A comparative study of ionothermal treatment of rice straw using triflate and acetate-based ionic liquids

Ionic liquids (ILs) have found applications in the pretreatment of waste lignocellulosic biomass by interacting with the carbohydrate molecules present in the biomass materials. Pretreatment is essential before biomass conversion into valuable chemicals, fuels, and many other value-added products. This comparative study mainly focused on the pretreatment ability of four ILs having acetate or triflate as a common anion with different cations. Among various studied ILs, diazabicyclo[5.4.0]undec-7-ene (DBU)-based acidic ionic liquid when used as a dual solvocatalyst showed significant structural modifications of the rice straw (RS) sample, through C6-O bond breakage assisted by the tertiary nitrogen in DBU cation. Structural modifications due to the pretreatment were confirmed through SEM, PXRD, and FTIR analysis. The elemental analysis confirmed that carbon content in original RS is reduced to 29% and 20% upon ionothermal treatment of RS with IL at 90 °C and 120 °C, respectively. Additionally, TGA indicated that further pyrolysis could be easier with the pretreated rice straw yielding biochar up to 9% thereby reducing wastes. Conversion of RS was found to be 60 % which reduced marginally to 50 % after three cycles of recycling IL. The findings of this work provide the proof of concept that studied ILs with high thermal stability and recyclability should act as a potential solvocatalyst in sustainable pretreatment and other biomass applications.

Quantum-Chemical Search for Keto Tautomers of Azulenols in Vacuo and Aqueous Solution

Keto-enol prototropic conversions for carbonyl compounds and phenols have been extensively studied, and many interesting review articles and even books appeared in the last 50 years. Quite a different situation takes place for derivatives of biologically active azulene, for which only scanty information on this phenomenon can be found in the literature. In this work, quantum-chemical studies have been undertaken for symmetrically and unsymmetrically substituted azulenols (constitutional isomers of naphthols). Stabilities of two enol (OH) rotamers and all possible keto (CH) tautomers have been analyzed in the gas phase {DFT(B3LYP)/6-311+G(d,p)} and also in aqueous solution {PCM(water)//DFT(B3LYP)/6-311+G(d,p)}. Contrary to naphthols, for which the keto forms can be neglected, at least one keto isomer (C1H, C2H, and/or C3H) contributes significantly to the tautomeric mixture of each azulenol to a higher degree in vacuo (non-polar environment) than in water (polar amphoteric solvent). The highest amounts of the CH forms have been found for 2- and 5-hydroxyazulenes, and the smallest ones for 1- and 6-hydroxy derivatives. The keto tautomer(s), together with the enol rotamers, can also participate in deprotonation reaction leading to a common anion and influence its acid-base properties. The strongest acidity in vacuo exhibits 6-hydroxyazulene, and the weakest one displays 1-hydroxyazulene, but all azulenols are stronger acids than phenol and naphthols. Bond length alternation in all DFT-optimized structures has been measured using the harmonic oscillator model of electron delocalization (HOMED) index. Generally, the HOMED values decrease for the keto tautomers, particularly for the ring containing the labile proton. Even for the keto tautomers possessing energetic parameters close to those of the enol isomers, the HOMED indices are low. However, some kind of parallelism exists for the keto forms between their relative energies and HOMEDs estimated for the entire molecules.

A ratiometric electrochemical microsensor for monitoring of chloride ion in vivo

Chloride ion (Cl-), the most common anion in animal brain, has been verified to play vital role in maintaining normal physiological processes. Thus, development of reliable platform to determine Cl-...

Masking Ability of Various Metal Complexing Ligands at 1.0 mM Concentrations on the Potentiometric Determination of Fluoride in Aqueous Samples

Fluoride is a common anion present in natural waters. Among many analytical methods used for the quantification of fluoride in natural waters, potentiometric analysis is one of the most widely used methods because of minimum interferences from other ions commonly present in natural waters. The potentiometric analysis requires the use of ionic strength adjusting buffer abbreviated as TISAB to obtain accurate and reproducible data. In most of the reported literature, higher concentrations of strong metal chelating ligands are used as masking agents generally in the concentration range of 1.0 to 0.01 M. In the present study, effectiveness of the masking agents, phosphate, citrate, CDTA ((1,2-cyclohexylenedinitrilo)tetraacetic acid), EDTA (ethylenediaminetetraacetic acid) HE-EDTA ((hydroxyethyl)ethylenediaminetriacetic acid)), triethanolamine, and tartaric acid at 1.0 mM in TISAB solutions was investigated. The experimental data were compared with a commercially available WTW 140100 TISAB solution as the reference buffer. According to the experimental data, the reference buffer always produced the highest fluoride concentrations and the measured fluoride concentrations were in the range of 0.611 to 1.956 mg/L. Out of all the masking agents investigated, only CDTA performed marginally well and approximately a quarter of the samples produced statistically comparable data to the reference buffer. All the other masking agents produced significantly low concentrations compared to the reference buffer. The most probable reasons for the underestimation of fluoride concentrations could be shorter decomplexing time and lower masking agent concentrations.

Selective removal of silicic acid by a gallic-acid modified resin

To remove silicic acid from aqueous solutions, a novel gallic acid-type resin (GA-type resin) was prepared by a grafting method. The effects of the adsorption capacity, pH and presence of NaCl, NaNO3, Na2SO4, and NaCO3 salts on the silicic acid removal were studied. The GA-type resin adsorbs monosilicic acid, silicate ions, and polymeric silicic acid. The adsorption capacity of 4.64–4.94 mg/g was achieved in a short adsorption time (Qm of 8.99 mg/g) and is 30–40 times larger than that of the OH-type resin. The silicic acid removal efficiency was almost unaffected by the pH and common anions when the common anion and silicic acid contents were similar, proving the GA-type resin exhibits an excellent performance for selective adsorption of silicic acid. The Temkin isotherm model can well describe the adsorption process, which is chemical adsorption, and indicates that the adsorption heat decreases with the increasing adsorption amount. The adsorption mechanism of silicic acid on the GA-type resin involves dehydration condensation reactions of the hydroxyl groups in silicic acid and gallic acid. The GA-type resin can be efficiently regenerated and reused after treatment with an HCl solution.