Dimeric Aggregates Research Articles

Effects of Surfactants on the Aggregation of 6,6'-Disubstituted Thiacarbocyanine Dyes in Aqueous Solutions

The aggregation properties of a number of 6,6'-substituted thiacarbocyanine dyes were studied by spectral-fluorescent methods: T-304, T-306, T-307, T-336 and, for comparison, thiacarbocyanine Cyan 2, which has no substituents in the 6,6'-positions, in aqueous buffer solutions and in the presence of various types of surfactants. The method of moments was used to characterize the absorption spectra (band positions, width, shape). Substituents in the 6,6'-positions significantly increase the ability of dyes T-304, T-306, T-307, T-336 to aggregation (dimerization, as well as to the formation of disordered aggregates with broad low-intensity absorption spectra). The introduction of surfactants leads to rearrangement of the spectra associated with the complex nature of the equilibria between monomers and aggregates of various structures (including surfactant molecules, if present), in particular, with a decrease in the contribution of disordered aggregates. However, the decomposition of dimeric aggregates of 6,6'-substituted cyanines is observed only at very high surfactant concentrations (~20 CMC and higher, where CMC is the critical micelle concentration). At the same time, the passing of surfactant concentrations through CMC does not significantly affect the spectral-fluorescent properties of the dyes, which is probably due to rather strong interactions of the dyes with individual surfactant molecules and premicellar associates of surfactants.

Water oxidation coupled singlet oxygen electrochemiluminescence at C4N3 nanosheets/TiO2 nanotubes/Ti electrodes and its sensing application

Singlet oxygen (1O2) electrochemiluminescence (ECL) induced by water oxidation might intrigue new kinds of ECL-based sensors to be developed, but remains nascent due to its difficulty to be achieved. Herein, we report a water oxidation coupled ECL emission from dimeric aggregates of 1O2 at C4N3 nanosheets (NSs)/TiO2 nanotubes (NTs)/Ti electrodes (C4N3/TiO2/Ti) in the presence of triethanolamine (TEOA) as the co-reactant. The half-metallic C4N3 NSs were introduced to TiO2 NTs/Ti electrodes via in-situ thermal polymorization of ionic liquid precursor, which endows the TiO2 NTs with more oxygen vacancies and faster charge transfer ability as well as provides more sites for oxygen enriching, leading to an ECL intensity being 5.5 folds that at the TiO2 NTs/Ti electrodes. Besides, the tubelike shape of TiO2 makes it easier for the generated 1O2 to react each other to form dimeric aggregates, resulting in a typical ECL emission peak at ∼ 642 nm. Using the 1O2 ECL to detect dopamine (DA) as a model target, a wide linear range from 20 pM to 400 nM is obtained with detection limit of 7.6 pM (S/N = 3). This work offers a deep insight into water oxidation coupled 1O2 ECL and also accelerates its biosensing applications.

Neutral and Anion Species of Quinoidal Thienothiophene Diketopyrrolopyrroles Display a Common Aggregation Mode.

A comprehensive investigation of two new molecular triads incorporating the diketopyrrolopyrrole unit into a quinoidized thienothiophene skeleton, which is further end-capped with dicyanomethylene (DPP-TT-CN) or phenoxyl groups (DPP-TT-PhO), has been carried out. A combination of UV-Vis-NIR and infrared spectroelectrochemical techniques and cryogenic UV-Vis-NIR absorption spectroscopy supported by theoretical calculations has been used. The main result is the formation of similar H-aggregates in the dimerization process of the neutral molecules and of the charged anionic species. The experimental absorption spectra of the aggregated species are accurately reproduced by quantum chemical calculations using the Spano's model, including excitonic coupling for the dimeric forms and full vibronic resolution of the absorption bands. The strong excitonic coupling taking place is key to understand the electronic structure of the dimeric species and has been instrumental to disentangle the type of H-aggregation. This study is of relevance to get a better understanding of the molecular aggregation of organic π-conjugated chromophores and is useful as a guideline for the refinement of the engineering of molecular materials for which supramolecular design is required.

Structural Characterization of Pyruvic Acid Dimers Formed inside Helium Nanodroplets by Infrared Spectroscopy and Ab Initio Study.

The structural arrangements of α-keto acid complexes hold significant interest across various fields of chemistry such as enzyme modeling, drug design, or polymer blending. Herein, we report mass-selective infrared (IR) spectra of pyruvic acid monomers and dimers in the range 1720-1820 cm-1 recorded in helium nanodroplets at 0.37 K. The monomer features IR bands at 1807.1 and 1734.5 cm-1, which are assigned to the carboxylic and ketonic C═O stretching vibrations, respectively. Furthermore, the pyruvic acid dimers generated inside the helium nanodroplets are characterized by carboxylic and ketonic C═O stretch vibrations appearing at 1799.2 and 1737.0 cm-1, respectively. This frequency shift of ±7 cm-1 for both C═O stretching bands from the monomer to the dimer demonstrates that the structural motif of the monomer is maintained upon dimer aggregation in helium nanodroplets. The structural assignments were supported by a comparison of the MP2/aug-cc-pVDZ-predicted harmonic vibrational spectra at the C═O stretching region with the experiments. The global minimum monomer structure with an intramolecular hydrogen bond and its dimer stabilized by both inter- and intramolecular hydrogen bonding interactions reproduce the experimental spectra from the monomer and dimer. This assigned dimer structure lies ca.11 kJ/mol above the corresponding global minimum and is favored in helium nanodroplets due to the long-range realignment of molecules via dipole-dipole interaction, followed by short-range stabilization upon intermolecular hydrogen bond formation. The barrier for reconfiguration of the precooled monomer conformer leading to the formation of the most stable dimer structure is around 58 kJ/mol, which is infeasible at 0.37 K.

Ionic Hydrogen Bond-Assisted Catalytic Construction of Nitrogen Stereogenic Center via Formal Desymmetrization of Remote Diols.

The control of noncarbon stereogenic centers is of profound importance owing to their enormous interest in bioactive compounds and chiral catalyst or ligand design for enantioselective synthesis. Despite various elegant approaches have been achieved for construction of S-, P-, Si- and B-stereocenters over the past decades, the catalyst-controlled strategies to govern the formation of N-stereogenic compounds have garnered less attention. Here, we disclose the first organocatalytic approach for efficient access to a wide range of nitrogen-stereogenic compounds through a desymmetrization approach. Intriguingly, the pro-chiral remote diols, which are previously not well addressed with enantiocontrol, are well differentiated by potent chiral carbene-bound acyl azolium intermediates. Preliminary studies shed insights on the critical importance of the ionic hydrogen bond (IHB) formed between the dimer aggregate of diols to afford the chiral N-oxide products that feature a tetrahedral nitrogen as the sole stereogenic element with good yields and excellent enantioselectivities. Notably, the chiral N-oxide products could offer an attractive strategy for chiral ligand design and discovery of potential antibacterial agrochemicals.

Ionic Hydrogen Bond‐Assisted Catalytic Construction of Nitrogen Stereogenic Center via Formal Desymmetrization of Remote Diols

AbstractThe control of noncarbon stereogenic centers is of profound importance owing to their enormous interest in bioactive compounds and chiral catalyst or ligand design for enantioselective synthesis. Despite various elegant approaches have been achieved for construction of S‐, P‐, Si‐ and B‐stereocenters over the past decades, the catalyst‐controlled strategies to govern the formation of N‐stereogenic compounds have garnered less attention. Here, we disclose the first organocatalytic approach for efficient access to a wide range of nitrogen‐stereogenic compounds through a desymmetrization approach. Intriguingly, the pro‐chiral remote diols, which are previously not well addressed with enantiocontrol, are well differentiated by potent chiral carbene‐bound acyl azolium intermediates. Preliminary studies shed insights on the critical importance of the ionic hydrogen bond (IHB) formed between the dimer aggregate of diols to afford the chiral N‐oxide products that feature a tetrahedral nitrogen as the sole stereogenic element with good yields and excellent enantioselectivities. Notably, the chiral N‐oxide products could offer an attractive strategy for chiral ligand design and discovery of potential antibacterial agrochemicals.

Designing High-Performance Rejuvenators: A Theoretical Approach to Asphaltene Dimer Aggregation and Disaggregation

Designing High-Performance Rejuvenators: A Theoretical Approach to Asphaltene Dimer Aggregation and Disaggregation

Synthesis and Characterization of Multiple Stimuli-Responsive Fluorescent Polymer Hydrogels Based on Terpyridine and N-Isopropylacrylamide.

A series of stimuli-responsive fluorescent hydrogels were successfully synthesized via micelle radical copolymerization of hydrophilic acrylamide (AM), hydrophobic chromophore terpyridine-based monomer (TPY), and N-isopropylacrylamide (NIPAM). These hydrogels presented blue emissions (423-440 nm) under room temperature, which is caused by the π-π* transition of the conjugated structures. Once the ambient temperature was increased to 55 °C, the fluorescence color changed from blue (430 nm) to pink (575 nm) within 10 min, subsequently to yellow (535 nm), and eventually back to pink. The thermal-responsive properties are attributed to the transition of the TPY units from unimer to dimer aggregation via the intermolecular charge transfer complex at high temperatures. The hydrogels showed pH-responsive properties. The emission peak of the hydrogel exhibited a blue shift of ~54 nm from neuter conditions to acidic conditions, while a 6 nm red shift to an alkaline environment was observed. The hydrogels demonstrated an obvious change in fluorescence intensity and wavelength upon adding different metal ions, which is caused by the coordination between the terpyridine units incorporated on the backbones and the metal ions. As a consequence, the hydrogels presented a sharp quenching fluorescence interaction with Fe2+, Fe3+, Cu2+, Hg2+, Ni2+, and Co2+, while it exhibited an enhanced fluorescence intensity interaction with Sn2+, Cd2+, and Zn2+. The microstructural, mechanical, and rheological properties of these luminescent hydrogels have been systematically investigated.

Molecular Driving Forces in the Self-Association of Silaffin Peptide R5 from MD Simulations.

The 19-residue silaffin-R5 peptide has been widely studied for its ability to precipitate uniform SiO2 particles through mild temperature and pH pathways, in the absence of any organic solvents. There is consensus that post-translational modification (PTM) of side chains has a large impact on the biomineralization process. Thus, it is imperative to understand the precise mechanisms that dictate the formation of SiO2 from R5 peptide, including the effects of PTM on peptide aggregation and peptide-surface adsorption. In this work, we use molecular dynamics (MD) simulations to study the aggregation of R5 dimer with multiple PTMs, with the presence of different ions in solution. Since this system has strong interactions with deep metastable states, we use parallel bias metadynamics with partitioned families to efficiently sample the different states of the system. We find that peptide aggregation is a prerequisite for biomineralization. We observe that the electrostatic interactions are essential in the R5 dimer aggregation; for wild type R5 that only has positively charged residues, phosphate ions HPO4 2- in the solution form a bridge between two peptides and are essential for peptide aggregation.

Synthesis, structural and computational study, DNA binding and cytotoxic activity of Cu(II) complexes of 6- and 7-chloro-2-oxo-1,2-dihydroquinoline-3-carbaldehyde-2-furoyl-hydrazones

Three new coordination complexes of Cu(II) ions made from two hydrazone ligands, 7-chloro-2-oxo-1,2-dihydroquinoline-3-carbaldehyde-2-furoyl-hydrazone (HL1) and 6-chloro-2-oxo-1,2-dihydroquinoline-3-carbaldehyde-2-furoyl-hydrazone (HL2) have been synthesized and fully characterized by spectroscopic techniques. Their crystal and molecular structures revealed distorted square pyramidal mononuclear complexes: [(L1)Cu(H2O)2](NO3)·3H2O, 1(NO3), [(L2)Cu(H2O)2](NO3)·2H2O·CH3OH, 2(NO3), and [(L2)Cu(NO3)(CH3OH)]·2CH3OH, 3, comprising the ligand (L1 and L2) in tridentate fashion (ONO) with two water molecules in 1+ and 2+, and a single methanol molecule and a nitrate ion in 3 in their respective copper coordination spheres. EPR spectra in frozen methanol revealed the occurrence of several species arising from different coordination environments. A detailed DFT investigation on the energetics of solvents exchange (H2O, MeOH, and DMSO) and simulation of the EPR parameters showed that the exchange processes occur easily in solution. The value gz indicated the occurrence of a dimeric aggregate for 2+. The new copper complexes exhibited a noticeable antiproliferative activity with IC50 values in the micromolar range against HCT-15, H157, BxPC3, PNS-1, and A431 cell lines and they were found to be 3-fold more effective than cisplatin against pancreatic PSN-1 cell lines. Cross-resistance tests on A2780 and LoVo cancer cell lines and the corresponding multidrug or oxaliplatin resistant sublines showed that complexes 1(NO3) and 2(NO3) were equally cytotoxic to sensitive and resistant cells, thus overcoming multidrug and oxaliplatin resistance.

Mechanism of Protein Aggregation Inhibition by Arginine: Blockage of Anionic Side Chains Favors Unproductive Encounter Complexes.

Aggregation refers to the assembly of proteins into nonphysiological higher order structures. While amyloid has been studied extensively, much less is known about amorphous aggregation, a process that interferes with protein expression and storage. Free arginine (Arg+) is a widely used aggregation inhibitor, but its mechanism remains elusive. Focusing on myoglobin (Mb), we recently applied atomistic molecular dynamics (MD) simulations for gaining detailed insights into amorphous aggregation (Ng J. Phys. Chem. B 2021, 125, 13099). Building on that approach, the current work for the first time demonstrates that MD simulations can directly elucidate aggregation inhibition mechanisms. Comparative simulations with and without Arg+ reproduced the experimental finding that Arg+ significantly decreased the Mb aggregation propensity. Our data reveal that, without Arg+, protein-protein encounter complexes readily form salt bridges and hydrophobic contacts, culminating in firmly linked dimeric aggregation nuclei. Arg+ promotes the dissociation of encounter complexes. These "unproductive" encounter complexes are favored because Arg+ binding to D- and E- lowers the tendency of these anionic residues to form interprotein salt bridges. Side chain blockage is mediated largely by the guanidinium group of Arg+, which binds carboxylates through H-bond-reinforced ionic contacts. Our MD data revealed Arg+ self-association into a dynamic quasi-infinite network, but we found no evidence that this self-association is important for protein aggregation inhibition. Instead, aggregation inhibition by Arg+ is similar to that mediated by free guanidinium ions. The computational strategy used here should be suitable for the rational design of aggregation inhibitors with enhanced potency.

Investigation of intermolecular interactions in butyl acetate using vibrational spectroscopy and non-empirical calculations

In this work, on the example of butyl acetate, the nature of intermolecular interactions was studied using vibrational spectroscopy (Raman and FTIR) and non-empirical calculations. The geometric structures of the most stable dimer and trimer aggregates of butyl acetate were optimized using the Density Functional Theory (DFT) method based on the B3LYP/6-311++G(d,p) basis set. Molecular aggregations in liquid butyl acetate were shown to be formed by dipole-dipole interactions and weak C-H…O hydrogen bonds. A potential energy distribution (PED) analysis was performed for the butyl acetate molecule, and experimental and calculated frequencies were found to be in good agreement. Frontier molecular orbitals such as the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the butyl acetate molecule were analyzed.

Effect of hydrophilicity-imparting substituents on exciton delocalization in squaraine dye aggregates covalently templated to DNA Holliday junctions.

Molecular aggregates exhibit emergent properties, including the collective sharing of electronic excitation energy known as exciton delocalization, that can be leveraged in applications such as quantum computing, optical information processing, and light harvesting. In a previous study, we found unexpectedly large excitonic interactions (quantified by the excitonic hopping parameter Jm,n) in DNA-templated aggregates of squaraine (SQ) dyes with hydrophilic-imparting sulfo and butylsulfo substituents. Here, we characterize DNA Holliday junction (DNA-HJ) templated aggregates of an expanded set of SQs and evaluate their optical properties in the context of structural heterogeneity. Specifically, we characterized the orientation of and Jm,n between dyes in dimer aggregates of non-chlorinated and chlorinated SQs. Three new chlorinated SQs that feature a varying number of butylsulfo substituents were synthesized and attached to a DNA-HJ via a covalent linker to form adjacent and transverse dimers. Various characteristics of the dye, including its hydrophilicity (in terms of log Po/w) and surface area, and of the substituents, including their local bulkiness and electron withdrawing capacity, were quantified computationally. The orientation of and Jm,n between the dyes were estimated using a model based on Kühn-Renger-May theory to fit the absorption and circular dichroism spectra. The results suggested that adjacent dimer aggregates of all the non-chlorinated and of the most hydrophilic chlorinated SQ dyes exhibit heterogeneity; that is, they form a mixture of dimers subpopulations. A key finding of this work is that dyes with a higher hydrophilicity (lower log Po/w) formed dimers with smaller Jm,n and large center-to-center dye distance (Rm,n). Also, the results revealed that the position of the dye in the DNA-HJ template, that is, adjacent or transverse, impacted Jm,n. Lastly, we found that Jm,n between symmetrically substituted dyes was reduced by increasing the local bulkiness of the substituent. This work provides insights into how to maintain strong excitonic coupling and identifies challenges associated with heterogeneity, which will help to improve control of these dye aggregates and move forward their potential application as quantum information systems.

Synthesis, crystal structures, supramolecular organization and Hirshfeld analysis of nickel(II) and cobalt(II) complexes based on (E)-N-(pyridin-2-ylmethylene)adamantan-1-amine

Nickel (II) and cobalt (II) complexes arising from the combination of the corresponding metal carboxylates with (E)-N-(pyridin-2-ylmethylene)adamantan-1-amine (L) are described. The compounds were characterized by means of elemental analysis, IR spectroscopy and single crystal X-ray crystallography, revealing isostructural compounds of composition [ML(OAc)2(H2O)]⋅H2O (1, M = Ni; 2, M = Co) with distorted octahedral molecular structures. In the crystalline state, the complex molecules form in first instance dimeric aggregates through O−H⋅⋅⋅O hydrogen bonding interactions, which are interconnected further into a 3D hydrogen-bonded network. The supramolecular description is accomplished by fingerprint plots based on Hirshfeld surface analysis, indicating that aside from O⋅⋅⋅H/H⋅⋅⋅O hydrogen bonds H⋅⋅⋅H contacts are of relevance.

Preparation of nanosized liquid-like clusters of irinotecan hydrochloride trihydrate for injection concentrate to reduce carbon footprint

The surprisingly stable irinotecan hydrochloride trihydrate injection concentrate having a supersaturated concentration of 20 mg/mL at 25 °C was due to the frustration of 150 nm sized liquid-like nanosized clusters formed by the aggregation of dimers of 1.5 nm in an aqueous phase, evidenced by the non-linearity of van’t Hoff plot and dynamic light scattering measurement. The adoption of this stable supersaturated solution at 20 mg/mL by manufacturers as the commercial concentration was beneficial due to the less volume being involved throughout the manufacturing, handling, storage and transportation of the commercial product, while also enabling a versatile on-site concentration adjustment by dilution prior to intravenous administration. Regarding the physical characteristic of the solid state of irinotecan hydrochloride trihydrate, it was found to exist as a channel hydrate as evidenced by single-crystal, and high-temperature X-ray diffraction experiments. Dehydration takes place at approximately 35 °C as demonstrated by thermogravimetric analysis. Because of its non-stoichiometric nature under various RH values revealed by dynamic vapor sorption, the irinotecan hydrate salt raw material must be kept at 25 °C or below, and under the relative humidity of 40 % to 60 % to maintain the original stoichiometric ratio of the raw material.

Dimeric cation-cation aggregates stabilized by 2Ch-2N chalcogen bonds: Crystallographic and theoretical evidences

2Ch-2N chalcogen bonds (ChBs) between a pair of homocations were characterized via crystal structure database analysis and quantum chemical computations. We first collected several crystal structures consisting of such interactions from the Cambridge Structural Database (CSD). Then, based on the CSD survey results, a series of model homodimers of organic chalcogenated cations were selected to theoretically study inter-cation 2Ch-2N ChBs for the first time. The dicationic complexes under investigation are unfavorable but metastable in gas phase. Immersion of these systems in solvents leads to a remarkable increase in dimer stability and produces stable ChB complexes. 2Ch-2N interactions in gas phase generally exhibit a positive electrostatic component, while the orbital and dispersion terms play a stabilizing role. When immersed in the solvent medium, the electrostatic interaction becomes more favorable, and the solvent energy contributes significantly to the stability of the complexes, resulting in attractive cation-cation ChBs.

Europium-Functionalized Graphitic Carbon Nitride for Efficient Chemiluminescence Detection of Singlet Oxygen.

Enhancing the sensitivity and selectivity of chemiluminescence (CL) sensors for detecting chemical species in complex samples poses a significant challenge in nanoparticle surface engineering. Graphitic carbon nitride (CN) shows promise but suffers from weak CL intensity and unknown luminescence mechanisms. In this study, we propose a nitrogen defect strategy to enhance the CL efficiency of europium-functionalized graphitic carbon nitride (Eu-CNNPs). By controlling the dosage of the europium modification, we can adjust the nitrogen defect content to reduce the energy gap and improve the CL performance. Remarkably, Eu-CNNPs with rich nitrogen defects exhibit strong chemiluminescence emission specifically for singlet oxygen (1O2) without responding to other reactive oxygen species (ROS). Building upon this finding, we developed a direct, selective, and sensitive CL sensing platform for 1O2 in PM2.5 and monitored 1O2 production in photosensitizers without interference from metal ions. Through extensive experiments, we attribute the 1O2-driven CL response to the presence of abundant nitrogen defects in the CN material, accelerating electron transfer and yielding a high generation of 1O2. Furthermore, chemiluminescence resonance energy transfer (CRET) between (1O2)2* (1O2 dimeric aggregate) and Eu-CNNPs contributes to strong CL emission. This work provides insights into enhancing the CL performance of CN and offers new possibilities for advancing the practical analysis of nanomaterials using the intriguing mechanism of nitrogen defects.

Structural and functional fine mapping of cysteines in mammalian glutaredoxin reveal their differential oxidation susceptibility

Protein-S-glutathionylation is a post-translational modification involving the conjugation of glutathione to protein thiols, which can modulate the activity and structure of key cellular proteins. Glutaredoxins (GLRX) are oxidoreductases that regulate this process by performing deglutathionylation. However, GLRX has five cysteines that are potentially vulnerable to oxidative modification, which is associated with GLRX aggregation and loss of activity. To date, GLRX cysteines that are oxidatively modified and their relative susceptibilities remain unknown. We utilized molecular modeling approaches, activity assays using recombinant GLRX, coupled with site-directed mutagenesis of each cysteine both individually and in combination to address the oxidizibility of GLRX cysteines. These approaches reveal that C8 and C83 are targets for S-glutathionylation and oxidation by hydrogen peroxide in vitro. In silico modeling and experimental validation confirm a prominent role of C8 for dimer formation and aggregation. Lastly, combinatorial mutation of C8, C26, and C83 results in increased activity of GLRX and resistance to oxidative inactivation and aggregation. Results from these integrated computational and experimental studies provide insights into the relative oxidizability of GLRX’s cysteines and have implications for the use of GLRX as a therapeutic in settings of dysregulated protein glutathionylation.

Excimer formation and site selectivity in single pyrene microcrystals

Thin microcrystals of pyrene have been recrystallized by using a surfactant. With a size-range of several hundred nm to a few micrometers, the crystals have been characterized by using standard techniques of X-ray and Raman spectroscopy besides the atomic force and scanning electron microscopy. The fluorescence microscopy of single microcrystal shows fluorescence due to monomer as well as the red-shifted broad, structureless excimer-type emission. The observed decay profiles of the red-shifted emission reveal existence of dimer and higher aggregates in the crystalline state when excited at the red-edge of the absorption band. This is in contrast to the excimer emission observed at higher energy excitation range corresponding to the monomer absorption. Distinctly different nature of time-resolved decay profiles differentiates the two mechanisms. The observations have been used to propose existence of different sites of crystal packing under two different excitations (370 nm and 408 nm). The structural anisotropy of these crystals makes them useful as a probe in crystal structure based molecular and biological sensing.

Spectrophotometric thermodynamic analysis of methylene blue aggregation in water by chemometrics; what comes in the presence of different cyclodextrins?

Spectrophotometry has been utilized to characterize the thermodynamic/dynamic properties of self-aggregation of methylene blue (MB) in water, particularly while interacting with a modulator like different cyclodextrins (α-, β-, hydroxypropyl-β- (HP-β-), and γ-CDs). These systems comprise many interactions that make such chemical systems sophisticated. We developed a mathematical modeling-fitting analysis for the simultaneous quantitative analysis of thermodynamic parameters of chemical reactions, relying on the fitting algorithm. Through analyzing simulated photometric titration data, we demonstrate the simultaneous determination of thermodynamic parameters of the different guest/host interactions. This first has brought the need for the calculation of the visible-light absorption spectrum and the thermodynamic parameters for the pure dimerization system. Therefore, the multiwavelength spectral-mole ratio data of aqueous solutions of MB over a concentration range of 2.5 × 10−5 to 4.5 × 10−5 M while temperature is changing; or being titrated with CDs solutions at various temperatures were collected, augmented, and then have been fed to solid mathematical routines to determine the potential existence of dimeric aggregates. The results of thermodynamics indicated that the positions of the monomer/dimer equilibria do not alter by the presence of α-CD. The apparent dimerization was suppressed upon addition of β- or HP-β-CDs, while the addition of γ-CD enhanced the dimerization.