Liquid Structure and Dynamics of Tetraalkylammonium Bromide-Based Deep Eutectic Solvents: Effect of Cation Chain Length

Hossain, Sk Saddam; Paul, Sneha; Samanta, Anunay

doi:10.1021/acs.jpcb.9b04955

Cited by 26 publications

(24 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For our data, this is clearly manifested by the decreased value of the exponent p (=0.82) from unity in the fitting of the average rotational time constants. Such a deviation has been shown in many ILs (including deep eutectic solvents, DESs) and explained as clear evidence of solution heterogeneity [42,67,68]. C obs values clearly show the extent of deviation from ideal (C obs = 1) and we note that the solvent coupling is less than 50% of the stick limit in neat EAN.…”

Section: Discussionsupporting

confidence: 70%

Coumarin 153 Dynamics in Ethylammonium Nitrate: The Effects of Dilution with Methanol

Heitz

Sabo

Robillard

2021

Sustainable Chemistry

View full text Add to dashboard Cite

Magic angle intensity decay and dynamic fluorescence anisotropy measurements were made on the binary solvent system composed of ethylammonium nitrate ([N2,0,0,0+][NO3−], EAN) + methanol (MeOH) across the complete EAN mole fraction range (xIL = 0–1) using the neutral dipolar solute coumarin 153 (C153) at 295 K. Stokes–Einstein–Debye (SED) hydrodynamic theory was used as a model framework to assess the C153 rotational reorientation dynamics. Departure from stick SED prediction was observed (in contrast to literature reports that used cationic or anionic dyes) and indicated a significant influence of domain nanoheterogeneity on probe dynamics. Steady-state spectroscopy indicated minimal changes in spectral peak and width with mole fraction, except at xIL = 0.3 where absorption widths decreased by ~170 cm−1, signaling that C153 sensed a change in solution heterogeneity. Magic angle intensity decays corroborated the steady-state observation and the excited-state lifetimes showed a marked change from xIL = 0.2–0.4 where EAN-EAN interactions became notably more significant. C153 average rotation times (⟨τrot⟩) showed significant solvent decoupling with increased EAN. The rotational data were fit to a power law dependence, ⟨τrot⟩ ∝ (ηT)p, where p = 0.82, demonstrating the presence of dynamic heterogeneity in the EAN/MeOH solutions. With increased EAN, rotation times showed that the heterogeneity became increasingly more significant since the rotation times systematically decreased away from the hydrodynamic stick limit.

show abstract

Section: Discussionsupporting

confidence: 70%

Coumarin 153 Dynamics in Ethylammonium Nitrate: The Effects of Dilution with Methanol

Heitz

Sabo

Robillard

2021

Sustainable Chemistry

View full text Add to dashboard Cite

show abstract

“…The structural identity of the DESs was confirmed by looking into FTIR spectra (Figure S2). Comparison of the NMR and FTIR spectra of the prepared DESs with the other reported DESs indicate that no side reactions occurred during the preparation of the DESs and the prepared liquids were pure. − …”

Section: Methodsmentioning

confidence: 81%

Structural Stability and Conformational Dynamics of Cytochrome c in Hydrated Deep Eutectic Solvents

2021

Self Cite

View full text Add to dashboard Cite

Many deep eutectic solvents (DESs) are currently being explored as environment-friendly media for biorelated applications. As an understanding of the effect of these solvents on the structure of biomolecules is crucial for these applications, we study how two DESs comprising trimethylglycine (TMG) and ethylene glycol (EG) or glycerol (GL) influence the structural stability and conformational dynamics of cytochrome c (Cytc) using single-molecule-based fluorescence correlation spectroscopy (FCS) technique and several other ensemble-based biophysical methods. The FCS studies on A488-labeled Cytc enable an estimation of the size (20.5 ± 1.5 Å) of the protein and capture its conformational dynamics (54 ± 2 μs) in aqueous buffered solution. It is observed that both size and conformational dynamics of the protein are influenced in the presence of the DESs, but this effect is more pronounced in the case of TMG-EG. The ensemble measurements on both labeled and wild-type Cytc reveal that the protein structure is unfolded completely by TMG-EG, whereas the structure is slightly altered by TMG-GL. The results suggest that the behavior of Cytc in hydrated DESs is determined by the strength of interactions between the DES constituents as well as that between the constituents and the water molecules present in the system.

show abstract

“…Poly( N -vinylcaprolactam) (PVCL) has received significant attention due to its characteristic features and diversified applications in biomedical science and pharmaceutical industries. − Owing to its tremendous sensitivity and biocompatibility, PVCL-based “smart” materials such as nanohybrids, microgels, hydrogels, and copolymers have been widely used in various applications. ,− PVCL can respond to different stimulants, such as proteins, temperature, ionic strength, and osmolytes. − Deep eutectic solvents (DESs) are an emerging class of benign liquid formulations that have gained popularity owing to idiosyncratic properties that outperform traditional ionic liquids (ILs). − High solubilization power, solventless preparation, low volatility, good stability, cost effectiveness, and wider availability are some of the properties of DESs that make them an ingenious and perfect solvent alternative. − The DESs consist of hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD) groups.…”

Section: Introductionmentioning

confidence: 99%

Tweaking Behavior of Hydrogen Bond Donor in Choline Chloride-Based Deep Eutectic Solvents for Regulating the Phase Transition of Poly(N-vinylcaprolactam): A Sustainable Medium for an Early Hydrophobic Collapse

Kumar

Umapathi

Bisht

et al. 2021

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Deep eutectic solvents (DESs) are recognized as a "green" alternative to conventional ionic liquids and organic solvents owing to their specific properties. In this study, the influence of DESs containing choline chloride (ChCl) as a hydrogen bond acceptor (HBA) and urea, ethylene glycol (EG), and lactic acid (LA) as hydrogen bond donors (HBD) on the thermoresponsive behavior of poly(N-vinylcaprolactam) (PVCL) is investigated using various techniques. Spectroscopic investigations indicate biased interactions of the HBD group present in the DESs with a hydration layer of PVCL. Dynamic light scattering and temperature-dependent fluorescence spectroscopy results clearly show a decrease in the lower critical solution temperature of PVCL in the presence of the DESs. The hydrophobic collapse of PVCL in the presence of the DESs follows the order ChCl:urea > ChCl:EG > ChCl:LA. It is proposed that the presence of DESs does not interfere with the functional groups present in PVCL; however, it ruptures the hydrogen bonding between PVCL and the water molecules and destabilizes the water gradient around PVCL. The DESs have provided an alternative platform for low-temperature dehydration of PVCL, which can be useful as a drug carrier agent.

show abstract

Liquid Structure and Dynamics of Tetraalkylammonium Bromide-Based Deep Eutectic Solvents: Effect of Cation Chain Length

Cited by 26 publications

References 61 publications

Coumarin 153 Dynamics in Ethylammonium Nitrate: The Effects of Dilution with Methanol

Coumarin 153 Dynamics in Ethylammonium Nitrate: The Effects of Dilution with Methanol

Structural Stability and Conformational Dynamics of Cytochrome c in Hydrated Deep Eutectic Solvents

Tweaking Behavior of Hydrogen Bond Donor in Choline Chloride-Based Deep Eutectic Solvents for Regulating the Phase Transition of Poly(N-vinylcaprolactam): A Sustainable Medium for an Early Hydrophobic Collapse

Contact Info

Product

Resources

About