J-aggregates Of Cyanine Dyes Research Articles

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).

Shielding Effects Provide a Dominant Mechanism in J-Aggregation-Induced Photoluminescence Enhancement of Carbon Nanotubes.

The unique photophysical properties of single-walled carbon nanotubes (SWCNTs) exhibit great potential for bioimaging applications. This led to extensive exploration of photosensitization methods to improve their faint shortwave infrared (SWIR) photoluminescence. Here, we report the mechanisms of SWCNT-assisted J-aggregation of cyanine dyes and the associated photoluminescence enhancement of SWCNTs in the SWIR spectral region. Surprisingly, we found that excitation energy transfer between the cyanine dyes and SWCNTs makes a negligible contribution to the overall photoluminescence enhancement. Instead, the shielding of SWCNTs from the surrounding water molecules through hydrogen bond-assisted macromolecular reorganization of ionic surfactants triggered by counterions and the physisorption of the dye molecules on the side walls of SWCNTs play a primary role in the photoluminescence enhancement of SWCNTs. We observed 2 orders of magnitude photoluminescence enhancement of SWCNTs by optimizing these factors. Our findings suggest that the proper shielding of SWCNTs is the critical factor for their photoluminescence enhancement, which has important implications for their application as imaging agents in biological settings.

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.

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.

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.

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.

J-Aggregates of Multi-Groups Cyanine Dye Under the Assistant of Amphiphilic Polypeptide for Efficient NIR-IIa Phototheranostics Under 1064 nm Irradiation

J-Aggregates of Multi-Groups Cyanine Dye Under the Assistant of Amphiphilic Polypeptide for Efficient NIR-IIa Phototheranostics Under 1064 nm Irradiation

Large optical nonlinearity enhancement under electronic strong coupling

Nonlinear optical responses provide a powerful way to understand the microscopic interactions between laser fields and matter. They are critical for plenty of applications, such as in lasers, integrated photonic circuits, biosensing and medical tools. However, most materials exhibit weak optical nonlinearities or long response times when they interact with intense optical fields. Here, we strongly couple the exciton of cyanine dye J-aggregates to an optical mode of a Fabry-Perot (FP) cavity, and achieve an enhancement of the complex nonlinear refractive index by two orders of magnitude compared with that of the uncoupled condition. Moreover, the coupled system shows an ultrafast response of ~120 fs that we extract from optical cross-correlation measurements. The ultrafast and large enhancement of the optical nonlinar coefficients in this work paves the way for exploring strong coupling effects on various third-order nonlinear optical phenomena and for technological applications.

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.

Switching resonance character within merocyanine stacks and its impact on excited-state dynamics

Summary In this study, the optical properties and excited-state dynamics of the unique self-assembled donor-acceptor (DA) merocyanine dye stacks from dimer up to octamer, prepared via dipole-dipole interactions, are reported in terms of coherent exciton dynamics and formation of an excimer-like state. Our findings are based on the steady-state absorption/emission, time-resolved fluorescence, and transient absorption (anisotropy) measurements, including wavepacket analysis and quantum mechanical calculations. Coherent exciton of torsional motions-restricted dye stacks rapidly localizes into the weakly emissive excimer-like state, by shortening the inter-moiety distance and changing the bond-length alternation pattern. The inner merocyanine moiety, having two neighboring units, has a reversed resonance character (non-polar (N) Z) in the ground state. This difference has led to two conclusions: (1) tetramers and octamers exhibit different features of excimer-like state than the dimer, and (2) octamers exhibit slower localization dynamics due to the enhanced homogeneity (six inner-moieties) compared with tetramers (two inner moieties).

Thermodynamic Control over Molecular Aggregate Assembly Enables Tunable Excitonic Properties across the Visible and Near-Infrared.

Specific molecular arrangements within H-/J-aggregates of cyanine dyes enable extraordinary photophysical properties, including long-range exciton delocalization, extreme blue/red shifts, and excitonic superradiance. Despite extensive literature on cyanine aggregates, design principles that drive the self-assembly to a preferred H- or J-aggregated state are unknown. We tune the thermodynamics of self-assembly via independent control of the solvent/nonsolvent ratio, ionic strength, or dye concentration, obtaining a broad range of conditions that predictably stabilize the monomer (H-/J-aggregate). Diffusion-ordered spectroscopy, cryo-electron microscopy, and atomic force microscopy together reveal a dynamic equilibrium between monomers, H-aggregated dimers, and extended J-aggregated 2D monolayers. We construct a model that predicts the equilibrium composition for a range of standard Gibbs free energies, providing a vast aggregation space which we access using the aforementioned solvation factors. We demonstrate the universality of this approach among several sheet-forming cyanine dyes with tunable absorptions spanning visible, near, and shortwave infrared wavelengths.

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.

Photochemical dynamics under incoherent illumination: Light harvesting in self-assembled molecular J-aggregates.

Transport phenomena in organic, self-assembled molecular J-aggregates have long attracted a great deal of attention due to their potential role in designing novel organic photovoltaic devices. A large number of theoretical and experimental studies have been carried out describing excitonic energy transfer in J-aggregates under the assumption that excitons are induced by a coherent laser-light source or initialized by a localized excitation on a particular chromophore. However, these assumptions may not provide an accurate description to assess the efficiency of J-aggregates, particularly as building blocks of organic solar cells. Under natural conditions, J-aggregates would be subjected to an incoherent source of light (as is sunlight), which would illuminate the whole photosynthetic complex rather than a single molecule. In this work, we present the first study of the efficiency of photosynthetic energy transport in self-assembled molecular aggregates under incoherent sunlight illumination. By making use of a minimalistic model of a cyanine dye J-aggregate, we demonstrate that long-range transport efficiency is enhanced when exciting the aggregate with incoherent light. Our results thus support the conclusion that J-aggregates are, indeed, excellent candidates for devices where efficient long-range incoherently induced exciton transport is desired, such as in highly efficient organic solar cells.

Optical properties of molecular layer of cyanine dye coated on Ag or Au island film

The absorption properties of molecular layer of cyanine dyes and its J-aggregates coated on the island films in the form of an inhomogeneous ensemble of silver or gold nanoparticles were studied. The different overlapping modes of layer absorption and plasmon resonance were obtained by varying the molecular length and the equivalent thickness of the film. It was shown the absorption of hybrid structure was not a simple sum of overlapping bands. Furthermore, the high enhancement of the molecular absorption was observed due to the influence of the near fields of plasmonic silver nanoparticles in comparison with gold island film. Besides, the induced transparency was observed at the absorption maximum of J-aggregates, which could indicate the interaction between the plasmons of metal nanoparticles and the excitons of the J-aggregate of cyanine dye.

Extinction Spectra of Bilayer Organometallic Nanoplatelets

Spectra of light extinction by metal nanoprisms and nanostars coated with molecular aggregates of organic dyes are calculated and theoretically analyzed. Qualitatively different nature of the spectra of organometallic nanoparticles under study is established when using J-aggregates of various cyanine dyes as their capping layer, as well as silver and gold as the cores. This results from the implementation of various plasmon-exciton coupling modes in the systems under consideration.

J-Aggregates of Cyanine Dye for NIR-II in Vivo Dynamic Vascular Imaging beyond 1500 nm.

Light in the second near-infrared window, especially beyond 1500 nm, shows enhanced tissue transparency for high-resolution in vivo optical bioimaging due to decreased tissue scattering, absorption, and autofluorescence. Despite some inorganic luminescent nanoparticles have been developed to improve the bioimaging around 1500 nm, it is still a great challenge to synthesize organic molecules with the absorption and emission toward this region. Here, we present J-aggregates with 1360 nm absorption and 1370 nm emission formed by self-assembly of amphiphilic cyanine dye FD-1080 and 1,2-dimyristoyl-sn-glycero-3-phosphocholine. Molecular dynamics simulations were further employed to illustrate the self-assembly process. Superior spatial resolution and high signal-to-background ratio of J-aggregates were demonstrated for noninvasive brain and hindlimb vasculature bioimaging beyond 1500 nm. The efficacy evaluation of the clinically used hypotensor is successfully achieved by high-resolution in vivo dynamic vascular imaging with J-aggregates.

Generalized Kasha’s Model: T-Dependent Spectroscopy Reveals Short-Range Structures of 2D Excitonic Systems

Summary Excitonic organic materials owe their tunable optoelectronic properties to intricate microscopic configurations, challenging for conventional characterization methods to resolve. We generalize Kasha’s model by incorporating the temperature (T)-dependent absorption peak shift, in addition to the monomer-aggregate absorption peak shift that defines J- and H-aggregates, to characterize the microscopic structures. We show that the short-range interactions dominate in determining the direction of the T-dependent peak shift, which accounts for previously observed T-dependent blueshifting J-aggregates (BJ-aggregates) that were not explained and predicts the existence of redshifting H-aggregates (RH-aggregates). This defines four types of excitonic aggregates: RJ-, BH-, BJ-, and RH-aggregates, where the latter two unconventional aggregates are possible because of the two dimensionality of excitonic systems and cannot be understood with the original Kasha’s theory. Our conceptual framework is useful for elucidating structure-function relationships in molecular excitonic systems and is fully compatible with existing tools. Possible extensions to other spectroscopic observables and related systems are discussed.

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.

Polymorphic Single-Layer and Fibrillar Nanostructures of J-Aggregates of a Carbocyanine Dye

Abstract—J-aggregates of a carbocyanine dye (pyridinium salt of 3,3'-di-(γ-sulfopropyl)-4,5,4',5'-di(tieno-3'',2'')-9‑ethyl-tiatrimethine cyanine betaine) (CC) were studied via the high-resolution AFM method at the mesoscale and nanoscale. They were found to exist in two structurally different polymorphic forms of single layers and fibrils. The class of single-layer J-aggregates consists of irregular micron sheets and giant submicron tubes, whose structure is identical to tubular J-aggregates of other cyanine dyes. The fibrillar J-aggregates are composed of 3-nm-high fibrils forming the networks owing to merging and branching, as well as of “elementary” fibrils with a height close to the molecular sizes of dye. Structural models of elementary fibril with molecular “staircase” and “ladder” stacking types were proposed as well.

Crystallography of the Destruction Fragments of Tubular Cyanine Dye J-Aggregates on the Mica Surface

Crystallography of the Destruction Fragments of Tubular Cyanine Dye J-Aggregates on the Mica Surface