Unlocking the anion effect on steerable production of 5-hydroxymethylfurfural.

Homogeneous metal salt catalysts play a pivotal role in industrial production of 5-hydroxymethylfurfural (HMF). Herein, we first proposed the anion effect on steerable production of HMF using metal salts with different anions as catalyst in a biphasic system of tetrahydrofuran (THF)/NaCl aqueous solution (NaCl aq). Notably, the anions affected the catalytic activity of the metal salts, leading to an order of magnitude difference in the HMF yields, i.e., AlBr3（74.0 mol%）> AlCl3 (60.8 mol%) > Al2(SO4)3 (35.2 mol%) > Al(NO3)3 (14.9 mol%). The anion effect on steerable production of HMF could be attributed to the proximity effect and electron tension. Anions form close-range interactions with glucose molecules by proximity effect to promote electron transfer, facilitating the isomerization of glucose to fructose. Besides, anions induce a reduction of the electron cloud density of glucose carbon atoms, generating electron tension that rapidly transforms glucose from the ground state to the transition state, thereby increasing the HMF yield. Based on the revelation of anions effect and evaluation of techno-economic process, we expect to provides theoretical guidance for high-throughput screening of metal salt catalysts in industrial biorefinery.

Effect of Halide Anions on Electrochemical CO2 Reduction in Non-Aqueous Choline Solutions using Ag and Au Electrodes.

In this study, the effect of halide anions on the selectivity of the CO2 reduction reaction to CO was investigated in choline-based ethylene glycol solutions containing different halides (ChCl : EG, ChBr : EG, ChI : EG). The CO2RR was studied using silver (Ag) and gold (Au) electrodes in a compact H-cell. Our findings reveal that chloride effectively suppresses the hydrogen evolution reaction and enhances the selectivity of carbon monoxide production on both Ag and Au electrodes, with relatively high selectivity values of 84 % and 62 %, respectively. Additionally, the effect of varying ethylene glycol content in the choline chloride-containing electrolyte (ChCl : EG 1 : X, X=2, 3, 4) was investigated to improve the current density during CO2RR on the Ag electrode. We observed that a mole ratio of 1 : 4 exhibited the highest current density with a comparable faradaic efficiency toward CO. Notably, an evident surface reconstruction process took place on the Ag surface in the presence of Cl- ions, whereas on Au, this phenomenon was less pronounced. Overall, this study provides new insights into anion-induced surface restructuring of Ag and Au electrodes during CO2RR, and its consequences on the reduction performance on such surfaces in non-aqueous electrolytes.

A combined experimental-molecular modeling study of crown ether europium complexes: Effects of the coordinated anion on structural and luminescence properties.

It is reported the synthesis, characterization by elemental analysis, thermogravimetry; electronic absorption, infrared, excitation, and emission spectroscopies of the [Eu(12C4)(phen)2(X)n]X2 complexes, where 12C4 = 12-crown-4, phen = 1,10-phenanthroline, and X  = F-, Cl-, Br-, SCN-, ClO4-, and NO3-. It is verified that the polarizability of the anion X- exerts remarkable effects on the emission process. As a general trend, lower wavenumbers for the 7F0→5L6, 7F0→5D2 and 7F0→5D1 transitions are associated with the anions with higher volumes and, consequently, higher polarizability. The molecular modeling results performed with quantum methods (RHF and DFT) suggest some relationships between the calculated structures, electronic, and luminescence properties with the presence of the LMCT (ligand-to-metal charge transfer) states, which explains the differences in the emission spectra of these complexes due to the coordinated anion.

Unexpectedly Enhanced Organics Removal in Persulfate Oxidation with High Concentration of Sulfate: The Origin and the Selectivity.

Massive anions in high saline wastewater are primary factors that restricted the efficiency of pollutant degradation in advanced oxidation processes (AOPs). Herein, we reported the influence laws of different anions at high concentration on the electron-transfer process in the activation of persulfate, and especially, the sulfate anion exhibited the excellent promotion effect. Depending on the ionic charge, polarizability, and size, the anions exerted diverse effects on the dispersed phase and zeta potential of carbonaceous catalysts, which further embodied in the removal of pollutants. Based on the differences of reaction rate constant in water solution and high saline solution, the order was ClO4- < NO3- < Cl- < SO42- < CO32-, obeying the Hofmeister series. The enhancement of the sulfate anion was widely confirmed with different carbonaceous catalysts and pollutants with various structures. It could be attributed to the higher oxidation capacity, the faster interfacial electron transfer, and the better catalyst dispersion in the high sulfate environment. On the other hand, the decrease of zeta potential of the catalyst induced by sulfate reinforced the electrostatic attraction or repulsion with pollutants, which caused the selectivity of the sulfate promotion effect. Overall, this study provides new insights into the mechanism of influence of anions on AOPs, which refreshed the cognition of the role of sulfate on pollutant degradation, and helps guide the treatment design of high salinity wastewater.

Selective Chirality Transfer to the Bis(trifluoromethylsulfonyl)imide Anion of an Ionic Liquid.

Chirality transfer from the chiral molecule (R)-1,2-propylene oxide to the achiral anion of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid is observed. The chiral probe selectively affects one part of the binary ionic liquid, i. e., it has previously been shown experimentally and theoretically that this particular imidazolium cation can be affected by chirality transfer, but in the present system chirality is almost exclusively transferred to the anion and not to both parts of the solvent (anion and cation). This observation is of high relevance because of its selectivity and because anion effects are usually much more important in ionic liquid research than cation effects. From ab initio molecular dynamics simulations, a conformational analysis and dissected vibrational circular dichroism spectra are obtained to study the chirality transfer. While in the neat ionic liquid two mirror imaged trans conformers of the anion occur almost equally, we observe an excess of one of these conformers in the presence of the chiral solute, causing optical activity of the anion. Although the cis conformers are not tremendously affected by the chirality transfer, they gain in total population when (R)-1,2-propylene oxide is dissolved in the ionic liquid.

Molecular logic of salt taste reception in special reference to transmembrane channel-like 4 (TMC4).

The taste is biologically of intrinsic importance. It almost momentarily perceives environmental stimuli for better survival. In the early 2000s, research into taste reception was greatly developed with discovery of the receptors. However, the mechanism of salt taste reception is not fully elucidated yet and many questions still remain. At present, next-generation sequencing and genome-editing technologies are available which would become pivotal tools to elucidate the remaining issues. Here we review current mechanisms of salt taste reception in particular and characterize the properties of transmembrane channel-like 4 as a novel salt taste-related molecule that we found using these sophisticated tools.

Structural Diversity of Mercury(II) Halide Complexes Containing Bis-pyridyl-bis-amide with Bulky and Angular Backbones: Ligand Effect and Metal Sensing.

Hg(II) halide complexes [HgCl2] 2L1 [L1 = N,N'-bis(3-pyridyl)bicyclo(2,2,2,)oct-7-ene-2,3,5,6-tetracarboxylic diamide), 1, [HgBr2(L1)]n, 2, [HgI2(L1)], 3, [Hg2X4(L2)2] [X = Cl, 4, Br, 5, and I, 6; L2 = N,N'-bis(4-pyridylmethyl)bicyclo(2,2,2,)oct-7-ene-2,3,5,6-tetracarboxylic diamide] and {[HgX2(L3)]⋅H2O}n [X = Cl, 7, Br, 8 and I, 9; L3 = 4,4'-oxybis(N-(pyridine-3-yl)benzamide)] are reported and structurally characterized using single-crystal X-ray diffraction analyses. The linear HgCl2 units of complex 1 are interlinked by the L1 ligands through Hg---N and Hg---O interactions, resulting in 1D supramolecular chains. Complex 2 shows 1D zigzag chains interlinked through the Br---Br interactions to form 1D looped supramolecular chains, while the mononuclear [HgI2L2] molecules of 3 are interlinked through Hg---O and I---I interactions, forming 2D supramolecular layers. Complexes 4-6 are isomorphous dinuclear metallocycles, and 7-9 form isomorphous 1D zigzag chains. The roles of the ligand type and the halide anion in determining the structural diversity of 1-9 is discussed and the luminescent properties of 7-9 evaluated. Complexes 7-9 manifest stability in aqueous environments. Moreover, complexes 7 and 8 show good sensing towards Fe3+ ions with low detection limits and good reusability up to five cycles, revealing that the Hg-X---Fe3+ (X = Cl and Br) interaction may have an important role in determining the quenching effect of 7 and 8.

Gutmann's Donor and Acceptor Numbers for Ionic Liquids and Deep Eutectic Solvents.

An experimental and computational methodology for the analysis of the Lewis acid/base responses of ionic liquids (ILs) and deep eutectic solvents (DES) is proposed. It is based on the donor and acceptor of the electronic charge ability of Lewis acid and bases concepts (donicity and acceptor numbers, DN and AN, respectively) proposed by Viktor Gutmann. The binding enthalpy between the IL/DES with the probe antimony pentachloride (SbCl5) in dichloroethane displays good correlations with experimental data. This approach could serve as a first approximation to predict the responses to H-bonding abilities of new IL or DES. Although useful, the problems encountered to model the electron AN of these solvents limit the usefulness of the approach to completely describe their polarity properties. The experimental data were recorded using UV-Vis spectroscopy for a wide range of ILs and a couple of DES. Two reactions were used as benchmarks to test the reliability of the DN model to discuss the reactivity of real systems in these neoteric solvents.

Electrochemical Reduction of CO2 to HCOOH over Copper Catalysts.

Although great progress has been made in the field of electrochemical CO2 reduction reaction (eCO2RR), inducing product selectivity is still difficult. We herein report that a thiocyanate ion (SCN-) switched the product selectivity of copper catalysts for eCO2RR in an H-cell. A cuprous thiocyanate-derived Cu catalyst was found to exhibit excellent HCOOH selectivity (faradaic efficiency = 70-88%) over a wide potential range (-0.66 to -0.95 V vs RHE). Furthermore, it was revealed that the formation of CO and C2H4 over commercial copper electrodes could be dramatically suppressed with the presence of SCN-, switching to HCOOH. Density functional theory calculations disclosed that SCN- made the formation of HCOO* easier than COOH* on Cu (211), facilitating the HCOOH generation. Our results provide a new insight into eCO2RR and will be helpful in the development of cheap electrocatalysts for specific utilization.

The anion of choline-based ionic liquids tailored interactions between ionic liquids and bovine serum albumin, MCF-7 cells, and bacteria.

Choline-based ionic liquids (ILs) have been widely applied because of their good biocompatibility. Herein, the toxicity of choline-based ILs containing different anions was studied by UV-vis absorption spectra, fluorescence spectra, MTT assays and antibacterial experiments. The results explained that choline chloride ([Ch][Cl]) had no obvious effect on the conformation of bovine serum albumin (BSA), while the conformation could be slightly changed by choline bromide ([Ch][Br]). In the presence of choline iodide ([Ch][I]), choline bitartrate ([Ch][Bit]) and choline dihydrogen citrate ([Ch][Dhc]), the conformation of BSA changed significantly. The quenching mechanisms of [Ch][Bit] and [Ch][Dhc] were static quenching procedure, while there were charge transfer quenching and static quenching for [Ch][I]. ILs combined with BSA in spontaneous manner driven by hydrogen bond and van der Waals force, which was proved by thermodynamic constants and molecular docking. The toxicity of the five ILs to mammalian cells and bacteria came to a similar conclusion. [Ch][Cl] had little toxicity to cells, which was less than [Ch][Br] and [Ch][I]. [Ch][Bit] and [Ch][Dhc] were more toxic. These results provide more information to understand the effect of anions on choline-based ILs, in order to find low toxic choline-based ILs that can be used in biological and pharmaceutical fields.

Anion-Dominated Copper Salicyaldimine Complexes-Structures, Coordination Mode of Nitrate and Decolorization Properties toward Acid Orange 7 Dye.

A salicyaldimine ligand, 3-tert-butyl-4-hydroxy-5-(((pyridin-2-ylmethyl)imino)methyl)benzoic acid (H2Lsalpyca) and two Cu(II)-salicylaldimine complexes, [Cu(HLsalpyca)Cl] (1) and [Cu(HLsalpyca)(NO3)]n (2), have been synthesized. Complex 1 has a discrete mononuclear structure, in which the Cu(II) center is in a distorted square-planar geometry made up of one HLsalpyca- monoanion in an NNO tris-chelating mode and one Cl- anion. Complex 2 adopts a neutral one-dimensional zigzag chain structure propagating along the crystallographic [010] direction, where the Cu(II) center suits a distorted square pyramidal geometry with a τ value of 0.134, consisted of one HLsalpyca- monoanion as an NNO tris-chelator and two NO3- anions. When the Cu∙∙∙O semi coordination is taken into consideration, the nitrato ligand bridges two Cu(II) centers in an unsymmetrical bridging-tridentate with a µ, κ4O,O':O',O″ coordination. Clearly, anion herein plays a critical role in dominating the formation of discrete and polymeric structures of copper salicyaldimine complexes. Noteworthy, complex 2 is insoluble but highly stable in H2O and various organic solvents (CH3OH, CH3CN, acetone, CH2Cl2 and THF). Moreover, complex 2 shows good photocatalytic degradation activity and recyclability to accelerate the decolorization rate and enhance the decolorization performance of acid orange 7 (AO7) dye by hydrogen peroxide (H2O2) under daylight.

A High-Power Aqueous Zinc-Organic Radical Battery with Tunable Operating Voltage Triggered by Selected Anions.

In contrast to traditional rechargeable rock-chair metal-ion batteries, dual-ion batteries (DIBs) involve redox reactions with anions rather than cations in p-type cathodes. In principle, regulating the electrochemical performance of the DIB by different anion species is highly feasible. Herein, the anion effect on the electrochemical performance of a DIB, the aqueous Zn- organic radical battery (Zn-ORB), consisting of a poly(2,2,6,6tetramethylpiperidinyloxy-4-yl vinyl ether) cathode and a Zn anode, was investigated by DFT calculations. SO4 2- , CF3 SO3 - , and ClO4 - with different molecular electrostatic potential values were selected as anion models. DFT calculations revealed that a stronger electrostatic interaction of the anion with the organic radical resulted in a higher operating voltage of the Zn-ORB, which was consistent with experimental results. These results bring new insight into the redox chemistry of p-type organic radicals with anions and will promote the development of high-power aqueous Zn-ORBs as well as inspire more investigations into the anion effect towards novel battery designs.

Synthesis of silver nanoparticles colloids in imidazolium halide ionic liquids and their antibacterial activities for gram-positive and gram-negative bacteria.

Four 1-butyl-3-methylimidazolium halide ionic liquids were synthesized via metathesis and anion exchange reactions. Silver nanoparticles (AgNPs) colloids were synthesized in four ionic liquids in the pressurized reactor by reduction of silver nitrate with hydrogen gas, without adding solvents or stabilizing agents. Antibacterial activities of base ionic liquids and AgNPs colloids in ionic liquids were reviewed by well-diffusion method for gram-positive Bacillus cereus (NCIM-2155) and gram-negative Escherichia coli (NCIM-2931) bacteria. Antibacterial activities of ionic liquids and AgNPs colloids in ionic liquids were observed to be controlled by ionic liquids anions and AgNPs particle size. The 1-butyl-3-methylimidazolium iodide ionic liquid exhibited higher antibacterial activities among the studied ionic liquids. Further, the presence of AgNPs in 1-butyl-3-methylimidazolium iodide, ionic liquid enhanced its antibacterial activity for Bacillus cereus and Escherichia coli bacteria.

Activation of peroxymonosulfate by BiOCl@Fe3O4 catalyst for the degradation of atenolol: Kinetics, parameters, products and mechanism.

BiOCl@Fe3O4 photocatalyst was synthesized to activate peroxymonosulfate (PMS) for atenolol (ATL) degradation under simulated sunlight irradiation in present study. XRD, SEM, adsorbability and pore size distribution of BiOCl@Fe3O4 were analyzed. Magnetic BiOCl performed high activity in PMS activation and could be easily solid-liquid separation by applying an external magnetic field. Many parameters were inspected, including scavengers, PMS concentration, catalyst dosage, pH, anions (Cl- and CO3-). h+, SO4-, HO, O2-, SO5- were involved in ATL degradation in BiOCl@Fe3O4/PMS/sunlight system. The second-order rate constant of the reaction between ATL and SO4- (kATL, SO4-) was estimated via laser flash photolysis experiments. Moreover, ATL mineralization was followed by TOC analyzer. Twelve possible intermediate products were identified through LC-QTOF-MS analysis, and six ATL degradation pathways were concluded. This type of magnetic photocatalyst is characterized by ease of separation, high activation and good reusability. It may have application potential in refractory organic pollutants degradation.

Activation of Electrophile/Nucleophile Pair by a Nucleophilic and Electrophilic Solvation in a SNAr Reaction.

Nucleophilic aromatic substitution reactions of 4-chloroquinazoline toward aniline and hydrazine were used as a model system to experimentally show that a substrate bearing heteroatoms on the aromatic ring as substituent is able to establish intramolecular hydrogen bond which may be activated by the reaction media and/or the nature of the nucleophile.

Formation of aluminum diphosphonate mesostructures: The effect of aluminum source.

Mesostructured aluminum phosphonates (AOP-x) bridging with 1,1'-hydroxyl ethylidene groups, including a lamellar mesostructure (AOP-N) with crystalline framework, a well-ordered 2D-hexagonal mesophase (AOP-Cl), and a particle-packed mesostructure (AOP-S), were simply synthesized in the presence of surfactant cetyltrimethylammonium bromide in the ethanol-water system, by choosing Al(NO3)3, AlCl3 and Al2(SO4)3 as the aluminum source, respectively. The crystallinity, morphology, mesophase, and skeletal structure of the as-prepared materials were characterized by XRD, TEM, SEM, 27Al, 31P and 13C MAS NMR, and nitrogen sorption techniques. After calcination under N2 at 350 °C, the calcined AOP-x samples consist of aluminum phosphonate and phosphate, possessing desirable specific surface areas of 116-585 m2/g. The effect of the inorganic counteranions (NO3-, Cl- and SO42-) from the aluminum source on the formation of different AOP-x mesostructures was discussed in terms of their bind strength to the headgroups of the surfactant micelles, suggesting the potential for designed synthesis of non-silica-based mesostructured organic-inorganic hybrid materials.

Polymeric ionic liquid-assembled graphene-immobilized silica composite for selective isolation of human serum albumin from human whole blood.

Polymeric ionic liquids (PILs) with 1-vinyl-3-ethylimidazolium cations and two different anions of Br- and PF6- were assembled onto the surface of graphene (G) nanosheets. The derived two composites, i.e., PIL(Br)-G and PIL(PF6)-G, were further efficiently immobilized onto the surface of silica nanoparticles via self-assembly technique. The obtained two PIL-G/SiO2 nanocomposites exhibited diverse adsorption performances toward proteins through adjusting the anions of PILs. Electrostatic attractions between proteins and the nanocomposites dominated protein adsorption, while the presence of PF6- anions weakened electrostatic interactions and deteriorated the selective adsorption of target protein, i.e., bovine serum albumin (BSA) in this case. Specifically, PIL(Br)-G/SiO2 nanocomposite displayed high selectivity toward BSA and a high adsorption efficiency of ca. 98% was achieved for 100 mg L-1 BSA in a Britton-Robinson (B-R) buffer at pH 5. HPLC analysis demonstrated the selectivity of PIL(Br)-G/SiO2 nanocomposite toward BSA in the presence of abundant hemoglobin and cytochrome c. The practical applicability was verified by performing selective isolation of human serum albumin (HSA) from human whole blood. Graphical abstract Selective isolation of human serum albumin from blood by polymeric ionic liquid assembled graphene immobilized silica nanocomposite with tunable anions.

Fluoride removal by Al, Ti, and Fe hydroxides and coexisting ion effect.

Batch experiments were conducted to evaluate fluoride removal by Al, Fe, and Ti-based coagulants and adsorbents, as well as the effects of coexisting ions and formation of aluminum-fluoride complexes on fluoride removal by co-precipitation with alum (Al2(SO4)3·18H2O). Aluminum sulfate was more efficient than the other coagulants for fluoride removal in the pH range between 6 and 8. Nano-crystalline TiO2 was more effective for fluoride removal than Al and Fe hydroxides in a pH range of 3-5. Coexisting anions in water decreased the removal of fluoride in the order: phosphate (2.5mg/L)>arsenate (0.1mg/L)>bicarbonate (200mg/L)>sulfate (100mg/L)=nitrate (100mg/L)>silicate (10mg/L) at a pH of 6.0. The effect of silicate became more significant at pH>7.0. Calcium and magnesium improved the removal of fluoride. Zeta-potential measurements determined that the adsorption of fluoride shifted the PZC of Al(OH)3 precipitates from 8.9 to 8.4, indicating the chemical adsorption of fluoride at the surface. The presence of fluoride in solution significantly increased the soluble aluminum concentration at pH<6.5. A Visual MINTEQ modeling study indicated that the increased aluminum solubility was caused by the formation of AlF2+, AlF2+, and AlF3 complexes. The AlFx complexes decreased the removal of fluoride during co-precipitation with aluminum sulfate.

Effective removal of contaminants in landfill leachate membrane concentrates by coagulation.

Leachate membrane concentrates containing high concentrations of organics and trace toxic compounds pose a major threat to the environment, and their treatment is an urgent issue. In this work, various coagulants were used to treat leachate membrane concentrates. Appropriate pH values for treatments with FeCl2, FeSO4, polyaluminum chloride, and FeCl3 were 3, 5, 5, and 4, respectively. FeCl3 achieved the highest total organic carbon (TOC) removal efficiency. The effect of the various anions in ferric coagulants [FeCl3, Fe2(SO4)3, and Fe(NO3)3] on the TOC removal efficiency was negligible. The main organics remaining in the leachate membrane concentrates after coagulation were humic and fulvic acids. The conditions for coagulation with FeCl3 were optimized using the response surface method (RSM). The highest TOC, chemical oxygen demand (COD), and chromaticity reduction efficiencies, 81%, 82%, and 97%, respectively, were achieved at pH 4 using FeCl3 (5 g L-1) and polyacrylamide (PAM; 0.07 g L-1). The COD of leachate membrane concentrates was reduced from 4000 to 718 mg L-1. The mole ratio of removed COD and Fe(III) (2.4 mol) at 5 g L-1 FeCl3 (pH 4, PAM 0.07 g L-1) was lower than that (3.8 mol) at 3 g L-1 FeCl3 (pH 4, PAM 0.07 g L-1); based on the cost and COD removal efficiency, the latter conditions were the best choice. Our work provides guidelines for the treatment of leachate membrane concentrates in engineering.

Anion effect controlling the selectivity in the zinc-catalysed copolymerisation of CO2 and cyclohexene oxide.

The choice of the anion has a surprisingly strong effect on the incorporation of CO2 into the polymer obtained during the zinc-catalysed copolymerisation of CO2 and cyclohexene oxide. The product span ranges from polyethercarbonates, where short polyether sequences alternate with carbonate linkages, to polycarbonates with a strictly alternating sequence of the repeating units. Herein, we report on the influence of the coordination ability of the anion on the selectivity and kinetics of the copolymerisation reaction.