In this work, analysis of ion transport parameters of polymer blend electrolytes incorporated with magnesium trifluoromethanesulfonate (Mg(CF3SO3)2) was carried out by employing the Trukhan model. A solution cast technique was used to obtain the polymer blend electrolytes composed of chitosan (CS) and poly (2-ethyl-2-oxazoline) (POZ). From X-ray diffraction (XRD) patterns, improvement in amorphous phase for the blend samples has been observed in comparison to the pure state of CS. From impedance plot, bulk resistance (Rb) was found to decrease with increasing temperature. Based on direct current (DC) conductivity (σdc) patterns, considerations on the ion transport models of Arrhenius and Vogel-Tammann-Fulcher (VTF) were given. Analysis of the dielectric properties was carried out at different temperatures and the obtained results were linked to the ion transport mechanism. It is demonstrated in the real part of electrical modulus that chitosan-salt systems are extremely capacitive. The asymmetric peak of the imaginary part (Mi) of electric modulus indicated that there is non-Debye type of relaxation for ions. From frequency dependence of dielectric loss (ε″) and the imaginary part (Mi) of electric modulus, suitable coupling among polymer segmental and ionic motions was identified. Two techniques were used to analyze the viscoelastic relaxation dynamic of ions. The Trukhan model was used to determine the diffusion coefficient (D) by using the frequency related to peak frequencies and loss tangent maximum heights (tanδmax). The Einstein-Nernst equation was applied to determine the carrier number density (n) and mobility. The ion transport parameters, such as D, n and mobility (μ), at room temperature, were found to be 4 × 10-5 cm2/s, 3.4 × 1015 cm-3, and 1.2 × 10-4 cm2/Vs, respectively. Finally, it was shown that an increase in temperature can also cause these parameters to increase.
Crystallization of the ionic liquid 3,3'-dimethyl-1,1'-(1,4-phenylenedimethylene)diimidazolium bis(tetrafluoroborate), C(16)H(20)N(4)(2+).2BF(4)(-), (I), from its solution in water has permitted the first single-crystal study of an imidazolium-based ionic liquid having a tetrafluoroborate ion as counter-ion. Despite the expectation that the anion would not participate in nonclassical hydrogen bonding, the ionic liquid features C-H...F hydrogen bonds. The dication lies about a center of inversion. The ionic liquid 3,3'-di-n-butyl-1,1'-(1,4-phenylenedimethylene)diimidazolium bis(trifluoromethanesulfonate), C(22)H(32)N(4)(2+).2CF(3)SO(3)(-), (II), features both C-H...F and C-H...O hydrogen bonds.
This paper reports the application of hexamethyldisilazane-trimethylsilyl trifluoromethanesulfonate (HMDS-TMSOTf) for the simultaneous silylation of 3-monochloro-1,2-propanediol (3-MCPD) and 1,3-dicholoropropanol (1,3-DCP) in solid and liquid food samples. 3-MCPD and 1,3-DCP are chloropropanols that have been established as Group 2B carcinogens in clinical testing. They can be found in heat-processed food, especially when an extended high-temperature treatment is required. However, the current AOAC detection method is time-consuming and expensive. Thus, HMDS-TMSOTf was used in this study to provide a safer, and cost-effective alternative to the HFBI method. Three important steps are involved in the quantification of 3-MCPD and 1,3-DCP: extraction, derivatization and quantification. The optimization of the derivatization process, which involved focusing on the catalyst volume, derivatization temperature, and derivatization time was performed based on the findings obtained from both the Box-Behnken modeling and a real experimental set up. With the optimized conditions, the newly developed method was used for actual food sample quantification and the results were compared with those obtained via the standard AOAC method. The developed method required less samples and reagents but it could be used to achieve lower limits of quantification (0.0043mgL(-1) for 1,3-DCP and 0.0011mgL(-1) for 3-MCPD) and detection (0.0028mgL(-1) for 1,3-DCP and 0.0008mgL(-1) for 3-MCPD). All the detected concentrations are below the maximum tolerable limit of 0.02mgL(-1). The percentage of recovery obtained from food sample analysis was between 83% and 96%. The new procedure was validated with the AOAC method and showed a comparable performance. The HMDS-TMSOTf derivatization strategy is capable of simultaneously derivatizing 1,3-DCP and 3-MCPD at room temperature, and it also serves as a rapid, sensitive, and accurate analytical method for food samples analysis.
In the current paper, ion transport parameters in poly (vinyl alcohol) (PVA) based solid polymer electrolyte were examined using Trukhan model successfully. The desired amount of lithium trifluoromethanesulfonate (LiCF3SO3) was dissolved in PVA host polymer to synthesis of solid polymer electrolytes (SPEs). Ion transport parameters such as mobility (μ), diffusion coefficient (D), and charge carrier number density (n) are investigated in detail using impedance spectroscopy. The data results from impedance plots illustrated a decrement of bulk resistance with an increase in temperature. Using electrical equivalent circuits (EEC), electrical impedance plots (ZivsZr) are fitted at various temperatures. The results of impedance study demonstrated that the resistivity of the sample decreases with increasing temperature. The decrease of resistance or impedance with increasing temperature distinguished from Bode plots. The dielectric constant and dielectric loss values increased with an increase in temperature. The loss tangent peaks shifted to higher frequency region and the intensity increased with an increase in temperature. In this contribution, ion transport as a complicated subject in polymer physics is studied. The conductivity versus reciprocal of temperature was found to obey Arrhenius behavior type. The ion transport mechanism is discussed from the tanδ spectra. The ion transport parameters at ambient temperature are found to be 9 × 10-8 cm2/s, 0.8 × 1017 cm-3, and 3 × 10-6 cm2/Vs for D, n, andμ respectively. All these parameters have shown increasing as temperature increased. The electric modulus parameters are studied in an attempt to understand the relaxation dynamics and to clarify the relaxation process and ion dynamics relationship.
Two different ionic liquid-based biopolymer electrolyte systems were prepared using a solution casting technique. Corn starch and lithium hexafluorophosphate (LiPF₆) were employed as polymer and salt, respectively. Additionally, two different counteranions of ionic liquids, viz. 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF₆) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (also known as 1-butyl-3-methylimidazolium triflate) (BmImTf) were used and studied in this present work. The maximum ionic conductivities of (1.47 ± 0.02) × 10(-4) and (3.21 ± 0.01) × 10(-4) S∙cm(-1) were achieved with adulteration of 50 wt% of BmImPF₆ and 80 wt% of BmImTf, respectively at ambient temperature. Activated carbon-based electrodes were prepared and used in supercapacitor fabrication. Supercapacitors were then assembled using the most conducting polymer electrolyte from each system. The electrochemical properties of the supercapacitors were then analyzed. The supercapacitor containing the triflate-based biopolymer electrolyte depicted a higher specific capacitance with a wider electrochemical stability window compared to that of the hexafluorophosphate system.
Chemical modification of natural rubber (NR) has frequently been attempted to improve the performance in specific application. 30% poly(methyl metacrylate) (PMMA) grafted into NR (MG30) has been explored as a potential candidate for polymer electrolytes. The complexation effect of salt and plasticizer in polymer host electrolytes had been investigated using FTIR. The carbonyl stretch of MG30 locates at 1729 cm-1, with the addition of lithium trimethanesulfonate (LiCF3SO3) salt, new band evolves at lower frequency region at 1643-1645 cm-1. The nondegenerate vibrational mode of nus(SO3) of salted electrolytes appearing at 1031-1034 cm-1 comes from 'free' trimethanesulfonate anions and the 1040-1046 cm-1 absorption from the monodentate ion paired with triflates. These indicate MG30-salt interaction. When MG30 and ethylene carbonate (EC) formed film, the CH3 asymmetric bend of MG30 appearing at 1447cm-1 is shifted to 1449 cm-1 in the EC-polymer complex. The CO stretching at 1729 cm-1 also shifted to 1728 cm-1. Hence, the EC-MG30 system is complexed to each other. EC-LiCF3SO3 interactions are indicated by the shifting of CO bending band of EC from 718 cm-1 being shifted to 720 cm-1 in the complex. In Li+-EC interaction where the ring breathing region at 897 cm-1 in EC has shifted to 899 cm-1 in EC-salt spectrum. The band appearing at 1643-1645 cm-1 due to the coordination of Li+
Solid polymer electrolytes electrolytes based Poly
(ethylene oxide) (PEO) complexed with sodium
trifluoromethanesulfonate (NaCF3SO3
) salt were prepared by
using solution cast technique. Ion-polymer ionic conductivity
and interaction studies have been reported by Electrical
Impedance spectroscopy (EIS) and Fourier transform infrared
spectroscopy (FTIR). FTIR studies suggested that there are
stronger interaction between Na+
ions and the polymer than
interaction of anions cations of the salt. The temperature
dependance electrical conductivity of polymer electrolytes films
follow Arrhenius relation and the low activation energy 0.2993
eV was observed for PEO-18 wt. % NaCF3SO3 below 323 K.
Polybutylene succinate (PBS)/rice starch (RS) blends were prepared via the hot-melt extrusion technique through the usage of a twin-screw extruder without and containing ionic liquid-based surfactants (ILbS). Two types of ILbS were used, specifically, 1-dodecyl-3-methylimidazolium trifluoromethanesulfonate, [C12mim][OTf] and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C12mim][NTf2] were mixed into the PBS/RS blends at the different contents (0-8 wt.%). The tensile and flexural results showed that the blends containing ILbS have a high tensile extension and tensile energy compared to the blend without ILbS. The blends containing ILbS also have a high flexural extension compared with the blend without ILbS. The blends containing [C12mim][NTf2] have a significant improvement in the tensile energy (up to 239%) and flexural extension (up to 17%) in comparison with the blends containing [C12mim][OTf]. The FTIR spectra demonstrated that the presence of ILbS in the blends generated the intermolecular interactions (ion-dipole force and hydrophobic-hydrophobic interaction) between PBS and RS. The DSC results exhibited that the melting points of the prepared blends are decreased with the addition of ILbS. However, the TGA results showed that the thermal decomposition of the blends containing ILbS are higher than the blend without ILbS. The values of decomposition temperature were 387.4 °C, 381.8 °C, and 378.6 °C of PBS/RS-[C12mim][NTf2], PBS/RS-[C12mim][OTf], and PBS/RS, respectively. In conclusion, the ILbS could significantly improve the physicochemical properties of the PBS/RS blends by acting as a compatibilizer.
The global emergence and dissemination of multidrug-resistant Gram-negative superbugs, particularly carbapenem-resistant Acinetobacter baumannii and Klebsiella pneumoniae, lead to the limited effectiveness of antibiotics for treating nosocomial infections. In most cases, polymyxins are the last resort therapy, and these antibiotics must be used intelligently to prolong their efficacy in clinical practice. Polymyxin B and colistin (polymyxin E) were introduced prior to modern drug regulation, and the majority of the 'old' drug information is unreliable. Recent pharmacokinetic data do not support the renal dose adjustment of intravenous (IV) polymyxin B as suggested by the manufacturer, and this drug must be scaled by the total body weight. Whereas IV colistin is formulated as an inactive prodrug, colistin methanesulfonate (CMS) has different pharmacokinetic profiles than polymyxin B. To achieve maximum efficacy, CMS should be administered as a loading dose scaled to body weight and a maintenance dose according to the renal profiles. Polymyxin combination therapy is suggested due to a sub-therapeutic plasma concentration in a significant proportion of patients and a high incidence of polymyxin hetero-resistance among Gram-negative superbugs. In conclusion, polymyxins must be reserved as a last resort and should be wisely used when truly indicated.