Fluorescence resonance energy transfer between two cationic laser dyes in presence of the series of reduced-charge montmorillonites: effect of the layer charge

Series of montmorillonites with systematically reduced layer charges represent a suitable model for studying various properties and interactions of layered inorganic compounds. The reduced-charge montmorillonites (RCMs) used in this study were prepared by a standard method of Li+-fixation in Nanocor montmorillonite at 100-300 degrees C. The layer charge gradually decreased with increasing temperature of RCM preparation. Li+-fixation led in some cases to the loss of expandability due to the formation of mixed swelling/nonswelling and homogeneous nonswelling phases. The interaction of two cationic dyes-rhodamine 3B (R3B) and oxazine 4 (Ox4)-with reduced-charge montmorillonites in dispersions was studied by means of UV/vis absorption and fluorescence spectroscopy. Montmorillonite with the highest charge density induced the formation of H-aggregates of the dye cations characterized by a sandwich-type structure. As the layer charge decreased, the amount of the H-aggregates was reduced in favor of H-dimers and monomers. RCMs with low charge density suppressed dye cation aggregation and mainly monomeric forms were detected. The process of energy transfer from R3B to Ox4 was detected as decreasing the emission from the energy donor and increasing the emission from the energy acceptor. The energy transfer was clearly influenced by the properties of RCM templates. The dye cations adsorbed at the surface of the highest-charge specimen formed H-aggregates, which were efficient luminescence quenchers. Fluorescence resonance energy transfer (FRET) gradually increased with the charge reduction to be optimal at the templates with medium layer charge. Substantial decrease of the layer charge and reduction of clay mineral swelling led to the decrease of both the luminescence and the efficiency of FRET. The relations of energy transfer processes to the layer charges and swelling properties of montmorillonite are analyzed in detail.     

Photoresponse and anisotropy of rhodamine dye intercalated in ordered clay layered films

In order to elaborate organized two-dimensional arrangements of fluorescent dyes in host solid layered materials, rhodamine 6G (R6G) is encapsulated in supported thin films of laponite (Lap) clay. Clay films are elaborated by the spin-coating technique and their surface morphology is analyzed by scanning electron (SEM) and atomic force (AFM) microscopies. The internal order of the stacked clay layers is checked by X-ray diffraction technique (DRX). The thermostability of R6G in the Lap films is discussed on the basis of several thermogravimetric and calorimetric techniques (TG, DTA and DSC). The R6G adsorbed species in Lap films are characterized by absorption and fluorescence (steady-state and time-resolved) spectroscopies. Monomers, dimers and higher-order aggregates are identified for very low (<0.1%), moderate (1–25%) and high (>40% of the total cation exchange capacity, CEC, of the clay) dye content, respectively. Both non-fluorescence H-type and fluorescent J-type aggregates of R6G in Lap films are characterized.Absorption and fluorescence techniques with linearly polarized light are applied to evaluate the anisotropic photoresponse of R6G in Lap films, from which the preferential orientation of dye molecules with respect to the clay layers can be evaluated. The validity of the newly established fluorescence polarization is contrasted with the well-established absorption polarization method, and the emission spectroscopy with linearly polarized light can be applied to establish the preferential orientation of fluorophore molecular probes incorporated in any rigid and ordered 2D host materials, including monolayers and biological membranes.     

A structural model for cyanine dyes templated into the minor groove of DNA

3,3-Diethylthiadicarbocyanine (DiSC₂(5)) is a monocationic dye which forms cofacial dimers that insert into the minor groove of DNA [J. Seifert, R. Conner, S. Kushon, M. Wang, B. Armitage, J. Am. Chem. Soc. 121 (1999) 2987]. These dyes self-assemble into long helical aggregates in AT-rich regions with the dimers aligned in an end-to-end fashion. A model is presented that allows for the construction of large helical aggregates with continuously variable structural parameters. The spectra or excited states are computed using a direct intermediate neglect of differential overlap (INDO) single configuration interaction (SCI) method. Results are reported for both H- and J-type aggregates ranging in size from 2 to 6 dimers. A more approximate model based on transition charge densities enables calculations of larger aggregates. These models are used to derive structural parameters of both H- and J-type aggregates from the available spectral data, resulting in a new structural model for J-type aggregation in these systems.     

Characterization of rhodamine 6G aggregates intercalated in solid thin films of laponite clay. 2 Fluorescence spectroscopy

The photoluminescence response of Rhodamine 6G (R6G) laser dye intercalated into solid thin films of Laponite (Lap) clay is studied as a function of dye loading. Fluorescence spectroscopy (steady-state and time-resolved techniques) was used to characterize the R6G species adsorbed into the solid films. For very diluted R6G loadings (40% CEC), with a reminiscent fluorescence band at around 600 nm.     

Optical properties of molecular aggregates of oxazine dyes in dispersions of clay minerals

The molecular aggregation of oxazine 1 (Ox1) and oxazine 4 (Ox4) in reduced charge montmorillonite (RCM) colloids was investigated by absorption and fluorescence spectroscopies. The aggregation was significantly influenced by the structure of dye cations. Presence of four hydrophobic ethyl groups attached to the ammonium substituents in Ox1 cation prevented formation of closely packed sandwich-type assemblies (H-aggregates). Significant effect of the layer charge was observed for Ox4/RCMs dispersions. Large amounts of the Ox4 H-aggregates were formed in the systems with RCMs of the highest layer charge and reflected in quenched fluorescence. The presence of J-aggregates was proven by absorption spectra for the systems with Ox4 and low-charge RCMs. The flocculation of the lowest charge RCM colloids led to an extensive reduction of the luminescence. The trends and effects of the dye molecular structure and RCM properties are compared with the results previously published for other types of dyes.     

Growth of Merocyanine Dye J-Aggregate Nanosheets by Living Supramolecular Polymerization

J-aggregates are highly desired dye aggregates but so far there has been no general concept how to accomplish the required slip-stacked packing arrangement for dipolar merocyanine (MC) dyes whose aggregation commonly affords one-dimensional aggregates composed of antiparallel, co-facially stacked MCs with H-type coupling. Herein we describe a strategy for MC J-aggregates based on our results for an amphiphilic MC dye bearing alkyl and oligo(ethylene glycol) side chains. In an aqueous solvent mixture, we observe the formation of two supramolecular polymorphs for this MC dye, a metastable off-pathway nanoparticle showing H-type coupling and a thermodynamically favored nanosheet showing J-type coupling. Detailed studies concerning the self-assembly mechanism by UV-Vis spectroscopy and the packing structure by atomic force microscopy and wide-angle X-ray scattering show how the packing arrangement of such amphiphilic MC dyes can afford slip-stacked two-dimensional nanosheets whose macrodipole is compensated by the formation of a bilayer structure. As an additional feature we demonstrate how the size of the nanosheets can be controlled by seeded living supramolecular polymerization.     

Adsorption of fluorescent R6G dye into organophilic C12TMA laponite films

The absorption and fluorescence properties of rhodamine 6G (R6G) in organophilic laponite (Lap) clay films are studied. For this purpose, organo-Lap clays are synthesized by the incorporation of dodecyltrimethylammonium (C12TMA) as surfactant into the interlayer space of Lap clays. Two organo-Lap clays are prepared: one with moderate surfactant content (around 70% of the total cation-exchange capacity (CEC) of the clay) and a second with a high surfactant loading (about 130% CEC). Supported films are elaborated by the spin-coating technique and characterized by several techniques such as atomic force microscopy, elemental CHN analysis, X-ray diffraction, and thermogravimetry. IR spectroscopy reveals that the intercalation of R6G into organo-Lap films takes place at the detriment of the adsorbed C12TMA molecules. The photophysical properties of R6G monomers in the interlayer space of Lap films are improved by the presence of surfactant molecules. Moreover, organophilic environments can reduce the dye aggregation and favor the formation of fluorescent J-type aggregates, enhancing the fluorescence ability of dye/clay films with high dye contents. This improvement depends on the surfactant content.     

Electron-Withdrawing Substituents Allow Boosted NIR-II Fluorescence in J-Type Aggregates for Bioimaging and Information Encryption

Developing molecular fluorophores with enhanced fluorescence in aggregate state for the second near-infrared (NIR-II) imaging is highly desirable but remains a tremendous challenge due to the lack of reliable design guidelines. Herein, we report an aromatic substituent strategy to construct highly bright NIR-II J-aggregates. Introduction of electron-withdrawing substituents at 3,5-aryl and meso positions of classic boron dipyrromethene (BODIPY) skeleton can promote slip-stacked J-type arrangement and further boost NIR-II fluorescence of J-aggregates via increased electrostatic repulsion and intermolecular hydrogen bond interaction. Notably, NOBDP-NO₂ with three nitro groups (−NO₂) shows intense NIR-II fluorescence at 1065 nm and high absolute quantum yield of 3.21 % in solid state, which can be successfully applied in bioimaging, high-level encoding encryption, and information storage. Moreover, guided by this electron-withdrawing substituent strategy, other skeletons (thieno-fused BODIPY, aza-BODIPY, and heptamethine cyanine) modified with −NO₂ are converted into J-type aggregates with enhanced NIR-II fluorescence, showing great potential to convert aggregation caused emission quenching (ACQ) dyes into brilliant J-aggregates. This study provides a universal method for construction of strong NIR-II emissive J-aggregates by rationally manipulating molecular packing and establishing relationships among molecular structures, intermolecular interactions, and fluorescence properties.     

Aggregation and decomposition of a pseudoisocyanine dye in dispersions of layered silicates

The optical properties of reaction systems composed from a pseudoisocyanine (PIC) solution and dispersed layered silicates were studied using visible spectroscopy. Two series of reduced-charge montmorillonites were used as the silicate materials. Each series consisted of eight samples with different layer charges, which were prepared from one parent material. Observed trends were verified with another series of dioctahedral and trioctahedral smectites of different layer charges, structure, and origin. The layer charge density of the silicates significantly affected the aggregation of PIC cations. In addition to the formation of J-aggregates, dye spectral bleaching was also observed. Silicates with very low charge densities induced neither significant aggregation nor spectral bleaching of the dye. The highest levels of PIC J-aggregate formation were found in dispersions of the layered silicates with a medium surface charge. However, reversible spectral bleaching was also observed in some cases. PIC dye cations probably change their conformations during the adsorption process, due to the tension resulting from the large size of the cations and the relatively high charge density at the silicate surface. The bleached dye recovers, at least partially, with the rearrangement and redistribution of the dye cations over the time. In contrast, the presence of silicates with very high charge densities (synthetic taeniolite and fluorohectorite) led to the very fast and irreversible decomposition of the PIC. Perhaps, the tension in adsorbed dye cations, induced by the high charge density at the silicate surface, resulted in significant destabilization and a decomposition reaction of the chromophore.     

Study of internal structure of meso-tetrakis (4-sulfonatophenyl) porphine J-aggregates in solution by fluorescence microscope imaging in a magnetic field

To determine the internal molecular arrangement of organic dye aggregates, a technique for observing the fluorescence microscope image of a solution consisting of dye aggregates in a magnetic field was developed. Using this technique, the fluorescence image of meso-tetrakis (4-sulfonatophenyl) porphine (TPPS) J-aggregates in a solution in a magnetic field of 10 T was observed. It was observed that individual rod-shaped TPPS aggregates (4-20 microm in length) were aligned parallel to the applied field. The polarized absorption spectra of the sample solution were also measured in the fields of up to 10 T. The spectra show the magnetic field dependence of the J-band intensity, reflecting the magnetic alignment of the aggregates. On the basis of the magnetic and optical properties obtained by the experiments, it was proposed that TPPS J-aggregates have a tube-like structure and are constructed from one-dimensional molecular arrays that are stacked parallel to the long axis of the tube.     

阴阳离子菁染料超快荧光动力学特性研究

采用飞秒荧光上转换技术,研究了阴阳离子菁染料及对应的阴离子和阳离子菁染料吸附在立方型和T型溴碘化银表面上形成J-聚集体的荧光衰减时间分辨特性,分析了几种菁染料增感体系的超快电子转移动力学过程及其对增感效率的影响.通过比较几种菁染料增感体系的荧光衰减特性,两种阴阳离子染料要明显快于阴离子染料、阳离子染料及二者的加合,说明阴阳离子染料聚集体到溴碘化银的电子注入速率较快,增感效果更好.对两种阴阳离子染料聚集体荧光衰减特性的比较,可以看出染料在T型颗粒溴碘化银上形成聚集体的荧光寿命更短,因而对T型颗粒的增感效果更好.染料Dye2的荧光衰减要快于染料Dye1,说明染料Dye2到溴碘化银的电子注入速率更快,增感效率更高.     

Molecular organization in binary mixtures of derivatives of naphthalenebicarboxylic acid and naphthoylenebenzimidazole with a liquid crystal in two-dimensional layers II. Langmuir-Blodgett films

Langmuir-Blodgett (LB) films of some dichroic dyes, namely derivatives of naphthalenebicarboxylic acid and derivatives of naphthoylenebenzimidazole, and of their mixtures with mesogens: 4-octyl-4'-cyanobiphenyl or 4-pentyl-4'-cyano-p-terphenyl were prepared. Absorption and fluorescence studies using unpolarized and linearly polarized light were carried out. Both absorption and fluorescence spectra indicated the formation of aggregates of dye molecules in monomolecular layers. Moreover, it was found that dye molecules are more tilted to the quartz surface in LB films than to the plane of the air-water interface in Langmuir films.     

Aggregation of rhodamine 3B adsorbed in Wyoming Montmorillonite aqueous suspensions

The adsorption of Rhodamine 3B (R3B) molecules in Wyoming Montmorillonite (Mont) particles suspended in water was studied by electronic absorption spectroscopy. Several adsorbed R3B species in the Mont tactoids were characterized from the observed changes in the absorption spectra by increasing the relative dye/clay concentration and the stirring time of the samples. R3B molecules can be adsorbed as monomeric units both in the water/clay interface and in the interlayer space, and head-to-tail R3B dimers and trimers were present in the external surface of Mont. The formation of internally adsorbed R3B monomers by the migration of the externally adsorbed species to the interlayer space leads to the deaggregation of the dye molecules in the external surface.     

Spectral properties of rhodamine 6G in smectite dispersions: effect of the monovalent cations

Montmorillonite monoionic forms with alkali metal and NH(4)(+)-cations were prepared by ion exchange. The hydration properties and binding of the ions to montmorillonite surface and the swelling properties of the mineral specimens were analyzed. Whereas Na(+)- and Li(+)-ions were fully hydrated over a large range of conditions, large size K(+), NH(4)(+), and mainly Rb(+) and Cs(+) ions were apt to bind directly to the oxygen atoms on the mineral surface. The forms with large ions exhibited reduced hydration and swelling and the absence of macroscopic swelling of the respective aqueous colloids. The interaction of laser dye rhodamine 6G (R6G) in montmorillonite colloids was investigated by absorption and steady-state fluorescence spectroscopies. Significant effects of the properties of both the inorganic ions and swelling properties of colloidal dispersions on R6G molecular aggregation were observed. Large amounts of the molecular aggregates were formed in the colloids of Na(+)- and Li(+)-montmorillonites. The aggregates absorbed light at significantly lower wavelengths (~460 nm) with respect to the light absorption by monomers (535 nm). Fluorescence spectroscopy provided a key evidence for the assignment of the type of the aggregates: The emission of the aggregates at relatively low energies proved these assemblies are rather a mixed H-/J-type than ideal H-aggregates. The presence of parent inorganic cations of larger size led to a significant lowering of the amount of the R6G aggregates in favor of the monomers. Investigations of the evolution of the dye aggregation with time indicated basic features of dye aggregation reaction: The size of parent inorganic ions did not affect the reaction mechanism, but rather limited the extent of the reaction. Probably the forms with large inorganic ions, such as Rb(+) and Cs(+), did not provide sufficient surface for the formation of the large size assemblies of the dye. This property can be explained in terms of strong association of the large alkali metal ions to clay mineral surface, as well as to reduced swelling in the colloidal systems of respective forms.     

Spectroscopic and fluorescence properties of silver-dye composite nanoparticles

The aim of this work was to investigate the formation of J-aggregates of thiacyanine dye (TC, 5,5′-disulfopropyl-3,3′-dichlorothiacyanine sodium salt) in the presence of 6 nm spherical silver nanoparticles (Ag NPs) using spectrophotometric and fluorescence methods. The formation of J-aggregates was concentration dependent and characterized by the appearance of the new absorption band with the maximum at 481 nm. Spectrophotometric study of J-aggregate formation and time stability suggested that they were formed on the account of monomer form of TC. Moreover, the stability of J-aggregates increased with the lowering AgNPs concentration. The measurements of fluorescence of the NPs—dye assembly clearly indicated that the fluorescence of TC was quenched by Ag NPs on the concentration dependent manner. The spectrophotometric and fluorescence properties of NPs—dye assembly were found to be quantitatively related to the surface coverage of the dye on the Ag NPs.     

Exciton energy transfer between optically forbidden states of molecular aggregates

3-ethyl-2-[3-(3-ethyl-2(3H)-benzoxazolylidene)-1-propenyl]benzoxazolium iodide (dye I) and pseudoisocyanine bromide are employed to form H aggregates as donors and J aggregates as acceptors. The energy of an H band of the H aggregates is higher than that of a J band of the J aggregates. It was confirmed that excitation of the H band does not emit fluorescence by comparison of excitation spectra of dye I H aggregates with that of dye I monomer. Absorption, fluorescence, and excitation spectra of spin-coated films of H aggregates mixed with various quantities of J aggregates have been observed. Excitation spectra probed at the J band are found to have a component of the H band. Fluorescence spectra originated from excitation of the H band are extracted and qualitatively analyzed. It is confirmed that excitation of the H band causes to emit fluorescence of a J band of the J aggregates. These phenomena show that exciton energy can transfer from the lowest energy in electronic states of the H aggregate, which state is optically forbidden, to electronic state of the J aggregate.     

Molecular orientation of rhodamine dyes on surfaces of layered silicates

Films of the layered silicates fluorohectorite (FH) and saponite (Sap) with various rhodamine dyes were prepared. The dyes with acidic as well as large hydrophobic groups in their molecule were not adsorbed on the surface of FH, which was interpreted in terms of high charge density on the surface of this silicate. All adsorbed dyes formed similar forms, such as isolated cations and H-type molecular aggregates, which were characterized by different spectral properties. Polarized ultraviolet-visible (UV-vis) spectroscopy was used for the characterization of the molecular orientation of dye chromophores on the silicate surface. The isolated dye cations and species, which absorbed light at the low energy part of the spectra, were only slightly tilted with respect to the plane of the silicate surface. The cations forming H-aggregates and absorbing light at low wavelengths were oriented in a nearly perpendicular fashion. The nearly perpendicular orientation was observed as a strong increase of dichroic ratio with film tilting. The orientation of the cations in H-aggregates depends partially on the structure of the dye molecule, namely, on the type of amino group (primary, secondary, or tertiary) in the dye molecule. The type of amino groups probably plays a role in the suitable orientation of dye cations for effective electrostatic interaction between the cations and the negatively charged siloxane surface. X-ray powder diffraction could not distinguish dye phases of dye monomers and molecular aggregates.     

Enhanced intra-aggregate charge separation from binary excitons in mixed J-aggregates of cyanine dyes

Well-ordered, two-dimensional, amalgamation-type J-aggregates consisting of two different kinds of structurally analogous anionic cyanine dyes were self-assembled on an amino-functionalized Au(111) electrode surface. Similar binary J-aggregates, though considerably less ordered in either one- or three-dimensional structure, could also be grown easily in a concentrated ( approximately 1.5 M) aqueous solution of NaCl. These binary J-aggregates are characterized by a singly peaked J-band associated with a unique molecular exciton shared by the two different dye components coherently. This cooperative binary excitonic state can live with substantial (more than 0.1 eV) energy gaps between the HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) levels of the two dyes mixed together. These energy gaps allow the binary exciton to relax very rapidly to an intra-aggregate charge-separated state in good competition with the metal-induced quenching of the excited-state energy. The enhanced charge separation leads to a high-efficiency photocurrent generation with a simple binary J-aggregate-coated Au(111) electrode in a reversible redox solution and results in strong quenching of the fluorescence from the corresponding aggregate grown in solution free from substrate-induced quenching.     

Influence of the layer charge and clay particle size on the interactions between the cationic dye methylene blue and clays in an aqueous suspension

The spectroscopic behavior of the dye MB in suspensions of different clays have been used for evaluating layer charge density influence on the adsorption properties of the particles. The clays with higher charge density, like SAz-1 and SCa-3, promote a higher aggregation and do not show deaggregation at longer times, so that practically only the aggregate peak at approximately 570 nm is observed, without any change with time. This is due to, on one side, the larger particle size that decreases the surface area available for adsorption. Additionally, the clay layers will be held together more tightly, avoiding the migration of the dye to the interlamellar region. On the other hand, SWy-1, having a lower charge density, shows a completely different behavior. The dye molecules, initially adsorbed as aggregates on the outer surface of the clay, deaggregate to form monomers that migrate to the interlamellar spaces, giving rise to absorption bands at 670 and 760 nm. Experiments using Ca-exchanged SWy-1, variation of the ionic strength by addition of salt, and the use of different size fractions of the clays confirm the finding that the main factor ruling the adsorption behavior of the probe is the size of the clay particles.     

水溶液中一种离子菁J-聚集体引起相反电荷离子菁形成J-聚集体的影响因素

水溶液中的聚电解质可引起离子菁生成聚集体,考虑到离子菁J-聚集体与聚电解质的一些相似性,我们研究了其对相反电荷离子菁J-聚集体生成的引发作用。本文分析了离子菁J-聚集体引起相反电荷离子菁生成J-聚集体的影响因素,讨论了引发聚集与被引发聚集的离子菁的电性、它们本身的结构之间的相互关系及外加无机盐对引发聚集效应产生的影响。