An enantioselective study of ß-cyclodextrin and ionic liquid-ß-cyclodextrin towards propranolol enantiomers by molecular dynamic simulations.

In this study, the enantioselectivity of ß-cyclodextrin and its derivatives towards propranolol enantiomers are investigated by molecular dynamic (MD) simulations. ß-cyclodextrin (ß-CD) have previously been shown to be able to recognize propranolol (PRP) enantiomers. To improve upon the enantioselectivity of ß-cyclodextrin, we propose the use of an ionic-liquid-modified-ß-cyclodextrin (ß-CD-IL). ß-CD-IL was found to be able to complex R and S propranolol enantiomers with differing binding energies. The molecular docking study reveals that the ionic liquid chain attached to the ß-CD molecule has significant interaction with propranolol. The formation of the most stable complex occurred between (S)-ß-CD-IL and (S)-propranolol with an energy of -5.80 kcal/mol. This is attributed to the formation of a hydrogen bond between the oxygen of the propranolol and the hydrogen on the primary rim of the (S)-ß-CD-IL cavity. This interaction is not detected in other complexes. The root mean-squared fluctuation (RMSF) value indicates that the NH group is the most flexible molecular fragment, followed by the aromatic group. Also of note, the formation of a complex between pristine ß-CD and (S)-propranolol is the least favorable.

AuNRs attached TiO2 NPs modified by cobalt-imidazolate frameworks as exceptional materials to improve the energy conversion efficiency of dye-sensitized solar cells.

This work reports a significant improvement in both the open-circuit voltage (VOC) and current density (J) of dye-sensitized solar cells (DSSCs) using gold nanorod-modified TiO2 nanoparticles (TiO2/AuNRs) together with a cobalt-imidazolate framework (ZIF-67) as an efficient photoanode. It was demonstrated that adding ZIF-67 (8 wt%) to TiO2 NPs increased the VOC by 160 mV and J by 2.5 times. This observation was described based on the significant increase in the amount of adsorbed dye in the presence of highly porous ZIF-67, which boosts the photoanode's light harvesting. Modifying TiO2 NPs with AuNRs also caused a remarkable enhancement in J (∼ 2.8 times), which can be explained via electron transfer between the TiO2 conduction band and AuNRs. It can result in a more efficient inhibiting effect on the interfacial charge recombination processes in TiO2/AuNRs/ZIF-67 because of the formation of a Schottky barrier at the interface between TiO2 and Au. These effects were confirmed by the reduction in the photoluminescence intensity of TiO2 in the presence of AuNRs. More reduction in the photoluminescence intensity was observed when ZIF-67 was added. The prepared photoanode showed an outstanding improvement in the overall efficiency of the DSSC (η) to 8.38% compared to the bare TiO2-based photoanode (1.83%). The notable improvement in the TiO2/AuNRs/ZIF-67 performance confirmed its practicality for high-efficiency DSSCs.

Rational Design of a Fluorescent Chromophore as a Calcium Receptor via DFT and Multivariate Approaches.

Computational and experimental approaches were adopted to utilize a chromophore diglycolic functionalized fluorescein derivative as a Ca2+ receptor. Fluorescein diglycolic acid (Fl-DGA, 1) was synthesized and used in multivariate determination of Ca2+ and K+. Full-structure computation shows that the complexes of 1 and Ca2+ have comparable energies regardless of additional interaction with lactone moiety. The initial formation of diglycolic-Ca2+ complex followed by macrocyclization is thermodynamically disfavored. A U-shaped pre-organized 1 allows Ca2+ to interact simultaneously with diglycolic and lactone motifs. Both motifs actively participate in Ca2+ recognition and the eleven methylene units in the undecyl arm provides excellent flexibility for reorganization and optimum interaction. Principal component analysis (PCA) of computational molecular properties reveals a simple method in evaluating motifs for cation recognition. Fragment models support full-structure results that negative charge causes significant structural changes, but do not reproduce the full extent of C-O bond breaking observed in the latter. Experimental optical responses show that 1 is selective towards Ca2+ and discriminates against K+ and Mg2+. PCA of emission intensities affords distinct clusters of 0.01, 0.1 and 1 mM Ca2+ and K+, and suggests applicability of this technique for simultaneous determination of cationic plant macronutrients in precision agriculture and a wide variety of other applications.

Synthesis of new Zn-decorated metal-organic frameworks for enhanced removal of carcinogenic textile dye: equilibrium and kinetic modeling studies.

This paper describes the synthesis and characterization of Zn2+ decorated (adipic and terephthalic acid as linkers) piperazine-based metal-organic framework (P-MOFs) and their extraction behavior toward the Chicago sky blue (CSB) dye. The formation of Zn2+-decorated P-MOFs was confirmed by FT-IR spectroscopy, energy-dispersive spectroscopy, X-ray diffraction, BET surface area analysis and TGA. Adsorption behavior of the synthesized P-MOFs was explored through solid-phase adsorption (batch method) prior to UV-Vis spectrophotometric determination. Adsorption parameters, including adsorbent dosage, pH of solution, dye concentration, and time, were optimized. Excellent percentage removal of 94% and 95% for AP-Zn-MOF and TP-Zn-MOF, respectively, was achieved at pH 7.5. Kinetics studies indicated that the synthesized adsorbents AP-Zn-MOF and TP-Zn-MOF followed the pseudo-second-order rate model with R2 value 0.9989. The Freundlich isotherm with high R2 value as compared to Langmuir isotherm indicated that CSB adsorption for the synthesized MOFs follows multilayer adsorption.

Palm Fatty Acid Functionalized Fe3O4 Nanoparticles as Highly Selective Oil Adsorption Material.

The present work highlights the facile synthesis of hydrophobic palm fatty acid functionalized Fe3O4 nanoparticles (MNP-FA) for the efficient removal of oils from the surface of water. An intense hydrophobic layer was introduced on the surface of Fe3O4 nanoparticles functionalized by the palm fatty acid obtained from the hydrolysis of palm olein. Scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), Energy dispersive X-ray spectroscopy (EDX) and water contact angle analysis (WCA) measurements were used to characterize the newly fabricated palm fatty acid adorned magnetic Fe3O4 nanoparticles (MNP-FA). The obtained results confirmed the successful synthesis of palm fatty acid-functionalized magnetic nanoparticles. Oil removal tests performed with MNP-FA revealed that this newly prepared material could selectively adsorb lubricating oil up to 3.5 times of the particles' weight while completely repelling water. The main parameters affecting the adsorption of oil i.e., sorption time, mass of sorbent and pH of water were optimized.

Bio-inspired magnetic chitosan/Iron oxide macromolecules for multiple anionic dyes adsorption from aqueous media.

Organic anionic dyes are major water pollutants due to their low degradability caused by complex aromatic structures. Not only do they exert toxic, mutagenic, teratogenic, tumorigenic, and genotoxic effects, but they also decrease fertility and cause irritation to the skin and respiratory system in humans. This long-term toxicity has detrimental effects on aquatic organisms and their surroundings, resulting in an imbalanced ecosystem. In this study, a Cs@Fe3O4 magnetic biosorbent was synthesised to uptake three anionic dyes and characterised for FTIR, BET/BJH, XRD, TGA, VSM, and FESEM analyses. The biosorbent average surface area was confirmed to be 52.6524 m2/g, with average pore sizes of 7.3606 nm and 6.9823 nm for adsorption-desorption processes, respectively. Batch adsorption studies pH values, contact times, temperature, initial dye concentrations, and adsorbent dosages were examined. Several isotherm and kinetic models were studied to determine the adsorption mechanism. The adsorption data of these dyes at equilibrium was observed to match Langmuir's isotherm and pseudo-second-order kinetic models. The thermodynamic study revealed that the adsorption process for these dyes was an exothermic reaction. Maximum adsorption capacities for congo red, methyl orange, and metanil yellow were 117.77 mg/g, 137.77 mg/g, and 155.57 mg/g, respectively. The reusability of recovered Cs@Fe3O4 after dye adsorption was evaluated up to five continuous adsorption-desorption cycles for its possible industrial applications.

The electrochemical behaviour of ferrocene in deep eutectic solvents based on quaternary ammonium and phosphonium salts.

The electrochemical behaviour of ferrocene (Fc) is investigated in six different deep eutectic solvents (DESs) formed by means of hydrogen bonding between selected ammonium and phosphonium salts with glycerol and ethylene glycol. Combinations of cyclic voltammetry and chronoamperometry are employed to characterise the DESs. The reductive and oxidative potential limits are reported versus the Fc/Fc(+) couple. The diffusion coefficient, D, of ferrocene in all studied DESs is found to lie between 8.49 × 10(-10) and 4.22 × 10(-8) cm(2) s(-1) (these do not change significantly with concentration). The standard rate constant for heterogeneous electron transfer across the electrode/DES interface is determined to be between 1.68 × 10(-4) and 5.44 × 10(-4) cm s(-1) using cyclic voltammetry. These results are of the same order of magnitude as those reported for other ionic liquids in the literature.

G3 assisted rational design of chemical sensor array using carbonitrile neutral receptors.

Combined computational and experimental strategies for the systematic design of chemical sensor arrays using carbonitrile neutral receptors are presented. Binding energies of acetonitrile, n-pentylcarbonitrile and malononitrile with Ca(II), Mg(II), Be(II) and H⁺ have been investigated with the B3LYP, G3, CBS-QB3, G4 and MQZVP methods, showing a general trend H⁺ > Be(II) > Mg(II) > Ca(II). Hydrogen bonding, donor-acceptor and cation-lone pair electron simple models were employed in evaluating the performance of computational methods. Mg(II) is bound to acetonitrile in water by 12.5 kcal/mol, and in the gas phase the receptor is more strongly bound by 33.3 kcal/mol to Mg(II) compared to Ca(II). Interaction of bound cations with carbonitrile reduces the energies of the MOs involved in the proposed σ-p conjugated network. The planar malononitrile-Be(II) complex possibly involves a π-network with a cationic methylene carbon. Fabricated potentiometric chemical sensors show distinct signal patterns that can be exploited in sensor array applications.

Magnetite carboxymethylcellulose as biological macromolecule-based absorbent for cationic dyes removal from environmental samples.

In this study, magnetite carboxymethylcellulose (CMC@Fe3O4) composite as magnetic biological molecules were synthetized for the use as adsorbent to remove four types of cationic dyes, namely Methylene Blue, Rhodamine B, Malachite Green, and Methyl Violet from aqueous solution. The characteristic of the adsorbent was achieved by Fourier Transform Infrared Spectroscopy, Field Emission Scanning Electron Microscope (FESEM), X-ray Diffraction, Vibrating Sample Magnetometer and Thermal Gravimetric Analysis techniques. Besides, essential influencing parameters of dye adsorption; the solution pH, solution temperature, contact time, adsorbent concentration and initial dye dosage were studied. FESEM analysis showed the magnetic Fe3O4-TB, Fe3O4@SiO2, Fe3O4@SiO2-NH2 and CMC@Fe3O4 composites were in spherical shape, with average size of 43.0 nm, 92.5 nm, 134.0 nm and 207.5 nm, respectively. On the saturation magnetization (Ms), the results obtained were 55.931 emu/g, 34.557 emu/g, 33.236 emu/g and 11.884 emu/g. From the sorption modelling of Isotherms, Kinetics, and Thermodynamics, the adsorption capacity of dyes is (MB = 103.33 mg/g), (RB = 109.60 mg/g), (MG = 100.08 mg/g) and (MV = 107.78 mg/g). With all the adsorption processes exhibited as exothermic reactions. The regeneration and reusability of the synthetized biological molecules-based adsorbent was also assessed.

Non-Enzymatic Glucose Sensors Involving Copper: An Electrochemical Perspective.

Non-enzymatic glucose sensors based on the use of copper and its oxides have emerged as promising candidates to replace enzymatic glucose sensors owing to their stability, ease of fabrication, and superior sensitivity. This review explains the theories of the mechanism of glucose oxidation on copper transition metal electrodes. It also presents an overview on the development of among the best non-enzymatic copper-based glucose sensors in the past 10 years. A brief description of methods, interesting findings, and important performance parameters are provided to inspire the reader and researcher to create new improvements in sensor design. Finally, several important considerations that pertain to the nano-structuring of the electrode surface is provided.

Free Fatty Acid from Waste Palm Oil Functionalized Magnetic Nanoparticles Immobilized on Surface Graphene Oxide as a New Adsorbent for Simultaneously Detecting Hazardous Polycyclic Aromatic Hydrocarbons and Phthalate Esters in Food Extracts.

A newly synthesized free fatty acids from waste palm oil functionalized magnetic nanoparticles immobilized on the surface of graphene oxide (FFA@MNP-GO) was successfully synthesized and characterized in this research. The combinations of long alkyl chain of free fatty acid with graphene oxide that consists of large delocalized 77-electron systems and abundant of hydrophilic groups with hydroxyl, epoxide and carboxylic groups offer the determination of simultaneous wide range of polarities of organic pollutants in real matrices through hydrogen bonding, hydrophobic and 77-77 interactions. The fabricated adsorbent was successfully applied as a magnetic solid phase extraction (MSPE) adsorbent for the simultaneous separation of selected phthalate esters (PAEs) and polycyclic aromatic hydrocarbons (PAHs) in apple and cabbage extracts prior to their high performance liquid chromatography with diode-array detector (HPLC-DAD) determination. Factors affecting the extraction efficiency such as amount of adsorbent, desorption solvent, volume of desorption solvent, extraction time, desorption time, pH and sample volume were investigated and optimized. The results revealed that under optimal conditions, the detection limit of selected PAEs and PAHs were in the range of 0.56-0.97 ng mL-1 and 0.02-0.93 ng mL-1, respectively. The spiked recoveries of real apple and cabbage extracts for PAEs and PAHs were in the range of 81.5-117.6% with good relative standard deviation (RSD) (n = 5) less than 10% and 86.7-118.2% with acceptable RSDs (n = 5) ranging from 1.5 to 11.0%, respectively. This study reported for the first time the use of MSPE procedure for simultaneous determination of chosen PAHs and PAEs in real samples including apple and cabbage extracts by using new adsorbent, FFA@MNP-GO.

Polyaniline-dicationic ionic liquid coated with magnetic nanoparticles composite for magnetic solid phase extraction of polycyclic aromatic hydrocarbons in environmental samples.

In this present study, magnetic nanoparticles (MNPs) nanocomposites modified with polyaniline (PANI) coated newly synthesised dicationic ionic liquid (DICAT) forming MNP-PANI-DICAT were successfully synthesised as new generation material for magnetic solid phase extraction (MSPE). MNP-PANI-DICAT was characterised by FT-IR NMR, CHN, BET, SEM, TEM, and VSM techniques and the results were compared with MNP-PANI and native MNP. This new material was applied as a magnetic adsorbent for the pre-concentration and separation of polycyclic aromatic hydrocarbons (PAHs) due to the π-π interaction between polyaniline shell and dicationic ionic liquid (DICAT) with PAHs compounds. Under the optimal conditions, the proposed method was evaluated and applied for the analysis of PAHs in environmental samples using gas chromatography-mass spectrometry (GC-MS). The validation method showed good linearity (0.005-500µgL-1) with the coefficient of determination (R2) > 0.999. The limits of detection (LOD) and quantification (LOQ) of the developed method (MNP-PANI-DICAT-MSPE) were in the range of 0.0008-0.2086µgL-1 and 0.0024-0.6320µgL-1, respectively. The enrichment factor (EF) of PAHs on MNP-PANI-DICAT-MSPE were in the range of 7.546-29.632. The extraction recoveries of natural water, sludge, and soil samples were ranged from 80.2% to 111.9% with relative standard deviation (RSD) less than 5.6%. The newly synthesised MNP-PANI-DICAT possess good sensitivity, reusability, and fast extraction of PAHs under the MSPE procedure in various environmental samples.

Polyaniline modified magnetic nanoparticles coated with dicationic ionic liquid for effective removal of rhodamine B (RB) from aqueous solution.

Polyaniline (PANI) modified magnetic nanoparticle (MNP) nanocomposites coated with newly synthesized dicationic ionic liquid (DICAT) forming MNP-PANI-DICAT were successfully synthesized as a potential material for the removal of Rhodamine B (RB) from water samples. The synthesized material was successfully characterized using a few techniques such as Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), thermo gravimetric analysis (TGA), Brunauer-Emmett-Teller (BET), and transmission electron microscopy (TEM) analysis. Several parameters have been optimized to enhance the efficiency of the removal process. The adsorption kinetics were investigated and the results showed that MNP-PANI-DICAT was best fitted to a pseudo-second order model for the adsorption of RB. As for the isotherm studies, Temkin's model was found to fit well with the adsorption isotherm of RB on MNP-PANI-DICAT. Other than that, thermodynamics results showed negative values of ΔG° for the adsorption of RB, which indicated that the process is thermodynamically feasible, spontaneous and chemically controlled at lower temperature. The negative value of enthalpy ΔH° (-40.41) indicated that the adsorption was an exothermic process. The percentage removal of RB was found to be 94.7% by MNP-PANI-DICAT under optimized conditions.

Novel Palm Fatty Acid Functionalized Magnetite Nanoparticles for Magnetic Solid-Phase Extraction of Trace Polycyclic Aromatic Hydrocarbons from Environmental Samples.

A novel adsorbent, palm fatty acid coated magnetic Fe3O4 nanoparticles (MNP-FA) was successfully synthesized with immobilization of the palm fatty acid onto the surface of MNPs. The successful synthesis of MNP-FA was further confirmed by X-Ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and Energy dispersive X-Ray spectroscopy (EDX) analyses and water contact angle (WCA) measurement. This newly synthesized MNP-FA was applied as magnetic solid phase extraction (MSPE) adsorbent for the enrichment of polycyclic aromatic hydrocarbons (PAHs), namely fluoranthene (FLT), pyrene (Pyr), chrysene (Cry) and benzo(a)pyrene (BaP) from environmental samples prior to High Performance Liquid Chromatography- Diode Array Detector (HPLC-DAD) analysis. The MSPE method was optimized by several parameters such as amount of sorbent, desorption solvent, volume of desorption solvent, extraction time, desorption time, pH and sample volume. Under the optimized conditions, MSPE method provided a low detection limit (LOD) for FLT, Pyr, Cry and BaP in the range of 0.01-0.05 ng mL-1. The PAHs recoveries of the spiked leachate samples ranged from 98.5% to 113.8% with the RSDs (n = 5) ranging from 3.5% to 12.2%, while for the spiked sludge samples, the recoveries ranged from 81.1% to 119.3% with the RSDs (n = 5) ranging from 3.1% to 13.6%. The recyclability study revealed that MNP-FA has excellent reusability up to five times. Chromatrographic analysis demonstrated the suitability of MNP-FA as MSPE adsorbent for the efficient extraction of PAHs from environmental samples.

The Effect of Temperature on Kinetics and Diffusion Coefficients of Metallocene Derivatives in Polyol-Based Deep Eutectic Solvents.

The temperature dependence of the density, dynamic viscosity and ionic conductivity of several deep eutectic solvents (DESs) containing ammonium-based salts and hydrogen bond donvnors (polyol type) are investigated. The temperature-dependent electrolyte viscosity as a function of molar conductivity is correlated by means of Walden's rule. The oxidation of ferrocene (Fc/Fc+) and reduction of cobaltocenium (Cc+/Cc) at different temperatures are studied by cyclic voltammetry and potential-step chronoamperometry in DESs. For most DESs, chronoamperometric transients are demonstrated to fit an Arrhenius-type relation to give activation energies for the diffusion of redox couples at different temperatures. The temperature dependence of the measured conductivities of DES1 and DES2 are better correlated with the Vogel-Tamman-Fulcher equation. The kinetics of the Fc/Fc+ and Cc+/Cc electrochemical systems have been investigated over a temperature range from 298 to 338 K. The heterogeneous electron transfer rate constant is then calculated at different temperatures by means of a logarithmic analysis. The glycerol-based DES (DES5) appears suitable for further testing in electrochemical energy storage devices.

Rational design of carbonitrile-carboxaldehyde cation receptor models: probing the nature of the heteroatom-metal interaction.

In this work, hybrid functional and G4 methods were employed in the rational design of carbonitrile-carboxaldehyde receptor models for cation recognition. Electron-sharing and ionic interactions between the models and the cations were analyzed utilizing the concepts of overlap population, atomic valence, electrostatic potential, and CHELPG charge in order to elucidate the nature of the heteroatom-metal interaction, the N versus O disparity, and the effect of pH. Receptor fragment models from ionomycin were employed to rationalize the selection of receptor models for discriminating group I cations and enhancing the selectivity for Mg(II) rather than Ca(II), and to examine the effects of keto-enol forms and negatively charged sites. The changes in geometries, overlap population, metal valence, and CHELPG charge upon solvation in heptane medium as compared to the gas phase were negligible. The optimized geometries reveal that the interaction between group II cations and the keto, enol, and enolate forms of 2-cyanoethanal causes 12 % bending of the C-C-N angle from linearity. Overlap populations show that the electron-sharing interaction favors group II cations but that the same mechanism allows Li(I) to compete. The total spin of Li(I) is 17 % greater than that of Ca(II), but the G4 binding energies of the two are separated by more than 50 kcal/mol, favoring group II cations, which may eliminate interference from Li(I). 1,2-Dicyanoethylene, which has only one form, shows similar characteristics. CHELPG analysis shows that Mg(II) transfers 25 and 18 % of its positive charge to 2-cyanoethanal enolate and 1,2-dicyanoethylene, respectively. Hydrogen atoms receive most of the positive charge in both receptors, but the N-termini exhibit strikingly different characteristics. Electrostatic potential contour profiles were found to be in good agreement with the atomic charge distributions. The application of uncharged 1,3-dicarbonyl and 2-cyanocarbonyl receptors and a judicious choice of polymeric membrane that suppresses the Hofmeister effect should lead to high selectivity for magnesium, whereas the utilization of multiple negatively charged ionophores should result in selectivity for calcium.