Cationic Species Research Articles

Multimodular Wide-Band Capturing Nanohybrids: Role of Carbon Nanotubes in Slowing Charge Recombination in Supramolecular C60-BisstyrylBODIPY-(Zinc Porphyrin)2 Donor-Acceptor Molecular Cleft.

The importance of diameter-sorted single-wall carbon nanotubes (SWCNTs) noncovalently bound to a donor-acceptor molecular cleft, 1, in prolonging the lifetime of charge-separated states is successfully demonstrated. For this, using a multistep synthetic procedure, a wide-band capturing, multimodular, C60-bisstyrylBODIPY-(zinc porphyrin)2, molecular cleft 1, was newly synthesized and shown to bind diameter-sorted SWCNTs. The molecular cleft and its supramolecular assemblies were characterized by a suite of physicochemical techniques. Free-energy calculations suggested that both the (6,5) and (7,6) SWCNTs bound to 1 act as hole acceptors during the photoinduced sequential electron transfer events. Consequently, selective excitation of 1 in 1:SWCNT hybrids revealed a two-step electron transfer, leading to the formation of charge-separated states. Due to the distant separation of the cation and anion radical species within the supramolecules, improved lifetimes of the charge-separated states could be achieved. The present supramolecular strategy of improving charge separation involving SWCNTs and donor-acceptor molecular clefts highlights the potential application of these hybrid materials for various light energy harvesting and optoelectronic applications.

Determination of Binding Constants for the Complexes Between Heavy Metal Ions and Cucurbit[n]uril

AbstractOne of the major concerns worldwide is the rapid increase in water pollution with hazardous heavy metals. The Cucurbit[n]uril (CB[n]) structure provides an inner hydrophobic cavity accessible through two electrostatically negative portals with polar carbonyl groups, allowing for charged ion–dipole interaction between cationic species with excellent binding affinities. In this work we selected CB[5], and CB[7] for the titrimetric and electrochemical evaluation of the heavy metal complexes formed with Copper(II), Cadmium(II) and Lead(II). The host–guest interaction was found by either attenuation of the redox peaks, the formation of a new peak, or the slight shift in the redox peaks of the heavy metal ions. Titration data were obtained for CB[n] with the heavy metal solutions to determine the molar coefficient of binding. The stoichiometry of the complexes was 1 : 1 by Job′s plot. We calculated the binding constants using the Benesi–Hildebrand method achieving relatively good binding constants (K) ranging from (1.80±0.14)×105–(4.98±0.13)×105 M−1. The results showed that the complexes of Cadmium(II) and Lead(II) with both CB[5] and CB[7] are highly stable in aqueous media. Copper(II) was able to bind to the smaller sized portal of CB[5], whereas with CB[7] the heavy metal ion could not form a favourable complex. This phenomenon suggests that the CB[5] is an ideal host at forming stable host–guest interactions than their larger homologue.

The Mechanism of Rh(I)-Catalyzed Coupling of Benzotriazoles and Allenes Revisited: Substrate Inhibition, Proton Shuttling, and the Role of Cationic vs Neutral Species.

Direct coupling of benzotriazole to unsaturated substrates such as allenes represents an atom-efficient method for the construction of biologically and pharmaceutically interesting functional structures. In this work, the mechanism of the N2-selective Rh complex-catalyzed coupling of benzotriazoles to allenes was investigated in depth using a combination of experimental and theoretical techniques. Substrate coordination, inhibition, and catalyst deactivation was probed in reactions of the neutral and cationic catalyst precursors [Rh(μ-Cl)(DPEPhos)]2 and [Rh(DPEPhos)(MeOH)2]+ with benzotriazole and allene, giving coordination, or coupling of the substrates. Formation of a rhodacycle, formed by unprecedented 1,2-coupling of allenes, is responsible for catalyst deactivation. Experimental and computational data suggest that cationic species, formed either by abstraction of the chloride ligand or used directly, are relevant for catalysis. Isomerization of benzotriazole and cleavage of its N-H bond are suggested to occur by counteranion-assisted proton shuttling. This contrasts with a previously proposed scenario in which oxidative N-H addition at Rh is one of the key steps. Based on the mechanistic analysis, the catalytic coupling reaction could be optimized, leading to lower reaction temperature and shorter reaction times compared to the literature.

Insight into Adsorption Kinetics of Cs+, Rb+, Co2+, and Sr2+ on a Zeolites-Based Composite: Comprehensive Diffusional Explanation and Modelling

Kaolinite-rich soils were used to prepare zeolite-based composites via alkaline activation. The porous material was characterized by conducting XRD and microporosity measurements, as well as ESEM microscopy. The Weber and Morris (W-M) model was used for studying adsorption kinetics of radioactive cations on synthesized alkali-activated material. These investigations evidenced the effects of pore structure and the importance of the intrinsic characteristics of hydrated cations (ionic potential; hydrated radius; B-viscosity parameter; molar Gibbs energy of hydration of cation) on W-M kinetic rate constants. The application of diffusion-based models permitted us to assess the key diffusion parameters controlling successive diffusion regimes, and to reveal strong contributions of surface diffusion to adsorption kinetics during the course of the second and third kinetics stages of the W-M model. The magnitude of the surface diffusion coefficient was related to the capacity of hydrated cationic species to lose water molecules when penetrating brick pores. The HSDM model were tested for predicting radionuclide adsorption in a fixed-bed column. A breakthrough curve simulation indicated the predominance of the surface diffusion regime, which was in agreement with mathematical analysis of (batch) adsorption kinetics data. Ionic diffusion was linked to the characteristics of capillary porosity and connectivity of capillary pores in the composite, suggesting the generation of hydrated nuclides and their immobilization in the form of outer-sphere complexes.

Effects of Salts and Other Contaminants on Ciprofloxacin Removal Efficiency of Green Synthesized Copper Nanoparticles.

Ciprofloxacin (CIP), a broad-spectrum fluoroquinolone antibiotic, is commonly used in aquaculture to prevent and treat bacterial infections in aquatic animals. For this reason, aquatic environments contain CIP and its derivatives, which lead to the development of drug-resistant bacteria. In the present study, copper nanoparticles were prepared using Garcinia mangostana extract (GME-CuNPs) as a reducing agent and evaluated for their CIP removal efficiency (CRE). The results demonstrate that within 20 min, GME-CuNPs at 25 mM possess a CRE of 92.02 ± 0.09% from CIP-containing aqueous media with pH 6-7. The CRE is influenced by both monovalent and divalent salts. A high salt concentration significantly reduces the CRE. Contaminants in fish wastewater can reduce the CRE, but phenolics, flavonoids, tannins, and ammonia do not affect the CRE. Our results reveal that the CRE is controlled by electrostatic attraction between the negatively charged GME-CuNPs and the cationic species of CIP. The CRE is reduced by wastewater with a pH higher than 8.0, in which the CIP molecules have a negative charge, resulting in a repulsive force due to the negative charge of GME-CuNPs. In fish wastewater with a pH lower than 7.0, GME-CuNPs show the potential to achieve a CRE above 80%. Therefore, pH adjustment to a range of 6-7 in fish wastewater before treatment is deemed imperative. It is concluded that the newly developed GME-CuNPs possess excellent activity in CIP elimination from actual fish wastewater samples. Our findings suggest that GME-CuNPs can be a promising tool to effectively eliminate antibiotics from the environment.

Tl(I) and Tl(III)-induce genotoxicity, reticulum stress and autophagy in PC12 Adh cells.

Thallium (Tl) and its two cationic species, Tl(I) and Tl(III), are toxic for most living beings. In this work, we investigated the effects of Tl (10-100µM) on the viability and proliferation capacity of the adherent variant of PC12 cells (PC12 Adh cells). While both Tl(I) and Tl(III) halted cell proliferation from 24h of incubation, their viability was ~ 90% even after 72h of treatment. At 24h, increased levels of γH2AX indicated the presence of DNA double-strand breaks. Simultaneously, increased expression of p53 and its phosphorylation at Ser15 were observed, which were associated with decreased levels of p-AKTSer473 and p-mTORSer2448. At 72h, the presence of large cytoplasmic vacuoles together with increased autophagy predictor values suggested that Tl may induce autophagy in these cells. This hypothesis was corroborated by images obtained by transmission electron microscopy (TEM) and from the decreased expression at 72h of incubation of SQSTM-1 and increased LC3β-II to LC3β-I ratio. TEM images also showed enlarged ER that, together with the increased expression of IRE1-α from 48h of incubation, indicated that Tl-induced ER stress preceded autophagy. The inhibition of autophagy flux with chloroquine increased cell mortality, suggesting that autophagy played a cytoprotective role in Tl toxicity in these cells. Together, results indicate that Tl(I) or Tl(III) are genotoxic to PC12 Adh cells which respond to the cations inducing ER stress and cytoprotective autophagy.

Thermal distribution evolution model of SEI in lithium metal anodes

Lithium metal batteries are considered an advantageous choice for high energy density batteries due to their extremely high theoretical specific capacity. However, the interface instability has always been the biggest challenge for the commercial development of lithium metal batteries. The evolution mechanism of the thermal field is a key factor affecting the cyclic life during the evolution of lithium metal interfaces. Herein, the interface evolution mechanism for the impact of thermal distribution on Li dendrites is revealed and quantified by the thermal distribution evolution model of the solid electrolyte interphase (SEI). Three influencing factors are outlined as follows: 1) the ratio of the SEI to electrolyte diffusion capability. 2) The SEI diffusion coefficients for both anionic and cationic species. 3) The anisotropy in the SEI. The results indicate that under the appropriate ratio, the temperature gradient at the tip of lithium dendrites and the SEI-electrolyte interface are lower, which is favorable for a more even distribution of heat within the SEI. Additionally, the diffusion of anions can also influence the temperature gradient during the evolution process of lithium dendrites. Furthermore, introducing anisotropy to the SEI can induce lateral growth of lithium dendrites and reduce the temperature gradient at the tip of the lithium dendrites and the SEI-electrolyte interface. This work provides valuable insights for the interface design of lithium metal batteries.

An interpretation for the components of 2p 3/2 core level x-ray photoelectron spectra of the cations in some inverse spinel oxides

In an effort to reconcile the various interpretations for the cation components of the 2p 3/2 observed in x-ray photoelectron spectroscopy (XPS) of several spinel oxide materials, the XPS spectra of both spinel alloy nanoparticles and crystalline thin films are compared. We observed that different components of the 2p 3/2 core level XPS spectra, of these inverse spinel thin films, are distinctly surface and bulk weighted, indicating surface-to-bulk core level shifts in the binding energies. Surface-to-bulk core level shifts in binding energies of Ni and Fe 2p 3/2 core levels of NiFe2O4 thin film are observed in angle-resolved XPS. The ratio between surface-weighted components and bulk-weighted components of the Ni and Fe core levels shows appreciable dependency on photoemission angle, with respect to surface normal. XPS showed that the ferrite nanoparticles Ni x Co1−x Fe2O4 (x = 0.2, 0.5, 0.8, 1) resemble the surface of the NiFe2O4 thin film. Surface-to-bulk core level shifts are also observed in CoFe2O4 and NiCo2O4 thin films but not as significantly as in NiFe2O4 thin film. Estimates of surface stoichiometry of some spinel oxide nanoparticles and thin films suggested that the apportionment between cationic species present could be farther from expectations for thin films as compared to what is seen with nanoparticles.

Glutamate Leaching of Spent Lithium-Ion Battery Cathode in Weak Acidic-Neutral Condition: New Insight on Kinetics and Dissolution Mechanism

ABSTRACT Organic acid leaching receives less attention than inorganic acids for Li-ion battery recycling process at the industrial scale due to the high consumption rate of the acids as leaching reagents. This paper reports an effective leaching of cobalt (Co) and lithium (Li) from spent battery cathode using low concentration of monosodium glutamate as lixiviants. More than 95% of Co and Li could be dissolved at leaching conditions MSG 0.1 M (18 g/L), pH 5, sodium sulfite 0.5 M as reductant, pulp density 20 g/L, room temperature and leaching time 6 h. Increasing the temperature to 80°C sped up the leaching process, where maximum recovery could be attained within 1 h. pH played a major role in the leaching efficiency (effective range pH 4–6). pH lower than 4 led to neutral and cationic glutamate species, which were ineffective in attracting cobalt ion. pH higher than 6 initiated the surface passivation by Co(OH)2. In the absence of a passivation layer, cobalt dissolution mechanism followed the chemical reaction-controlled model, while in the presence of the layer, the mechanism switched to diffusion through product layer. Kinetic studies demonstrated that aside from pH, the formation of passivation layer was hypothetically regulated by adjusting the other leaching parameters. Aside from the observation on kinetic study, the proposed leaching mechanism was supported by characterization (particle size analysis, SEM-EDS, FT-IR) results.

Biochar from sugarcane bagasse: Synthesis, characterization, and application in an electrochemical sensor for copper (II) determination

Biochar (BC) is a carbonaceous material obtained from the thermal decomposition of organic matter under limited oxygen supply that plays an attractive role in waste management. In this study, biochar was prepared from sugarcane bagasse, using pyrolysis temperatures from 300 to 700 °C, and chemically activated with HNO3. Structural characterizations showed that degradation increased as pyrolysis temperature increased. Furthermore, a higher number of functional groups were observed for the materials produced under the lowest temperatures. Chemical activation resulted in oxidation and nitration of carbonaceous structure, increasing the number of functional groups on the materials. All materials were evaluated for the construction of electrochemical sensors towards Cu2+ ions voltammetric determination. The material produced at 400 °C pyrolysis temperature and activated (BCA400) provided the most intense response, which can be related to the presence of one of the highest numbers of surface groups, such as oxygen groups, on it. A method for Cu2+ determination was successfully developed based on differential pulse adsorptive stripping voltammetry (DPAdSV). A linear dynamic range (LDR) from 1.0 to 15.0 μmol L−1 was achieved, with limit of detection (LOD) of 0.36 μmol L−1, and limit of quantification (LOQ) of 1.09 μmol L−1. The method was also adequate in terms of accuracy and precision, as well as selective against most cationic species commonly found in tap water. The analyte was determined in tap water samples, in natura and spiked with the maximum concentration allowed by Brazilian legislation, and successful recovery values were obtained. Therefore, biochar from sugarcane bagasse, an environmentally-friendly material, was successfully used to construct an electrochemical sensor and determining an environmental and health interest analyte.

Insights into self-discharge processes of Al-graphite batteries

Aluminum graphite dual ion batteries (AGDIB) have been widely explored thanks to abundant electrode materials, a long cycle life and high power density. However, the shelf life of AGDIBs is so far barely understood. This work's detailed self-discharge investigations allow the quantification of capacity losses for up to 4 weeks, confirm a deintercalation mechanism by Raman spectroscopy and X-ray diffraction, and furthermore give insight to influence factors. While a cell employing typical materials such as a natural graphite cathode, Mo current collector and AlCl3/[EMIm]Cl=1.5 ionic liquid electrolyte exhibits a capacity loss of 10 % in 24 h, this value can be significantly reduced to 3 % in 24 h when using a glassy carbon current collector and AlCl3/Et3NHCl=1.5 electrolyte instead. Iron impurities within the electrolyte do not affect battery capacities or self-discharge, since it is deposited on the Al anode within the battery soon after assembly. In general, the instability of the current collector material, gas evolution due to electrolyte oxidation at high cell potentials, and cationic electrolyte species greatly influence the self-discharge independently. Electrolyte speciation changes directly related to self-discharge processes are revealed by IR spectroscopy.

3,4-selective polymerization of isoprene by iron-based system: The key role of borate salts for enhancing catalytic activities and broadening 1,10-phenanthroline ligand scope

The catalytic system of iron(III) compound/alkylaluminum/1,10-phenothroline(Phen) has been long disclosed for efficient 3,4-selective polymerization of isoprene to achieve semi-crystalline 3,4-polyisoprene product, that finds important application in the current tire industry. Nevertheless, such a system is highly sensitive to the steric nature of Phen ligands, even a subtle variation (e.g. introducing methyl group to its 2,9-position) will result in significantly decreased catalytic activities. In this research, we disclose a facile method, i.e. in-situ addition of borate salts, that can well address such a long unsolved issue. By doing such, the pristine catalytic activities were able to be greatly enhanced (ca. 4-fold higher) without damaging the selectivity of the active species. Such a method was also applicable for various substituted Phen ligands, such as Phen2,9-(nBu)2, Phen2,9-(sBu)2, Phen2,9-(tBu)2, Phen2,9-(nHex)2, etc., which greatly broadens the ligand scope of such iron(III) based catalytic system. Mechanistic studies revealed that the attraction of alkyl group by borate salts to form the cationic active species might play a governing role in enhancing the activities.

Enhancing Uptake Capability of Green Carbon Black Recycled from Scrap Tires for Water Purification

This study reports on the highly simple fabrication of green carbon black (GCB) generated from scrap tires with acetic acid to improve the adsorption efficiency for water purification, which is thoroughly compared with conventional carbon black (CB) obtained from petrochemicals. Unlike traditional modification processes with strong acids or bases, the introduction of a relatively mild acid readily allowed for the effective modification of GCB to increase the uptake capability of metal ions and toxic organic dyes to serve as effective adsorbents. The morphological features and thermal decomposition patterns were examined by electron microscopy and thermogravimetric analysis (TGA). The surface functional groups were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The structural information (ratio of D-defects/G band-graphitic domains) obtained by Raman spectroscopy clearly suggested the successful fabrication of GCB (ID/IG ratio of 0.74), which was distinctively different from typical CB (ID/IG ratio of 0.91). In the modified GCB, the specific surface area (SBET) gradually increased with the reduction of pore size as a function of acetic acid content (52.97 m2/g for CB, 86.64 m2/g for GCB, 102.10-119.50 m2/g for acid-treated GCB). The uptake capability of the modified GCB (312.5 mg/g) for metal ions and organic dyes was greater than that of the unmodified GCB (161.3 mg/g) and typical CB (181.8 mg/g), presumably due to the presence of adsorbed acid. Upon testing them as adsorbents in an aqueous solution, all these carbon materials followed the Langmuir isotherm over the Freundlich model. In addition, the removal rates of cationic species (>70% removal of Cu2+ and crystal violet in 30 min) were much faster and far greater than those of anionic metanil yellow (<40% removal in 3 h), given the strong electrostatic interactions. Thus, this work demonstrates the possibility of recycling waste tires in the powder form of GCB as a cost-effective and green adsorbent that can potentially substitute traditional CB, and the modification strategy provides a proof of concept for developing simple fabrication guidelines of other carbonaceous materials.

Electroreduction mechanisms of meso-Tetraphenylphlorin cation in strongly acidic media of benzonitrile

In nonaqueous media free-base porphyrins are easily protonated by strong proton donors to form the diprotonated porphyrins. The two-electron reduction of these species leads to phlorin cation species. To investigate the electroreduction products that follow the formation of these species, we evaluate the effect of increasing amounts of HClO4 on the electroreduction mechanism of the phlorin cation of meso-tetraphenyl porphyrin. We demonstrate that the phlorin cation undergoes a reversible protonation reaction to form a porphodimethene, which is further reduced to yield the chlorin-phlorin cation, a 4-electron reduced phlorin macrocycle with a hydrogenated pyrrolic Cβ = Cβ double bond. This undergoes further protonation and a 2-electron reduction to form a phlorin macrocycle, the bacteriochlorin-phlorin cation, wherein two pyrrole rings are hydrogenated. All these reduction processes occur at similar potential values, yet we managed to selectively form the 2-, 4- or 6- electron reduced product by a strict control of the number of protons in the medium. To the best of our knowledge, this is the first report of the electrochemical reduction of Cβ = Cβ bonds of pyrrolic rings. Thus, a new pathway for the electrochemical reduction of porphyrins is proposed.

Efficient removal of tetracycline and Cu2+ by honeycomb derived magnetic carbon: Adsorption mechanism and advanced oxidation regeneration mechanism

The honeycomb magnetic carbons (xFe@HCNs) were prepared by sacrificial template method novelty using polyacrylamide resin (PAAS) as template and ammonium pyrrolidine dithioate/Fe3+ complex (APDC-Fe) as carbon skeleton and metal source. Tetracycline (TC) and copper (Cu2+) as target pollutants were used to investigate the adsorption properties of xFe@HCNs in single or binary TC and Cu2+ systems. The adsorption capacity sequence for TC among the adsorbents was (mmol·g−1): 2Fe@HCNs (0.088) > 8Fe@HCNs (0.061) > HCNs (0.054) > RC (0.036), and for Cu2+ was (mmol·g−1): 2Fe@HCNs (1.120) > 8Fe@HCNs (1.026) > RC (0.792) > HCNs (0.681). 2Fe@HCNs demonstrated notable affinity for adsorbing both TC and Cu2+. Additionally, the influence of hydrochemical factors (i.e., cation species, anion species, and pH) on the adsorption properties of 2Fe@HCNs. Combined with advanced oxidation technology, the regeneration methods of magnetic adsorbent were explored using oxidizing agents (e.g., H2O2 and peroxymonosulfate) as eluents which could increase the adsorption sites of magnetic carbon adsorbents during the regenerating process, which was the novelty of the study. Furthermore, the regeneration mechanisms of H2O2 as eluent were investigated. This study discussed the application and regeneration methods of magnetic adsorbents in water treatment, offering new insights into environmental remediation using magnetic materials.

Surface Extraction Process During Initial Oxidation of Pt(111): Effect of Hydrophilic/Hydrophobic Cations in Alkaline Media.

The surface oxidation states of the metal electrodes affect the activity, selectivity, and stability of the electrocatalysts. Oxide formation and reduction on such electrodes must be comprehensively understood to achieve next-generation electrocatalysts with outstanding performance and stability. Herein, the initial electrochemical oxidation of Pt(111) in alkaline media containing hydrophilic and hydrophobic cations is investigated by X-ray crystal truncation rod (CTR) scattering, infrared (IR) spectroscopy, and nanoparticle-based surface-enhanced Raman spectroscopy (SERS). Structural determination using X-ray CTR revealed surface buckling and Pt extraction at the initial stage of surface oxidation, depending on the cationic species. Vibrational spectroscopy is performed to identify the potential- and cation-dependent formation of three oxide species (IR-active OHad, Raman-active OHad/Oad(H2O), and Raman-active Oad). Hydrophilic alkali metal cations (Li+) inhibit surface roughening via irreversible oxide formation. Hydrophilic Li+ can strongly stabilize IR-active OHad, hindering the extraction of Pt surface atoms. Interestingly, bulky hydrophobic cations such as tetramethylammonium (TMA+) cation also reduce the extent of irreversible oxidation despite the absence of IR-active OHad. Hydrophobic TMA+ inhibits the formation of Raman-active OHad/Oad(H2O) associated with Pt extraction. In contrast, the moderate hydrophilicity of K+ has no protective effect against irreversible oxidation. Moderate hydrophilicity enables the coadsorption of Raman-active OHad/Oad(H2O) and Raman-active Oad. The electrostatic repulsion between Raman-active OHad/Oad(H2O) and neighboring Raman-active Oad promotes Pt extraction. These results provide insights into controlling the surface structures of electrocatalysts using cationic species during the oxide formation and reduction processes.

Ion Pairing Enables Targeted Prodrug Activation via Red Light Photocatalysis: A Proof-of-Concept Study with Anticancer Gold Complexes.

Photocatalysis has found increasing applications in biological systems, for example, in localized prodrug activation; however, high-energy light is usually required without giving sufficient efficiency and target selectivity. In this work, we report that ion pairing between photocatalysts and prodrugs can significantly improve the photoactivation efficiency and enable tumor-targeted activation by red light. This is exemplified by a gold-based prodrug (1d) functionalized with a morpholine moiety. Such a modification causes 1d to hydrolyze in aqueous solution, forming a cationic species that tightly interacts with anionic photosensitizers including Eosin Y (EY) and Rose Bengal (RB), along with a significant bathochromic shift of absorption tailing to the far-red region. As a result, a high photoactivation efficiency of 1d by EY or RB under low-energy light was found, leading to an effective release of active gold species in living cells, as monitored by a gold-specific biosensor (GolS-mCherry). Importantly, the morpholine moiety, with pKa ∼6.9, in 1d brings in a highly pH-sensitive and preferential ionic interaction under a slightly acidic condition over the normal physiological pH, enabling tumor-targeted prodrug activation by red light irradiation in vitro and in vivo. Since a similar absorption change was found in other morpholine/amine-containing clinic drugs, photocages, and precursors of reactive labeling intermediates, it is believed that the ion-pairing strategy could be extended for targeted activation of different prodrugs and for mapping of an acidic microenvironment by low-energy light.

Carbocationoids, a concept for controlling highly reactive cationic species

Carbocations, which are positively charged highly electrophilic intermediates, are efficacious for the direct alkylation of low-reactive nucleophiles. The utilization of carbocations in SN1 reactions relies on the activation of their precursors in the presence of a nucleophile. However, undesirable interactions between the nucleophile and the leaving group activator limit the scope of acceptable nucleophiles. Here we report a strategy to conduct SN1 reactions involving unstable carbocations in an alternative stepwise procedure, which was demonstrated by the benzylation of various neutral nucleophiles. In the first step, carbocations were accumulated in a nucleophile-free solution in the form of carbocationoids utilizing the coordinative stabilization of triazinediones. Subsequently, the addition of these solutions in the second step enabled room-temperature alkylation without the need for acidic additives. This methodology overcomes the inherent challenges of carbocations in SN1 reactions.

Nickel-Catalyzed Ethylene Copolymerization with Vinylalkoxysilanes: A Computational Study.

Since the discovery of α-diimine catalysts in 1995, an extensive series of Brookhart-type complexes have shown their excellence in catalyzing ethylene polymerizations with remarkable activity and a high molecular weight. However, although this class of palladium complexes has proven proficiency in catalyzing ethylene copolymerization with various polar monomers, the α-diimine nickel catalysts have generally exhibited a much worse performance in these copolymerizations compared to their palladium counterparts. Recently, Brookhart et al. reported a notable exception, demonstrating that α-diimine nickel catalysts could catalyze the ethylene copolymerization with some vinylalkoxysilanes effectively, producing functionalized polyethylene incorporating trialkoxysilane (-Si(OR)3) groups. This breakthrough is significant since Pd-catalyzed copolymerizations are commercially less usable due to the high cost of palladium. Thus, the utilization of Ni, given its abundance in raw materials and cost-effectiveness, is a landmark in ethylene/polar vinyl monomer copolymerization. Inspired by these findings, we used density functional theory (DFT) calculations to investigate the mechanistic study of ethylene copolymerization with vinyltrimethoxysilane (VTMoS) catalyzed by Brookhart-type nickel catalysts, aiming to elucidate the molecular-level understanding of this unique reaction. Initially, the nickel complexes and cationic active species were optimized through DFT calculations. Subsequently, we explored the mechanisms including the chain initiation, chain propagation, and chain termination of ethylene homopolymerization and copolymerization catalyzed by Brookhart-type complexes. Finally, we conducted an energetic analysis of both the in-chain and chain-end of silane enchainment. It was found that chain initiation is the dominant step in the ethylene homopolymerization catalyzed by the α-diimine Ni complex. The 1,2- and 2,1-insertion of vinylalkoxysilane exhibit similar barriers, explaining the fact that both five-membered and four-membered chelates were identified experimentally. After the VTMoS insertion, the barriers of ethylene reinsertion become higher, indicating that this step is the rate-determining step, which could be attributed to the steric hindrance between the incoming ethylene and the bulky silane substrate. We have also reported the energetic analysis of the distribution of polar substrates. The dominant pathway of chain-end -Si(OR)3 incorporation is suggested as chain-walking → ring-opening → ethylene insertion, and the preference of chain-end -Si(OR)3 incorporation is primarily attributed to the steric repulsion between the pre-inserted silane group and the incoming ethylene molecule, reducing the likelihood of in-chain incorporation.

From proton transfer to ionic liquids: How isolated domains of ion pairs grow to form extended network in diphenyl phosphate-bis(2-ethylhexyl) amine mixtures

HypothesisDiphenyl phosphate (DPP)/bis(2-ethylhexyl) amine (BEEA) liquid mixtures are expected to show peculiar self-assembly behavior due to their, respectively, acidic and basic nature which can trigger acid-base reaction. ExperimentThe properties of DPP/BEEA mixtures of different compositions are explored by a combined theoretical (Ab initio calculations) and experimental (rheology, X-ray and light scattering) approach. Findings(i) a proton transfer from DPP to BEEA takes place with formation of cationic and anionic species in liquid phase (ion pair formation); (ii) due to the strong and long-range electrostatic interactions, each of the two charged species is preferentially surrounded by the other one, in a picture resembling the structure of ionic materials; (iii) this gives rise to a striking viscosity increase takes place as DPP concentration increases; (iv) the composition dependencies of all measured parameters show clear deviations around DPP molar fraction of 0.2, indicating unequivocally the formation of isolated domains, formed by DPP-BEEA pairs which coalescence/percolate into a unique, extended, network at higher DPP concentrations.