The c-myc proto-oncogene product, Myc, is a transcription factor that binds thousands of genomic loci 1 . Recent work suggested that rather than up-and down-regulating selected groups of genes 1-3 , Myc targets all active promoters and enhancers in the genome (a phenomenon termed "invasion") and acts as a general amplifier of transcription 4,5 . However, the available data did not readily discriminate between direct and indirect effects of Myc on RNA biogenesis. We addressed this issue with genome-wide chromatin immunoprecipitation and RNA expression profiles during Bcell lymphomagenesis in mice, in cultured B-cells and fibroblasts. Consistent with long-standing observations 6 , we detected general increases in total RNA or mRNA copies per cell (hereby termed "amplification") 4,5 when comparing actively proliferating cells with control quiescent cells: this was true whether cells were stimulated by mitogens (requiring endogenous Myc for a proliferative response) 7,8 or by deregulated, oncogenic Myc activity. RNA amplification and promoter/enhancer invasion by Myc were separable phenomena that could occur without one another. Moreover, whether or not associated with RNA amplification, Myc drove the differential expression of distinct subsets of target genes. Hence, while having the potential to interact with all active/poised regulatory elements in the genome 4,5,9-11 , Myc does not directly act as a global *
Low‐power photon upconversion (UC) based on sensitized triplet–triplet annihilation (sTTA) is considered as the most promising upward wavelength‐shifting technique to enhance the light‐harvesting capability of solar devices. Colloidal nanocrystals (NCs) with conjugated organic ligands have been recently proposed to extend the limited light‐harvesting capability of molecular absorbers. Key to their functioning is efficient energy transfer (ET) from the NC to the triplet state of the ligands that sensitize free annihilator moieties responsible for the upconverted luminescence. The ET efficiency is typically limited by parasitic processes, above all nonradiative hole‐transfer to the ligand highest occupied molecular orbital (HOMO). Here, a new exciton‐manipulation approach is demonstrated that enables loss‐free ET by electronically doping CdSe NCs with gold impurities that introduce a hole‐accepting intragap state above the HOMO energy of 9‐anthracene acid ligands. Upon photoexcitation, the NC photoholes are rapidly routed to the Au‐level, producing a long‐lived bound exciton in perfect resonance with the ligand triplet. This hinders hole‐transfer leading to ≈100% efficient ET that translates into an upconversion quantum yield as high as ≈12% (≈24% in the normalized definition), which is the highest performance for NC‐based upconverters based on sTTA to date and approaches the record efficiency of optimized organic systems.
Photon upconversion based on sensitized triplet−triplet annihilation (sTTA) is considered as a promising strategy for the development of light-managing materials aimed to enhance the performance of solar devices by recovering unused low-energy photons. Here, we demonstrate that, thanks to the fast diffusion of excitons, the creation of triplet pairs in metal−organic framework nanocrystals (nMOFs) with size smaller than the exciton diffusion length implies a 100% TTA yield regardless of the illumination condition. This makes each nMOF a thresholdless, single-unit annihilator. We develop a kinetic model for describing the upconversion dynamics in a nanocrystals ensemble, which allows us to define the threshold excitation intensity I th box required to reach the maximum conversion yield. For materials based on thresholdless annihilators, I th box is determined by the statistical distribution of the excitation energy among nanocrystals. The model is validated by fabricating a nanocomposite material based on nMOFs, which shows efficient upconversion under a few percent of solar irradiance, matching the requirements of real life solar technologies. The statistical analysis reproduces the experimental findings, and represents a general tool for predicting the optimal compromise between dimensions and concentration of nMOFs with a given crystalline structure that minimizes the irradiance at which the system starts to fully operate.
Photon upconversion based on sensitized triplet–triplet annihilation (sTTA‐UC) is a wavelength‐shifting technique with potential use in actuators, sensing, and solar technologies. In sTTA‐UC, the upconverted photons are the result of radiative recombination of high‐energy singlets, which are created through the fusion of metastable triplets of two annihilator/emitter molecules. The emitter triplets are populated via energy transfer (ET) from a low‐energy absorbing light‐harvester/sensitizer. The process is highly efficient at low powers in solution but becomes relatively ineffective in solid matrices since the limited molecular mobility precludes bimolecular interactions. The realization of efficient solid‐state upconverters that exhibit long‐term stability and are compatible with industrial fabrication processes is an open challenge. Here, nanophase‐separated polymer systems synthesized under ambient conditions that contain the upconverting dyes in liquid nanodomains is reported. The nanostructured polymers show an excellent optical quality, an outstanding upconversion efficiency of up to ≈23%, and excellent stability in air, with only negligible performance losses over a period of three months. Moreover, the dyes’ confinement in nanosized domains <50 nm results in an increased effective local density of chromophores that enables hopping‐assisted ET and TTA and confers to the upconversion process peculiar kinetics that enhances the material performance at low powers.
Photon up-conversion based on triplet–triplet annihilation (TTA) in a hybrid system exploits the annihilation of optically dark triplets of an organic emitter, sensitized by a semiconductor nanocrystal, to produce high-energy singlets that generate high energy emission.
Photon upconversion assisted by sensitized triplet–triplet annihilation (sTTA-UC) is a wavelength-shifting technique where high-energy photons are emitted from the radiative recombination of high-energy singlets populated through the annihilation of the metastable triplets of two annihilator/emitter molecules. The emitter triplets are previously populated via energy transfer from a light-harvester/sensitizer moiety that absorbs the incident low-energy photons. In solutions, this process is efficient even at low excitation powers, whereas the limited molecular mobility and short exciton lifetimes typically observed in solid matrices hinder the bi-molecular interactions making the sTTA-UC process rather ineffective. We show here that controlling the confinement of the upconverting dye pairs in nanostructured or nanosized materials results in an increased effective local density of the excitation energy. This also activates a specific sTTA-UC kinetics independent of the triplet excitons’ mobility that improves the material performance at low powers. We provide a complete modeling of the sTTA-UC process in confined systems. The results obtained afford useful guidelines for the future development of upconverting photonic devices operating at subsolar irradiances suitable for technological implementation.
Owing to the unique feature of the high conversion efficiency from low-energy photons to high-energy photons, triplet-triplet annihilation (TTA) based photon upconversion is a promising strategy for harvesting the low-energy...
The photon upconversion based on sensitized triplet−triplet annihilation (sTTA-UC) is a spin-flip mechanism exploited to recover the energy stored on dark triplet states in conjugated systems. In this process, a high-energy fluorescent singlet is created through the collision and fusion of two low-energy triplets belonging to different diffusing molecules. Its high yield in solution under low excitation intensity and noncoherent light highlighted the huge potential of sTTA-UC to provide a breakthrough in solar technologies. However, its diffusion-limited nature restrains its efficiency in the solid state. To overcome this issue, we propose a single-molecule system that is able to host simultaneously more than one triplet, thus enabling a diffusion-free intramolecular TTA. We obtain the first direct demonstration of intramolecular triplet fusion by tailored photoluminescence spectroscopy experiments, thus opening the way to realize a new family of single-molecule upconverters with huge potential in solar and lighting technologies by accessing the natural triplets' energy reservoir.
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