Cationic Species Research Articles

Supported Co3O4 catalyst on modified UiO-66 by Ce4+ for completely catalytic oxidation of toluene

Creating a new low-temperature catalyst in decreasing the emission of volatile organic compounds (VOCs) has great significance under different industrial production situations. In particular, the Zr-UiO-66 is optimized by different amounts of cerium, which not only enhances the physicochemical stability but also increases the number of active sites of CexZryUiO-66. Furthermore, the catalysts with Co3O4 nanoparticles supported on CexZryUiO-66 were successfully prepared via impregnation method. In the process of toluene degradation, the Co/Ce1Zr2-UiO-66 attains a 90% conversion rate at 210 °C with a space velocity of 60000 mL/(g·h) and toluene concentration at 1000×10–6. Meanwhile, the carbon dioxide selectivity reaches 100% at 218 °C. The Co/Ce1Zr2-UiO-66 shows great water resistance (3 vol% H2O). Multiple characterization methods were used to figure out the physicochemical properties of the catalysts. It is found that the addition of an appropriate amount of cerium can enhance stability of UiO-66 and surface lattice oxygen proportion. Additionally, the stronger electron transfer between Ce4+ and Co2+ enables the Co/Ce1Zr2-UiO-66 to possess more active surface oxygen species and Co3+ cationic species in all samples.

Gas-Phase Characterization of Redox-Active Manganese Complexes.

Manganese complexes exhibit a rich redox chemistry, usually accompanied by structural reorganization during the redox processes often followed by ligand dissociation or association. The push-pull ligand 2,6-diguanidylpyridine (dgpy) stabilizes manganese in the oxidation states +II, +III, and + IV in the complexes [Mn(dgpy)2]n+ (n = 2-4) without change in the coordination sphere in the condensed phase [Heinze et al., Inorganic Chemistry, 2022, 61, 14616]. In the condensed phase, the manganese(IV) complex is a very strong oxidant. In the present work, we investigate the stability and redox activity of the MnIV complex and its counterion (PF6-) adducts in the gas phase, using two modified 3D Paul ion trap mass spectrometers. Six different cationic species of the type [Mnx(dgpy)2(PF6)y]n+ (x = II, III, IV, y = 0-3, n = 1-3) could be observed for the three oxidation states MnIV, MnIII, and MnII, of which one observed complex also contains a reduced dgpy ligand. MnII species showed the highest relative stability in collision induced dissociation and UV/vis photo dissociation experiments. The lowest stability is observed in the presence of one or more counterions, which correlates to a lower total charge n+. Gas phase UV/vis spectra show similar features as the condensed phase spectra only differing in relative band intensities. The strongly oxidizing MnIV complex reacts with triethylamine (NEt3) in the gas phase to give MnIII, while MnIII species show little reactivity toward NEt3.

Reflection coefficient of a natural sodium bentonite in aqueous mixed electrolyte solutions: positive and negative anomalous osmosis

A natural sodium bentonite was tested in the laboratory to measure its reflection coefficient, ω, in equilibrium with mixed aqueous solutions of sodium chloride (NaCl) and potassium chloride (KCl), with the aim of assessing the relative contribution of chemico-osmosis and diffusion induced electro-osmosis to the non-hydraulic component of the liquid flux in the presence of two cationic species, which diffuse at different rates in the pore solution. The former chemico-osmotic contribution is only related to the ionic partition effect in the bentonite pores, and causes ω to vary in the 0 to 1 range, whereas the latter electro-osmotic contribution is controlled by the diffusion potential, which spontaneously builds up across the bentonite layer in response to the different aqueous-phase diffusion coefficients of the ionic species. The theoretical interpretation of the obtained test results demonstrated that chemico-osmosis was the major contribution to ω when the testing solutions only comprised KCl. However, significant deviations in the values of ω from those expected for pure chemico-osmosis were observed for mixtures of NaCl and KCl, with both negative ( ω = −1.234) and positive ( ω = 1.040) anomalous values of the reflection coefficient, resulting from the enhanced influence of diffusion induced electro-osmosis.

Synergy of {Co(H2O)6}2+ with a Polyoxometalate Leads to Aqueous Homogeneous Hydrogen Evolution: Experiments and Computations.

In this work, we have described a polyoxometalate (POM)-based inexpensive and easily synthesizable compound [Co(H2O)6]2[{K(H2O)}2V10O28]·2H2O (1), which exhibits electrocatalytic hydrogen evolution in its aqueous solution without its decomposition (or electrodeposition), acting as a rare homogeneous electrocatalyst. Even though the compound [Co(H2O)6]2[{K(H2O)}2V10O28]·2H2O (1) (soluble in water) shows electrocatalytic hydrogen evolution reaction (HER) activity because of the Coulombic attraction, including H-bonding interactions, between the [Co(H2O)6]2+ cationic species and [{K(H2O)}2V10O28]4-anionic species, the individual homogeneous solutions of [V10O28]6- (source: Na6[V10O28]·18H2O) and [Co(H2O)6]2+ (source: CoCl2·6H2O) do not show any electrocatalytic HER activity. We have thus established that the synergy of [V10O28]6- with [Co(H2O)6]2+ in crystal matrix as well as in the aqueous solution of 1 makes the compound 1 a stable and highly active electrocatalyst for homogeneous HER in an aqueous solution. In order to corroborate these homogeneous HER studies, we performed density functional theory (DFT) calculations to show that decavanadate cluster anion [V10O28]6- interacts with hexa-aqua complex cation [Co(H2O)6]2+ via strong H-bonding interactions, leading to a synergy effect that enables the cobalt center of [Co(H2O)6]2+ to be an active site of HER in the present work.

Counterion Effects in [Ru(bpy)3](X)2-Photocatalyzed Energy Transfer Reactions.

Photocatalysis that uses the energy of light to promote chemical transformations by exploiting the reactivity of excited-state molecules is at the heart of a virtuous dynamic within the chemical community. Visible-light metal-based photosensitizers are most prominent in organic synthesis, thanks to their versatile ligand structure tunability allowing to adjust photocatalytic properties toward specific applications. Nevertheless, a large majority of these photocatalysts are cationic species whose counterion effects remain underestimated and overlooked. In this report, we show that modification of the X counterions constitutive of [Ru(bpy)3](X)2 photocatalysts modulates their catalytic activities in intermolecular [2 + 2] cycloaddition reactions operating through triplet-triplet energy transfer (TTEnT). Particularly noteworthy is the dramatic impact observed in low-dielectric constant solvent over the excited-state quenching coefficient, which varies by two orders of magnitude depending on whether X is a large weakly bound (BArF 4 -) or a tightly bound (TsO-) anion. In addition, the counterion identity also greatly affects the photophysical properties of the cationic ruthenium complex, with [Ru(bpy)3](BArF 4)2 exhibiting the shortest 3MLCT excited-state lifetime, highest excited state energy, and highest photostability, enabling remarkably enhanced performance (up to >1000 TON at a low 500 ppm catalyst loading) in TTEnT photocatalysis. These findings supported by density functional theory-based calculations demonstrate that counterions have a critical role in modulating cationic transition metal-based photocatalyst potency, a parameter that should be taken into consideration also when developing energy transfer-triggered processes.

Revisited Synthesis of Trispyrazolylborate Aluminum Halides Suban Kundu, Raju Chambenahalli, Alex P. Andrews and Ajay Venugopal*

Tris(3,5‐dimethylpyrazolyl)borate aluminum dihalides TpMe2AlX2 (X=Cl, Br and I) can be potential precursors for preparing highly electrophilic dications as well as low oxidation state aluminum compounds. However, the coordinative unsaturation in TpMe2AlX2 makes them susceptible to rearrangement to [Tp2Al][AlX4]. In this work, we revisited the synthesis of TpMe2AlX2 by isolating the solvent‐stabilized tris(3,5‐dimethylpyrazolyl)borate aluminum dihalides TpMe2AlX2(L) (X=Cl, Br; L = THF, HPMA). Efforts to isolate TpMe2All2 resulted in the ring opening of THF revealing the mediation of a highly reactive cationic aluminum species. The monocationic, [TpMe2AlCl(THF)2][B{C6H3(CF3)2}4] was prepared from TpMe2AlCl2(THF) via silver salt metathesis. Attempts to prepare the dicationic species [TpMe2Al(THF)3]2+ resulted in the instantaneous ring‐opening polymerization of THF.

Solar Photodegradation of a Novel des-F(6)-Fluoroquinolone, Garenoxacin, and Ecotoxicity of Its Phototransformation Products.

Garenoxacin (GRNX) is a novel des-F(6)-fluoroquinolone on the horizon; thus, its fate and risk in the aquatic environment deserve attention. This study systematically investigated, for the first time, the phototransformation of GRNX under simulated and natural sunlight and assessed the ecotoxicity of its photodegradation products. Phototransformation of GRNX was observed to depend strongly on its ionization state, with direct photolysis and self-sensitized photolysis having comparable contributions for the cationic and zwitterionic species, while the latter dominated for the anionic species. Singlet oxygen generated via the self-sensitized photolysis of GRNX was the major reactive oxygen species in its photodegradation. Phototransformation of GRNX in different ionization states followed distinct pathways, with defluorination of the difluoromethyl group occurring only for the zwitterionic and anionic species. GRNX photodegradation in natural water could be described by a simple kinetic model based on the measured steady-state concentrations of 1O2 and ·OH. Toxicity tests with Vibrio fischeri and Chlorella vulgaris consistently indicate that the generation of hydroxylation and decarboxylation products during photodegradation of GRNX increased the acute toxicity. These findings not only provide insights into the fate of GRNX in sunlit surface water but also reveal the potentially significant risk of its photodegradation products to the aquatic ecosystem.

Selective mono/divalent ion separation in bifunctional ionomeric capacitive deionization incorporated with counter-charge ionomer layer

In this study, a carbon-based bifunctional ionomeric capacitive deionization (BICDI) system was successfully developed by applying a counter-charge ionomer layer to the BICDI electrode without the need of a monovalent ion exchange membrane (M-IEM) for the selective separation of mono/divalent ions. The counter-charge ionomer layer facilitates the selective separation of mono/divalent ions through a combination of mechanisms involving electrostatic repulsion, steric hindrance, and hydrophobic interactions. Meanwhile, the BICDI electrode matrix serves as an ion transport channel, enabling seamless ion transport and improving the electrosorption capacity of the electrode. SEM and EDS analyses have confirmed the presence of a counter-charge ionomer layer encapsulating the BICDI electrode. Notably, BICDI-C cell with counter-charge ionomer layer exhibits higher Li+ ion adsorption capacity and selectivity (321.6 μmol/g, βMg2+Li+=6.6) compared to commercial monovalent cation exchange membrane CDI (MCDI-C) cell (206.4 μmol/g, βMg2+Li+=1.4). The selectivity of the BICDI-C cell for mono/divalent ions can be optimized by adjusting various testing parameters, including flow rate, voltage, etc. More importantly, this versatile method is not only applicable for the separation of monovalent cation, but can also enhance the monovalent anion adsorption capacity and selectivity of BICDI-A (43.6 μmol/g, βSO42-Cl-=7.3) cell by incorporating a counter-charge ionomer layer onto the BICDI cathode. This approach allows for the efficient separation of both cationic and anionic species, broadening the range of potential applications for BICDI technology.

Photocatalyst-Free Visible Light-Induced C(sp2)-H Arylation of Quinoxalin-2(1H)-ones and Coumarins.

Herein, we describe a visible light-induced C(sp2)-H arylation method for quinoxalin-2(1H)-ones and coumarins using iodonium ylides without the need for external photocatalysts. The protocol demonstrates a broad substrate scope, enabling the arylation of diverse heterocycles through a simple and mild procedure. Furthermore, the photochemical reaction showcases its applicability in the efficient synthesis of biologically active molecules. Computational investigations at the CASPT2//CASSCF/PCM level of theory revealed that the excited state of quinoxalin-2(1H)-one facilitates electron transfer from its π bond to the antibonding orbital of the C-I bond in the iodonium ylide, ultimately leading to the formation of an aryl radical, which subsequently participates in the C-H arylation process. In addition, our calculations reveal that during the single-electron transfer (SET) process, the C-I bond cleavage in iodonium ylide and new C-C bond formation between resultant aryl radical and cationic quinoxaline species take place in a concerned manner. This enables the arylation reaction to efficiently proceed along an energy-efficient route.

Silylation of phosphorylated cellulosic fibers with an aminosilane

In this work, phosphorylated cellulosic fibers were functionalized with an aminosilane ((3-aminopropyl)triethoxysilane, APTES) using a simple and economical method. Several characterization were performed to determine the types of bonds between phosphorylated fibers and grafted APTES. The thermal behavior, hydrophobicity and surface charge variation as a function of pH of the multifunctional cellulose fibers were determined.Results demonstrate that APTES should proceed through Si-O-C, and possibly Si-O-P, covalent bonds with cellulose although the dimerization of silane through Si-O-Si bonds has also been observed. The terminal amino groups are expected to be partially involved in hydrogen bonds with phosphate hydroxyl groups found at phosphorylated cellulose fiber surface, causing a pulling in the configuration of the grafted APTES. The two chemical modifications proposed in this work do not significantly modify the morphology of cellulose fibers. XRD analysis also shows that the crystal structure of the phosphorylated fibers did not change after functionalization with APTES. The silylated phosphorylated fibers show potential flame-retardant properties with improved hydrophobicity. Furthermore, the functionalization of phosphorylated fibers with APTES changes the pH of zero charge point from 3.2 to 9.4 and providing a zwitterionic structure suitable for the simultaneous adsorption of both cationic and anionic species.

Back Cover

This paper presents a novel macrocycle based on conformation‐adaptive and electron‐rich dihydrophenazine. The macrocycle exhibits host‐guest interaction with tetracyanoquinodimethane (TCNQ) driving by charge transfer interaction between them. The host‐guest complex forms stable radical cation species upon oxidation, resulting in the release of TCNQ from the macrocyclic cavity, thereby successfully achieving the reversible binding of guest molecules. More details are discussed in the article by Yang et al. on page 1895—1900.image

Mechanistic Insight into the Thermal "Blueing" of Cyanine Dyes.

In recent work to develop cyanine dyes with especially large Stokes shifts, we encountered a "blueing" reaction, in which the heptamethine cyanine dye Cy7 (IUPAC: 1,3,3-trimethyl-2-((1E,3E,5E)-7-((E)-1,3,3-trimethylindolin-2-ylidene)hepta-1,3,5-trien-1-yl)-3H-indol-1-ium) undergoes shortening in two-carbon steps to form the pentamethine (Cy5) and trimethine (Cy3) analogs. Each step blue-shifts the resulting absorbance wavelength by ca. 100 nm. Though photochemical and oxidative chain-shortening reactions had been noted previously, it is simple heating alone or with amine bases that effects this unexpected net C2H2 excision. Explicit acetylene loss would be too endothermic to merit consideration. Our mechanistic studies using 2H labeling, mass spectrometric and NMR spectroscopic analyses, and quantum chemical modeling point instead to electrocyclic closure and aromatization of the heptamethine chain in Cy7 forming Fischer's base FB (1,3,3-trimethyl-2-methyleneindoline), a reactive carbon nucleophile that initiates chain shortening of the cyanine dyes by attack on their polymethine backbones. The byproduct is the cationic indolium species TMP (IUPAC: 1,3,3 trimethyl-2-phenyl indolium).

Charge Transfer Mechanism in Guanine-Based Self-Assembled Monolayers on a Gold Surface.

In this work, we have theoretically determined the one-electron oxidation potentials and charge transfer mechanisms in complex systems based on a self-assembled monolayer of guanine molecules adsorbed on a gold surface through different organic linkers. Classical molecular dynamics simulations were carried out to sample the conformational space of both the neutral and the cationic species. Thus, the redox potentials were determined for the ensembles of geometries through multiscale quantum-mechanics/molecular-mechanics/continuum solvation model calculations in the framework of the Marcus theory and in combination with an additive scheme previously developed. In this context, conformational sampling, description of the environment, and effects caused by the linker have been considered. Applying this methodology, we unravel the phenomena of electric current transport by evaluating the different stages in which charge transfer could occur. The results revealed how the positive charge migrates from the organic layer to the gold surface. Specifically, the transport mechanism seems to take place mainly along a single ligand and driven with the help of the electrostatic interactions of the surrounding molecules. Aside, several self-assembled monolayers with different linkers have been analyzed to understand how the nature of that moiety can tune the redox properties and the efficiency of the transport. We have found that the conjugation between the guanine and the linker, at the same time conjugated to the gold surface, gives rise to a more efficient transport. In conclusion, the established computational protocol sheds light on the mechanism behind charge transport in electrochemical DNA-based biosensor nanodevices.

Spatial adaptation of eosinophils and their emerging roles in homeostasis, infection and disease.

Eosinophils are bone marrow-derived granulocytes that are traditionally associated with type 2 immune responses, such as those that occur during parasite infections and allergy. Emerging evidence demonstrates the remarkable functional plasticity of this elusive cell type and its pleiotropic functions in diverse settings. Eosinophils broadly contribute to tissue homeostasis, host defence and immune regulation, predominantly at mucosal sites. The scope of their activities primarily reflects the breadth of their portfolio of secreted mediators, which range from cytotoxic cationic proteins and reactive oxygen species to multiple cytokines, chemokines and lipid mediators. Here, we comprehensively review basic eosinophil biology that is directly related to their activities in homeostasis, protective immunity, regeneration and cancer. We examine how dysregulation of these functions contributes to the physiopathology of a broad range of inflammatory diseases. Furthermore, we discuss recent findings regarding the tissue compartmentalization and adaptation of eosinophils, shedding light on the factors that likely drive their functional diversification within tissues.

Cation-Stacking Approach Enabling Interconversion between Bis(xanthylium) and its Reduced Species.

Cyclophane-type dications with two units of xanthylium were designed, with the expectation that intramolecular interaction between cation units could induce changes in absorption and redox behavior. The desired dications were synthesized via the macrocyclic diketone as a key intermediate, which was efficiently obtained by a stepwise etherification. X-ray and UV/Vis measurements revealed that the cyclophane-type dications adopt a stacking structure in both the crystal and solution. Due to the intramolecular interaction caused by π-π stacking of the xanthylium units, a considerable blue shift compared to the corresponding monocations and a two-stage one-electron reduction process were observed in the dications. Furthermore, upon electrochemical reduction of dications, the formation of biradicals via radical cation species was demonstrated by UV/Vis spectroscopy with several isosbestic points at both stages. Therefore, the cation-stacking approach is a promising way to provide novel properties due to perturbation of their molecular orbitals and to stabilize the reduced species even though they have open-shell characters.

Yielding behaviour of chemically treated Pseudomonas fluorescens biofilms

The mechanics of biofilms are intrinsically shaped by their physicochemical environment. By understanding the influence of the extracellular matrix composition, pH and elevated levels of cationic species on the biofilm rheology, novel living materials with tuned properties can be formulated. In this study, we examine the role of a chaotropic agent (urea), two divalent cations and distilled deionized water on the nonlinear viscoelasticity of a model biofilm Pseudomonas fluorescens. The structural breakdown of each biofilm is quantified using tools of non-linear rheology. Our findings reveal that urea induced a softening response, and displayed strain overshoots comparable to distilled deionized water, without altering the microstructural packing fraction and macroscale morphology. The absorption of divalent ferrous and calcium cations into the biofilm matrix resulted in stiffening and a reduction in normalized elastic energy dissipation, accompanied by macroscale morphological wrinkling and moderate increases in the packing fraction. Notably, ferrous ions induced a predominance of rate dependent yielding, whereas the calcium ions resulted in equal contribution from both rate and strain dependent yielding and structural breakdown of the biofilms. Together, these results indicate that strain rate increasingly becomes an important factor controlling biofilm fluidity with cation-induced biofilm stiffening. The finding can help inform effective biofilm removal protocols and in development of bio-inks for additive manufacturing of biofilm derived materials.

Synthesis and Catalytic Performance of Bimetallic Oxide-Derived CuO-ZnO Electrocatalysts for CO2 Reduction.

Steering the selectivity of electrocatalysts toward the desired product is crucial in the electrochemical reduction of CO2. A promising approach is the electronic modification of the catalyst's active phase. In this work, we report on the electronic modification effects on CuO-ZnO-derived electrocatalysts synthesized via hydrothermal synthesis. Although the synthesis method yields spatially separated ZnO nanorods and distinct CuO particles, strong restructuring and intimate atomic mixing occur under the reaction conditions. This leads to interactions that have a profound effect on the catalytic performance. Specifically, all of the bimetallic electrodes outperformed the monometallic ones (ZnO and CuO) in terms of activity for CO production. Surprisingly, on the other hand, the presence of ZnO suppresses the formation of ethylene on Cu, while the presence of Cu improves CO production of ZnO. In situ X-ray absorption spectroscopy studies revealed that this catalytic effect is due to enhanced reducibility of ZnO by Cu and stabilization of cationic Cu species by the intimate contact with partially reduced ZnO. This suppresses ethylene formation while favoring the production of H2 and CO on Cu. These results show that using mixed metal oxides with different reducibilities is a promising approach to alter the electronic properties of electrocatalysts (via stabilization of cationic species), thereby tuning the electrocatalytic CO2 reduction reaction performance.

Uniformly deposition of iron phosphide quantum dots on the microscopic spongy B-C3N4 and its efficient degradation of ciprofloxacin by photo-self-Fenton process

In this research, iron phosphide quantum dots (FeP QDs) are synthesized and anchored on the microporous spongy BxCN uniformly through a novel hydrothermal-phosphorization processes. FeP@BxCN shows excellent photo-self-Fenton capability and applies to eliminate CIP from aqueous solution. Results indicate both photocatalysis and self-Fenton processes contribute to CIP degradation (photocatalysis: 69.1 %; self-Fenton: 28.2 %). The decoration of FeP QDs could effectively suppress the recombination of photogenerated carriers and improve the photocatalysis performance. They also accelerate the transformation of in situ H2O2 to •OH radicals thus enhance the efficiency of self-Fenton process. Furthermore, FeP QDs shows pretty low consumption during the self-Fenton process because of the regeneration mechanism between cationic iron species, H2O2 and anionic phosphorus. The existence of intermediate valence iron (Feɛ+) and anionic phosphorus (Pɛ-) ensured the regeneration of Fe(II) and the circulation between Fe(II), Feɛ+ and Fe(III). Optimal CIP degradation efficiency could be achieved under neutral condition and the corresponding CIP removal efficiency are 97.3 % when the initial concentration is 30 mg•L−1 and reaction within 120 min. Results propose a meaningful exploration for antibiotics degradation via photocatalytic-self-Fenton technology.

A Practical Electrochemical Approach for Synthesizing Selenyl-Dihydrobenzofurans and Chromane with a Tetrasubstituted Carbon Center

AbstractA straightforward and efficient electrochemical method for the anodic oxidative selenenylation of 2-(2-arylallyl)phenols and a 2-(3-arylbut-3-en-1-yl)phenol with diselenides under ambient air conditions has been outlined. This method allows for the synthesis of selenyl-dihydrobenzofurans and a chromane featuring a sterically hindered tetrasubstituted carbon center, demonstrated through 25 examples with yields reaching up to 98%. Initial mechanistic investigations suggest the likely participation of pivotal seleniranium cation species in regulating the reactivity.

The Chlorido-Bismuth Dication: A Potent Lewis Acid Captured in a Hepta-Coordinate Species with a Stereochemically Active Lone Pair.

The stabilization of simple, highly reactive cationic species in molecular complexes represents an important strategy to isolate and characterize compounds with uncommon or even unprecedented structural motifs and properties. Here we report the synthesis, isolation, and full characterization of chlorido-bismuth dications, stabilized only by monodentate dimethylsulfoxide (dmso) ligands: [BiCl(dmso)6][BF4]2 (1) and [BiCl(μ2-dmso)(dmso)4]2[BF4]4 (2). These compounds show unusual distorted pentagonal bipyramidal coordination geometries along with high Lewis acidities and have been analyzed by multinuclear NMR spectroscopy, elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, and density functional theory calculations. Attempts to generate the bromido- and iodido-analogs gave dmso-stabilized tricationic bismuth species.