Reddicherla Umapathi

Thermophysical Properties of Aqueous Solution of Ammonium-Based Ionic Liquids

Experimental densities (ρ), ultrasonic sound velocities (u), viscosities (η), and refractive indices (n(D)) of binary mixtures of ammonium-based ionic liquids (ILs) such as diethylammonium acetate (DEAA) [(CH3CH2)2NH][CH3COO], triethylammonium acetate (TEAA) [(CH3CH2)3NH][CH3COO], diethylammonium hydrogen sulfate (DEAS) [(CH3CH2)2NH][HSO4], triethylammonium hydrogen sulfate (TEAS) [(CH3CH2)3NH][HSO4], trimethylammonium acetate (TMAA) [(CH3)3NH][CH3COO], and trimethylammonium hydrogen sulfate (TMAS) [(CH3)3NH][HSO4] with water are reported over the wide composition range at 25 °C under atmospheric pressure. The excess molar volumes (V(E)), deviation in isentropic compressibilities (Δκ(s)), deviation in viscosities (Δη) and deviation in refractive indices (Δn(D)) are calculated from experimental values and are correlated by Redlich-Kister polynomial equations. The V(E) and Δκ(s) values for the aforesaid systems are negative over the entire composition range while the Δη and Δn(D) values are positive under the same experimental conditions. The intermolecular interactions and structural effects were analyzed on the basis of measured and derived properties. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions and hydrogen bonding between ILs and water. Furthermore, the hydrogen bonding features between ILs with water were analyzed by using a molecular modeling program with the help of HyperChem7.

Structural insights into the effect of cholinium-based ionic liquids on the critical micellization temperature of aqueous triblock copolymers

Symmetrical poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG) triblock copolymer with 82.5% PEG as the hydrophilic end blocks, and PPG as the hydrophobic middle block, was chosen to study the effect of ionic liquids (ILs) on the critical micellization temperature (CMT) of block copolymers in aqueous solution. In the present work, cholinium-based ILs were chosen to explore the effect of the anions on the copolymer CMT using fluorescence spectroscopy, dynamic light scattering (DLS), viscosity (η), FT-IR spectroscopy, nuclear magnetic resonance (NMR), and direct visualization of the various self-assembled nanostructures by scanning electron microscopy (SEM). The result suggests that ILs have the ability to decrease the CMT of the aqueous copolymer solution which is dependent on the nature of the anions of the ILs. The present study reveals that the hydrophobic part PPG of the copolymer has more influence on this behavior than the PEG hydrophilic part.

The biological stimuli for governing the phase transition temperature of the "smart" polymer PNIPAM in water.

A lack of sufficient knowledge regarding the behaviour of stimuli-responsive polymers to biological stimuli hinders the potential use of responsive polymers as biomaterials and medical devices. Hence, in this study, we demonstrate the impact of various globular proteins on the phase transition temperature of poly(N-isopropylacrylamide) (PNIPAM) in an aqueous solution through the use of fluorescence spectroscopy, dynamic light scattering (DLS), Fourier transform infrared (FTIR) spectroscopy and field-emission scanning electron microscopy (FESEM). Furthermore, we describe the molecular interaction of PNIPAM with proteins by the MolDock method. Our experimental and docking studies revealed that such proteins as α-chymotrypsin (CT), insulin (In) and haemoglobin (Hb) decreased the lower critical solution temperature (LCST) of the polymer, whereas succinyl-concanavalin A (SCA) increased the LCST of PNIPAM. The LCST changed upon increasing the concentration of protein from 0.5mg/mL to 1mg/mL. The thermoresponsive behaviour of PNIPAM can be significantly altered by the functional groups present in the protein. The findings of the present study can be used in the engineering of bioresponsive smart PNIPAM-based devices.

Thermo-responsive triblock copolymer phase transition behaviour in imidazolium-based ionic liquids: Role of the effect of alkyl chain length of cations

Different biophysical techniques such as fluorescence spectroscopy, dynamic light scattering (DLS), viscosity (η) and Fourier transform infrared (FTIR) spectroscopy have been carried out to characterize the effect of imidazolium-based ionic liquids (ILs) on the thermo-responsive triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly-(ethylene glycol) (PEG-PPG-PEG). In addition, to demonstrate the distinct morphological changes of various self-assembled morphologies, we further employed field emission scanning electron microscope (FESEM). To investigate the effect of alkyl chain length of the cation, concentration of the ILs and the related Hofmeister series on the phase behaviour of PEG-PPG-PEG, we used a series of ILs possessing same Cl- anion and a set of cation [Cnmim]+ with increasing alkyl chain length of cation such as 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]), 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]), 1-hexyl-3-methylimidazolium chloride ([Hmim][Cl]) and 1-decyl-3-methylimidazolium chloride ([Dmim][Cl]). The critical micellization temperature (CMT) of the copolymer in the presence of well hydrated cations is directly correlated to their hydration. The overall specific ranking of ILs in decreasing the CMT of PEG-PPG-PEG in aqueous solution was [Emim][Cl]>[Bmim][Cl]>[Hmim][Cl]>[Dmim][Cl]. The trend of these ILs followed the well-known Hofmeister series of cations of ILs. The present study provides important information about the solution properties that can be helpful to tune the IL or temperature-sensitive copolymer CMT and micelle shapes which are crucial for understanding the drug delivery mechanisms.

Comprehensive Computational and Experimental Analysis of Biomaterial toward the Behavior of Imidazolium-Based Ionic Liquids: An Interplay between Hydrophilic and Hydrophobic Interactions

To provide insights into the aggregation behavior, hydration tendency and variation in phase transition temperature produced by the addition of ionic liquids (ILs) to poly(N-isopropylacrylamide) (PNIPAM) aqueous solution, systematic physicochemical studies, and molecular dynamic simulations were carried out. The influence of ILs possessing the same [Cl]- anion and a set of cations [Cnmim]+ with increasing alkyl chain length such as 1-ethyl-3-methylimidazolium ([Emim]+), 1-allyl-3-methylimidazolium ([Amim]+), 1-butyl-3-methylimidazolium ([Bmim]+), 1-hexyl-3-methylimidazolium ([Hmim]+), 1-benzyl-3-methylimidazolium ([Bzmim]+), and 1-decyl-3-methylimidazolium ([Dmim]+) on the phase transition of PNIPAM was monitored by the aid of UV-visible absorption spectra, fluorescence intensity spectra, viscosity (η), dynamic light scattering (DLS), and Fourier transform infrared (FTIR) spectroscopy. Furthermore, to interpret the direct images and surface morphologies of the PNIPAM-IL aggregates, we performed field emission scanning electron microscopy (FESEM). The overall specific ranking of ILs in preserving the hydration layer around the PNIPAM aqueous solution was [Emim][Cl] > [Amim][Cl] > [Bmim][Cl] > [Hmim][Cl] > [Bzmim][Cl] > [Dmim][Cl]. Moreover, to investigate the molecular mechanism behind the change in the lower critical solution temperature (LCST) of the polymer in the presence of the ILs, a molecular dynamics (MD) study was performed. The MD simulation has clearly shown the reduction in hydration shell of the polymer after interacting with the ILs at their respective LCST. MD study revealed significant changes in polymer conformation because of IL interactions and strongly supports the experimental observation of polymer phase transition at a temperature lower than typical LCST for all the studied ILs. The driving force for concomitant sharp configurational transition has been attributed to the displacement of water molecules on the polymer surface by the ILs because of their hydrophobic interaction with the polymer.

Assessing the efficiency of imidazolium-based ionic liquids on the phase behavior of a synthetic biomedical thermoresponsive polymer

HYPOTHESIS Temperature-responsive polymers (TRPs) with a phase transition temperature close to human physiological body temperature have attracted much attention in biomedical and pharmaceutical fields. Addition of small amount of cosolvent to TRPs is expected to influence the molecular interactions, thereby affecting the phase transition temperature of TRPs. Hence, it is possible to tune the phase behavior of TRPs and also drive transitions in TRPs by variation of chemical structure of cosolvent. EXPERIMENTS To elucidate the conformational changes of the phase transition of TRP aqueous solution in ionic liquids (ILs), poly(N-vinylcaprolactam) (PVCL), a well known TRP was synthesized by solution polymerization. The lower critical solution temperature (LCST) behavior of polymer aqueous solution, with the addition of imidazolium-based ILs possessing same Cl- anion and a set of cations [Cnmim]+ such as 1-ethyl-3-methylimidazolium ([Emim]+), 1-butyl-3-methylimidazolium ([Bmim]+), 1-hexyl-3-methylimidazolium ([Hmim]+), 1-decyl-3-methylimidazolium ([Dmim]+), 1-allyl-3-methylimidazolium ([Amim]+) and 1-benzyl-3-methylimidazolium ([Bzmim]+), was monitored by using various sophisticated experimental techniques. FINDINGS The modulations on the LCST of PVCL aqueous solutions follow the order of [Emim][Cl]<[Amim][Cl]<[Bmim][Cl]<[Hmim][Cl]<[Bzmim][Cl]<[Dmim][Cl]. This order shows that the LCST value increase with increasing the alkyl chain length of cation from [Emim]+ to [Dmim]+ of IL. To the best of our knowledge, this is the first report on comprehensive unequivocal evidence of the phase transition behavior of PVCL in presence of imidazolium-based ILs.