Polysaccharide Ecocomposite Materials: Materials: Synthesis, Characterization and Application for Removal of Pollutants and Bacteria

A novel, simple and totally recyclable method has been developed for the synthesis of nontoxic, biocompatible and biodegradable composite materials from cellulose and chitosan. In this method, [BMIm+Cl-], an ionic liquid (IL), was used as a solvent to dissolve and synthesize the [CEL+CS] composite materials. Since the IL can be removed from the materials by washing them with water, and recovered from the washed solution, the method is totally recyclable. XRD, FTIR, NIR and SEM were used to characterize the materials and to confirm that CEL and CS were successfully regenerated by the method without any chemical transformation. More importantly, we have successfully demonstrated that [CEL+CS] material can serve as an effective adsorbent for removal of various endocrine disruptors including polychlorophenols and bisphenol A. This is because the composites have combined advantages of their components, namely superior chemical stability and mechanical stability (from CEL) and excellent adsorption capability for pollutants (from CS)

Nontemplated approach to tuning the spectral properties of cyanine-based fluorescent NanoGUMBOS

Template-free controlled aggregation and spectral properties in fluorescent organic nanoparticles (FONs) is highly desirable for various applications. Herein, we report a nontemplated method for controlling the aggregation in near-infrared (NIR) cyanine-based nanoparticles derived from a group of uniform materials based on organic salts (GUMBOS). Cationic heptamethine cyanine dye 1,1′,3,3,3′,3′-hexamethylindotricarbocyanine (HMT) was coupled with five different anions, viz., [NTf2-], [BETI -], [TFPB-], [AOT-], and [TFP4B-], by an ion-exchange method to obtain the respective GUMBOS. The nanoGUMBOS obtained via a reprecipitation method were primarily amorphous and spherical (30-100 nm) as suggested by selected area electron diffraction (SAED) and transmission electron microscopy (TEM). The formation of tunable self-assemblies within the nanoGUMBOS was characterized using absorption and fluorescence spectroscopy in conjunction with molecular dynamics simulations. Counterion-controlled spectral properties observed in the nanoGUMBOS were attributed to variations in J/H ratios with different anions. Association with the [AOT-] anion afforded predominant J aggregation enabling the highest fluorescence intensity, whereas [TFP4B-] disabled the fluorescence due to predominant H aggregation in the nanoparticles. Analyses of the stacking angle of the cations based on molecular dynamic simulation results in [HMT][NTf2], [HMT][BETI], and [HMT][AOT] dispersed in water and a visual analysis of the representative simulation snapshots also imply that the type of aggregation was controlled through the counterion associated with the dye cation. © 2010 American Chemical Society

Perspectives on moving ionic liquid chemistry into the solid phase

Ionic liquid (IL) chemistry has evolved over the past century, such that these organic salts have impacted virtually every area of science and engineering. In the area of chemistry, initial applications of these salts were primarily the domain of chemists or chemical engineers who desired to manipulate the properties of IL solvents for a variety of applications including tuning various chemical processes. Since then, the chemistry of these organic salts has progressed such that changing an important property of a solvent (e.g., melting point or hydrophobicity) often involves simply altering the counterion of the organic salt. It is with this simplicity in mind that we have recently embarked upon the use of such chemistry to manipulate important properties of solid-phase ionic organic materials. To differentiate this chemistry from ionic liquid chemistry, we have coined the acronym GUMBOS (group of uniform materials based on organic salts). In this perspective article, we describe and demonstrate how ionic liquid chemistry can provide distinct and sometimes unique chemistry for solid-phase applications. Solid phase properties which can be manipulated via this chemistry include, but are not limited to, magnetism, melting point, hydrophobicity, fluorescence quantum yields, nanoformulations, material aggregation, viscosity, viscoelasticity, and cytotoxicity. In addition, we discuss a few examples to demonstrate how GUMBOS chemistry, until now, has been beneficial to the general area of materials chemistry and, more broadly, to the field of analytical chemistry. We also project future applications of this technology. © 2014 American Chemical Society

Short-Time Fourier Transform Analysis of Current Charge/Discharge Response of Lithium-Sulfur Batteries

Measurements acquired on batteries in the form of time signals such as voltage-time and capacity-time to assess their cyclability performance can be supplemented by examining their frequency-domain response. This allows one to determine the global characteristics of the signals and the battery, but not the local behavior, which is very important for determining for example battery fading. In this study we examine the short-time Fourier transform for time-frequency deconstruction of galvanostatic charge/discharge signals of lithium-sulfur batteries, taken as an example. The results displayed in terms of spectrograms show how the frequency content of such signals (e.g. charge and voltage time series) evolve with the lifetime of the batteries allowing the detection of critical changes in the response that may lead to fading and eventually default

Mechanism of Ionic Impedance Growth for Palladium-Containing CNT Electrodes in Lithium-Oxygen Battery Electrodes and its Contribution to Battery Failure

The electrochemical oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) and on CNT (carbon nanotube) cathode with a palladium catalyst, palladium-coated CNT (PC-CNT), and palladium-filled CNT (PF-CNT) are assessed in an ether-based electrolyte solution in order to fabricate a lithium-oxygen battery with high specific energy. The electrochemical properties of the CNT cathodes were studied using electrochemical impedance spectroscopy (EIS). Palladium-filled cathodes displayed better performance as compared to the palladium-coated ones due to the shielding of the catalysts. The mechanism of the improvement was associated to the reduction of the rate of resistances growth in the batteries, especially the ionic resistances in the electrolyte and electrodes. The scanning electron microscopy (SEM) and spectroscopy were used to analyze the products of the reaction that were adsorbed on the electrode surface of the battery, which was fabricated using palladium-coated and palladium-filled CNTs as cathodes and an ether-based electrolyte

An Organic Soluble Lipase for Water-Free Synthesis of Biodiesel

Abstract Lipase AK was modified with short alkyl chains to form a highly organic soluble enzyme and was used to catalyze the synthesis of biodiesel from soybean oil in organic media. The effects of several key factors including water content, temperature, and solvent were examined for the solubilized enzyme in comparison with several other commercially available lipases. Whereas native lipases showed no activity in the absence of water, the organic soluble lipase demonstrated reaction rates of up to 33 g-product/g-enzyme h. The biocatalyst remains soluble in the biodiesel product, and therefore, there is no need to be removed because it is expected to be burned along with the diesel in combustion engines. This provides a promising one-pot mix-and-use strategy for biodiesel production

Ratiometric COumarin-NEutral Red (CONER) nanoprobe for detection of hydroxyl radicals

Excessive production of reactive oxygen species can lead to alteration of cellular functions responsible for many diseases including cardiovascular diseases, neurodegenerative diseases, cancer, and aging. Hydroxyl radical is a short-lived radical which is considered very aggressive due to its high reactivity toward biological molecules. In this study, a COumarin-NEutral Red (CONER) nanoprobe was developed for detection of hydroxyl radical based on the ratiometric fluorescence signal between 7-hydroxy coumarin 3-carboxylic acid and neutral red dyes. Biocompatible poly lactide-co-glycolide (PLGA) nanoparticles containing encapsulated neutral red were produced using a coumarin 3-carboxylic acid conjugated poly(sodium N-undecylenyl-Nε-lysinate) (C3C-poly-Nε- SUK) as moiety reactive to hydroxyl radicals. The response of the CONER nanoprobe was dependent on various parameters such as reaction time and nanoparticle concentration. The probe was selective for hydroxyl radicals as compared with other reactive oxygen species including O2•-, H2O2, 1O2, and OCl-. Furthermore, the CONER nanoprobe was used to detect hydroxyl radicals in vitro using viable breast cancer cells exposed to oxidative stress. The results suggest that this nanoprobe represents a promising approach for detection of hydroxyl radicals in biological systems. © 2011 American Chemical Society

Highly efficient extraction of phenols from aqueous solution using magnetic room temperature ionic liquids

Water-insoluble magnetic room temperature ionic liquid (MRTIL), [3C 6PC14][FeCl4], was synthesized from trihexyltetradecylphosphonium chloride and FeCl3·6H 2O. The MRTIL was used for solvent extraction of phenols from aqueous solution. Due to its strong paramagneticity, [3C6PC 14][FeCl4] can respond to an external magnetic field, which was employed to design a novel magnetic extraction technique. Extraction conditions such as extraction time, volume ratio between MRTIL and aqueous phase, and pH were optimized. Phenols with multiple chlorine substituents exhibited higher distribution ratios. Compared with four traditional non-magnetic ionic liquids, the MRTIL exhibited significantly higher extraction efficiency. ©The Electrochemical Society

Composite Gel Polymer Electrolyte for Improved Cyclability in Lithium–Oxygen Batteries

Gel polymer electrolytes (GPE) and composite GPE (cGPE) using one-dimensional glass microfillers have been developed for their use in lithium–oxygen batteries. Using glass microfillers, tetraglyme solvent, UV-curable polymer, and lithium salt at various concentrations, the preparation of cGPE yielded free-standing films. These cGPEs, with 1 wt % of microfillers, demonstrated increased ionic conductivity and lithium transference number over GPEs at various concentrations of lithium salt. Improvements as high as 50% and 28% in lithium transference number were observed for 0.1 and 1.0 mol kg^–1 salt concentrations, respectively. Lithium–oxygen batteries containing cGPE similarly showed superior charge/discharge cycling for 500 mAh g^–1 cycle capacity with as high as 86% and 400% increase in cycles for cGPE with 1.0 and 0.1 mol kg^–1 over GPE. Results using electrochemical impedance spectroscopy, Raman spectroscopy, and scanning electron microscopy revealed that the source of the improvement was the reduction of the rate of lithium carbonates formation on the surface of the cathode. This reduction in formation rate afforded by cGPE-containing batteries was possible due to the reduction of the rate of electrolyte decomposition. The increase in solvated to paired Li⁺ ratio at the cathode, afforded by increased lithium transference number, helped reduce the probability of superoxide radicals reacting with the tetraglyme solvent. This stabilization during cycling helped prolong the cycling life of the batteries