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.
Multiphoton excited fluorescent probes
with highly emissive, photostable,
low cytotoxic properties are very important for photodynamic therapy,
sensing, and bioimaging, etc., even though still challenging. Here,
we report the synthesis and spectroscopic studies of two statistical
Zn(II)-coordinated copolymers containing different donor types and
the same acceptor type (a dithienylbenzothiadiazole-based ditopic
terpyridine ligand), aiming to achieving efficient multiphoton harvesting
systems. Our results indicate that an angular carbazole-based ditopic
terpyridine ligand donor shows a strong tendency to form a twisted
intramolecular charge transfer (TICT) state. Taking advantage of the
large multiphoton absorption coefficient in the donor and efficient
Förster resonance energy transfer (FRET) mediated by TICT state,
efficiently enhanced fluorescence from the acceptor under two- and
even three-photon excitation is consequently achieved. In contrast,
for a linear carbazole-based ditopic terpyridine ligand donor, the
enhanced multiphoton excited fluorescence from the acceptor originates
from reabsorption effect instead of FRET. For the first time, we have
reported the multiphoton harvesting properties of metal–organic
complexes, especially stressing the crucial role of TICT state in
multiphoton excited FRET, which sheds light on how to design efficient
multiphoton harvesting systems in general.
Multiphoton excited fluorescence of organic molecules is promising in the applications of efficient nonlinear optical devices and bioimaging. However, they usually have disadvantages of poor photostability and serious fluorescence quenching in aqueous media or solid state, which seriously limit their related applications. In this work, for the first time, the two‐photon excited Förster resonance energy transfer (FRET) process is used to enhance the solid‐state fluorescence of the supramolecular centre (acceptor) in an artificial 3D metal–organic complex (MLC), in which a 3D Zn (II)‐coordinated tetrahedral core is utilized as the donor. More interestingly, the two‐photon light harvesting system, which can be pumped with an optical intensity as low as 1 MW/cm2, exhibits an ultrafast energy transfer rate (∼6.9 × 108 s−1) and ultrahigh photostability. The underlying physical mechanisms are revealed through comprehensive steady‐state and time‐resolved spectroscopic analysis. This work demonstrates that the 3D MLC can be directly used in two‐photon bioimaging and also sheds light on developing other multiphoton harvesting systems, such as metal–organic frameworks.
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.
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.
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.
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