Cascade Energy Transfer Research Articles

Luminescent molecular solar concentrators made of multi-Bodipy dyes

Abstract The synthesis of photoactive arrays consisting of Bodipy scaffoldings is described. The synthetic strategy involved first the construction of functionalised modules, then the use of specific Knoevenagel reactions. Boron-protection is required to avoid self-condensation. Comparison of thienylBodipy dyes with their phenyl analogues showed them to be both less chemically stable and more weakly fluorescent. In the multichromophoric species, efficient cascade energy transfer occurs upon absorption in the highest energy unit. The redox activity of the mixed dyes is analysed in terms of the behaviour of specific reference compounds.

Synthesis of Luminescent Ethynyl‐Extended Regioisomers of Borate Complexes Based on 2‐(2′‐Hydroxyphenyl)benzoxazole

A series of thirteen luminescent tetrahedral borate complexes based on the 2-(2'-hydroxyphenyl)benzoxazole (HBO) core is presented. Their synthesis includes the incorporation of an ethynyl fragment by Sonogashira cross-coupling reaction, with the goal of extending the conjugation and consequently redshifting their emission wavelength. Different regioisomers, substituted in the 3-, 4-, or 5-position of the phenolate side of the HBO core, were studied in order to compare their photophysical properties. The complexes were characterized by X-ray diffraction and NMR, UV/Vis, and emission spectroscopy in solution and in the solid state. In all cases, complexation to boron leads to a donor-acceptor character that impacts their photophysical properties. Complexes with a 3- or 5-substituted fragment display mild to pronounced internal charge transfer (ICT), a feature strengthened by the presence of p-dibutylaminophenylacetylene in the molecular structure, protonation of the nitrogen atom of which leads to a significant blueshift and an increase in quantum yield. On the contrary, when the ethynyl module is grafted on the 4-position, narrow, structured, symmetrical absorption/emission bands are observed. Moreover, the fact that protonation has little effect on the emission maximum wavelength reveals singlet excited-state decay. Solid-state emission properties reveal a redshift compared to solution, explained by tight packing of the π-conjugated systems and the high planarity of the dyes. Subsequent connection of these complexes to other photoactive subunits (BODIPY, Boranil) provides dyads in which efficient cascade energy transfer is observed.

Integration of multiple chromophores with native photosynthetic antennas to enhance solar energy capture and delivery

Native length bacterial light-harvesting peptides carrying covalently attached designer chromophores have been created that self-assemble with native bacteriochlorophyll a (BChl a) to afford stable antennas with enhanced spectral coverage. Native (or native-like) α- and β-peptides interact with each other and BChl a to form a heterodimeric (αβ-dyad) unit that can then oligomerize to form biohybrid analogs of the bacterial core light-harvesting complex (LH1). Pairs of distinct synthetic chromophores were incorporated in αβ-dyads at selected distances from the BChl a target site (position 0). Two designs were explored. One design used green-yellow absorbing/emitting Oregon Green at the −34 position (toward the N-terminus relative to the BChl a coordination site) of β and orange-red absorbing/emitting Rhodamine Red at the −20 position of α, which combine with BChl a to give homogeneous oligomers. A second design used two different β-peptide conjugates, one with Oregon Green at the −34 position and the second with a near-infrared absorbing/emitting synthetic bacteriochlorin at the −14 position, which combine with α and BChl a to give a heterogeneous mixture of oligomers. The designs afford antennas with ∼45 to ∼60 pigments, provide enhanced spectral coverage across the visible and near-infrared regions relative to native antennas, and accommodate pigments at remote sites that contribute to solar light harvesting via an energy-transfer cascade. The efficiencies of energy-transfer to the BChl a target in the biohybrid antennas are comparable to native antennas, as revealed by static and time-resolved absorption and emission studies. The results show that the biohybrid approach, where designer chromophores are integrated via semisynthesis with native-like scaffolding, constitutes a versatile platform technology for rapid prototyping of antennas for solar energy capture without the laborious synthesis typically required for creating artificial photosynthetic light-harvesting architectures.

High-intensity near-IR fluorescence in semiconducting polymer dots achieved by cascade FRET strategy.

Near-IR (NIR) emitting semiconducting polymer dots (Pdots) with ultrabright fluorescence have been prepared for specific cellular targeting. A series of π-conjugated polymers were synthesized to form water dispersible multicomponent Pdots by an ultrasonication-assisted co-precipitation method. By optimizing cascade energy transfer in Pdots, high-intensity NIR fluorescence (φ = 0.32) with tunable excitations, large absorption-emission separation (up to 330 nm), and narrow emission bands (FWHM = 44 nm) have been achieved. Single-particle fluorescence imaging show that the as-prepared NIR Pdots were more than three times brighter than the commercially available Qdot705 with comparable sizes under identical conditions of excitation and detection. Because of the covalent introduction of carboxylic acid groups into polymer side chains, the bioconjugation between NIR-emitting Pdots and streptavidins can be readily completed via these functional groups on the surface of Pdots. Furthermore, through flow cytometry and confocal fluorescence microscopy the NIR-emitting Pdot-streptavidin conjugates proved that they could effectively label EpCAM receptors on the surface of MCF-7 cells, via specific binding between streptavidin and biotin.

Wide‐Range Light‐Harvesting Donor–Acceptor Assemblies through Specific Intergelator Interactions via Self‐Assembly

We have synthesized two new low-molecular-mass organogelators based on tri-p-phenylene vinylene derivatives, one of which could be designated as the donor whereas the other one is an acceptor. These were prepared specifically to show the intergelator interactions at the molecular level by using donor-acceptor self-assembly to achieve appropriate control over their macroscopic properties. Intermolecular hydrogen-bonding, π-stacking, and van der Waals interactions operate for both the individual components and the mixtures, leading to the formation of gels in the chosen organic solvents. Evidence for intergelator interactions was acquired from various spectroscopic, microscopic, thermal, and mechanical investigations. Due to the photochromic nature of these molecules, interesting photophysical properties, such as solvatochromism and J-type aggregation, were clearly observed. An efficient energy transfer was exhibited by the mixture of donor-acceptor assemblies. An array of four chromophores was built up by inclusion of two known dyes (anthracene and rhodamine 6G) for the energy-transfer studies. Interestingly, an energy-transfer cascade was observed in the assembly of four chromophores in a particular order (anthracene-donor-acceptor-rhodamine 6G), and if one of the components was removed from the assembly the energy transfer process was discontinued. This allowed the build up of a light-harvesting process with a wide range. Excitation at one end produces an emission at the other end of the assembly.

Exploiting Direct and Cascade Energy Transfer for Color-Tunable and White-Light Emission in Three-Component Self-Assembled Nanofibers

The co-self-assembly of a blue-light emitting organogelator and specifically designed green and red emitting hosts yields light-harvesting nanofibers with tunable emissive properties. In particular, under near-UV excitation white-light emission is achieved in organogels and their constituting nanofibers as demonstrated by confocal fluorescence microspectroscopy. Steady-state and time-resolved emission spectroscopies reveal that color tuning in three component nanofibers is achieved exploiting excitation energy transfers occurring between the blue-emitting anthracene derivative and the green- and red-emitting tetracenes, whereas the latter emission is further sensitized through a cascade blue-to-green-to-red transfer sequence. Moreover, excitation energy migrates through the blue-emitting components by exciton hopping before being transferred to the acceptors, thus contributing to the light-harvesting process.

Multifluorescently Traceable Nanoparticle by a Single-Wavelength Excitation with Color-Related Drug Release Performance

Monodisperse and nanometer-sized periodic mesoporous organosilicas co-doped with fluorescence resonance energy transfer cascades composed of triple fluorophores at various ratios were prepared. These nanoparticles exhibit multifluorescent emissions by a single-wavelength excitation and were designed for the application as multichannelly traceable drug carriers. Different from the hydrophilic framework of inorganic mesoporous silica and hydrophobic framework of mesoporous carbon, these multifluorescent nanoparticles have intrinsically different and finely tunable pore surface polarities governed by the type and amount of fluorophore inside the framework. When applied as drug carriers, they can achieve synchronous or asynchronous release of different drugs by simply choosing different colored nanoparticles. These colorful mesoporous composites with finely tunable color-related drug release performance provide a strong barcoding system for the potential applications of fluorescent nanoparticles in effective screening of drugs and therapeutic protocols for diseases.

Improving color stability of blue/orange complementary white OLEDs by using single-host double-emissive layer structure: Comprehensive experimental investigation into the device working mechanism

In this paper, we successfully improved the spectral stability in blue/orange complementary white organic light-emitting diodes (OLEDs) by utilizing hole-type single host double emissive layer structure. The demonstrated double emissive layer structure effectively suppresses the direct recombination of electron–hole pairs on the hole-trapping orange phosphor and thus reduces the deteriorated effect of charge trapping on electroluminescence spectrum stability by controlling exciton recombination zone. It is shown that the white light emission is a cascade energy transfer process from host to blue phosphor and then to orange phosphor, which seems to be less affected by the driving conditions. Thus, the change in Commission Internationale de L’Eclairage coordinates (CIE) in the white OLEDs is less than (±0.010, ±0.007) as the voltage increases from 4V to 9V, which correspond to the luminance increasing from 200cdm−2 to about 20,000cdm−2. This is superior to that of co-doped single emissive layer devices, which show much larger CIEs variation of (±0.05, ±0.02) in the same driving voltage range. We gave detailed analysis on the exciton recombination processes and well elucidated the working mechanism of the fabricated double emissive layer structure white OLEDs.

Step-by-step self-assembled hybrids that feature control over energy and charge transfer

In the current work, we have documented the use of two complementary supramolecular motifs, namely multipoint hydrogen bonding and metal complexation, as a means to control the step-by-step assembly of a panchromatically absorbing and highly versatile solar energy conversion system. On one hand, two different perylenediimides (1a/1b) have been integrated together with a metalloporphyrin (2) by means of the Hamilton receptor/cyanuric acid hydrogen bonding motif into energy transduction systems 1a•2 or 1b•2. Steady-state and time-resolved measurements corroborated that upon selective photoexcitation of the perylenediimides (1a/1b), an energy transfer evolved from the singlet excited state of the perylenediimides (1a/1b) to that of the metalloporphyrin (2). On the other hand, fullerene (3) and metalloporphyrin (2) form the electron donor-acceptor system 2•3 via axial complexation. Photophysical measurements confirm that an electron transfer prevails from the singlet excited state of 2 to the electron-accepting 3. The correspondingly formed radical ion pair state decays with a lifetime of 1.0 ± 0.1 ns. As a complement to the aforementioned, the energy transduction features of 1a•2 were combined with the electron donor-acceptor characteristics of 2•3 to afford 1a•2•3. To this end, time-resolved measurements reveal that the initially occurring energy-transfer interaction (53 ± 3 ps) between 1a/1b and 2 is followed by an electron transfer (12 ± 1 ps) from 2 to 3. From multiwavelength analyses, the lifetime of the radical ion pair state in 1a•2•3-as a product of a cascade of light-induced energy and electron transfer-was derived as 3.8 ± 0.2 ns.

Lasing Action in Dual-Doped Organic Microcavity with Cascade Energy Transfer

In this paper, we studied lasing action in dual-doped organic microcavity with cascade Forster energy transfer between polymer and two fluorescent dyes in surface emitting microcavities, which formed by sandwiching a poly(N-vinylcarzole) (PVK) film doped with 8-trishydroxyquinoline (Alq3) and 4-(dicyanomethylene)-2-tert-butyl-6 (1, 1, 7, 7-tet ramethyljulolidyl-9-enyl)-4H–pyran (DCJTB) between a distributed Bragg reflector (DBR) and a silver film mirror. The sample was optically pumped by a frequency-tripled Nd:YAG laser delivering 5.55ns pulses at 355nm with a 10Hz repetition rate. By optimizing the concentrations of Alq3 and DCJTB in PVK, a low lasing threshold of about 9.5µJ per pulse attributed to efficient cascade Forster energy transfer form PVK and Alq3 to DCJTB was obtained. The full width at half maximum (FWHM) of the emission was about 2nm with the peak wavelength at 628nm. Our results demonstrate that the PVK:Alq3:DCJTB could be a promising candidate as gain medium for red organic diode lasers.

Artificial photosynthetic reaction centers coupled to light-harvesting antennas

We analyze a theoretical model for energy and electron transfer in an artificial photosynthetic system. The photosystem consists of a molecular triad (i.e., with a donor, a photosensitive unit, and an acceptor) coupled to four accessory light-harvesting-antenna pigments. The resonant energy transfer from the antennas to the artificial reaction center (the molecular triad) is described here by the Förster mechanism. We consider two different kinds of arrangements of the accessory light-harvesting pigments around the reaction center. The first arrangement allows direct excitation transfer to the reaction center from all the surrounding pigments. The second configuration transmits energy via a cascade mechanism along a chain of light-harvesting chromophores, where only one chromophore is connected to the reaction center. We show that the artificial photosynthetic system using the cascade energy transfer absorbs photons in a broader wavelength range and converts their energy into electricity with a higher efficiency than the system based on direct couplings between all the antenna chromophores and the reaction center.

Synthesis of Luminescent 2-(2′-Hydroxyphenyl)benzoxazole (HBO) Borate Complexes

Complexation of boron trifluoride by a series of electron donor/acceptor substituted 2-(2'-hydroxy phenyl)benzoxazole (HBO) derivatives yields luminescent B(III) complexes with an emission wavelength ranging from 385 to 425 nm in dichloromethane or toluene. Appropriate chemical functionalization of these new dyes allows connection to different photoactive subunits (Boranil, BODIPY), endowing an efficient cascade energy transfer.

DNA-Directed Artificial Light-Harvesting Antenna

Designing and constructing multichromophoric, artificial light-harvesting antennas with controlled interchromophore distances, orientations, and defined donor-acceptor ratios to facilitate efficient unidirectional energy transfer is extremely challenging. Here, we demonstrate the assembly of a series of structurally well-defined artificial light-harvesting triads based on the principles of structural DNA nanotechnology. DNA nanotechnology offers addressable scaffolds for the organization of various functional molecules with nanometer scale spatial resolution. The triads are organized by a self-assembled seven-helix DNA bundle (7HB) into cyclic arrays of three distinct chromophores, reminiscent of natural photosynthetic systems. The scaffold accommodates a primary donor array (Py), secondary donor array (Cy3) and an acceptor (AF) with defined interchromophore distances. Steady-state fluorescence analyses of the triads revealed an efficient, stepwise funneling of the excitation energy from the primary donor array to the acceptor core through the intermediate donor. The efficiency of excitation energy transfer and the light-harvesting ability (antenna effect) of the triads was greatly affected by the relative ratio of the primary to the intermediate donors, as well as on the interchromophore distance. Time-resolved fluorescence analyses by time-correlated single-photon counting (TCSPC) and streak camera techniques further confirmed the cascading energy transfer processes on the picosecond time scale. Our results clearly show that DNA nanoscaffolds are promising templates for the design of artificial photonic antennas with structural characteristics that are ideal for the efficient harvesting and transport of energy.

Solution Processed Red Phosphorescent Organic Light-Emitting Diodes with Green Phosphorescent Ir Sensitizer

We fabricated the organic light-emitting diodes (OLEDs) with sensitizer by solution process. The addition of sensitizer into the emission layer improved the device efficiency. 4,4′-N,N′-dicarbazole-biphenyl (CBP), bis(2-phenylquinoline)iridium(III) (acetylacetonate) [Ir(pq)2(acac)], tris(2-phenylpyridine)iridium [Ir(ppy)3] were used as host, red emitting dopant, and sensitizer, respectively. The sensitizer leads to the cascade energy transfer from the host into the red emitting dopant. The doping concentration of sensitizer was varied as 0∼20 wt% and optimized. As a result, the device with 5% Ir(ppy)3 shows the luminous efficiency, power efficiency, and quantum efficiency of 5.1 cd/A, 4.0 lm/W, and 3.0%, respectively. These efficiencies are about 3 times as high as that of device without sensitizer.

Cascaded Energy Transfer for Efficient Broad‐Band Pumping of High‐Quality, Micro‐Lasers

Micro-ring lasers that exhibit a quality factor (Q) larger than 5.2 × 10{sup 6} with a direct-illumination, non-resonant pump are demonstrated. The micro-rings are coated with three organic dyes forming a cascaded energy-transfer, which reduces material-losses by a factor larger than 10{sup 4}, transforming incoherent light to coherent light with high quantum-efficiency. The operating principle is general and can enable fully integrated on-chip, high-Q micro-lasers.

Energy Transfer and Dual Cascade in Kinetic Magnetized Plasma Turbulence

The question of how nonlinear interactions redistribute the energy of fluctuations across available degrees of freedom is of fundamental importance in the study of turbulence and transport in magnetized weakly collisional plasmas, ranging from space settings to fusion devices. In this Letter, we present a theory for the dual cascade found in such plasmas, which predicts a range of new behavior that distinguishes this cascade from that of neutral fluid turbulence. These phenomena are explained in terms of the constrained nature of spectral transfer in nonlinear gyrokinetics. Accompanying this theory are the first observations of these phenomena, obtained via direct numerical simulations using the gyrokinetic code AstroGK. The basic mechanisms that are found provide a framework for understanding the turbulent energy transfer that couples scales both locally and nonlocally.

Removal of Synthetic Textile Dyes From Wastewaters: A Critical Review on Present Treatment Technologies

Azo dyes represent the largest class of industrial colorants. These are no longer used only for the coloration of textiles, plastics, paints, inks, and lacquers, but rather serve as key components in high-tech applications such as optical data storage, reprographics, display devices, dye-sensitized solar cells, energy transfer cascades, light-emitting diodes, laser welding processes, or heat management systems. Azo dyes are also of growing importance in the medical and biomedical fields. In most of these applications, the color is largely irrelevant and it is the ability of the colorants to absorb visible electromagnetic radiation with high efficiency, or other functional property, that is exploited. With the growing awareness and environmental concerns, it is imperative that the hierarchy of reduce, reuse, and degrade be adopted and measures be taken to remove color from the industrial discharge. The present review (a) embodies a comparison of the present decolorization/degradation techniques for water-soluble and insoluble dyes, (b) describes their advantages and limitations, (c) discusses various mechanisms, and (d) focuses on the present literature on microbial decolorization of textile dyes specifically by using bacteria, fungus, yeast, and algae. Also, for the first time an attempt has been made to comprehensively compile chemical and biological decolorization/degradation of disperse dyes. The research on the decolorization of textile dyes has mainly been focused on water-soluble dyes, while decolorization of disperse dyes that are water insoluble have received only scant attention and constitutes a topical area of concern as these dyes persist for a longer duration in textile effluents. Given the limitations (vide infra) of the chemical treatment methods, decolorization using biological means is an interesting option.

Facile Construction of Multicompartment Multienzyme System through Layer-by-Layer Self-Assembly and Biomimetic Mineralization

In nature, some organelles such as mitochondria and chloroplasts possess multicompartment structure, which render powerful and versatile performance in cascade conversion, selective separation, and energy transfer. In this study, mitochondria-inspired hybrid double membrane microcapsules (HDMMCs) were prepared through synergy between biomimetic mineralization and layer-by-layer (LbL) self-assembly using double templating strategy. The organic inner membrane was acquired via LbL self-assembly of oxidized alginate (o-alginate) and protamine on the CaCO(3) template, the silica template layer was then formed onto the inner membrane through biomimetic silicification using protamine as inducer and silicate as precursor, the organic-inorganic hybrid outer membrane was acquired via biomimetic mineralization of titanium precursor. After the CaCO(3) template and the silica template are removed subsequently, multicompartment microcapsules with microscale lumen and nanoscale intermembrane space were obtained. The double membrane structure of the HDMMCs was verified by high resolution scanning electron microscopy (HRSEM), and the superior mechanical stability of HDMMCs was demonstrated by osmotic pressure experiment and fluorescence microscopy. A multienzyme system was constructed by following this protocol: the first enzyme was encapsulated in the lumen of the HDMMCs, whereas the second enzyme was encapsulated in the intermembrane space. Compared to encapsulated multienzyme in single-compartment microcapsules (SCMCs) or in free form in aqueous solution, enzymatic activity, selectivity, and recycling stability of HDMMCs-enabled multienzyme system were significantly improved. Because of the inherent gentle and generic feature, the present study can be utilized to create a variety of compartment structures for the potential applications in chemical/biological catalysis and separation, drug/gene delivery systems, and biosensors.

Selective Detection of Neurotoxin by Photoluminescent Peptide Nanotubes

Photoluminescent peptide nanotubes undergo a drastic quenching of their emission within a few seconds of exposure to paraoxon, a nitro-functionalized neurotoxin. The photoluminescence quenching occurs due to the interruption of cascaded energy transfer from peptide nanotubes to lanthanide ions. The assay platform provides high selectivity toward paraoxon, among other organophosphates, nitro-group compounds, and common organic chemicals; this capability is attributed to the role of the diphenylalanine nanotubes as a host matrix for lanthanide complexes.

Three dye energy transfer cascade within DNA thin films

An efficient cascade FRET was realized in solid state DNA-CTMA thin films using a three chromophore system without any covalent attachments. The extent of energy transfer from Cm102 to SRh was studied and found to improve eight-fold using the bridging dye Pm567.