Aggregation Of Cyanine Dyes Research Articles

Ionic Liquid Induced Aggregation and Precipitation Behavior of Pinacyanol

AbstractIn this paper, we demonstrate the unique role of ionic liquids (ILs) as dye aggregation and precipitation promoter. Specifically, we have observed that the presence of small amount of IL such as 1‐butyl‐3‐methylimidazolium hexaflurophosphate ([bmim][PF6]), 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf2N]), 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate ([bmim][OTf]), 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim][BF4]) and 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([bmpyrr][Tf2N]) in aqueous milieu can help in the conversion of a cyanine dye 1,1’‐Diethyl‐2,2’‐carbocyanine iodide (Pinacyanol iodide) into J‐ and H‐aggregates followed by time dependent precipitation of the dye. The anion of the added IL strongly affects the aggregation process in aqueous solution. Addition of small amount of BF4− anion based IL [bmim][BF4] to aqueous solution of the dye initially induces J‐ and H‐aggregation followed by quick precipitation of the dye in time dependent manner. Presence of small amount of other anion containing ILs such as ([bmim][PF6]), ([bmim][OTf]), ([bmim][Tf2N]) and ([bmpyrr][Tf2N]) strongly supports H‐aggregation of the dye in aqueous solution whereas higher wt % of added ILs also caused precipitation of the dye in a time dependent manner. The nature of the IL anion, wt % of added IL and temperature conditions decides efficiencies of aggregation and precipitation processes. The dual yet unique behavior of ILs as an additive influence the aggregation of cyanine dyes and precipitation has been demonstrated. The observed results can contribute towards various application for dye aggregates and in the removal of dyes from water. The developed process can find potential applications in the field of material science, wastewater treatment, future light harvesting systems, and opto‐electronics related fields.

Ultrafast Super-Resolution Imaging Exploiting Spontaneous Blinking of Static Excimer Aggregates.

Single-molecule localization methods have been popularly exploited to obtain super-resolved images of biological structures. However, the low blinking frequency of randomly switching emission states of individual fluorophores greatly limits the imaging speed of single-molecule localization microscopy (SMLM). Here we present an ultrafast SMLM technique exploiting spontaneous fluorescence blinking of cyanine dye aggregates confined to DNA framework nanostructures. The DNA template guides the formation of static excimer aggregates as a "light-harvesting nanoantenna", whereas intermolecular excitation energy transfer (EET) between static excimers causes collective ultrafast fluorescence blinking of fluorophore aggregates. This DNA framework-based strategy enables the imaging of DNA nanostructures with 12.5-fold improvement in speed compared to conventional SMLM. Further, we demonstrate the use of this strategy to track the movement of super-resolved DNA nanostructures for over 20 min in a microfluidic system. Thus, this ultrafast SMLM holds great potential for revealing the dynamic processes of biomacromolecules in living cells.

Fast tumor imaging using pH-responsive aggregation of cyanine dyes with rapid clearance

Rapid and selective tumor detection using conventional pH-activatable chemical probes as contrast agents is challenging. Moreover, a large proportion of the contrast agent is usually retained in the body long-term, which causes potential toxicity risks. In this study, we developed a fluorescent sensor, CypH2S, with a pH-sensitive cyclic substructure for detection of acidic tumor microenvironment. Upon pH variation, the sensor underwent structural changes: the closed-ring form, CypH2S-C, exhibited suppressed dye aggregation, while the open-ring form, CypH2S-O, tended to aggregate in aqueous solutions under slightly acidic conditions. Importantly, CypH2S facilitated rapid and selective tumor visualization in a living mouse model via fluorescence imaging of its pH-responsive aggregation with a 1.9-fold tumor/background ratio (< 1 h). Furthermore, prompt clearance of CypH2S from the bloodstream post-tumor detection occurred because of the relatively small size of the aggregates and cell impermeability. These properties would make CypH2S a promising candidate for clinical tumor diagnosis.

Poly(dopamine) coated H-aggregates of amphoteric charged near-infrared absorbing cyanine dyes for enhanced photothermal tumor imaging and therapy

Cancer and tumors pose a formidable danger to health, with clinical treatments often beset by adversities such as deleterious side effects, suboptimal therapeutic outcomes, and the propensity for subsequent recurrence and metastasis. In this work, we present a self-assembled organic dyes as an innovative approach for the photothermal imaging and therapy for tumors. Cyanine aggregation nanoparticles (Cy-aggregate) were prepared by autonomous aggregation of amphoteric charged cyanine dyes in the near-infrared spectral range, and after the formation of aggregates, a new absorption peak of H-aggregates appeared around 808 nm, which were subsequently modified with dopamine to obtain cyanine aggregate@PDA nanoparticles (Cy-aggregate@PDA). The nanoparticle exhibits distinctive electrostatic gravitation-mediated H-type aggregation, resulting in the quenching of near-infrared fluorescence. Upon exposure to 808 nm laser irradiation, the self-aggregated cyanine dyes do not emit the absorbed energy through fluorescence as conventional organic dyes do, but efficiently converts the energy into heat, with a photothermal conversion efficiency of up to 51.4%, which can facilitate photothermal therapy and imaging. The inclusion of poly(dopamine) engenders heightened photothermal conversion efficiency, improved stability, and diminished cytotoxicity within the nanoparticles. Moreover, the nanoparticles manifest remarkable dispersion, biocompatibility, and stable photothermal properties, thus bestowing upon them a novel avenue for the photothermal treatment of tumors.

Synergistic Inter‐ and Intramolecular Aggregation of Dimeric Cyanine Dyes Affords Highly Efficient In Vivo Self‐Delivery and Photothermal Therapy

AbstractAdvancing photothermal therapy hinges on developing PTAs with robust in vivo delivery and therapeutic efficacy. However, effective molecular design approaches for high‐performance PTAs remain lacking. Herein a strategic design of dimeric heptamethine cyanine (Cy7) molecules is presented, covalently linked via ortho/meta/para‐phenyldithiol. These designs facilitate spontaneous nanoparticle assembly in water, attributed to efficient intermolecular aggregation, enhancing in vivo delivery. Additionally, aggregation between intramolecular Cy7 units promotes superior photothermal conversion efficiency (PCE) up to 74.1% for meta‐dimer. Remarkably, the para‐dimer variant not only achieves a high PCE of 61.1% but also exhibits the most effective pharmacokinetic profile, leading to unparalleled anticancer efficacy in vivo. This dual aggregation strategy, leveraging both inter‐ and intramolecular dynamics, equips dimeric Cy7 with superior self‐delivery and photothermal efficacy, offering a promising approach for the next generation of photothermal therapeutics.

Orientational effects in the polarized absorption spectra of molecular aggregates.

We present a detailed theoretical analysis of polarized absorption spectra and linear dichroism of cyanine dye aggregates whose unit cells contain two molecules. The studied threadlike ordered system with a molecular exciton delocalized along its axis can be treated as two chains of conventional molecular aggregates, rotated relative to each other at a certain angle around the aggregate axis. Our approach is based on the general formulas for the effective cross section of light absorption by a molecular aggregate and key points of the molecular exciton theory. We have developed a self-consistent theory for describing the orientational effects in the absorption and dichroic spectra of such supramolecular structures with nonplanar unit cell. It is shown that the spectral behavior of such systems exhibits considerable distinctions from that of conventional cyanine dye aggregates. They consist in the strong dependence of the relative intensities of the J- and H-type spectral bands of the aggregate with a nonplanar unit cell on the angles determining the mutual orientations of the transition dipole moments of constituting molecules and the aggregate axis as well as on the polarization direction of incident light. The derived formulas are reduced to the well-known analytical expressions in the particular case of aggregates with one molecule in the unit cell. The calculations performed within the framework of our excitonic theory combined with available vibronic theory allow us to quite reasonably explain the experimental data for the pseudoisocyanine bromide dye aggregate.

The Aggregates of Near-Infrared Cyanine Dyes in Phototherapy.

Cyanines in the near-infrared region are a typical example of a classic fluorescent dye that has garnered significant attention and widespread use in the life sciences and biotechnology. Their character to form assemblies or aggregates has inspired the development of various functional cyanine dye aggregates in phototherapy. This article provides a brief summary of the strategies used to prepare these cyanine dye aggregates. The reports in this concept suggest that the self-assembly of cyanine dyes can enhance their photostability, opening up new possibilities for their application in phototherapy. This concept may encourage researchers to explore the development of functional fluorescent dye aggregates further.

Aggregates of Cyanine Dyes: When Molecular Vibrations and Electrostatic Screening Make the Difference.

Aggregates of cyanine dyes are currently investigated as promising materials for advanced electronic and photonic applications. The spectral properties of aggregates of cyanine dyes can be tuned by altering the supramolecular packing, which is affected by the length of the dye, the presence of alkyl chains, or the nature of the counterions. In this work, we present a joint experimental and theoretical study of a family of cyanine dyes forming aggregates of different types according to the length of the polymethinic chain. Linear and nonlinear optical spectra of aggregates are rationalized here in terms of an essential-state model accounting for intermolecular interactions together with the molecular polarizability and vibronic coupling. A strategy is implemented to properly account for screening effects, distinguishing between electrostatic intermolecular interactions relevant to the ground state (mean-field effect) and the interactions relevant to the excited states (excitonic effects). To the best of our knowledge, this is the first attempt to simulate nonlinear spectral properties of aggregates of symmetric dyes accounting for molecular vibrations.

Conjugate and non-conjugate controls of a sensitizer to enhance dye-sensitized upconversion luminescence

Structural modification and triethylamine were used to suppress the aggregation of cyanine dyes on the UCNP surface to improve the upconversion luminescence.

Excited-State Lifetimes of DNA-Templated Cyanine Dimer, Trimer, and Tetramer Aggregates: The Role of Exciton Delocalization, Dye Separation, and DNA Heterogeneity.

DNA-templated molecular (dye) aggregates are a novel class of materials that have garnered attention in a broad range of areas including light harvesting, sensing, and computing. Using DNA to template dye aggregation is attractive due to the relative ease with which DNA nanostructures can be assembled in solution, the diverse array of nanostructures that can be assembled, and the ability to precisely position dyes to within a few Angstroms of one another. These factors, combined with the programmability of DNA, raise the prospect of designer materials custom tailored for specific applications. Although considerable progress has been made in characterizing the optical properties and associated electronic structures of these materials, less is known about their excited-state dynamics. For example, little is known about how the excited-state lifetime, a parameter essential to many applications, is influenced by structural factors, such as the number of dyes within the aggregate and their spatial arrangement. In this work, we use a combination of transient absorption spectroscopy and global target analysis to measure excited-state lifetimes in a series of DNA-templated cyanine dye aggregates. Specifically, we investigate six distinct dimer, trimer, and tetramer aggregates—based on the ubiquitous cyanine dye Cy5—templated using both duplex and Holliday junction DNA nanostructures. We find that these DNA-templated Cy5 aggregates all exhibit significantly reduced excited-state lifetimes, some by more than 2 orders of magnitude, and observe considerable variation among the lifetimes. We attribute the reduced excited-state lifetimes to enhanced nonradiative decay and proceed to discuss various structural factors, including exciton delocalization, dye separation, and DNA heterogeneity, that may contribute to the observed reduction and variability of excited-state lifetimes. Guided by insights from structural modeling, we find that the reduced lifetimes and enhanced nonradiative decay are most strongly correlated with the distance between the dyes. These results inform potential tradeoffs between dye separation, excitonic coupling strength, and excited-state lifetime that motivate deeper mechanistic understanding, potentially via further dye and dye template design.

Development of biotin-tagged near-infrared fluorescence probes for tumor-specific imaging

Near-infrared (NIR) probes are applicable for tumor imaging due to deep tissue penetration and low background signal. And cyanine dyes with long emission wavelength are excellent fluorophores to develop NIR probes. However, the aggregation of cyanine dyes in aqueous solution reduces the utilization of light. To solve this problem, polyethylene glycol (PEG) was introduced into the probes to reduce their aggregation. In our work, two new NIR probes G1 and G2 were designed and prepared by conjugating the cyanine dye G0 with Biotin-PEG5-Azide. The conjugated biotin could enhance the target specificity of probes. And the photophysical and photochemical parameters demonstrated that G1 and G2 had a reduced aggregation tendency. In vitro fluorescence imaging proved that these two probes could be specifically taken up by HeLa cells, and in vivo imaging demonstrated that these two probes could specifically target tumors with large tumor-to-muscle (T/M) ratios. All these results indicated that G1 and G2 are promising NIR fluorescent contrast agents for tumor-specific imaging.

Davydov Split Aggregates of Cyanine Dyes on Self-Assembled Nanotubes.

The Davydov splitting of dye aggregates represents unique molecular excitons. In this paper, we report the formation of Davydov split aggregates of 3,3'-diethylthiacarbocyanine iodide (DiSC2 (3)) and 3,3'-diethylthiadicarbocyanine iodide (DiSC2 (5)) templated by the helical nanotubes of lithocholic acid (LCA). The templated Davydiv split aggregates show a strong J-band and a weak H-band in the adsorption spectra. As the LCA helical nanotubes transform into a straight shape, the relative intensities of the J-band and the H-band of the templated Davydov split aggregates become roughly equal. The twisted angle change of the transition moment of DiSC2 (3) and DiSC2 (5) molecules in the templated Davydov split aggregates in response to the helical-to-straight shape transformation of LCA nanotubes is estimated. The templated Dvaydov split aggregates with well-defined shapes and molecular excitons are of interest for artificial light-harvesting and optoelectronic devices.

A thiamonomethinecyanine probe for detection of Pb2+ based on transformation from dimer to monomer by aptamer

A simple method based on a thiamonomethinecyanine dye (dye2) and duplex DNA system was constructed to detect Pb2+ by UV–Vis spectra. The absorption spectra of dye2 show dimers and monomers peak and the monomer–dimer equilibrium could be regulated with environmental change. Duplex DNA as a template was used to regulate distinct aggregates of cyanine dye in the presence of Pb2+. This system shows a specific absorption signal for Pb2+ detection.

Concentration-dependent dye aggregation and disassembly triggered by the same artificial helical foldamer

Abstrct Constructing and regulating the cyanine dye aggregates have been constantly pursued because of their wide applications in photosensitizers, biological fluorescence probes, nonlinear optics, etc. However, to realize such a process using a single additive still remains a formidable challenge. Here, the aggregation and disassembly of positively charged 3,3-diethyloxadicarbocyanine iodide (DiOC2(5)) have been demonstrated just by changing the concentration of an artificial poly(phenylenediethynylene)-based helical foldamer (Poly-1) bearing L-alanine sodium pendants with an amide linker. Poly-1 possessed the negatively charged pendants and hydrophobic helical grooves. Upon simple mixing of equal DiOC2(5) and Poly-1, DiOC2(5) molecules were mainly enriched on Poly-1 surface driven by electrostatic interaction and arranged along the main chain of Poly-1, resulting in the formation of chiral H-aggregates. But, the excessive Poly-1 would attract some DiOC2(5) molecules in H-aggregates via electrostatic interaction. The isolated monomers were easy to orderly disperse into the helical grooves due to hydrophobic interaction. Meanwhile, during the aggregation and disassembly, the solution color changed from peachblow to purple red and then to purple and finally to navy blue.

Interaction of a dimeric carbocyanine dye aggregate with bovine serum albumin in non-aggregated and aggregated forms.

The interaction of fluorescent dyes with serum proteins has garnered significant interest owing to potential for non-covalent labeling and imaging applications. In this work, dimeric benzothiazole-based trimethine cyanine dyes are synthesized and their interaction with bovine serum albumin studied. The dimeric cyanine dyes mainly exist as H-dimers and H-aggregates in aqueous solution. A combination of absorbance, fluorescence, circular dichroism spectroscopy and atomic force and fluorescence microscopy indicate the formation of dye-BSA complexes. Binding of one of the dimeric dyes on BSA with a Ka of 1.49×105M-1 results in disruption of dye self-aggregates and unfolding of the dyes into the monomeric or open conformation. Fluorescence enhancement experienced by the dimeric dyes upon interaction with BSA is superior to that registered by Thioflavin T. Surfactant SDS has been used to further tune the self-aggregation of the dimeric dye resulting in a 200-fold fluorescence enhancement in presence of BSA. Interaction of a dimeric dye with BSA under conditions favoring protein aggregation is found to result in faster dye binding and the resulting fluorescence enhancement is easily visualized by fluorescence microscopy. The interaction of a dimeric cyanine dye aggregate with BSA is promising for non-covalent labeling applications in sharp contrast to the monomeric dye counterpart.

J-Aggregates of Indoheptamethine Cyanine Dye

The effect of doubly charged inorganic and organic cations on the aggregation of anionic indoheptamethine cyanine dyes has been studied in aqueous solutions. It is shown that the effective formation of J-aggregates with narrow exciton absorption bands in the IR region of the spectrum with λmax = 920 nm is characteristic only of a dye with SO 3 - groups in the 6,6′-positions of the benzoindolenine ring. It is found that bis-quaternary salt based on α-picolinium is particularly effective as a J-aggregating agent and causes J-aggregation at a concentration close to the dye concentration. It follows that the introduction of sulfogroups at the 6,6′-positions of the benzoindolenine ring creates optimal conditions for packing the molecules of the indolenine dye into a highly organized structure of a “brickwork” type under the action of multiply charged cations. It is shown that the J-aggregates of the indoheptamethine cyanine dye are photoelectric converters for the IR region of the spectrum.

Aggregation of Anionic Cyanine Dyes by Electron-Withdrawing Organic Polycations

It is shown that bis-quaternary salts of 4,4′-dipyridyl (viologens) stimulate the J-aggregation of anionic cyanine dyes in an aqueous solution. It is concluded that the behavior of multiply charged inorganic and organic cations is similar: both types of polycations result in the self-assembly of ordered J-aggregate structures from dimers. It is found that multichromic J-aggregates with the participation of cationic cyanine dyes are formed on the “platform” of J-aggregates built of anionic cyanine dyes and dications of viologens. Thus, we discuss the self-assembly of highly organized structures in which, along with photosensitive exciton semiconductors from organic dyes, π-conjugated organic molecules are included that can participate in secondary dark processes of separation of charges of Frenkel excitons.

Programmed coherent coupling in a synthetic DNA-based excitonic circuit.

Natural light-harvesting systems spatially organize densely packed chromophore aggregates using rigid protein scaffolds to achieve highly efficient, directed energy transfer. Here, we report a synthetic strategy using rigid DNA scaffolds to similarly program the spatial organization of densely packed, discrete clusters of cyanine dye aggregates with tunable absorption spectra and strongly coupled exciton dynamics present in natural light-harvesting systems. We first characterize the range of dye-aggregate sizes that can be templated spatially by A-tracts of B-form DNA while retaining coherent energy transfer. We then use structure-based modelling and quantum dynamics to guide the rational design of higher-order synthetic circuits consisting of multiple discrete dye aggregates within a DX-tile. These programmed circuits exhibit excitonic transport properties with prominent circular dichroism, superradiance, and fast delocalized exciton transfer, consistent with our quantum dynamics predictions. This bottom-up strategy offers a versatile approach to the rational design of strongly coupled excitonic circuits using spatially organized dye aggregates for use in coherent nanoscale energy transport, artificial light-harvesting, and nanophotonics.

Optical properties and photoinduced aggregation of cyanine dyes on silver island films

The optical properties and photoinduced modification of hybrid nanostructures, which are silver island films coated with a layer of cyanine dye, were studied. Experiments were conducted on three dye homologs and films differing in the equivalent thickness of the deposited silver. It was shown that the absorption of a hybrid film is not the sum of the absorption of the molecular layer and the plasmon absorption of the silver. The near fields of nanoparticles (NPs) that form island films increase the absorption of organic molecules, with the greatest increase observed in the band of J-aggregates. The influence of the near fields can be reduced by distancing the molecules from the NPs using an insulating polymer layer. In the presence of silver NPs, the photoinduced modification of the component composition of the layers of the dyes occurs at far lower energy densities. Resonant nanosecond laser pulses lead to the aggregation of molecules in hybrid films.

Emergence of Additional Visible-Range Photoluminescence Due to Aggregation of Cyanine Dye: Astraphloxin on Carbon Nanotubes Dispersed with Anionic Surfactant

Self-organization of organic molecules with carbon nanomaterials leads to formation of functionalized molecular nano-complexes with advanced features. We present a study of physical and chemical properties of carbon nanotube-surfactant-indocarbocyanine dye (astraphloxin) in water focusing on aggregation of the dye and resonant energy transfer from the dye to the nanotubes. Self-assembly of astraphloxin is evidenced in absorbance and photoluminescence depending dramatically on the concentrations of both the dye and surfactant in the mixtures. We observed an appearance of new photoluminescence peaks in visible range from the dye aggregates. The aggregates characterized with red shifted photoluminescence peaks at 595, 635 and 675 nm are formed mainly due to the presence of surfactant at the premicellar concentration. The energy transfer from the dye to the nanotubes amplifying near-infrared photoluminescence from the nanotubes is not affected by the aggregation of astraphloxin molecules providing important knowledge for further development of advanced molecular nano-complexes. The aggregation with the turned-on peaks and the energy transfer with amplified photoluminescence create powerful tools of visualization and/or detection of the nanotubes in visible and near-infrared spectral range, respectively, boosting its possible applications in sensors, energy generation/storage, and healthcare.