Enzymatic synthesis of fluorescent oligomers assembled on a DNA backbone

A number of research laboratories have investigated the properties of multichromophore molecules and their applications in materials science and in biotechnology. Previous approaches for preparing such molecules have involved traditional organic synthesis. Here we describe the one-step enzymatic synthesis of such a multichromophore species by using a DNA-polymerizing enzyme (terminal deoxynucleotidyl transferase (TdT)). We find that a nucleotide-like molecule with pyrene replacing the DNA base (dPTP) can be accepted as a substrate for this enzyme to produce discrete chromophores that have 3 or 4 pyrenes consecutively, depending on which anomer (alpha or beta) is used. Products were characterized by gel electrophoresis, mass spectrometry, and fluorescence. The reaction was found to change the fluorescence emission of the chromophore from a maximum at 375 nm (the monomer nucleotide) to 490 nm in the oligomeric product. This new green-white emission is consistent with the formation of a pyrene excimer between adjacent pyrene glycosides, which exhibit a large Stokes shift of 130 nm. The enzymatic synthesis of the pyrene excimer might have applications in homogeneous biological assays for DNA fragments, such as those that arise during apoptosis.     

Color Tuning of Avobenzone Boron Difluoride as an Emitter to Achieve Full‐Color Emission

Organic light‐emitting diodes (OLEDs) displaying a wide range of emission colors with emission peaks from 450 to 665 nm using a single emitting material, avobenzone boron difluoride (AVB‐BF₂), are reported. Color tuning is achieved by controlling the aggregation of AVB‐BF₂ and the formation of a “triadic” exciplex of an AVB‐BF₂ dimer and a host molecule. Various electroluminescent devices containing AVB‐BF₂ cover the whole visible light spectrum and a white‐emitting device with CIE coordinates of (0.35, 0.37) is obtained with a single emitting material in a single emissive layer. Furthermore, an exceptionally high external quantum efficiency of nearly 13% is achieved for a green‐emitting OLED because AVB‐BF₂ exhibits thermally activated delayed fluorescence by forming the exciplex.     

Pyrene-modified unlocked nucleic acids: synthesis, thermodynamic studies, and fluorescent properties

Two pyrene-modified UNA monomers were synthesized and incorporated into 21-mer DNA oligonucleotides. Melting temperatures and thermodynamic properties of the modified duplexes were measured, and the fluorescence properties of single strands and duplexes containing one or more pyrene-UNA modifications were studied. It was found that incorporation of pyrene-UNA monomers increased duplex stability relative to UNA monomers, and thermodynamic studies revealed significant mismatch discriminative capabilities of the pyrene-UNA modified oligonucleotides. Furthermore, the steady-state fluorescence emission intensities of pyrene-UNA modified oligonucleotides were increased upon hybridization to DNA, which to the best of our knowledge is unprecedented for an acyclic pyrene modification in DNA. Interestingly, pyrene excimer emission was observed for single-stranded oligonucleotides containing three pyrene-UNA modifications, whereas this excimer emission disappeared after hybridization to DNA. In view of both the pyrene monomer and the excimer fluorescence emission, the triply modified oligonucleotides show intriguing properties relating to the development of new DNA/RNA detection tools.     

Tetradentate Platinum Complexes for Efficient and Stable Excimer‐Based White OLEDs

A series of tetradentate platinum complexes that exhibit both efficient monomer and excimer emission are synthesized. Via small modifications to the cyclometalating ligands, both the monomer and excimer emission energy can be separately tuned. Devices employing all of the developed emitters demonstrate impressively high external quantum efficiencies (EQEs) within the range of 22% to 27% for concentrations between 2% and 16%. The halogen‐free design of the complexes also enables the fabrication of single, doped, white organic light‐emitting diodes (OLEDs) with long operational lifetimes. A balanced white device employing the complex Pt2O2, achieves a device operational lifetime to 80% of the initial luminance estimated at over 200 h at 1000 cd m^–2, while also achieving 12.5% peak EQE for a warm white light with a color rendering index of 80. Furthermore, a highly doped device exhibiting nearly exclusive excimer emission showed an impressive operational lifetime, which is estimated at more than 400 h for 1000 cd m^‐2.     

Molecular Gelation‐Induced Functional Phase Separation in Polymer Film for Energy Transfer Spectral Conversion

A new strategy for creating the energy transfer spectral conversion thin film by using fluorophore‐functionalized molecular gelation is proposed. This is based on the facts that nanofibrillar phase separation of the self‐assembling pyrene derivative as a fluorophore is formed in a bulk polymer‐containing organic gel, and consequently that the phase‐separated nano domain in a polymer thin film is enough small to keep the transparency but also extremely high Storks shift is gained by efficient excimer formation through highly ordered stacking among the pyrene moieties. When the phase separation‐mediated functional polymer is applied as spectral conversion films (SCFs) for copper–indium–gallium–selenide (CIGS) solar cell, the SCF‐covered solar cell exhibits significant improvement of power conversion efficiency by increase of photocurrent. In this paper, the FRET efficiency and emission wavelength are also demonstrated to be thermotropically switchable since order‐to‐disordered transitions are essential characteristics of as non‐covalent low molecular assembling.