Dye Assemblies Research Articles

Disentangling the Orientations of Spectrally Overlapping Transition Dipoles in Dense Dye Layers

The transition dipole orientations of dye assemblies in heterostructures have a crucial impact on the efficiency of novel optoelectronic devices such as organic thin-film transistors and light-emitting diodes. These devices are frequently based on heterojunctions and tandem structures featuring multiple optical transitions. Precise knowledge of preferred orientations, spatial order, and spatial variations is highly relevant. We present a fast and universal large-area screening method to determine the transition dipole orientations in dye assemblies with diffraction-limited spatial resolution. Moreover, our hyperspectral imaging approach disentangles the orientations of different chromophores. As a demonstration, we apply our technique to dye monolayers with two optical transitions sandwiched between two ultrathin silicate nanosheets. A comprehensive model for dipole orientation distributions in monolayers reveals a long-range orientational order and a strong correlation between the two transitions.

Advances in orderly assembly of fluorescent small molecular probes and related bioimaging applications

<p indent="0mm">Fluorescence imaging technology based on small molecule probes has the advantages of high sensitivity, simple operation, fast response speed, small sample damage and high spatial and temporal resolution, and is a powerful tool for obtaining biochemical information at the cellular and living level. Among them, the orderly assembled fluorescent small molecule probes have better imaging performance than traditional small-molecule fluorescent probes (such as strong anti-diffusion ability, high imaging contrast, and good photostability due to their unique assembly methods and recognition modes). This article summarizes the applications of several common organic dye aggregates and corresponding small molecule fluorescent probes in the field of bioimaging. Subsequently, the design and optimization strategies of organic dye assemblies represented by HPQ and its derivatives with hydrogen-bond-driven ordered assembly and their applications in the biomedical field are highlighted. Finally, the problems existing in the design and application of ordered assembled fluorescent small molecule probes are discussed, which provides ideas for the design of new ordered assembled fluorescent small molecule probes.

Impact of ethanol and NaCl on the acid yellow dye mediated self-aggregation of sodium dodecyl sulfate: A combined investigation by conductivity and molecular dynamics simulation

Herein, we report the micellization behavior of the mixture of sodium dodecyl sulfate (SDS), and acid yellow (AY) dye in water, water + ethanol, and water + NaCl media. The degree of interaction between SDS and AY has been assessed quantitatively from the estimated values of critical micelle concentration (cmc). Three cmc values were observed for the AY + SDS systems at each temperature and solvents utilized, which exhibit a reversed U-shaped variation with respect to the change of temperature in aqueous/NaCl solution while increased monotonically in ethanolic medium almost in all cases. The extent of micellization was found to be disfavored in presence of AY dye. The micellization was also found to be disfavored up to 15% ethanol and favored in the addition of electrolyte species. The values of counterion binding were found to be temperature dependent. The Gibbs free energy (ΔGmo), which was found negative, reveal a spontaneous micellization of AY + SDS system. The other thermodynamic parameters, like enthalpy (ΔHmo) and entropy (ΔSmo) of micellization along with different transfer energies, were also assessed to have an insight on the mode of interaction of surfactant and dye assemblies. The molecular level interaction between SDS and AY has been unveiled by Molecular Dynamics (MD) simulation and exhibits good agreement with experimental results.

Inside Front Cover: Organic dye assemblies with aggregation‐induced photophysical changes and their bio‐applications

Photophysical property changes of organic dye can be realized by controlling their aggregation state. These changes result in red/blue shift of absorption/emission band, activation of phosphorescence, or photothermal/photodynamic effect (generating heat or ROS). Because of dye self-assembly in aqueous environment, the obtained nanoaggregates show great potential for optical diagnosis and therapy of cancer. (Aggregate. 2021;2:e39)

Organic dye assemblies with aggregation‐induced photophysical changes and their bio‐applications

AbstractPhototheranostics provide a safe, effective, and noninvasive way for the diagnosis and treatment of contemporary diseases, and organic dyes play a vital role. For example, chemical modification endowed dyes with powerful reactive oxygen species or heat generation ability, favoring for photodynamic therapy and photoacoustic (PA) imaging guided photothermal therapy (PTT) of serious diseases. Therefore, photophysical properties manipulation of dyes has become the focus in current dye chemistry research. The development of aggregate science has made great effort to solve this problem. In recent years, a large number of studies have focused on molecular aggregation behavior and its effect on photophysical performance. The most famous example is the discovery of aggregation‐induced emission (AIE) phenomenon. Based on AIE theory, more theories for revealing the relationship between molecular aggregation behavior and photophysical properties were proposed and elucidated. The photophysical property changes caused by dye aggregation have become a unique discipline, guiding the development of molecular science and material science. With the help of molecular self‐assembly, controllable aggregation of dyes can be realized, and stable nano‐theranostic reagents can be obtained. Furthermore, constructing dye assemblies with various photophysical properties will greatly reduce the cost of theranostic reagents, thus, expanding biomedical applications of organic dyes. Therefore, this review focuses on the photophysical characteristic changes caused by dye aggregation and their biological applications including, fluorescence/phosphorescence/PA imaging as well as photodynamic and PTT. This review will provide guidance for the design of organic dyes, the development of controllable aggregation methods, and the construction of multifunctional phototheranostic reagents.

G-quadruplex apurinic site-programmed chiral cyanine assemblies for specifically recognizing guanosine and guanine.

DNA-tuned dye assemblies have received considerable attention toward developing various devices. Owing to easy conformation implementation, G-quadruplexes (G4s) have been extensively used as initiators to grow dye assemblies with controllable chiralities. However, programmed chirality regulation of dye assemblies for a given G4 sequence has not been realized in a straightforward manner. In this work, we replaced a middle guanine in the G-tracts of a human telomeric G4 with an apurinic site (AP site) to meet the programmed dye assemblies. Although all of the AP site replacements altered the G4 conformation from the hybrid to the antiparallel folding, the handedness of pinacyanol (PIN) assemblies grown on the AP site-containing G4 was programmably regulated. The G4 with the AP site at the 5'-most G-tract grew right-handed assemblies, while that with the AP site at the 3'-most G-tract grew left-handed assemblies. The handedness of assemblies almost totally mirrored each other within 450-700 nm. Interestingly, we found that the AP site provided a specific binding site for guanosine and guanine, and this binding event sensitively broke the chiral assemblies. Thus, dye assembly-based sensors can be easily established based on the chiral responses with a high selectivity and sensitivity. Our work first demonstrates the AP site programmed chirality regulation of G4-grown dye assemblies and will find wide application in chiral devices.

Concurrent formation of H- and J-aggregates of dyes with chiralities individually determined by G-quadruplex handedness

DNA templated dye assemblies pave an easy way to regulate the optical properties of molecular aggregates. G-quadruplexes (G4s) provide versatile DNA platforms for the dye assemblies since their foldings can be easily tuned by cation ions and sequences. In this work, we found that the G4 handedness can be used to control the aggregate chirality of a dye of 3,3′-diethylthiacarbocyanine (DiSC2(3)). The left-handed and right-handed G4s can template the concurrent formation of the J- and H-aggregates of DiSC2(3) with emergence of the featured absorption spectra. However, the chiral J-aggregate of DiSC2(3) can be formed only on the left-handed G4s, while the chiral H-aggregate is otherwise grown only on the right-handed G4s, as confirmed by the induced circular dichroism (ICD) spectra with the characteristic splitting bands. Additionally, these G4s even at tens of nM level are efficient to produce these chiral aggregates, demonstrating the high sensitivity of G4s in creating these optically active dye assemblies. The possible growth sites of the aggregates are proposed by the sequence length-dependent assemblies. Our work will provide a new way to control the chiral assemblies of dye aggregates via the G4 handedness.

Porphyrin‐Ryleneimide Hybrids: Low‐Bandgap Acceptors in Energy‐Transfer Cassettes

Efficient energy and electron transfer in photoexcited dye assemblies is of fundamental importance in both biological and artificial light-harvesting systems. Efficient transfer according to the Förster mechanism is now reported in multi-chromophore cassettes consisting of four BODIPY units rigidly linked to a pseudo-tetrahedral acceptor dye. This central chromophore was obtained by fusing porphyrin and perylenediimide motifs and displays strong absorption extending into the near infrared. More information can be found in the Communication by Dongho Kim, Marcin Stępień et al.

Ultrafast Relaxations in Ruthenium Polypyridyl Chromophores Determined by Stochastic Kinetics Simulations.

Maximizing the efficiency of solar energy conversion using dye assemblies rests on understanding where the energy goes following absorption. Transient spectroscopies in solution are useful for this purpose, and the time-resolved data are usually analyzed with a sum of exponentials. This treatment assumes that dynamic events are well separated in time, and that the resulting exponential prefactors and phenomenological lifetimes are related directly to primary physical values. Such assumptions break down for coincident absorption, emission, and excited state relaxation that occur in transient absorption and photoluminescence of tris(2,2'-bipyridine)ruthenium(2+) derivatives, confounding the physical meaning of the reported lifetimes. In this work, we use inductive modeling and stochastic chemical kinetics to develop a detailed description of the primary ultrafast photophysics in transient spectroscopies of a series of Ru dyes, as an alternative to sums of exponential analysis. Commonly invoked three-level schemes involving absorption, intersystem crossing (ISC), and slow nonradiative relaxation and incoherent emission to the ground state cannot reproduce the experimentally measured spectra. The kinetics simulations reveal that ultrafast decay from the singlet excited state manifold to the ground state competes with ISC to the triplet excited state, whose efficiency was determined to be less than unity. The populations predicted by the simulations are used to estimate the magnitudes of transition dipoles for excited state excitations and evaluate the influence of specific ligands. The mechanistic framework and methodology presented here are entirely general, applicable to other dye classes, and can be extended to include charge injection by molecules bound to semiconductor surfaces.

Two Orthogonal Halogen-Bonding Interactions Directed 2D Crystalline Supramolecular J-Dimer Lamellae.

Dye assemblies exhibit fascinating properties and performances, both of which depend critically on the mutual packing arrangement of dyes and on the supramolecular architecture. Herein, we engineered, for the first time, an intriguing chlorosome-mimetic 2D crystalline J-dimer lamellar structure based on halogenated dyes in aqueous media by employing two distinct orthogonal halogen-bonding (XB) interactions. As the only building motif, antiparallel J-dimer was formed and stabilized by single π-stacking and dual halogen⋅⋅⋅π interactions. With two substituted halogen atoms acting as XB donors and the other two acting as acceptors, the constituent J-dimer units were linked by quadruple highly-directional halogen⋅⋅⋅halogen interactions in a staggered manner, resulting in unique 2D lamellar dye assemblies. This work champions and advances halogen-bonding as a remarkably potent tool for engineering dye aggregates with a controlled molecular packing arrangement and supramolecular architecture.

The Interplay between Solvation and Stacking of Aromatic Rings Governs Bright and Dark Sites of Benzo[g]coumarins.

Coumarins are classic, strongly polarized fluorophores with multiple applications, and significant efforts have been put into modifying their emission characteristics and elucidating their photophysics. Expecting that π-expansion of these donor-acceptor chromophores could modify their ground- and excited-state characteristics, the authors performed combined, detailed photophysical and computational studies of linearly π-expanded coumarins, that is, 8-dialkylamino-3-carboxyalkyl-benzo[g]coumarins. The investigation led to the conclusion that emission is only possible thanks to the stabilizing effect of the solvent and that breaking of the lactone ring leads to the conical intersection with the ground state and induces the radiationless decay of the electronic excitation. Aiming at the fine-tuning the excited state properties through the construction of covalently linked dye assemblies, the authors designed and synthesized a new bis(benzo[g]coumarin), built from two similar moieties that exhibit different degrees of polarization due to the electron donor at position 8: one possesses a dialkylamino, and the other a weaker amide donor. Comprehensive studies have shown that the observed weak fluorescence of the system is the result of the interplay between the solvation-induced separation of the benzo[g]coumarin moieties, which stabilizes the emitting locally excited singlet state and the π-stacking interactions, favoring their sandwiched orientation and leading to the non-emissive charge-transfer state.

Discrete π-Stacks from Self-Assembled Perylenediimide Analogues.

The formation of well-defined finite-sized aggregates represents an attractive goal in supramolecular chemistry. In particular, construction of discrete π-stacked dye assemblies remains a challenge. Reported here is the design and synthesis of a novel type of discrete π-stacked aggregate from two comparable perylenediimide (PDI) dyads (PEP and PBP). The criss-cross PEP-PBP dimers in solution and (PBP-PEP)-(PEP-PBP) tetramers in the solid state are well elucidated using single-crystal X-ray diffraction, dynamic light scattering, and diffusion-ordered NMR spectroscopy. Extensive π-π stacking between the PDI units of PEP and PBP as well as repulsive interactions of swallow-tailed alkyl substituents are responsible for the selective formation of discrete dimer and tetramer stacks. Our results reveal a new approach to preparing discrete π stacks that are appealing for making assemblies with well-defined optoelectronic properties.

Discrete π‐Stacks from Self‐Assembled Perylenediimide Analogues

AbstractThe formation of well‐defined finite‐sized aggregates represents an attractive goal in supramolecular chemistry. In particular, construction of discrete π‐stacked dye assemblies remains a challenge. Reported here is the design and synthesis of a novel type of discrete π‐stacked aggregate from two comparable perylenediimide (PDI) dyads (PEP and PBP). The criss‐cross PEP‐PBP dimers in solution and (PBP‐PEP)‐(PEP‐PBP) tetramers in the solid state are well elucidated using single‐crystal X‐ray diffraction, dynamic light scattering, and diffusion‐ordered NMR spectroscopy. Extensive π–π stacking between the PDI units of PEP and PBP as well as repulsive interactions of swallow‐tailed alkyl substituents are responsible for the selective formation of discrete dimer and tetramer stacks. Our results reveal a new approach to preparing discrete π stacks that are appealing for making assemblies with well‐defined optoelectronic properties.

Directed Energy Transfer through DNA-Templated J-Aggregates.

Strongly coupled molecular dye aggregates have unique optoelectronic properties that often resemble those of light harvesting complexes found in Nature. The exciton dynamics in coupled dye aggregates could enhance the long-range transfer of optical excitation energy with high efficiency. In principle, dye aggregates could serve as important components in molecular-scale photonic devices; however, rational design of these coupled dye aggregates with precise control over their organization, interactions, and dynamics remains a challenge. DNA nanotechnology has recently been used to build an excitonic circuit by organizing pseudoisocyanine (PIC) dyes forming J-aggregates on the templates of poly(dA)-poly(dT) DNA duplexes. Here, the excitonic properties of the PIC J-aggregates on DNA are characterized spectroscopically in detail using poly(dA)-poly(dT) tract lengths of 24 and 48 base pairs. The excitonic properties of these DNA templated dye assemblies depend on the length and sequence of the DNA template. The incorporation of a gap of two GC base pairs between two segments of poly(dA)-poly(dT) DNA markedly reduces the delocalization of excitation in the J-aggregates. With a quantum dot (QD) as the light absorber and energy donor and using Alexa Fluor 647 (AF647) as the energy acceptor, with a DNA-templated J-aggregate in between, significant energy transfer from QD to AF647 is observed over a distance far longer than possible without the aggregate bridge. By comparing the efficiency of energy transfer through a continuous J-aggregate with the efficiency when the aggregate has a discontinuity in the middle, the effects of energy transfer within the aggregate bridge between the donor and acceptor are evaluated.

Multipronged Biomimetic Approach To Create Optically Tunable Nanoparticles

AbstractCurrent biomimetics for medical applications use a single biomimetic approach to imitate natural structures, which can be insufficient for reconstructing structurally complex natural systems. Multipronged efforts may resolve these complexities. To achieve interesting nanostructure‐driven optical properties, a dual‐biomimetic system contained within a single nanoagent was engineered to recapitulate chlorosomes, efficient light‐harvesting organelles that have unique dye assemblies and tunable photonic properties. A series of chlorin dyes was synthesized, and these hydrophobic assemblies were stabilized inside a high‐density lipoprotein, a second biomimetic that enabled in vivo utility. This system resulted in tunable tumor imaging of intact (photoacoustic) and disrupted (activatable fluorescence) nanostructures. The successful demonstration of this multipronged biomimetic approach opens the door for reconstruction of complex natural systems for biomedical applications.

Multipronged Biomimetic Approach To Create Optically Tunable Nanoparticles.

Current biomimetics for medical applications use a single biomimetic approach to imitate natural structures, which can be insufficient for reconstructing structurally complex natural systems. Multipronged efforts may resolve these complexities. To achieve interesting nanostructure-driven optical properties, a dual-biomimetic system contained within a single nanoagent was engineered to recapitulate chlorosomes, efficient light-harvesting organelles that have unique dye assemblies and tunable photonic properties. A series of chlorin dyes was synthesized, and these hydrophobic assemblies were stabilized inside a high-density lipoprotein, a second biomimetic that enabled in vivo utility. This system resulted in tunable tumor imaging of intact (photoacoustic) and disrupted (activatable fluorescence) nanostructures. The successful demonstration of this multipronged biomimetic approach opens the door for reconstruction of complex natural systems for biomedical applications.

NIR-Emitting Alloyed CdTeSe QDs and Organic Dye Assemblies: A Nontoxic, Stable, and Efficient FRET System.

In the present work, we synthesize Near Infrared (NIR)-emitting alloyed mercaptopropionic acid (MPA)-capped CdTeSe quantum dots (QDs) in a single-step one-hour process, without the use of an inert atmosphere or any pyrophoric ligands. The quantum dots are water soluble, non-toxic, and highly photostable and have high quantum yields (QYs) up to 84%. The alloyed MPA-capped CdTeSe QDs exhibit a red-shifted emission, whose color can be tuned between visible and NIR regions (608–750 nm) by controlling the Te:Se molar ratio in the precursor mixtures and/or changing the time reaction. The MPA-capped QDs were characterized by UV-visible absorption spectroscopy, fluorescence spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), and zeta potential measurements. Photostability studies were performed by irradiating the QDs with a high-power xenon lamp. The ternary MPA-CdTeSe QDs showed greater photostability than the corresponding binary MPA-CdTe QDs. We report the Förster resonance energy transfer (FRET) from the MPA-capped CdTeSe QDs as energy donors and Cyanine5 NHS-ester (Cy5) dye as an energy acceptor with efficiency (E) up to 95%. The distance between the QDs and dye (r), the Förster distance (R0), and the binding constant (K) are reported. Additionally, cytocompatibility and cell internalization experiments conducted on human cancer cells (HeLa) cells revealed that alloyed MPA-capped CdTeSe QDs are more cytocompatible than MPA-capped CdTe QDs and are capable of ordering homogeneously all over the cytoplasm, which allows their use as potential safe, green donors for biological FRET applications.

Unravelling the High-Pressure Behaviour of Dye-Zeolite L Hybrid Materials

Self-assembly of chromophores nanoconfined in porous materials such as zeolite L has led to technologically relevant host-guest systems exploited in solar energy harvesting, photonics, nanodiagnostics and information technology. The response of these hybrid materials to compression, which would be crucial to enhance their application range, has never been explored to date. By a joint high-pressure in situ synchrotron X-ray powder diffraction and ab initio molecular dynamics approach, herein we unravel the high-pressure behaviour of hybrid composites of zeolite L with fluorenone dye. High-pressure experiments were performed up to 6 GPa using non-penetrating pressure transmitting media to study the effect of dye loading on the structural properties of the materials under compression. Computational modelling provided molecular-level insight on the response to compression of the confined dye assemblies, evidencing a pressure-induced strengthening of the interaction between the fluorenone carbonyl group and zeolite L potassium cations. Our results reveal an impressive stability of the fluorenone-zeolite L composites at GPa pressures. The remarkable resilience of the supramolecular organization of dye molecules hyperconfined in zeolite L channels may open the way to the realization of optical devices able to maintain their functionality under extreme conditions.

Near-Infrared-Emissive Amphiphilic BODIPY Assemblies Manipulated by Charge-Transfer Interaction: From Nanofibers to Nanorods and Nanodisks.

A novel near-infrared (NIR)-emissive amphiphilic BODIPY derivative, BBDP, was successfully prepared and thoroughly characterized. The photophysical properties in various organic solvents and THF/H2 O mixtures with different fractions of water were investigated. BBDP self-assembled into nanofibers in a water environment owing to its amphiphilic properties. Through charge-transfer interactions, BBDP co-assembled with a perylene bisimide derivative, PBI, and a viologen derivative, MV, to generate two superamphiphiles. These two superamphiphiles were able to aggregate in water media at appropriate concentrations. The BBDP-PBI charge-transfer complex formed nanorods, whereas the BBDP-MV aggregates expressed a disk-like morphology. This research paves the way for us to manipulate the morphology of dye assemblies.

Dendrimer–Dye Assemblies as Templates for the Formation of Gold Nanostructures

Dendrimer–dye assemblies are used as novel supramolecular nanoreactors for the formation of various gold nanostructures. The organic–inorganic hybrid systems are investigated with dynamic light scattering, UV–vis spectroscopy, and transmission electron microscopy (TEM) as well as cryo-TEM and high-resolution TEM (HRTEM). We show that the shape of the hybrid assemblies is determined by the choice and the ratio of the building blocks. Shape and size of the gold nanoparticles within the assemblies are controlled by the reducing agent. The accessible range of gold morphologies extends from small and spherical, over ellipsoidal, faceted, and large to highly anisotropic. The approach may open the way to new hybrid systems with applications in catalysis or in the biomedical field.