and accordingly, a high RNA affinity can be achieved. Interestingly, the aggregation affinities of platinum(II) complexes enable them to display remarkable luminescence turn-on upon RNA binding, which is a result of the strengthening of noncovalent Pt(II)···Pt(II) and π-π stacking interactions. The complexes exhibit not only intriguing spectroscopic changes and luminescence enhancement after RNA binding but also specific nucleolus imaging in cells. As compared to fluorescent dyes, the low-energy red luminescence and large Stokes shifts of platinum(II) complexes afford a high signal-to-background autofluorescence ratio in nucleolus imaging. Additional properties, including long phosphorescence lifetimes and low cytotoxicity, have endowed the platinum(II) complexes with the potential for biological applications. Also, platinum(II) complexes have been adopted to monitor the dynamics of the nucleolus induced by the addition of RNA synthesis inhibitors. This capability allows the screening of inhibitors and can be advantageous for the development of antineoplastic agents. This work provides a novel strategy for exploring the application of platinum(II) complex-based cell imaging agents based on the mechanism of supramolecular self-assembly. It is envisaged that platinum(II) complexes can be utilized as valuable probes because of the aforementioned appealing advantages.

Amyloid Protein-Induced Supramolecular Self-Assembly of Water-Soluble Platinum(II) Complexes: A Luminescence Assay for Amyloid Fibrillation Detection and Inhibitor Screening.

Amyloid fibrillation has been acknowledged as a hallmark of a number of neurodegenerative ailments such as Alzheimer's disease. Accordingly, efficient detection of amyloid fibrillation will allow for great advances in the field of biomedical applications as well as in achieving early medical diagnosis. In this work, a luminescence assay for the sensitive and specific detection of amyloid fibrillation was developed by using platinum(II) complexes as sensing platforms. Supramolecular self-assembly of platinum(II) complexes was induced upon addition of amyloid, leading to alterations in the spectroscopic and luminescence properties of the complexes. As compared to fluorescent dyes, luminescent platinum(II) complexes exhibit attractive large Stokes shifts, phosphorescence lifetimes in the microsecond to submicrosecond regime, and low-energy red emission after aggregation, which are advantageous to biological imaging. At the same time, the platinum(II) complex adopted herein was found to have high photostability, high selectivity and specificity, and low cytotoxicity. The proposed design is the very first approach to detect amyloid fibrillation through the supramolecular self-assembly of luminescent platinum(II) complexes.

Arginine-Rich Peptide-Induced Supramolecular Self-Assembly of Water-Soluble Anionic Alkynylplatinum(II) Complexes: A Continuous and Label-Free Luminescence Assay for Trypsin and Inhibitor Screening.

A water-soluble anionic alkynylplatinum(II) 2,6-bis(benzimidazol-2'-yl)pyridine (bzimpy) complex has been strategically designed and synthesized to show supramolecular self-assembly with cationic arginine-rich peptides through unique noncovalent Pt(II)···Pt(II) and π-π stacking interactions. Upon introduction of trypsin, the arginine-rich peptides can be hydrolyzed into small fragments and deaggregation of the platinum(II) complex molecules is observed. The aggregation-deaggregation process has been probed by UV-vis absorption, emission, and resonance light scattering (RLS) studies. This platinum(II) complex has been employed for developing a new, continuous and label-free luminescence assay for trypsin as well as for inhibitor screening, and has been successfully applied to detect trypsin in diluted serum solutions.