J-aggregates Of Dyes Research Articles

Facilely Achieving Near-Infrared-II J-Aggregates through Molecular Bending on a Donor-Acceptor Fluorophore for High-Performance Tumor Phototheranostics.

Constructing J-aggregated organic dyes represents a promising strategy for obtaining biomedical second near-infrared (NIR-II) emissive materials, as they exhibit red-shifted spectroscopic properties upon assembly into nanoparticles (NPs) in aqueous environments. However, currently available NIR-II J-aggregates primarily rely on specific molecular backbones with intricate design strategies and are susceptible to fluorescence quenching during assembly. A facile approach for constructing bright NIR-II J-aggregates using prevalent donor-acceptor (D-A) molecules is still lacking. In this study, we present a facile method that transforms D-A molecules into J-aggregates by simply bending the molecule through introducing a methyl group, enabling high-performance NIR-II phototheranostics. The TAA-BT-CN molecule exhibits hypsochromic-shift absorption upon forming H-aggregated NPs, while the designed mTAA-BT-CN with a bent structure demonstrates a bathochromic shift of over 100 nm in absorption upon forming J-aggregated NPs, leading to much enhanced NIR-II emission beyond 1100 nm. With respect to its H-aggregated counterpart with the aggregation-caused quenching (ACQ) phenomenon, the J-aggregated mTAA-BT-CN NPs exhibit a 7-fold increase in NIR-II fluorescence owing to their aggregation-induced emission (AIE) property as well as efficient generation of heat and reactive oxygen species under 808 nm light excitation. Finally, the mTAA-BT-CN NPs are employed for whole-body blood vessel imaging using NIR-II technology as well as imaging-guided tumor phototherapies. This study will facilitate the flourishing advancement of J-aggregates based on prevalent D-A-type molecules.

Phthalocyanine J-aggregate nanoparticles with enormous-redshifted and intense absorption: Potential structure-J-aggregation relationships and application in tumor-associated macrophages-targeted phototheranostics

Phthalocyanines (Pcs) are considered promising in cancer phototherapy. However, their maximum absorption wavelengths are only around 700 nm, which cannot allow deep tissue penetration and leads to poor therapeutic efficacy. To expand their clinical application, significantly shifting their absorption to longer wavelengths is urgently required. Dye J-aggregates exhibit a redshifted absorption relative to its monomer. However, Pc J-aggregates with enormous-redshifted and intense absorption is rarely reported, and little is known about the relationships between Pc structure and J-aggregation. Herein, such Pc J-aggregates are ingeniously conceived. With a yeast β-D-glucan-ursodeoxycholic acid conjugate as a potential tumor-associated macrophages (TAMs)-targeting carrier and 1-(4-carboxyethylphenoxy) zinc (II) phthalocyanine (Pc1) as a model, Pc1 J-aggregate nanoparticle (NanoPc1) is obtained via ultrasonication-aided emulsification-solvent evaporation technique. NanoPc1 displays strong absorption at 830 nm, with a 156 nm redshift. Further investigation on another twenty-four Pcs demonstrates that unsubstituted zinc (II) or magnesium (II) Pc and hydrophobic mono-substituted zinc (II) or magnesium (II) Pcs with mono-substituted phenoxy or phenylthio or naphthoxy as a substituent can readily form desired Pc J-aggregates with significant redshifts (140–165 nm). The other Pcs fail to form expected J-aggregates probably due to absence of central metals, steric hindrance on central metals (atoms), forming axial coordination on central metals, disorder tendency during self-assembly or hydrophilicity. The theoretical calculation indicates that Pc1 in its J-aggregates exhibits a spiral-like arrangement, and the reduction in the energy gap between HOMO and LUMO and variation of intermolecular π-π interaction caused by J-aggregate formation are responsible for the huge redshift. Additionally, using NanoPc1 as an exemplar, such Pc J-aggregate nanoparticles are substantiated to afford TAMs-targeted and efficient tri-modal imaging and photothermal therapy in a H22 mouse model.

Plasmon-Exciton Interaction at the Nanoscale: Silver Is More "Precious" than Gold!

Predictive understanding of factors affecting plasmon-exciton coupling is crucial for the successful realization of the exciting potentials of plexcitonic nanostructures. Here, we systematically investigate the role of plasmonic metals in controlling the plasmon-exciton coupling strength. We use gold and silver nanoprisms, having identical LSPR maxima, as the plasmonic components and form two plexciton hybrids with the J-aggregates of a cyanine dye. Single-particle spectroscopy is employed to study and compare the abilities of gold and silver in influencing plasmon-exciton interaction at the nanoscale. Despite much faster plasmon dephasing than its gold counterpart, the silver nanoprism exhibits greater Rabi splitting. We reveal that the smaller plasmon mode-volume despite having larger physical volume, superior local electric-field enhancement, and smaller Ohmic losses compared to gold, enables the silver nanoprism to defy the pronounced plasmon decoherence effects and to show stronger plasmon-exciton coupling. These findings suggest that silver nanostructures should be the unequivocal choice over gold when "strong coupling" is desired for any application.

J-aggregates of multi-groups cyanine dye for NIR-IIa fluorescence-guided mild photothermal therapy under 1064 nm irradiation

NIR-IIa fluorescence imaging (FI) and NIR-II photothermal therapy (PTT) have gained popularity due to the advantages of high temporal and spatial resolution and deep penetration. However, the hyperthermia (>48 °C) of conventional PTT with nonspecific warming and thermal diffusion may inevitably cause damage to healthy tissues or organs surrounding the tumor. Therefore, it is highly desirable to provide effective cancer treatment by implementing mild photothermal therapy (mPTT) at mild temperatures with lower laser power density. Here, the nanotheranostic platform FN@P-GA NPs with NIR-II absorption and NIR-IIa emission was developed by constructing J-aggregates. FN@P-GA possesses good biocompatibility, favorable NIR-IIa FI performance, decent stability, and high photothermal conversion efficiency (57.6 %), which lays a solid foundation for FI-guided mPTT. Due to its ability to effectively down-regulate the expression of HSP90 and reduce cellular thermoresistance to kill cancer cells, FN@P-GA successfully achieved NIR-IIa FI-guided mPTT and demonstrated its potent anti-tumor effect under 1064 nm laser irradiation at mild temperature and low power density (0.3 W/cm2).

J-Aggregate Promoting NIR-II Emission for Fluorescence/Photoacoustic Imaging-Guided Phototherapy.

J-aggregate is a promising strategy to enhance second near-infrared window (NIR-II) emission, while the controlled synthesis of J-aggregated NIR-II dyes is a huge challenge because of the lack of molecular design principle. Herein, bulk spiro[fluorene-9,9'-xanthene] functionalized benzobisthiadiazole-based NIR-II dyes (named BSFX-BBT and OSFX-BBT) are synthesized with different alkyl chains. The weak repulsion interaction between the donor and acceptor units and the S…N secondary interactions make the dyes to adopt a co-planar molecular conformation and display a peak absorption >880nm in solution. Importantly, BSFX-BBT can form a desiring J-aggregate in the condensed state, and femtosecond transient absorption spectra reveal that the excited states of J-aggregate are the radiative states, and J-aggregate can facilitate stimulated emission. Consequently, the J-aggregated nanoparticles (NPs) display a peak emission at 1124nm with a high relative quantum yield of 0.81%. The efficient NIR-II emission, good photothermal effect, and biocompatibility make the J-aggregated NPs demonstrate efficient antitumor efficacy via fluorescence/photoacoustic imaging-guided phototherapy. The paradigm illustrates that tuning the aggregate states of NIR-II dye via spiro-functionalized strategy is an effective approach to enhance photo-theranostic performance.

Surface exciton polariton enhanced Goos-Hänchen and Imbert-Fedorov shifts and their applications in refractive index sensing.

The spatial and angular Goos-Hänchen shifts (GHSs) and Imbert-Fedorov shifts (IFSs) are theoretically investigated in a modified Kretschmann-Raether configuration consisting of glass prism, J-aggregate cyanine dye, and air. With the excitation of surface excitation polaritons (SEPs), the spatial and angular GHSs and IFSs for the transverse magnetic polarized light are strongly enhanced around the resonant angle of SEP. A highly sensitive gas sensor based on the SEP enhanced GHS (or IFS) is proposed, which exhibits the refractive index sensitivity on the order of 106λ/RIU (or 105λ/RIU) (λ: illumination wavelength; RIU: refractive index unit) for the GHS- (or IFS-) based gas sensor, respectively.

Plexcitonic Nanorattles as Highly Efficient SERS-Encoded Tags.

Plexcitonic nanoparticles exhibit strong light-matter interactions, mediated by localized surface plasmon resonances, and thereby promise potential applications in fields such as photonics, solar cells, and sensing, among others. Herein, these light-matter interactions are investigated by UV-visible and surface-enhanced Raman scattering (SERS) spectroscopies, supported by finite-difference time-domain (FDTD) calculations. Our results reveal the importance of combining plasmonic nanomaterials and J-aggregates with near-zero-refractive index. As plexcitonic nanostructures nanorattles are employed, based on J-aggregates of the cyanine dye 5,5,6,6-tetrachloro-1,1-diethyl-3,3-bis(4-sulfobutyl)benzimidazolocarbocyanine (TDBC) andplasmonic silver-coated gold nanorods, confined within mesoporous silica shells, which facilitate the adsorption of the J-aggregates onto the metallic nanorod surface, while providing high colloidal stability. Electromagnetic simulations show that the electromagnetic field is strongly confined inside the J-aggregate layer, at wavelengths near the upper plexcitonic mode, but it is damped toward the J-aggregate/water interface at the lower plexcitonic mode. This behavior is ascribed to the sharp variation of dielectric properties of the J-aggregate shell close to the plasmon resonance, which leads to a high opposite refractive index contrast between water and the TDBC shell, at the upper and the lower plexcitonic modes. This behavior is responsible for the high SERS efficiency of the plexcitonic nanorattles under both 633nm and 532nm laser illumination. SERS analysis showed a detection sensitivity down to the single-nanoparticle level and, therefore, an exceptionally high average SERS intensity per particle. These findings may open new opportunities for ultrasensitive biosensing and bioimaging, as superbright and highly stable optical labels based on the strong coupling effect.

Quantum Kinetics of the Electronic Energy Transformation in Molecular Nanostructures

A quantum theory of electronic energy transfer in a layered nanostructure with molecular J-aggregates of polymethine dyes was proposed. An expression for the exciton-plasmon bond energy depending on various parameters of the system was given. The rate of non-radiative Fὄrster resonance energy transfer (FRET) from surface plasmon polaritons (SPPs) of a metal substrate to Frenkel excitons of J-aggregates was determined and dispersion dependences for hybrid states were obtained. It was established that the energy transfer rate can reach values of 1012–1013 s–1, and the value of the Rabi splitting is up to 100 MeV. The kinetics of the process under strong exciton-plasmon interaction was investigated. The time dependence of the energy exchange between the system components had the form of damped oscillations depending on the relaxation parameters, the Rabi frequency, and the response to resonance. In addition, the exciton FRET between two parallel monolayers of J-aggregates of polymethine dyes separated by a nanometer-thick metal film was investigated. It was found that the presence of the metal layer increases the FRET rate. The spin evolution of a pair of two triplet (T) molecules localized in the nano-cell region under the over-barrier jumps regime in a magnetic field was studied. The influence of the parameters of the two-dimensional potential on the frequency of inter-dimensional motions and the population of triplets was considered. The spin dynamics of molecular T-T pairs in the magnetic field of a ferromagnetic globular nanoparticle under free surface diffusion of a spin-carrying molecule was investigated.

Spectral features of the dispersion of carbocyanine dye J-aggregates in a liquid crystal matrix

Formation of J-aggregates of the anionic cyanine dye TDBC in a nematic liquid crystal (LC) matrix is reported, with analysis of optical-fluorescent and electro-optical properties of the obtained novel material. The TDBC J-aggregates show a rather long lifetime and high photostability in the nematic matrix. The electro-optical characteristics of the LC matrix are substantially modified, with the Fredericks transition threshold slightly increased, which is, on the other hand, accompanied by the improvement of the optical contrast. Only a minor effect of the forming J-aggregates on the molecular order of the LC structure could be noted.

Multifunctional broadband visible-light absorbing selenophene modified bodipy photosensitizers

Large π-conjugated organic systems with effective photosensitization are highly desirable for many photochemical applications. Herein, a series of π-conjugated selenophene-substituted boron dipyrromethene (known as bodipy) dyes (MB-Se, 2B–Se, MB-Se-2Br) were prepared by appending selenophene electron-donor to the core of bodipy acceptors via alkynyl bridge and their excited state properties were investigated. Optical spectroscopy revealed that although these three selenophene-substituted bodipy dyes have nearly identical molecular profiles, their photophysical properties and excited state dynamics are drastically different. Higher triplet quantum efficiency (ΦΔ = 82%) was observed for MB-Se, derivative in which α,β-positions of bodipy decorated with methyl substituents, compared to another dye 2B–Se, which showed inefficient triplet population (ΦΔ = 25%). Employing steady-state absorption and emission spectroscopies, we demonstrated that the designed selenophene-substituted bodipy dyes has excellent J-aggregation capabilities. Notably, the J-aggregates of selenophene-substituted bodipy dyes display NIR emission. The potential of devised selenophene-substituted bodipy dyes in triplet fusion upconversion was also demonstrated; a blue upconverted emission was realized upon irradiating the mixture of bodipy dyes and TIPS-AC acceptor with 589 nm CW-laser. The selenophene-substituted bodipy dyes were also confirmed to be a potent photodynamic therapeutic reagent; with an IC50 value of 0.76 μM, nearly 6 times lower than that of the iodide-appended bodipy photosensitizer (BDP-2I, 6.0 μM). This study hopes to provide valuable guidelines for the future development of multipurpose triplet photosensitizers.

Plasmon–Exciton Strong Coupling Effects of the Chiral Hybrid Nanostructures Based on the Plexcitonic Born–Kuhn Model

A deep understanding of the optical properties of the chiral plexcitonic systems not only adds a new dimension to the exploration of the strong plasmon–exciton interaction but also provides a new method to design chiroptical devices. We develop a plexcitonic Born–Kuhn model to explore the strong coupling dynamics of the chiral hybrid nanostructures made of corner-stacked nanorod dimers and molecules from the chiroptical perspective. As a consequence of strong interaction between plasmons and excitons, double normal mode splittings/Rabi splittings and an anti-crossing phenomenon appear in circular dichroism (CD) spectroscopy. The character of dual plexciton (symmetric and anti-symmetric plexciton) and associated chiroptical properties have been demonstrated. The interplay between mirror symmetry breaking and plasmon–plasmon/plasmon–exciton interaction leads to an optimal configuration with the maximal chiroptical response. Moreover, chirality (of incident light) selective excitation of plexcitonic modes has been achieved by structural design. Finally, we verify our theory experimentally by synthesizing chiral plasmonic nanodimers and coating these structures with J-aggregate dye molecules.

Features of cyanine dyes aggregation on differently charged TiO2 matrices

Changing the polycondensation reaction route, positively and negatively charged TiO2 nanoparticles have been synthesized. On the base of the synthesized TiO2 nanoparticles, porous TiO2 films have been formed with different surface charges. J-aggregates of two anionic dyes were formed on positively charged TiO2 films, while J-aggregates of cationic dye was formed on negatively charged one. Combining J-aggregates with different J-band spectral positions, we have obtained two composites consisting of J-aggregates pairs with an effective excitation energy transfer between them. In both cases, simple mixing of J-aggregate in solution did not result in the composite formation and only sequential deposition of J-aggregate from corresponding solutions was successful. Interesting, not only charge alternating composite of cationic pseudoisocyanine J-aggregates and anionic thiacarbocyanine J-aggregates was realized, but also the same was done in the case of the composite of two anionic carbocyanine J-aggregates.

Mueller Matrix Polarimetry on Cyanine Dye J-Aggregates.

Cyanine dyes are known to form H- and J-aggregates in aqueous solutions. Here we show that the cyanine dye, S0271, assembles in water into vortex induced chiral J-aggregates. The chirality of the J-aggregates depends on the directionality of the vortex. This study utilised both conventional benchtop CD spectropolarimeters and Mueller matrix polarimetry. It was found that J-aggregates have real chirality alongside linear dichroism and linear and circular birefringence. We identify the factors that are key to the formation of metastable chiral J-aggregates and propose a mechanism for their assembly.

Assembling Near-Infrared Dye on the Surface of Near-Infrared Silica-Coated Copper Sulphide Plasmonic Nanoparticles.

Functionalization of colloidal nanoparticles with organic dyes, which absorb photons in complementary spectral ranges, brings a synergistic effect for harvesting additional light energy. Here, we show functionalization of near-infrared (NIR) plasmonic nanoparticles (NPs) of bare and amino-group functionalized mesoporous silica-coated copper sulphide (Cu2-xS@MSS and Cu2-xS@MSS-NH2) with specific tricarbocyanine NIR dye possessing sulfonate end groups. The role of specific surface chemistry in dye assembling on the surface of NPs is demonstrated, depending on the organic polar liquids or water used as a dispersant solvent. It is shown that dye binding to the NP surfaces occurs with different efficiency, but mostly in the monomer form in polar organic solvents. Conversely, the aqueous medium leads to different scenarios according to the NP surface chemistry. Predominant formation of the disordered dye monomers occurs on the bare surface of mesoporous silica shell (MSS), whereas the amino-group functionalized MSS accepts dye predominantly in the form of dimers. It is found that the dye-NP interaction overcomes the dye-dye interaction, leading to disruption of dye J-aggregates in the presence of the NPs. The different organization of the dye molecules on the surface of silica-coated copper sulphide NPs provides tuning of their specific functional properties, such as hot-band absorption and photoluminescence.

Integrating Highly Luminescent Lanthanides with Strongly Coupled Dye J-Aggregates on Nanotubes for Efficient Cascade Energy Transfer

Photoluminescent one-dimensional hybrid nanostructured materials having outstanding inorganic–organic advantages are gaining significant attention on account of their intriguing applications in nanoscale optoelectronic devices, (bio)sensors, and energy harvesting and conversion technologies. Here, we first report on the development of highly photoluminescent lanthanide organic hybrid nanotubular assemblies through in situ incorporation of a trivalent lanthanide ion, terbium (Tb3+), along with organic photosensitizers 2,3-dihydroxynaphthalene (DHN) or 1,10-phenanthroline (Phen) into the self-assembled nanotubes of sodium lithocholate (NaLC). Both the photosensitizers (DHN/Phen) are effective in sensitizing intense narrow emission peaks of Tb3+ on the nanotubes. Next, we utilize these luminescent lanthanides containing hybrid nanotubular assemblies as templates for spontaneous integration of strongly coupled pseudoisocyanine (PIC) dye J-aggregates with a sharp J-band absorption at 555 nm and strong fluorescence emission at 570 nm. The presence of the significant spectral overlap between the luminescence peak of Tb3+ at 545 nm and the J-aggregate absorption band results in efficient cascade energy transfer from photosensitizers to Tb3+ to the coherently coupled PIC dye J-aggregates. These NaLC nanotube-templated photosensitizer-Tb3+-J-aggregate hybrid systems have great potential for sensing and optoelectronic applications.

Tuning nanoscale plasmon-exciton coupling via chemical interface damping.

Understanding the exact role of each plasmon decay channel in the plasmon-exciton interaction is essential for realizing the translational potential of nanoscale plexciton hybrids. Here, using single-particle spectroscopy, we demonstrate how a particular decay channel, chemical interface damping (CID), influences the nanoscale plasmon-exciton coupling. We investigate the interaction between cyanine dye J-aggregates and gold nanorods in the presence and absence of CID. The CID effect is introduced via surface modification of the nanorods with 4-nitrothiophenol. The relative contribution of CID is systematically tuned by varying the diameter of the nanorods, while maintaining the aspect ratio constant. We show that the incorporation of the CID channel, in addition to other plasmon decay channels, reduces the plasmon-exciton coupling strength. Nanorods' diameter-dependency measurements reveal that in the absence of CID contribution, the plasmon mode-volume factor gradually dominates over the plasmon decoherence effects as the diameter of the nanorods decreases, resulting in an increase in the plasmon-exciton coupling strength. However, the situation is entirely different when the CID channel is active: plasmon dephasing determines the plasmon-exciton coupling strength by outweighing the influence of even a very small plasmon mode-volume. Most importantly, our findings indicate that CID can be used to controllably tune the plasmon-exciton coupling strength for a given plexciton system by modifying the nanoparticle's surface with suitable adsorbates without the need for altering either the plasmonic or excitonic systems. Thus, judicious exploitation of CID can be tremendously beneficial in tailoring the optical characteristics of plexciton hybrid systems to suit any targeted application.

J-Aggregated Dyes for Dye-Sensitized Solar Cells: Suppressing Aggregation-Induced Excited-State Quenching by Intramolecular Charge Separation

J-Aggregated Dyes for Dye-Sensitized Solar Cells: Suppressing Aggregation-Induced Excited-State Quenching by Intramolecular Charge Separation

Strong coupling for bifunctionality in organic systems

In this paper, we exploit the strong light–matter coupling to hybridize two materials for bifunctionality properties. The strong coupling has been achieved between a surface plasmon and two organic emitters: a J-aggregate cyanine dye, known for its high absorption and emission properties and a photochromic material in which absorption can be optically switched on and off. The optical properties are drastically modified between the activated and deactivated forms of the photochromic material coupled to the cyanine dye. In particular, the emission of the structure can be energy shifted by several hundreds of meV providing a way to build a tunable emission system. This system also reveals its potential for modifying the fluorescence of photochromes thanks to light–matter interaction instead of functionalization using covalent bonding.

Cross Determination of Exciton Coherence Length in J-Aggregates.

The coherence length of the Frenkel excitons (Ncoh) is one of the most critical parameters governing many key features of supramolecular J-aggregates. Determining experimentally the value of Ncoh is a nontrivial task since it is sensitive to the technique/method applied, causing discrepancies in the literature data even for the same chemical compound and aggregation conditions. By using a combination of different experimental techniques including UV-vis-NIR, fluorescence emission, time-resolved photoluminescence, and transient absorption spectroscopies, we determined Ncoh values for J-aggregates of a cyanine dye. We found that the absorption spectroscopy alone - a widely used technique- fails in determining right value for Ncoh. The correct approach is based on the modification of photoluminescence lifetime and nonlinear response upon aggregation and careful analysis of the Stokes shift and electron-phonon coupling strength. This approach revealed that Ncoh of JC-1 J-aggregates ranges from 3 to 6.

The behavior of thiacarbocyanine dyes on the surface of few-layered hexagonal boron nitride

The adsorption and self-assembly of several thiacarbocyanine dyes on hexagonal boron nitride (hBN) was investigated by combining steady-state spectroscopy and atomic force microscopy. The adsorption isotherms indicate that at saturation the density of the cationic TDC (5,5-dichloro-3-3′-diethyl-9-ethyl-thiacarbocyanine) molecules on hBN is similar to that of TD2 (3-3′-diethyl-9-ethyl-thiacarbocyanine) molecules, while the densities of TD0 (3-3′-diethyl-thiacarbocyanine) molecules and the zwitterionic THIATS (5,5-dichloro-3-3′-disulfopropyl-9-ethyl-thiacarbocyanine) molecules are significantly higher. The intermolecular distances between neighboring adsorbed dyes, calculated from these saturation densities indicate a flat-on adsorption for TDC, TD2 and TD0 and a partial edge-on adsorption for THIATS. AFM micrographs of the adsorbed TDC, TD0 and THIATS molecules indicate that already at low dye concentrations in the solution, where only a small fraction of the hBN surface is covered, the dye molecules already form upon adsorption to hBN aggregates of at least 10 nm, separated by areas where no adsorbed dye molecules can be detected. The resolution of the micrographs was however insufficient to show details of the packing of the adsorbed molecules. For THIATS, the thickness of the adsorbed layer is compatible with an edge-on adsorption, while for TDC and TD0, the thickness of the adsorbed layer is twice the thickness expected for flat-on adsorption. The exciton interaction extracted from the steady-state spectroscopy of the adsorbed dyes is much smaller than observed for H- or J-aggregates of the same dyes in solution or adsorbed to other surfaces such as Langmuir films or silver halides. For TDC, TD2 and TD0, the values of the exciton interaction are compatible with a close packed flat-on adsorption. Hence, optimizing the interaction between the adsorbed dye and hBN rather than between the adsorbed dye molecules governs the packing of the adsorbed dye molecules. The observation of the spectral shifts attributed to the exciton interaction at low average coverage of the hBN surface indicates that the exciton interaction already occurs at low coverage of the hBN surface. This observation is in agreement with the AFM micrographs, which show clustering of the adsorbed dye molecules already at low coverages.