J-aggregated Cyanine Research Articles

Structurally Modulated Formation of Cyanine J-Aggregates with Sharp and Tunable Spectra for Multiplexed Optoacoustic and Fluorescence Bioimaging.

J-aggregation brings intriguing optical and electronic properties to molecular dyes and significantly expands their applicability across diverse domains, yet the challenge for rationally designing J-aggregating dyes persists. Herein, we developed a large number of J-aggregating dyes from scratch by progressively refining structure of a common heptamethine cyanine. J-aggregates with sharp spectral bands (full-width at half-maximum≤38 nm) are attained by introducing a branched structure featuring a benzyl and a trifluoroacetyl group at meso-position of dyes. Fine-tuning the benzyl group enables spectral regulation of J-aggregates. Analysis of single crystal data of nine dyes reveals a correlation between J-aggregation propensity and molecular arrangement within crystals. Some J-aggregates are successfully implemented in multiplexed optoacoustic and fluorescence imaging in animals. Notably, three-color multispectral optoacoustic tomography imaging with high spatiotemporal resolution is achieved, owing to the sharp and distinct absorption bands of the J-aggregates.

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.

Corrigendum: Theoretical Models, Preparation, Characterization and Applications of Cyanine J-Aggregates: A Minireview.

The name of the second author needs to be corrected due to a typographical error in the original article. The author line and address shown below are correct. The changes do not affect the contents and conclusions of this review article. Corrected author line: Nitzan Dar*[a] and Rinat Ankri[a] [a] Dr. N. Dar, Dr. R. Ankri Department of Physics, Faculty of Natural Science Ariel University, Ariel 40700 (Israel)

Strong Coupling of Chiral Frenkel Exciton for Intense, Bisignate Circularly Polarized Luminescence.

We show that chiral Frenkel excitons yield intense circularly polarized luminescence with an intrinsic dissymmetry factor in emission glum as high as 0.08. This outstanding value is measured through thin films of cyanine J-aggregates that form twisted bundles. Our measurements, obtained by a Mueller polarization analysis, are artifact-free and reveal a quasi-perfect correlation between the dissymmetry factors in absorption, gabs , and in emission glum . We interpret the bisignate dissymmetry factors as the signature of a strong coupling between chiral Frenkel excitons longitudinally excited along the bundles. We further resolve by polarimetry analysis the split in energy between the excited states with a Davydov splitting as small as 28 meV. We finally show the anti-Kasha nature of the chiral emission bands with opposite optical chirality. These mirror-imaged emissive chiroptical features emerge from the structural rigidity of the bundles that preserves the ground- and excited-state chirality.

J-Aggregates Formed by NaCl Treatment of Aza-Coating Heptamethine Cyanines and Their Application to Monitoring Salt Stress of Plants and Promoting Photothermal Therapy of Tumors.

The cationic nature of heptamethine cyanines gives them the capacity to form aggregates with salts by electrostatic interactions. In this work, NaCl promoted J-aggregate formation of aza-coating heptamethine cyanines is explored. NaCl can induce the N-benzyloxycarbonyl Cy-CO2 Bz to assemble into a J-aggregate having an absorption at 890 nm. Its excellent fluorescence response to NaCl implies that it has great potential for use as a probe for tracing salt stress in plants. Moreover, NaCl also promotes formation of J-aggregates from the N-ethyloxycarbonyl Cy-CO2 Et. The aggregate shows an intense absorption at 910 nm compared to the monomer which absorbs at 766 nm. Its J-aggregated form can serve as a photothermal agent. And the photothermal conversion efficiency is increased from 29.37 % to 57.59 %. This effort leads to the development of two applications of new cyanine J-aggregates including one for tracing salt stress of plants and the other for promoting photothermal therapy of tumors.

Theoretical Models, Preparation, Characterization and Applications of Cyanine J-Aggregates: A Minireview.

Cyanines are one of the few kinds of molecules whose absorbance and emission can be shifted in a broad spectral range from the ultraviolet to the near infrared. They can easily transform into J-aggregates with narrow absorption and emission peaks, along with a redshift in their spectra. This mini-review presents cyanine dyes and their J-aggregates and discusses their structure and spectral properties that illustrate their specificities. We summarize the theoretical and experimental state of the art on cyanine J-aggregates and their applications, also laying the groundwork for cyanine J-aggregates synthesis and characterization methods.

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.

Plexcitonic Nanohybrids Based on Gold Nanourchins: The Role of the Capping Layer

Plexcitonic nanohybrids are plasmonic–excitonic novel materials whose peculiar properties are attracting considerable attention in photonics, solar cells, and sensing. These materials can be synthesized and characterized easily by assembling organic or inorganic dyes on plasmonic nanoparticles as support. However, the main factors controlling the assembly process and the occurrence of the plexcitonic coupling are still unclear. To fill this gap, in this work, we studied the plexciton coupling of 12 different dyes with a series of gold nanourchins with various coatings and sizes. Among 24 combinations tested, we observed the formation of plexcitonic hybrids only in five cases. Most of them had cyanine J-aggregates as excitonic counterparts. Stronger plexcitonic couplings were obtained when nanourchins were coated with an exchangeable citrate capping layer rather than a strong ionic thiols capping layer. We propose that the presence of a strongly bound capping layer, as in this latter case, reduces the effective volume available to the dyes.

Tailoring surface plasmon-exciton polariton for high-performance refractive index monitoring

We report coupling between surface plasmon polariton (SPP) and surface exciton polariton (SEP) as hybrid mode; surface plasmon exciton polariton (SPEP) that can be utilized for highly sensitive and accurate refractive index monitoring. The proposed structure comprises of a thin layer of organic semiconductor; J-aggregate cyanine dye (5,5′,6,6′-tetrachloro-1,10-diethyl-3, 30-di(4-sulfobutyl) benzimidazolo-carbocyanine (TDBC)) having, strong dipole moment resulting from linear chain-like structure, over plasmon active metal coated on prism. It is found that due to SPEP excitation, the sensitivity of the proposed refractometer is ∼84% higher as compared to that of conventional plasmonic sensor at λ = 532 nm and has high tolerance towards 10 nm of metal thickness. The wavelength dependent performance analysis of SPEP modes reveals that for high energy SPEP (mode-1 at λ = 532 nm), sensitivity as well as figure of merit (FOM) of the proposed refractometer is ∼80% and ∼200% respectively higher than low energy SPEP (mode-2 at λ = 633 nm). We believe that the study will open a new window for a diverse range of biochemical and gaseous sensing applications.

Enhanced Room-Temperature Photoluminescence Quantum Yield in Morphology Controlled J-Aggregates.

Supramolecular assemblies from organic dyes forming J‐aggregates are known to exhibit narrowband photoluminescence with full‐width at half maximum of ≈9 nm (260 cm−1). Applications of these high color purity emitters, however, are hampered by the rather low photoluminescence quantum yields reported for cyanine J‐aggregates, even when formed in solution. Here, it is demonstrated that cyanine J‐aggregates can reach an order of magnitude higher photoluminescence quantum yield (increase from 5% to 60%) in blend solutions of water and alkylamines at room temperature. By means of time‐resolved photoluminescence studies, an increase in the exciton lifetime as a result of the suppression of non‐radiative processes is shown. Small‐angle neutron scattering studies suggest a necessary condition for the formation of such highly emissive J‐aggregates: the presence of a sharp water/amine interface for J‐aggregate assembly and the coexistence of nanoscale‐sized water and amine domains to restrict the J‐aggregate size and solubilize monomers, respectively.

Plexcitonic nose based on an organic semiconductor

A highly sensitive and accurate plexcitonic nose based on an organic semiconductor, J-aggregate cyanine dye [5,5′,6,6′-tetrachloro-1,10-diethyl-3, 30-di(4-sulfobutyl) benzimidazolo carbocyanine (TDBC)], is proposed. The signature of the plexciton is evidently studied by implanting a TDBC layer over plasmon active metals. The interaction between the strong dipole moment of the TDBC molecules residing at the metal-TDBC interface and the electric field generated by the plasmons is responsible for the transfer of energy between plasmon and exciton modes. We have demonstrated that the coupling between the plasmon and the Lorentzian oscillator (i.e., exciton-based system) gives rise to two plexciton modes, namely, upper plexciton (UP) and lower plexciton (LP). We have clearly shown the excitation of the UP (LP) for λ < 589 nm (λ > 589 nm). We observed that the UP exhibits strong dispersion, resulting in high sensitivity. Furthermore, depending upon the nature of the analyte, the change to the organic semiconductor like the TDBC film can be reversible or irreversible. Accordingly, the probe can be reused with a polar analyte like ammonia as such gas desorbs from the surface once removed from the environment. We believe that the plexcitonic nose can open a platform for analyzing food freshness by sensing propanol and acetic acid, identifying traces of explosives and nerve gas, and detecting hazardous chemicals in work environments.

Surface Exciton Polaritons: A Promising Mechanism for Refractive-Index Sensing

The possibility of constructing a surface exciton polariton (SEP) based sensor at room temperature is explored. The proposed SEP sensor is based on the Kretschmann-Raether configuration of conventional surface plasmon resonance (SPR) sensor, where the metal thin film was replaced by the J-aggregate cyanine dye film. The excitation of SEP results in a strong electric field at the interface of TDBC and analyte, and exponentially decaying into the analyte, which is sensitive to the refractive index variations of analyte. The sensitivity of 118.1818 $^\circ/\text{RIU}$ (140.4286 $^\circ/\text{RIU}$) was achieved for the proposed SEP sensor within the refractive index range 1.0-1.001 (1.33-1.36) of gaseous analyte (aqueous solutions), which is about 2 (3.5) times higher than that of conventional gold-based SPR sensor. The significant superiority of the SEP sensor in sensitivity revealing SEP as a new promising mechanism for sensing applications.

Highly-Soluble Cyanine J-aggregates Entrapped by Liposomes for In Vivo Optical Imaging around 930 nm.

Near infrared (NIR) dyes are useful for in vivo optical imaging. Liposomes have been used extensively for delivery of diverse cargos, including hydrophilic cargos which are passively loaded in the aqueous core. However, most currently available NIR dyes are only slightly soluble in water, making passive entrapment in liposomes challenging for achieving high optical contrast.Methods: We modified a commercially-available NIR dye (IR-820) via one-step Suzuki coupling with dicarboxyphenylboronic acid, generating a disulfonated heptamethine; dicarboxyphenyl cyanine (DCP-Cy). DCP-Cy was loaded in liposomes and used for optical imaging.Results: Owing to increased charge in mildly basic aqueous solution, DCP-Cy had substantially higher water solubility than indocyanine green (by an order of magnitude), resulting in higher NIR absorption. Unexpectedly, DCP-Cy tended to form J-aggregates with pronounced spectral red-shifting to 934 nm (from 789 nm in monomeric form). J-aggregate formation was dependent on salt and DCP-Cy concentration. Dissolved at 20 mg/mL, DCP-Cy J-aggregates could be entrapped in liposomes. Full width at half maximum absorption of the liposome-entrapped dye was just 25 nm. The entrapped DCP-Cy was readily detectable by fluorescence and photoacoustic NIR imaging. Upon intravenous administration to mice, liposomal DCP-Cy circulated substantially longer than the free dye. Accumulation was largely in the spleen, which was visualized with fluorescence and photoacoustic imaging.Conclusions: DCP-Cy is simple to synthesize and exhibits high aqueous solubility and red-shifted absorption from J-aggregate formation. Liposomal dye entrapment is possible, which facilitates in vivo photoacoustic and fluorescence imaging around 930 nm.

Fano Resonance in Waveguide Coupled Surface Exciton Polaritons: Theory and Application in Biosensor.

Surface exciton polaritons (SEPs) are one of the three major elementary excitations: Phonons, plasmons and excitons. They propagate along the interface of the crystal and dielectric medium. Surface exciton polaritons hold a significant position in the aspect of novel sensor and optical devices. In this article, we have realized a sharp Fano resonance (FR) by coupling the planar waveguide mode (WGM) and SEP mode with Cytop (perfluoro (1-butenyl vinyl ether)) and J-aggregate cyanine dye. After analyzing the coupling mechanism and the localized field enhancement, we then applied our structure to the imaging biosensor. It was shown that the maximum imaging sensitivity of this sensor could be as high as 5858 RIU−1, which is more than three times as much as classical FR based on metal. A biosensor with ultra-high sensitivity, simple manufacturing technique and lower cost with J-aggregate cyanine dye provides us with the most appropriate substitute for the surface plasmon resonance sensors with the noble metals and paves the way for applications in new sensing technology and biological studies.

Fluorescent Cyanine Dye J-Aggregates in the Fluorous Phase.

We present a perfluorocarbon-hydrocarbon amphiphilic cyanine dye that J-aggregates in fluorous solvent. J-Aggregation is a special type of fluorophore aggregation, affording enhanced photophysical properties. Cyanine dyes are excellent J-aggregators in water but, until now, cyanine J-aggregates have not been translated to nonaqueous media. The fluorous phase J-aggregate displays enhanced photostability and processability compared to analogous aqueous aggregates.

Surface exciton polaritons supported by a J-aggregate-dye/air interface at room temperature

Surface exciton polaritons (SEPs) are very important for the realization of novel sensors and next-generation optical devices. Here we propose for the first time, to the best of our knowledge, a Kretschmann-Raether device that is able to induce SEPs propagating along the interface between a J-aggregate cyanine dye and air at room temperature. This configuration has the advantages of being straightforward to realize and easy to study because the Kretschmann-Raether approach is the most simple and fundamental from the theoretical point of view. Here a J-aggregate cyanine dye produces strong binding energy due to Frenkel excitons, and this enables the observation of SEPs easily at room temperature. One of the advantages of the use of the J-aggregate cyanine dye is the simple device preparation. This is because the J-aggregate cyanine dye can be easily deposited on any arbitrary substrates with a spincoating or dip-coating technique from its aqueous solution in ambient condition. We observed SEPs at room temperature, and the deepest resonant peak was obtained for a 94nm thick 5,6-dichloro-2-[[5,6-dichloro-1-ethyl-3-(4-sulfobutyl)-benzimidazol-2-ylidene]-propenyl]-1-ethyl-3-(4-sulfobutyl)-benzimidazolium hydroxide film at 532nm wavelength. Our results may pave the way for the realization of novel SEP biosensors in a simple and straightforward way at room temperature.

Organic Exciton in Strong Coupling with Long-Range Surface Plasmons and Waveguided Modes

In this Letter, we demonstrate experimentally the strong interaction between organic semiconductor excitons and long-range surface plasmons. For this purpose, a thin J-aggregated cyanine dye layer is deposited on a thin silver film bounded by two poly(vinyl alcohol) layers. An anticrossing between the long-range surface plasmon and the dye exciton is measured in the dispersion relation and confirmed in luminescence experiments, showing unambiguously the hybridization between the long-range surface plasmon and the dye exciton. The extension of the polaritonic states deduced from the dispersion curves is 50 μm, which represents an increase of more than 1 order of magnitude compared to usual surface plasmon-based polaritons. We believe that the extension of the polariton coherence length can have direct applications to the energy transfer between molecules over long distances in strong coupling, as well as in the modification of the properties of materials (conductivity, second harmonic generation). Strong c...

Robust Colloidal Nanoparticles of Pyrrolopyrrole Cyanine J-Aggregates with Bright Near-Infrared Fluorescence in Aqueous Media: From Spectral Tailoring to Bioimaging Applications.

Colloidal nanoparticles (NPs) containing near-infrared-fluorescent J-aggregates (JAGGs) of pyrrolopyrrole cyanines (PPcys) stabilized by amphiphilic block co-polymers were prepared in aqueous medium. JAGG formation can be tuned by means of the chemical structure of PPcys, the concentration of chromophores inside the polymeric NPs, and ultrasonication. The JAGG NPs exhibit a narrow emission band at 773 nm, a fluorescence quantum yield comparable to that of indocyanine green, and significantly enhanced photostability, which is ideal for long-term bioimaging.

Exploring the Optical Nonlinearities of Plasmon-Exciton Hybrid Resonances in Coupled Colloidal Nanostructures

Strong coupling of plasmons and excitons can form hybrid states, the so-called “plexcitons”. Although plasmons have a low quality factor, the exceptionally high coupling strength with molecular aggregates, in particular J-aggregates, allows the realization of strong interaction. Despite several studies in recent years showing the formation of plexcitonic states, their nature, especially at very short times, is still insufficiently investigated. In this article, we identify the nonlinear optical behavior of plexcitons formed on gold nanorods coated with J-aggregated cyanine molecules at short times by transient absorption spectroscopy and a simple Lorentz oscillator model. We control the spectral overlap of the two resonances and analyze the effect of detuning as well as the effect of off- and on resonance excitation on the hybrid states. We demonstrate that at ultrashort time scales plexcitons show tunable plasmonic and excitonic nonlinear performance according to the hybridization model. In a first appro...

Non-Radiative Energy Transfer Mediated by Hybrid Light-Matter States.

We present direct evidence of enhanced non-radiative energy transfer between two J-aggregated cyanine dyes strongly coupled to the vacuum field of a cavity. Excitation spectroscopy and femtosecond pump-probe measurements show that the energy transfer is highly efficient when both the donor and acceptor form light-matter hybrid states with the vacuum field. The rate of energy transfer is increased by a factor of seven under those conditions as compared to the normal situation outside the cavity, with a corresponding effect on the energy transfer efficiency. The delocalized hybrid states connect the donor and acceptor molecules and clearly play the role of a bridge to enhance the rate of energy transfer. This finding has fundamental implications for coherent energy transport and light-energy harvesting.