Deciphering the Role of Anions of Ionic Liquids in Modulating the Structure and Stability of ct-DNA in Aqueous Solutions.

Stabilizing biomolecules under ambient conditions can be extremely beneficial for various biological applications. In this context, the utilization of ionic liquids (ILs) in enhancing the stability and preservation of nucleic acids in aqueous solutions is found to be promising. While the role of the cationic moiety of ILs in the said event has been thoroughly explored, the importance of the anionic moiety in ILs, if any, is rather poorly understood. Herein, we examine the function of anions of ILs in nucleic acid stabilization by examining the stability and structure of calf thymus-DNA (ct-DNA) in the presence of various ILs composed of a common 1-ethyl-3-methylimidazolium cations (Emim+) and different anions, which includes Cl-, Br-, NO3-, Ac-,HSO4-and BF4- by employing various spectroscopic techniques as well as Molecular Dynamics (MD) simulation studies. Analysis of our data suggests that the chemical nature of anions including polarity, basicity, and hydrophilicity become an important factor in the overall DNA-IL interaction event. At lower concentrations, the interplay of intermolecular interaction between the IL anions with their respective cations and the solvent molecules becomes a very crucial factor in inducing their stabilizing effect on ct-DNA. However, at higher concentrations of ILs, the ct-DNA stabilization is additionally governed by specific-ion effect. MD simulation studies have also provided valuable insights into molecular-level understanding of the DNA-IL interaction event. Overall, the present study clearly demonstrated that along with the cationic moiety of ILs, the anions of ILs can play a significant role in deciding the stability of duplex DNA in aqueous solution. The findings of this study are expected to enhance our knowledge on understanding of IL-DNA interactions in a better manner and will be helpful in designing optimized IL systems for nucleic acid based applications.

Assessing the impact of choline chloride and benzyltrimethylammonium chloride-based deep eutectic solvents on the structure and conformational dynamics of bovine serum albumin: a combined steady-state, time-resolved fluorescence and fluorescence correlation spectroscopic study.

Although deep eutectic solvents (DESs) are regarded as useful substitutes for both ionic liquids and common organic solvents for storage and applications of biomolecules, it is still unclear whether all DESs or only specific types of DESs will be suitable for the said purpose. In view of this, the current study aims to report on the structure and conformational dynamics of BSA in the presence of two DESs, namely ethaline (choline chloride:ethylene glycol) and BMEG (benzyltrimethyl ammonium chloride:ethylene glycol), having the same hydrogen bond donor but with a distinct hydrogen bond acceptor, so that how small changes in one constituent of a DES alter the protein-DES interaction at the molecular level can be understood. The protein-DES interaction is investigated by exploiting both ensemble-averaged measurements like steady-state and time-resolved fluorescence spectroscopy, circular dichroism (CD) spectroscopy, and single-molecule sensitive techniques based on fluorescence correlation spectroscopy (FCS). Interestingly, the results obtained from these studies have demonstrated that while a very small quantity of BMEG completely unfolds the native structure of the protein, it remains in a partially unfolded state even at very high ethaline content. More interestingly, it has been found that at very high concentrations of BMEG, the unfolded protein undergoes enhanced protein-protein interaction resulting in the aggregation of BSA. All of the results obtained from these investigations have essentially suggested that both protein-DES interaction and interspecies interaction among the constituent of DESs play a crucial role in governing the overall stability and conformational dynamics of the protein in DESs.

Understanding the mechanism of the energy transfer process from non-plasmonic fluorescence bimetallic nanoparticles to plasmonic gold nanoparticles.

Understanding the fundamentals behind the photophysical response of a fluorescing species in the vicinity of plasmonic nanoparticles is of great interest due to the importance of this event in various applications. The present work has been carried out to throw light on how plasmonic nanoparticles electronically interact with non-plasmonic nanoparticles. Specifically, in this work, the excitation energy transfer (EET) from fluorescence bimetallic silver capped gold (F-AgAu) to gold nanoparticles (AuNPs) and how this process can be modulated by cetyltrimethylammonium bromide (CTAB) have been investigated at both ensemble average and single particle levels. Steady-state and time-resolved fluorescence studies have revealed that the fluorescence intensity and lifetime of F-AgAu in the presence of AuNPs are significantly quenched. Cyclic voltammetry (CV) and polarity-dependent studies have ruled out the possibility of an electron transfer mechanism. The increased non-radiative decay rate has substantiated that the photoluminescence quenching is due to excitation energy transfer from F-AgAu to AuNPs. Interestingly, investigations have revealed that the energy transfer efficiency is reduced from 87% to 28% in the presence of CTAB due to the formation of a CTAB bilayer over AuNPs. Analysis of the data by conventional EET, nano surface energy transfer (NSET), and stretched exponential models have firmly established that the EET process follows a 1/d4 distance dependence (NSET) rather than conventional 1/d6 distance dependence as predicted with the Förster resonance energy transfer model. Additionally, single particle level measurements through fluorescence lifetime imaging microscopy (FLIM) studies have clearly demonstrated that the surfactant (CTAB) can play an important role in controlling the EET process from non-plasmonic to plasmonic nanoparticles. The outcome of the present EET between two different classes of nanoparticles is expected to be useful in developing nanoscale systems for various optoelectronic applications.

Insight into the structure and transport properties of pyrrolidinium-based geminal dicationic-organic ionic crystals: unravelling the role of alkyl-chain length.

The present study has been undertaken with an aim to design and develop safer and more efficient all solid-state electrolytes, so that the issues associated with the use of conventional room temperature ionic liquid-based electrolytes can be tackled. To fulfil this objective, a series of geminal di-cationic Organic Ionic Crystals (OICs), based on C3-, C6-, C8- and C9-alkylbridged bis-(methylpyrrolidinium)bromide are synthesized, and the structural features, thermal properties and phase behaviours of these as synthesized OICs have been investigated. Additionally, a number of electro-analytical techniques have been employed to assess their suitability as an efficient electrolyte composite (OIC:I2:TBAI) for all solid-state dye sensitised solar cells (DSSCs). The structural analysis has revealed that along with excellent thermal stability and well-defined surface morphology, all thsese OICs exhibit a well-ordered three-dimensional network of cations and anions that can serve as a conducting channel for the diffusion of iodide ions. Electrochemical investigations have shown that OICs with an intermediate length of alkyl bridge (C6- and C8-alkyl bridged) show better electrolytic performance than those that are based on OICs with a relatively shorter (C3-) or longer (C9-) alkyl-bridge chain. A careful analysis of the above data has essentially demonstrated that the length of the alkyl bridge chain plays a significant role in determining the structural organisation, morphology and eventually the ionic conductivity of OICs. Overall, the comprehensive knowledge on OICs that has been extracted from the current study is expected to be helpful to explore further new types of OIC-based all solid-state electrolytes with improved electrolytic performance for targeted applications.

Assessing the Suitability of a Dicationic Ionic Liquid as a Stabilizing Material for the Storage of DNA in Aqueous Medium.

The present study has been undertaken with an objective to find out a suitable medium for the long-term stability and storage of the ct-DNA structure in aqueous solution. For this purpose, the potential of a pyrrolidinium-based dicationic ionic liquid (DIL) in stabilizing ct-DNA structure has been investigated by following the DNA-DIL interaction. Additionally, in order to understand the fundamental aspects regarding the DNA-DIL interaction in a comprehensive manner, studies are also done by employing structurally similar monocationic ionic liquids (MILs). The investigations have been carried out both at ensemble-average and single molecular level by using various spectroscopic techniques. The molecular docking study has also been performed to throw more light into the experimental observations. The combined steady-state and time-resolved fluorescence, fluorescence correlation spectroscopy, and circular dichroism measurements have demonstrated that DILs can effectively be used as better storage media for ct-DNA as compared to MILs. Investigations have also shown that the extra electrostatic interaction between the cationic head group of DIL and the phosphate backbone of DNA is primarily responsible for providing better stabilization to ct-DNA, retaining its native structure in aqueous medium. The outcomes of the present study are also expected to provide valuable insights in designing new polycationic IL systems that can be used in nucleic acid-based applications.

Realization of a Model-Free Pathway for Quantum Dot-Protein Interaction Beyond Classical Protein Corona or Protein Complex.

Although in recent times nanoparticles (NPs) are being used in various biological applications, their mechanism of binding interactions still remains hazy. Usually, the binding mechanism is perceived to be mediated through either the protein corona (PC) or protein complex (PCx). Herein, we report that the nanoparticle (NP)-protein interaction can also proceed via a different pathway without forming the commonly observed PC or PCx. In the present study, the NP-protein interaction between less-toxic zinc-silver-indium-sulfide (ZAIS) quantum dots (QDs) and bovine serum albumin (BSA) was investigated by employing spectroscopic and microscopic techniques. Although the analyses of data obtained from fluorescence and thermodynamic studies do indicate the binding between QDs and BSA, they do not provide clear experimental evidence in favor of PC or PCx. Quite interestingly, high-resolution transmission electron microscopy (HRTEM) studies have shown the formation of a new type of species where BSA protein molecules are adsorbed onto some portion of a QD surface rather than the entire surface. To the best of our knowledge, we believe that this is the first direct experimental evidence in favor of a model-free pathway for NP-protein interaction events. Thus, the outcome of the present study, through experimental evidence, clearly suggests that NP-protein interaction can proceed by following a pathway that is different from classical PC and PCx.

Choline chloride and ethylene glycol based deep eutectic solvent (DES) versus hydroxyl functionalized room temperature ionic liquids (RTILs): assessing the differences in microscopic behaviour between the DES and RTILs.

With the aim of understanding the differences in the behavior of deep eutectic solvents (DESs) and room temperature ionic liquids (RTILs) in terms of their structure, dynamics, and intra- and intermolecular interactions, three different ILs and one DES having similar functionalities (hydroxyl) have been investigated by using both ensembled average and single-molecule spectroscopic techniques. Specifically, for this purpose, a choline chloride based DES (ethaline) and three hydroxyl functionalized ILs (1-(2-hydroxyethyl)-3-imidazolium bis(trifluoromethanesulfonyl)imide ([OHEMIM][NTF2]), N-(2-hydroxyl ethyl)-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([OHEMPy][NTf2]), and N-(2-hydroxyethyl)-N,N-dimethylpropan-1-aminium bis(trifluoromethanesulfonyl)imide ([OHC3CH][NTf2])) are employed and investigated by EPR, time-resolved fluorescence, NMR and FCS studies. Estimation of polarity through EPR spectroscopy has revealed that the hydroxyl ILs employed in these studies are hyper-polar (close to water) in nature, whereas the polarity of the DES is found to be close to those of aliphatic polyhydroxy-alcohols. Interestingly, both time-resolved fluorescence anisotropy and FCS studies on these systems have suggested that the hydroxyl ILs are more dynamically heterogeneous than the DES. More interestingly, PFG-NMR measurements have indicated that the fluid structure of ethaline is relatively more associated as compared to those of the ILs despite the fact that all the cations have the same hydroxyl functionalities. All these investigations have essentially demonstrated that, despite having similar functionalities, both the DES and hydroxyl ILs employed in the present study exhibit microscopic behaviours that are significantly different from each other, indicating the interplay of various intermolecular interactions within the constituent species in governing the behaviours of these solvent systems.

Effect of Lithium-Ion on the Structural Organization of Monocationic and Dicationic Ionic Liquids.

In recent times, ionic liquid-based (ILs) electrolytic system has emerged as suitable alternative to the conventional organic solvent-based electrolytic system. However, since, anion of ILs is known to form aggregates in the presence of lithium-ions (Li+), and this can influence the transport properties of Li+ ion in a significant manner, it is, therefore, important to understand how lithium-ions influence the structure and dynamics of ILs. With this objective, in the present study, intermolecular interaction, structural organization, and dynamics of monocationic ILs (MILs) and dicationic IL (DIL) have been studied in the absence and presence of lithium salt. Specifically, for this purpose, two MILs, 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide ([C3C1im][NTf2]), 1-hexyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide ([C6C1im][NTf2]), and a DIL, 1,6-bis(3-methylimidazolium-1-yl)hexane bis(trifluoromethylsulfonyl)amide ([C6(mim)2][NTf2]2) have been chosen in such a way that either the alkyl chain of MILs becomes equal or half of the spacer chain length of DIL. To understand the effect of the addition of lithium-ion on the structural organization of MILs and DIL, steady-state absorption and fluorescence spectroscopies, time-resolved fluorescence anisotropy and nuclear magnetic resonance (NMR) techniques have been used. Structural organization in the apolar and polar domains of ILs has been probed by following the rotational diffusion of suitably chosen solute in the concerned media through time-resolved fluorescence anisotropy (TRFA) measurements. TRFA studies have revealed that with the addition of Li+ ion, coordination between the Li+ ions and anions of MILs and DILs takes place in the ionic region leading to a change in the structural organization of the apolar regions of the respective medium. In fact, upon adding lithium-ions, a reduction in the packing of alkyl chains has also been observed for the MILs. However, not much change in the structural organization of the apolar region of the DIL has been observed when Li+ ion is added to it. In the presence of Li+ ions, a similar trend in the change of structural organization of polar regions for both MILs and DIL has been observed. Further, measurements of the self-diffusion coefficient through NMR have also supported the observation that Li+ ion also perturbs the nanostructural organization of the MIL in a significant manner than that it does for the DIL. The behavior of DIL in the presence of Li+ ion, as revealed by the present study, has been rationalized by considering the folded arrangement of DIL in the fluid-structure. Essentially, all of these investigations have suggested that the addition of lithium-ion significantly alters the microscopic behavior of MILs in comparison to that of DIL. The outcome of this study is expected to be helpful in realizing the potentials of these media as electrolytes in battery applications.

Comparison between pyrrolidinium-based and imidazolium-based dicationic ionic liquids: intermolecular interaction, structural organization, and solute dynamics.

With an aim to understand the difference in the behaviour of imidazolium and pyrrolidinium-based dicationic ionic liquids (DILs) in terms of the intermolecular interactions, microscopic-structure and dynamics, two DILs, the imidazolium-based 1,9-bis(3-methylimidazolium-1-yl)nonane bis(trifluoromethanesulfonyl)imide and the pyrrolidinium-based 1,9-bis(1-methylpyrrolidinium-1-yl)nonane bis(trifluoromethanesulfonyl)imide, have been synthesized and subsequently investigated by exploiting combined steady sate and time resolved fluorescence, electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopic techniques. Data obtained for DILs have also been compared with their corresponding mono-cationic counterpart (MILs) to evaluate and understand the distinctive characteristics of the DILs in contrast with the corresponding MILs. Steady state emission and EPR data have revealed that the pyrrolidinium-based DIL is slightly less polar than the imidazolium-based DIL. Temperature-dependent fluorescence anisotropy decay of two probes, perylene and MPTS (8-methoxypyrene-1,3,6-trisulfonate), has been measured in DILs as well as in MILs. Solute-solvent coupling constants obtained from the experimentally measured rotational correlation times with the aid of Stokes-Einstein-Debye hydrodynamic theory have indicated appreciable differences in the dynamics of both the solutes on going from MILs to DILs. More interestingly, the outcome of the NMR study has suggested that the alkyl spacer chain in the imidazolium-based DIL exists in the folded form, but the pyrrolidinium-based DIL remains in the straight chain conformation. Inherently, the outcomes of all of these studies have depicted that the microscopic structural organisations in imidazolium and pyrrolidinium-based DILs are different from each other as well as from their respective mono-cationic counterparts.

Binary mixtures of ionic liquids: Ideal, non-ideal, or quasi-ideal?

The mixing of ILs provides an opportunity for fine tuning the physiochemical properties of ILs for various applications. However, a suitable mixture having desired properties can only be designed when the physiochemical properties of the mixtures of ILs along with their spectroscopic properties are well understood. With an aim to achieve this objective, three different mixtures with a common anion, namely, [C2C1im][C4C1im][NTf2], [C3C1pyr][C4C1pyr][NTf2], and [C3C1im][C3C1pyr][NTf2], have been investigated in the current study. Investigations have been carried out at the macroscopic level by observing the thermophysical properties, such as molar volume and thermal expansion coefficient, and at the microscopic level with time-resolved fluorescence measurements and the pulse field gradient nuclear magnetic resonance (NMR) technique. The results obtained from the thermophysical study have indicated that excess molar volume for imidazolium-based IL-IL mixtures may be linked to the free volume created by the alkyl chain of the imidazolium cation whereas for the mixture of pyrrolidinium ILs, lowering of density can give rise to free volume. Analysis of time-resolved fluorescence anisotropy data has provided clear evidence in favor of the presence of free volume in the binary mixture of ILs. NMR studies have also supported the fluorescence anisotropy data. The outcome of the present investigation reveals that the mixtures show appreciable deviation from ideal behavior and the deviation from the ideal behavior is caused due to the generation of free volume in the resultant mixture, describing these IL mixtures as quasi-ideal rather than ideal or non-ideal.

Probing How Various Metal Ions Interact with the Surface of QDs: Implication of the Interaction Event on the Photophysics of QDs.

With an aim to understand the mechanism of interaction between quantum dots (QDs) and various metal ions, fluorescence response of less-toxic and water-soluble glutathione-capped Zn-Ag-In-S (GSH@ZAIS) QDs in the presence of different metal ions has been investigated at both ensemble and single-molecule level. Fourier transform infrared (FT-IR) spectroscopy has also been performed to obtain a molecular level understanding of the interaction event. The steady-state data reveal no significant change in QD emission for alkali and alkaline earth metal ions, while there is a decrease in fluorescence intensity for transition metal (TM) and some heavy transition metal (HTM) ions. Interestingly, a significant fluorescent enhancement (FE) (19-96%) of QDs is found for Cd2+ ions. Time-resolved fluorescence studies reveal that all the three decay components of QDs decrease in the presence of first-row TM ions. However, in the case of Cd2+, the shorter component is found to increase while the longer one decreases. The analysis of data reveals that photoinduced electron transfer is responsible for fluorescence quenching of QDs in the presence of first-row TM ions and destruction/removal of trap/defect states in the case of Cd2+ causes the FE. In FT-IR experiments, a prominent peak at 670 cm-1, corresponding to Cd-S stretching vibrations, indicates strong ground-state interactions between the -SH of GSH and Cd2+ ions. Moreover, a decrease in the diffusion coefficient of QDs in the presence of Cd2+ ions during fluorescence correlation spectroscopy (FCS) studies further substantiates the removal of GSH by Cd2+ from the surface of QDs. The optical output of this study demonstrates that ZAIS can be used for fluorescence signaling of various metal ions and in particular selective detection of Cd2+. More importantly, these results also suggest that Cd2+ can effectively be used for enhancing the fluorescence quantum yield of thiol-capped QDs such as GSH@ZAIS.

Probing the Interaction of Bovine Serum Albumin with Copper Nanoclusters: Realization of Binding Pathway Different from Protein Corona.

With an aim to understand the interaction mechanism of bovine serum albumin (BSA) with copper nanoclusters (CuNCs), three different types CuNCs having chemically different surface ligands, namely, tannic acid (TA), chitosan, and cysteine (Cys), have been fabricated, and investigations are carried out in the absence and presence of protein (BSA) at ensemble-averaged and single-molecule levels. The CuNCs, capped with different surface ligands, are consciously chosen so that the role of surface ligands in the overall protein-NCs interactions is clearly understood, but, more importantly, to find whether these CuNCs can interact with protein in a new pathway without forming the "protein corona", which otherwise has been observed in relatively larger nanoparticles when they are exposed to biological fluids. Analysis of the data obtained from fluorescence, ζ-potential, and ITC measurements has clearly indicated that the BSA protein in the presence of CuNCs does not attain the binding stoichiometry (BSA/CuNCs > 1) that is required for the formation of "protein corona". This conclusion is further substantiated by the outcome of the fluorescence correlation spectroscopy (FCS) study. Further analysis of data and thermodynamic calculations have revealed that the surface ligands of the CuNCs play an important role in the protein-NCs binding events, and they can alter the mode and thermodynamics of the process. Specifically, the data have demonstrated that the binding of BSA with TA-CuNCs and Chitosan-CuNCs follows two types of binding modes; however, the same with Cys-CuNCs goes through only one type of binding mode. Circular dichroism (CD) measurements have indicated that the basic structure of BSA remains almost unaltered in the presence of CuNCs. The outcome of the present study is expected to encourage and enable better application of NCs in biological applications.

Highly efficient energy transfer from a water soluble zinc silver indium sulphide quantum dot to organic J-aggregates.

The present work has been carried out with the aim to design and develop an efficient light harvesting inorganic-organic hybrid nanoscale material by employing a less toxic, environment friendly inorganic substance and also to understand the mechanism of inter-particle electronic interaction between the inorganic and organic components of the nanomaterial. Specifically, the inorganic-organic hybrid associate has been made by integrating water soluble semiconductor (zinc-silver-indium-sulfide (ZAIS)) QDs and organic J-aggregates of a cyanine dye (S2165). The fabrication of the present nano-hybrid system has been achieved via electrostatically driven self-assembly of organic dyes over ZAIS QDs. The interaction between QD and J-aggregates has been investigated by using steady state and time resolved fluorescence measurements. Zeta potential measurements have also been performed to understand the role of electrostatic interaction and thermodynamic feasibility of the association process. The investigations have revealed that the energy transfer (ET) process between QD and J-aggregates was mediated through a dipole-dipole mechanism. Interestingly, data analysis based on Förster theory has further revealed that the ET from QD to J-aggregates is very high, indicating efficient electronic coupling between the inorganic QD and the organic J-aggregates. Zeta potential measurements and thermodynamic calculations have demonstrated that the interaction between QD and organic dye is electrostatically driven and the association of organic dyes over QDs is thermodynamically feasible. The outcome of the present study is expected to be helpful in designing efficient nanoscale light harvesting devices. Additionally, fluorescence microscopy and toxicity studies on the QDs have also shown their suitability for biological applications.

How Does Addition of Lithium Salt Influence the Structure and Dynamics of Choline Chloride-Based Deep Eutectic Solvents?

In recent times, deep eutectic solvents (DESs) have emerged as an environment-friendly alternative to both common organic solvents and ionic liquids (ILs). The present study has been undertaken with an objective to understand the intermolecular interaction, structural organization, and dynamics of two DES systems in the absence and presence of lithium salt so that the potential of these mixtures in electrochemical application is realized. For this purpose, the steady-state, time-resolved fluorescence, electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR) behavior of two DESs (ethaline and glyceline) and their mixture with lithium bis(trifluoromethylsulfonyl) imide (LiNTf2) has been investigated. Measurements of polarity through EPR technique have revealed that the polarities of DESs are close to aliphatic polyhydroxy alcohol and the polarities of the medium increase with the increase in lithium salt concentration. Studies on solvation dynamics have indicated that there is an increase in average solvation time with the increase in lithium salt concentration. Investigation of rotational dynamics of some selected fluorophore in these media has shown that addition of lithium salt significantly alters the nano/microstructural organization of both DESs. Further, measurements of the self-diffusion coefficient through NMR have also supported the perturbation of the nanostructural organization of the solvent systems by addition of lithium salts. Essentially, all of these investigations have suggested that addition of lithium salt significantly alters the microscopic behavior of DESs. The outcome of this study is expected to be helpful in realizing the potential of these media for various electrochemical applications including application in lithium-ion battery.

Interaction of Lysozyme with Monocationic and Dicationic Ionic Liquids: Toward Finding a Suitable Medium for Biomacromolecules.

With an objective to understand the differences in the behavior of monocationic and dicationic ionic liquids (ILs) in their interaction with protein, we have investigated the binding interaction of lysozyme enzyme with two monocation ionic liquids (MILs), [C3MIm][Br], [C6MIm][Br], and one dicationic ionic liquid (DIL), [C6(MIm)2][Br]2, by exploiting various experimental methods. These ILs are purposefully chosen so that the effect of both hydrophobicity and structural arrangements of the cationic moiety of ionic liquids (ILs), if any, on the interaction event is understood. Both average ensemble and single molecule pathways have been adopted to obtain a comprehensive picture. For ensemble averaged measurements, the interaction events have been investigated by steady-state and time-resolved fluorescence spectroscopy, whereas for single molecule measurements, fluorescence correlation spectroscopy (FCS) has been utilized. Additionally, the behavior of protein in the absence and presence of ILs has also been investigated through circular dichroism (CD) measurements. The investigations have revealed that MILs and DIL interact differently with the protein. In particular, as compared to MILs, the influence of DIL toward protein is observed to be significantly less in terms of change in the structure and dynamics of protein. The outcome of the present work has demonstrated that imidazolium-based DIL can be a better choice over MILs for retaining native structure of protein in aqueous medium.

Understanding the Behavior of Monocationic and Dicationic Room-Temperature Ionic Liquids through Resonance Energy-Transfer Studies.

The present work has been undertaken with an objective to understand the differences in the local structural organization of imidazolium-based monocationic ionic liquids (MILs) and dicationic ionic liquids (DILs) through resonance energy-transfer (RET) studies. In this study, a neat IL is used as a donor and a charged species rhodamine 6G (R6G) is used as an acceptor unit because of the fact that they satisfy the spectroscopic criteria that are needed for an RET event to take place. Additionally, R6G, being a charged species, is expected to facilitate the electrostatic interactions with the ILs which are also charged. Specifically, two imidazolium-based germinal DILs and their monocationic counterparts are used for the present investigations. Additionally, the studies are carried out in some selected MILs where the lengths of the alkyl side chains are kept unchanged for MILs and DILs. Interestingly, the present data reveal that the RET interaction is more favorable for DILs than for MILs, even though the DILs are relatively bulkier than their monocationic counterparts. More interestingly, the RET interaction is also found to be more favorable for DILs than for MILs, where the length of the alkyl group is kept fixed for MILs and DILs. The result of the present study delineates that the alkyl chain length on the cation is not the sole factor contributing to the RET outcomes for DILs and MILs but the local structure of DILs also contributes significantly to the same. The current investigation clearly indicates that DILs have a more compact local structure than that of MILs. Essentially, the current study highlights that a cost-effective, noninvasive technique such as RET is quite effective in capturing the differences in the nanostructural organization of MILs and DILs.

Probing the Interactions of 1-Alkyl-3-methylimidazolium Tetrafluoroborate (Alkyl = Octyl, Hexyl, Butyl, and Ethyl) Ionic Liquids with Bovine Serum Albumin: An Alkyl Chain Length-Dependent Study.

Herein, we have investigated the binding interaction of bovine serum albumin (BSA) with a series of 1-alkyl-3-methylimidazolium tetrafluoroborate (alkyl = ethyl, butyl, hexyl, and octyl) ionic liquids (ILs) in physiological buffer medium. The ILs are chosen basically to understand the effect of alkyl chain length on IL-protein interaction. Experiments have shown that the quenching of fluorescence of BSA is induced by relatively longer alkyl chain-containing ILs, [OMIM][BF4] and [HMIM][BF4]. The enthalpy-driven spontaneous binding (-ve Δ G) of hexyl and octyl chain-containing ILs with the protein is mediated by both hydrogen-bonding and van der Waals interactions. The experimental data have categorically explained the denaturation of protein conformation upon interaction with both [OMIM][BF4] and [HMIM][BF4]. The molecular docking calculation nicely corroborates the experimentally obtained results. The present study reveals that neither a smaller alkyl group-containing IL nor a very large alkyl group-containing IL is necessary to have effective protein-IL interactions. The study also reveals the influence of hydrophobic interaction over and above the hydrogen-bonding interaction on protein-IL binding events and essentially gives an idea about the optimum hydrophobic character of the ILs that is necessary to induce protein-IL interaction and consequently the denaturation of the protein structure.

Understanding the Microscopic Behavior of Binary Mixtures of Ionic Liquids through Various Spectroscopic Techniques.

In recent times, it has been shown that certain binary mixtures of pure ionic liquids having appropriate chemical composition can behave like a new chemical entity. However, current knowledge about the microscopic behavior of these interesting systems is rather limited. The present study is undertaken with an objective to understand the microscopic behavior in terms of intermolecular interaction, structure, and dynamics of these systems. In the present study, few (IL + IL) mixtures are chosen with a common cation and a variation of anion. The investigations are also carried out by taking individual pure ILs so that the difference in the behavior of pure IL and (IL + IL) mixtures is understood. Initially, the systems have been investigated by studying the thermophysical properties of the concerned mixtures. The synergistic effect between combining pure ILs through photochromism has also been studied. These mixtures have been investigated further through steady-state and time-resolved fluorescence spectroscopy, electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR), and fluorescence correlation spectroscopy (FCS). Interestingly, time-resolved fluorescence data also pointed out that (IL + IL) mixtures are not only spatially heterogeneous but also dynamically heterogeneous. EPR measurements have suggested that the micropolarity ( ET(30)) of the (IL + IL) mixture is close to that of aliphatic polyalcohols. Measurements of translational diffusion coefficients of the diffusing species through NMR and FCS studies have provided an idea about the nanostructural organization within (IL + IL) binary mixtures. The analysis of data essentially reveals that the mixtures of ILs that are used in the current study do not behave like a nonideal solution. The behavior of the IL mixtures is observed to be more like quasi-ideal type.

Differences in the behavior of dicationic and monocationic ionic liquids as revealed by time resolved-fluorescence, NMR and fluorescence correlation spectroscopy.

With an aim to understand the behavior in terms of the intermolecular interactions, structure and dynamics of dicationic and monocationic ionic liquids (ILs), two imidazolium-based dicationic ionic liquids (DILs), 1,8-bis-(3-methylimidazolium-1-yl)octane bis-(trifluoromethylsulfonyl)amide ([C8(mim)2][NTf2]2), 1,9-bis-(3-methylimidazolium-1-yl)nonane bis-(trifluoromethylsulfonyl)amide ([C9(mim)2][NTf2]2), and one monocationic ionic liquid (MIL), 1-butyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide ([C4(mim)][NTf2]), have been investigated through combined fluorescence, electron paramagnetic resonance (EPR), NMR and fluorescence correlation spectroscopy (FCS). The DILs were synthesized by following a standard synthetic protocol and subsequently characterized by different analytical techniques. Steady state absorption, emission and EPR spectroscopic data reveal that DILs are less polar compared to MIL. The polarities of the DILs and MIL were found to be close to those of acetonitrile and short chain alcohols, respectively. The excitation wavelength dependent emission data reveals that DILs are more micro-heterogeneous in nature than MIL. The rotational diffusion of two organic solutes, perylene and 8-methoxypyrene-1,3,6-sulfonate (MPTS), were examined in the DILs and MIL. The rotational diffusion data for perylene and MPTS were analyzed in light of the Stokes-Einstein-Debye (SED) hydrodynamic theory. The rotation of perylene in the DILs was observed to be relatively faster to that in the MIL, and it goes beyond the limit predicted by the SED theory. In order to explain the rotational motion of perylene in DILs, the data was analyzed further by invoking quasi-hydrodynamic theory. The observed rotational behavior of perylene has been explained by considering the fact that perylene is located in the nonpolar region of ILs, and larger solvent molecules (DILs) induce a lower friction to the rotating solute. Interestingly, unlike perylene, rotations of MPTS in both of the ILs were observed to be much hindered indicating a relatively stronger MPTS-IL interaction than perylene-IL interaction. More interestingly, rotation of MPTS was observed to be faster in the DILs than that in the MIL despite the fact that DILs are more viscous than MILs. Relatively faster rotation of MPTS in DILs has been explained by resorting to NMR and FCS studies. The outcomes of the NMR and FCS studies revealed that DILs in the experimental condition exist in their folded form and because of this structural restriction of DILs it becomes difficult for the bulky MPTS to make stronger hydrogen bonding interactions with DILs, which eventually makes the rotation of MPTS in DILs faster. Essentially, the outcomes of all of these studies have demonstrated that the behavior of DILs is quite different to that of the usual MILs.

Evidence of homo-FRET in quantum dot-dye heterostructured assembly.

With an aim to understand the intermolecular/particle interaction and the optical properties of the inorganic-organic hybrid nanostructured materials, Förster resonance energy transfer (FRET) between negatively charged CdS quantum dots (donor) and positively charged Oxazine 170 perchlorate (acceptor) has been investigated by employing steady-state and time-resolved fluorescence spectroscopy. Investigations revealed that size-dependent changes in the FRET efficiency of different QD-dye FRET pairs occurred mainly due to the electrostatic effects. Interestingly, the present study also reveals that at a higher concentration of dye molecules, aggregation occurs on the QD surface and the quenching of dye fluorescence occurs due to homo-FRET process. The homo-FRET process in this case has been established by exploiting steady-state fluorescence anisotropy measurements. The feasibility of aggregate formation and the homo-FRET interaction between the dye molecules has also been demonstrated through quantum mechanical calculations.