Dependency of Anion and Chain Length of Imidazolium Based Ionic Liquid on Micellization of the Block Copolymer F127 in Aqueous Solution: An Experimental Deep Insight

Lunagariya, Jignesh; Kumar, Nadavala Siva; Asif, Mohammad; Dhar, Abhishek; Vekariya, Rohit L.

doi:10.3390/polym9070285

Cited by 19 publications

(20 citation statements)

References 41 publications

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“…The model captured the complexities of Pluronic micelle formation and the influence of the PPG content, the PEG to PPG ratio, or the Pluronic molecular weight on the cloud point temperature. As such, it provides a valuable framework to study the influence of SAIL addition to Pluronic aqueous solutions on the thermal response of the system and complement existing experimental studies. − …”

Section: Introductionmentioning

confidence: 99%

“…As such, it provides a valuable framework to study the influence of SAIL addition to Pluronic aqueous solutions on the thermal response of the system and complement existing experimental studies. 18,19,28,29,[20][21][22][23][24][25][26][27] In this work four selected Pluronics were studied in conjunction with imidazolium and phosphonium-based SAILs to determine the influence of the ILs as additives on the cloud points and thermo-responsiveness of the system. Both normal (PEG-PPG-PEG) and reverse (PPG-PEG-PPG) Pluronics were studied as these structural changes induce major micelle surface variations from star-like to flower-like shaped micelles, respectively, as well as the occurrence of physical cross linkage between reverse Pluronic micelles.…”

Section: Introductionmentioning

confidence: 99%

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Unravelling the Interactions between Surface-Active Ionic Liquids and Triblock Copolymers for the Design of Thermal Responsive Systems

et al. 2020

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The tunable properties of surface-active ionic liquids (SAILs) and Pluronics are dramatically magnified by combining them in aqueous solutions. The thermo-controlled character of both, essential in the extraction of valuable compounds, can be fine-tuned by properly selecting the Pluronic and SAIL nature. However, further understanding of the nanoscale interactions directing the aggregation in these complex mixtures is needed to effectively design and control these systems. In this work, a simple and transferable coarse-grained model for molecular dynamics simulations, based on the MARTINI force field, is presented to study the impact of SAILs in Pluronics aggregation in aqueous solutions. The diverse amphiphilic characteristics and micelle morphologies were exemplified by selecting four archetypical nonionic Pluronicstwo normal, L-31 and L-35, and two reverse, 10R5 and 31R1. The impact of the alkyl chain length and the headgroup nature were evaluated with the imidazolium-based [C10mim]Cl and [C14mim]Cl and phosphonium-based [P4,4,4,14]Cl SAILs. Cloud point temperature (CPT) measurements at different Pluronic concentrations with 0.3 wt % of SAIL in aqueous solution emphasized the distinct impact of SAIL nature on the thermo-response behavior. The main effect of SAIL addition to nonionic Pluronics aqueous solutions is the formation of Pluronic/SAIL hybrid micelles, where the presence of SAIL molecules introduces a charged character to the micelle surface. Thus, additional energy is necessary to induce micelle aggregation, leading to the observed increase in the experimental CPT curves. The SAIL showed a relatively weak impact in Pluronic micelles with relatively high PPG hydrophobic content, whereas this effect was more evident when the Pluronic hydrophobic/hydrophilic strength is balanced. A detailed analysis of the Pluronic/SAIL micelle density profiles showed that the phosphonium head groups were positioned inside the micelle core, whereas smaller imidazolium head groups were placed much closer to the hydrophilic PEG corona, leading to a distinct effect on the cloud point temperature for those two classes of SAILs. Herein, the phosphonium-based SAIL induces a lower repulsion between neighboring micelles than the imidazolium-based SAILs, resulting in a less pronounced increase of the CPT. The model presented here offers, for the first time, an intuitive and powerful tool to unravel the complex thermo-response behavior of Pluronic and SAIL mixtures and support the design of tailor-made thermal controlled solvents.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Unravelling the Interactions between Surface-Active Ionic Liquids and Triblock Copolymers for the Design of Thermal Responsive Systems

et al. 2020

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“…The effects of ILs on the aggregation properties, critical micellar concentration (cmc), and hydration behavior of different kinds of surfactants have been reported in several studies and found to be important for fine-tuning the surfactant properties for specific applications. − Yue et al had employed aprotic 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF 4 ) and protic ethylammonium nitrate (EAN) to investigate the aggregation behavior of phytosterolethoxylate surfactant (BPS-10), which showed a higher effectiveness of EAN over [Bmim]BF 4 in promoting nonionic BPS-10 aggregation . Later, the aggregation behavior of the alkyl triphenylphosphonium bromides, C n TPB, in aprotic and protic ILs was also investigated, where a stronger solvophobic effect between C n TPB and protic EAN was evidenced than aprotic [Bmim][BF 4 ] .…”

Section: Introductionmentioning

confidence: 99%

Understanding Differential Interaction of Protic and Aprotic Ionic Liquids inside Molecular Confinement

et al. 2017

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Considering the contemporary interests of water-free reverse micelles (RMs) in the field of organic reaction medium and potential drug delivery carrier, we synthesized two different classes of ionic liquids (ILs), protic N-methyl-2-pyrrolidonium hexanoate, [NMP][Hex], and aprotic choline hexanoate, [Chl][Hex], and subsequently incorporated them in a mixture of polyoxyethylene (20) sorbitan monooleate (Tween-80) and cyclohexane. In order to understand the differential nature of interinterionic interaction of two ILs, we performed DFT calculations on pure ILs to correlate with experimental results. The formation of IL-in-oil RMs was confirmed from phase behavior and DLS studies. Interestingly, [NMP][Hex]-based systems showed a larger monophasic region and droplet size along with higher shear viscosity compared to [Chl][Hex]-based systems. Stronger interaction between [NMP] and Tween-80 due to their protic nature might be the driving force for such observations which supported the resonance stabilization energy [E] and charge population analysis by NBO calculation. Smaller E values along with lesser NBO charges on atoms involved in H-bonding in pure [NMP][Hex] than [Chl][Hex] corroborated with the experimental observations. This primary hypothesis was further confirmed from FTIR and time-resolved fluorescence studies. These systems showed efficient thermal stability. Taking all of the results together, we anticipate that these RMs could be used as efficient delivery systems and for nanomaterial synthesis.

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“…F127 was also studied by DLS in aqueous solutions containing [C N C 1 im] halide ILs ( N = 4, 6, and 8) at 100 mM. 72 The study found that the micelles became smaller with the various ILs. However, there was no strong trend related to the alkyl chain length.…”

Section: Discussionmentioning

confidence: 99%

Impact of Two Water-Miscible Ionic Liquids on the Temperature-Dependent Self-Assembly of the (EO)₆–(PO)₃₄–(EO)₆ Block Copolymer

Heller

2022

ACS Omega

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There are many studies on the self-assembly of triblock poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) copolymers in aqueous solution. These polymers display a rich phase diagram as a function of block length, concentration, temperature, and additives. Here, we present a small-angle neutron scattering study of the impact of two water-miscible ionic liquids, 1-butyl-3-methylimidazolium chloride ([C 4 C 1 mim][Cl]) and 1-butyl-3-methylpyrrolidinium chloride ([C 4 C 1 pyrr][Cl]), on the temperature-dependent self-assembly of (EO) 6 –(PO) 34 –(EO) 6 , also known as L62 Pluronic, in aqueous solution. Both ionic liquids depress the temperatures of the various structural transitions that take place, but ([C 4 C 1 pyrr][Cl]) has a stronger effect. The structures that the triblock copolymer self-assembles into do not dramatically change nor do they significantly change the series of structures that the system transitions through as a function of temperature relative to the various transition temperatures.

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Dependency of Anion and Chain Length of Imidazolium Based Ionic Liquid on Micellization of the Block Copolymer F127 in Aqueous Solution: An Experimental Deep Insight

Cited by 19 publications

References 41 publications

Unravelling the Interactions between Surface-Active Ionic Liquids and Triblock Copolymers for the Design of Thermal Responsive Systems

Unravelling the Interactions between Surface-Active Ionic Liquids and Triblock Copolymers for the Design of Thermal Responsive Systems

Understanding Differential Interaction of Protic and Aprotic Ionic Liquids inside Molecular Confinement

Impact of Two Water-Miscible Ionic Liquids on the Temperature-Dependent Self-Assembly of the (EO)₆–(PO)₃₄–(EO)₆ Block Copolymer

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Dependency of Anion and Chain Length of Imidazolium Based Ionic Liquid on Micellization of the Block Copolymer F127 in Aqueous Solution: An Experimental Deep Insight

Cited by 19 publications

References 41 publications

Unravelling the Interactions between Surface-Active Ionic Liquids and Triblock Copolymers for the Design of Thermal Responsive Systems

Unravelling the Interactions between Surface-Active Ionic Liquids and Triblock Copolymers for the Design of Thermal Responsive Systems

Understanding Differential Interaction of Protic and Aprotic Ionic Liquids inside Molecular Confinement

Impact of Two Water-Miscible Ionic Liquids on the Temperature-Dependent Self-Assembly of the (EO)6–(PO)34–(EO)6 Block Copolymer

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Impact of Two Water-Miscible Ionic Liquids on the Temperature-Dependent Self-Assembly of the (EO)₆–(PO)₃₄–(EO)₆ Block Copolymer