Assessing hydrophobic deep eutectic solvents for intramolecular excimer formation.

Intramolecular excimer formation by a dipyrenyl probe, 6-(1-pyrenyl)hexyl-11(1-pyrenyl)-undecanoate [1-Py(CH2)10COO(CH2)61-Py], is used to assess hydrophobic deep eutectic solvents (HDESs) for the purpose. n-Decanoic acid (DA), L(-)-menthol (Men) and thymol (Thy) have been utilized to form HDESs with different pairs of constituents in different molar ratios, namely Men : DA (2 : 1, 1 : 1, and 1 : 2), Thy : DA (2 : 1, 1 : 1, and 1 : 2), and Thy : Men (5 : 1, 2 : 1, 1 : 1, 1 : 2, and 1 : 5). The maximum of the excimer-to-monomer emission intensity ratio, (IE/IM)max, is observed at 343.15-353.15 K for all DESs irrespective of the constitution, and it varies in a narrow range exhibiting no correlation with the dynamic viscosity (η) of the DES which varies between 2.05 and 3.56 mPa s. Excited-state intensity decay data reveal excimer dissociation back to the excited monomer to be negligible in all DESs at lower temperatures (T ≤ 323.15 K); the simplistic Birks scheme is followed at higher temperatures (T > 323.15 K). The rate constant for excimer formation/association, ka, ranges from (3.00 ± 0.50) × 106 s-1 to (103 ± 10) × 106 s-1, which is similar to that reported in other media. The temperature-dependence of the equilibrium constant for excimer formation follows the van't Hoff equation with recovered standard enthalpy (ΔaH*⊖) and standard entropy (ΔaS*⊖) changes, indicating the reversible intramolecular excimer formation to be exothermic and energetically-favorable but entropically unfavorable. A plot of kavs. T/η for all the DES systems investigated exhibits a fairly good linear correlation, indicating the adherence to the Stokes-Einstein formulation within the HDESs further emphasizing the homogeneous nature of the solubilizing media. The work helps to highlight the potential of HDESs for intramolecular excimer formation involving non-polar reactants.

Highly Efficient Intramolecular Excimer Formation in a Disulfide-Linked Dipyrenyl Compound: Proton Recognition and Fluidity Assessment.

Intramolecular excimer formation has been utilized extensively in chemical sciences, especially to probe solvation within complex media as well as to assess physicochemical properties of the solubilizing milieu. Pyrene has been employed extensively as a fluorescence probe for this purpose due to its favorable multidimensional fluorescence properties. Termini-capped dipyrenyl scaffolds possessing various functionalities comprise the majority of such compounds. A new both end-tagged dipyrenyl compound DTP is designed and synthesized, which exhibits significantly high intramolecular excimer formation efficiency in polar solvents. The presence of a -NH-(CO)- and/or -S-S- functionality on the chain linking the two pyrenyl groups facilitates intramolecular excimer formation. Excited-state emission intensity decay reveals that the excimer formation exclusively takes place in the excited state with only one excimer conformation. The rate constant of excimer formation is found to be higher for DTP as compared to a similar compound with an alkyl backbone. The dependence of the excimer formation on the solvent (protic versus aprotic) as well as on temperature reveals further insights into the excimer formation process. The excimer formation by DTP is found to be highly sensitive to the presence of H+: the relative excimer formation efficiency decreases drastically in the presence of a small amount of H+ (∼10-5 M). Further, the recognition of protons by DTP via intramolecular excimer formation is also observed to be highly selective in nature. Based on the observation that both the excimer formation efficiency and kinetics depend on the viscosity of the solubilizing milieu, fluidity assessment of the (dimethyl sulfoxide + acetonitrile) mixture was carried out using DTP. Further, DTP is found to be an effective probe for the assessment of the amount of water in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide as well as in a deep eutectic solvent composed of choline chloride and urea in a 1:2 mol ratio. Highly efficient and rapid intramolecular excimer formation not only establishes DTP as a useful and versatile probe but also offers strategic pathways for designing effective excimer-forming compounds.

Fluorescence of pyrene and its derivatives to reveal constituent and composition dependent solvation within hydrophobic deep eutectic solvents.

Depending on their constituents and composition, deep eutectic solvents (DESs) may exhibit widely varying physicochemical properties. Based on the miscibility of water in a DES, it can broadly be classified as 'hydrophobic' or 'hydrophilic'. The polarity offered by hydrophobic DESs as compared to common organic solvents in the context of solute solubilization thus becomes of the utmost importance. A versatile fluorescence probe, pyrene (Py), its aldehyde derivative, pyrene-1-carboxaldehyde (PyCHO), and a termini end-tagged dipyrenyl polydimethylsiloxane polymer (Py-PDMS-Py) are employed to assess the solvation environment afforded by DESs composed of thymol (Thy), (-)-menthol (Men), and n-decanoic acid (DA). To decipher the effect of the constituents and composition on solute solvation, DESs composed of different pairs of constituents in different molar ratios, namely Thy : Men (1 : 1 and 1 : 2), DA : Men (1 : 1 and 1 : 2), and Thy : DA (2 : 1, 1 : 1, and 1 : 2), are investigated. Pyrene, through its band 1-to-band 3 emission intensity ratio (Py I1/I3), displays higher cybotactic region dipolarity in Thy-containing DESs due to the phenyl ring of Thy; the sensitivity of Py I1/I3 towards temperature is also higher in Thy DESs. The fluorescence lifetime of pyrene and its temperature dependence are higher in Men-containing DESs in comparison. Quenching of pyrene fluorescence by nitromethane in these DESs is dynamic in nature and the recovered bimolecular quenching rate constants (kq) reveal efficient diffusion of the fluorophore-quencher pair in these DESs as compared to other iso-viscous media. The kq adheres to the Stokes-Einstein relation, implying inherent homogeneity associated to these DESs. PyCHO emission spectra show a high energy structured band in Thy : Men DESs, whereas the band shifts bathochromically and becomes broad in DA-containing DESs. The PyCHO cybotactic region is relatively nonpolar in Thy : Men DESs as compared to Thy : DA and Men : DA DESs. The extent of intramolecular excimer formation by Py-PDMS-Py reveals these DESs to be "good" solvents for polymer solvation where DES-polymer interactions are maximized. The microviscosity (ηµ) surrounding Py-PDMS-Py correlates with the bulk dynamic viscosity (ηbulk) within the investigated DESs, further corroborating the absence of microheterogeneity. Overall, the observations reveal the similarity of these hydrophobic DESs to common organic solvents in the context of solute solubilization.

Classifying deep eutectic solvents for polymer solvation via intramolecular dimer formation.

Deep eutectic solvents (DESs) have emerged as versatile and inexpensive solubilizing media with widely varying physicochemical properties. Establishing the characteristics of a novel solvent milieu for polymer dissolution is an important exercise. The assessment of two DESs obtained by mixing choline chloride (ChCl) salt with H-bond donors (HBDs) glycerol (Gly) and urea in a 1 : 2 molar ratio (named ChCl:Gly and ChCl:urea, respectively) as solvents for polydimethylsiloxane (PDMS) solvation is carried out via the investigation of intramolecular dimerization by pyrene (Py) end-tagged PDMS of MW 3100 (Py-PDMS-Py) as a fluorescent probe in the temperature range of 293.15-363.15 K. The outcomes are compared with those in liquid PDMS of average MW 2000 (PDMS2000; a similar solvent to that of the polymer) and in glycerol (the HBD constituent of the DES ChCl:Gly). While the intramolecular dimerization by Py-PDMS-Py occurs exclusively in the excited state in liquid PDMS2000, wavelength-dependent fluorescence excitation spectra along with excited-state intensity decay kinetics reveal the presence of ground-state interactions between the pyrenyl moieties in ChCl:Gly, ChCl:urea and glycerol. This leads to the proposition that PDMS prefers to stay in predominantly the coiled form in DESs and glycerol, as opposed to that in PDMS2000 where the PDMS-PDMS contact is maximized leading to the absence of ground-state heterogeneity. Thus, while the liquid PDMS2000 is characterized as a 'good' solvent, the DESs ChCl:Gly and ChCl:urea along with glycerol may be designated as 'bad' solvents for PDMS dissolution.

Contrasting ground- and excited-state intramolecular aggregation in choline chloride-based deep eutectic solvents versus a liquid polymer.

Although the pyrenyl (Py) groups in several dipyrenyl (or bispyrenyl) compounds do not dimerize in the ground-state, they are known to intramolecularly aggregate exclusively in the excited-state to form excimers in common organic solvents. We present contrasting intramolecular aggregation behaviour of such a prototypical compound, 1,3-bis(1-pyrenyl)propane [1Py(3)1Py], dissolved in judiciously selected liquids having relatively high dynamic viscosities (η). Specifically, the intramolecular aggregation of 1Py(3)1Py is investigated in a liquid polymer polydimethylsiloxane with number average MW 2000, PDMS2000 (η293.15K = 21.4 mPa s), and is compared with aggregation of 1Py(3)1Py in deep eutectic solvents (DESs) constituted of the H-bond acceptor (HBA) choline chloride (ChCl) and H-bond donors (HBDs) urea and glycerol in a 1 : 2 mole ratio of ChCl : urea (η293.15K = 1372.0 mPa s) and ChCl : Gly (η293.15K = 473.0 mPa s), respectively, in 293.15 to 363.15 K temperature range. The HBD constituent of ChCl : Gly, glycerol (Gly) (η293.15K = 1412.0 mPa s) is also investigated for comparison purposes. It is found that while in PDMS2000, 1Py(3)1Py intramolecularly aggregates exclusively in the excited-state, thus forming a classical excimer, ground-state heterogeneity is clearly evident in both the DESs and Gly. High viscosity, a consequence of the extensive H-bonding in DESs/Gly, appears to induce the two Py units, both in the ground-state, to exist partly in a configuration where the interaction, albeit a weak one, takes place between the two. This ground-state interaction is not present in relatively low viscosity media PDMS2000 as observed in the common organic solvents. The role of viscosity/H-bonding of the solubilizing milieu on differential intramolecular aggregation in ground- and excited-states is highlighted.

Donor-acceptor complex formation in tetra-n-butylammonium chloride: n-decanoic acid deep eutectic solvent.

Complex formation between pyrene (Py) and N,N-dimethylaniline (DMA) is presented in a deep eutectic solvent constituting of tetra-n-butylammonium chloride (TBAC) and n-decanoic acid (DA) in a 1:2 mol ratio, respectively, named TBAC:DA. The addition of DMA to a Py solution of TBAC:DA results in the formation of a fluorescent Py-DMA charge-transfer complex, which is manifested via a broad structureless bathochromically shifted band centered at 550(±2) nm. The solvatochromic nature of the Py-DMA fluorescent complex indicates the solvent polarity of TBAC:DA to be higher than that of methanol. The absence of a negative pre-exponential factor in the intensity decay at 550 nm combined with the excitation scans implies the presence of weak interaction between Py and DMA in the ground-state, leading to the rapid formation of a Py-DMA complex possibly at a sub-nanosecond time scale. The Stern-Volmer quenching constant (KSV) varies from 53(±2) to 96(±1) M-1, and the bimolecular quenching rate constant (kq) varies from 3.0(±0.4) × 108 to 8.8(±1.3) × 108 M-1 s-1 by increasing the temperature (T) from 283.15 to 313.15 K, implying efficient deactivation of electron-acceptor Py in the excited-state induced effectively by the electron-donor DMA within TBAC:DA. ln kq varies linearly with 1/T with an activation energy (Ea) of 26.4(±0.4) kJ mol-1. The linear behavior between kq and 1/η suggests conformity to the Stokes-Einstein relationship within TBAC:DA. The Py-DMA complex formation efficiency increases with an increase in T and reaches maxima at 298.15 K before decreasing with a further increase in T. The initial reduction in η favors Py-DMA complex formation; this effect is overcome by preferential thermal deactivation of the Py-DMA fluorescent complex as compared to that of pyrene.

Fluorescence Quenching of Dipyrenylalkanes by an Electron/Charge Acceptor.

Compounds possessing two fluorophoric moieties may exhibit dual fluorescence, one characterizing the monomeric fluorophore unit and the other characterizing the intramolecular aggregate. Fluorescence quenching of two dipyrenylalkanes, 1,3-bis(1-pyrenyl)propane [1Py(3)1Py] and 1,10-bis(1-pyrenyl)decane [1Py(10)1Py] having different alkyl chains separating the two termini pyrenyl groups that are capable of forming an intramolecular excimer, by an electron/charge-accepting quencher, nitromethane, is investigated in four different solvents-nonpolar (cyclohexane (CH)), polar-aprotic (acetonitrile (ACN)), polar-protic (ethanol (EtOH)), and chlorinated (dichloromethane (DCM))-under ambient conditions. For a given probe in a solvent, fluorescence from the monomer and the intramolecular excimer are quenched with similar efficiencies; the efficiency of quenching is higher for the probe with the longer alkyl chain separating the two fluorophores. Quenching efficiency is significantly higher in chlorinated solvent DCM. The bimolecular quenching rate constants for intramolecular excimer, however, are either comparable or lower for the longer alkyl chain compound. It is suggested that, while the donor electronic excited-state energetics is more favorable for the long alkyl chain compound, the approach of the quencher to the intramolecular excimer appears to be hindered by the presence of a longer alkyl chain.

Photophysical Behavior and Fluorescence Quenching of l-Tryptophan in Choline Chloride-Based Deep Eutectic Solvents.

Intrinsic fluorescence from l-tryptophan (l-Trp) is routinely used to obtain insight into the structural features and dynamics of proteins and enzymes. In contrast to aqueous enzymology, different parameters that control and influence the behavior of proteins and enzymes in nonaqueous media depend heavily on the solvent. Detailed analysis of the intrinsic fluorescence from l-Trp dissolved in two deep eutectic solvents (DESs), reline and glyceline, prepared by mixing salt choline chloride with H-bond donors urea and glycerol, respectively, in a 1:2 molar ratio within 298.15-358.15 K temperature range, is presented. Fluorescence emission maxima of l-Trp dissolved in DESs show bathochromic shift with increasing temperature. In comparison to water and several organic solvents, the fluorescence quantum yields of l-Trp in both DESs are significantly higher. While the rates of nonradiative decay in the two DESs are comparable and increase with increasing temperature, radiative decay rates are independent of temperature and are higher in glyceline than in reline, resulting in a higher fluorescence quantum yield of l-Trp in glyceline. Excited-state emission intensity decays of l-Trp fit best to a double exponential model irrespective of the identity of the DES and temperature. Average lifetime decreases with increasing temperature due to increased thermal deactivation; however, this decrease is much slower in DESs as compared to that in water. Both steady-state fluorescence anisotropy and rotational reorientation times for l-Trp are governed by the inherent complexity of the DESs as solubilizing milieu resulting in noncompliance to simple hydrodynamic treatment. Fluorescence quenching of l-Trp by acrylamide in reline is purely dynamic in nature. This is in contrast to the aqueous media where the decrease in fluorescence is a combined result of both dynamic and static quenching. The quenching within reline is fairly efficient considering the high viscosity of the medium. Significantly lower activation energy of the bimolecular quenching process as compared to the activation energy of the viscous flow indicates facilitation of the electron/charge transfer quenching of l-Trp by acrylamide within the ionic environment offered by reline. The effect of high viscosity is partly overcome by the strongly ionic environment of reline during the electron/charge transfer between l-Trp and acrylamide. The results highlight the structural complexity of these DESs especially within the cybotactic region of the probe, which is absent in common molecular solvents of similar high viscosity.

Unprecedented Intramolecular Association-Induced Fluorescence in Tryptophan-Conjugated Peptidomimetics.

We report herewith tryptophan (Trp)-conjugated peptidomimetics that show intramolecular through-space association between the Trp units. Our investigation revealed that the proximal placement of Trp can lead to the emergence of a new and unanticipated fluorescent entity constituting a Trp-Trp dimer. Proton-induced modulation of fluorescence is a consequence of this work. Investigations with control compounds unequivocally revealed that the fluorescence property is not originated from the localized excited state but from the unprecedented Trp-Trp intramolecular dimer in the ground state itself. The present findings will initiate the biophysical scientists to have a relook at the fluorescence properties of Trp-containing proteins.