Tailoring Conformation-Induced Chromism of Polythiophene Copolymers for Nucleic Acid Assay at Resource Limited Settings.

Here we report on the design and synthesis of cationic water-soluble thiophene copolymers as reporters for colorimetric detection of microRNA (miRNA) in human plasma. Poly(3-alkoxythiophene) (PT) polyelectrolytes with controlled ratios of pendant groups such as triethylamine/1-methyl imidazole were synthesized for optimizing interaction with target miRNA sequence (Tseq). Incorporation of specific peptide nucleic acid (PNA) sequences with the cationic polythiophenes yielded distinguishable responses upon formation of fluorescent PT-PNA-Tseq triplex and weakly fluorescent PT-Tseq duplex, thereby enabling selective detection of target miRNA. Unlike homopolymers of PT (hPT), experimental results indicate the possibility of utilizing copolymers of PT (cPT) with appropriate ratios of pendant groups for miRNA assay in complex matrices such as plasma. As an illustration, colorimetric responses were obtained for lung cancer associated miRNA sequence (mir21) in human plasma, with a detection limit of 10 nM, illustrating the feasibility of proposed methodology for clinical applications without involving sophisticated instrumentation. The described methodology therefore possesses high potential for low-cost nucleic acid assays in resource-limited settings.

Visual detection of Al(3+) ions using conjugated copolymer-ATP supramolecular complex.

A colorimetric Al(3+) sensor based on fluorescence recovery of a conjugated copolymer-ATP complex is proposed. An optimized ratio of two polythiophene (PT) monomers is utilized to synthesize copolymer (CP) that yielded maximized colorimetric response for Al(3+) in deionized (DI) and tap water. The electrostatic disassembly of CP-ATP upon addition of Al(3+) led to an evident visual color change. The lowest concentration of Al(3+) for naked eye observation is around 4 µM, which is below the threshold levels in drinking water according to European Economic Community (EEC) standard. Besides, the proposed assay showed a similar response to Al(3+) in tap water. The proposed methodology showed selective and sensitive detection for Al(3+) in analytically relevant concentration ranges without involving sophisticated instrumentation, illustrating the applicability for on-site drinking water monitoring.

Polythiophene derivative on quartz resonators for miRNA capture and assay.

A novel approach for miRNA assay using a cationic polythiophene derivative, poly[3-(3'-N,N,N-triethylamino-1'-propyloxy)-4-methyl-2,5-thiophene hydrobromide] (PT), immobilized on a quartz resonator is proposed. The cationic PT enables capturing of all RNA sequences in the sample matrix via electrostatic interactions, resulting in the formation of PT-RNA duplex structures on quartz resonators. Biotinylated peptide nucleic acid (b-PNA) sequences are subsequently utilized for the RNA assay, upon monitoring the PT-RNA-b-PNA triplex formation. Signal amplification is achieved by anchoring avidin coated nanoparticles to b-PNA in order to yield responses at clinically relevant concentration regimes. Unlike conventional nucleic acid assay methodologies that usually quantify a specific sequence of RNA, the proposed approach enables the assay of any RNA sequence in the sample matrix upon hybridization with a PNA sequence complementary to the RNA of interest. As an illustration, successful detection of mir21, (a miRNA sequence associated with lung cancer) is demonstrated with a limit of detection of 400 pM. Furthermore, precise quantification of mir21 in plasma samples is demonstrated without requiring PCR and sophisticated instrumentation.

Self-Assembly of Conjugated Units Using Metal-Terpyridine Coordination.

Due to their inherently dynamic natures and fascinating photoluminescent/photoelectronic properties, coordination compounds of metal ions and conjugated terpyridine ligands have attracted considerable attention as functional materials for a variety of potential applications. In this feature article, a summary of recent work toward the development of one- (1D), two- (2D), and three-dimensional (3D) supramolecular polymers, networks, and metallomacrocycles based on zinc metal ion coordination of conjugated units bearing terpyridine ligands is presented, and it is shown how it fits within the overall framework of work in this field. Here, a sequential study from terpyridines as basic building blocks to their zinc-coordinated supramolecular 1D polymers, 2D macrocycles, and 2D and 3D networks is developed. These networks are compared with respect to their thermal stabilities, molecular organization, and linear and nonlinear optical properties. This work opens new prospects for the development of supramolecular chemistry of terpyridines and other transition metal ions, and also their application in future optoelectronic devices.

Large two-photon absorption of terpyridine-based quadrupolar derivatives: towards their applications in optical limiting and biological imaging.

Developing organic chromophores with large two-photon absorption (TPA) in both organic solvents and aqueous media is crucial owing to their applications in solid-state photonic devices and biological imaging. Herein, a series of novel terpyridine-based quadrupolar derivatives have been synthesized. The influences of electron-donating group, type of conjugated bridge, as well as solvent polarity on the molecular TPA properties have been investigated in detail. In contrast to the case in organic solvents, bis(thienyl)-benzothiadiazole as a rigid conjugated bridge will completely quench molecular two-photon emission in aqueous media. However, the combination of alkylcarbazole as the donor and bis(styryl)benzene as a conjugation bridge can enlarge molecular TPA cross-sections in both organic solvent and aqueous media. The reasonable two-photon emission brightness for the organic nanoparticles of chromophores 3-5 in the aqueous media, prepared by the reprecipitation method, enables them to be used as probes for in vivo biological imaging.