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The Hofmeister series characterizes the ability of salt anions to precipitate polyampholytes/proteins. However, the variation of protein size in the bulk solution of acids and the effect of salts on the same have not been studied well. In this article, the four acids (CH3COOH, HNO3, H2SO4, and HCl) and their effects on the hydrodynamic radius (RH) of gelatin in the bulk solution are investigated. The effects of Na salt with the same anions are also considered to draw a comparison between the interactions of acids and salts with polyampholytes. It is suggested that the interactions of polyampholytes with acids are different from those of salts. The interaction series of polyampholytes with acids with respect to the RH of the polyampholyte is C H 3 CO O − > N O 3 − > C l − > S O 4 2 − whereas the interaction series with salts is S O 4 2 − > C H 3 CO O − > C l − > N O 3 − . These different interactions are due to equilibration between acid dissociation and protonation of polyampholytes. Another important factor contributing to the interactions in weak acids is the fact that undissociated acid hinders the movement of dissociated acid. Experiments and simulations were performed to understand these interactions, and the results were identical in terms of the trend in RH (from the experiments) and the radius of gyration (Rg) (from the simulations). It is concluded that the valence of ions and dissociation affect the interaction in the case of acids. However, the interactions are influenced by the kosmotropic and chaotropic effect, hydration, and mobility in the case of salts. [ABSTRACT FROM AUTHOR]

Electronic (e-) cigarette formulations containing nicotine salts from a range of organic acid conjugates and pH values have dominated the commercial market. The acids in the nicotine salt formulations may alter the redox environment in e-cigarettes, impacting free radical formation in e-cigarette aerosol. Here, the generation of aerosol mass and free radicals from a fourth-generation e-cigarette device was evaluated at 2 wt % nicotine salts (pH 7, 30:70 mixture propylene glycol to vegetable glycerin) across eight organic acids used in e-liquids: benzoic acid (BA), salicylic acid (SLA), lactic acid (LA), levulinic acid (LVA), succinic acid (SA), malic acid (MA), tartaric acid (TA), and citric acid (CA). Furthermore, 2 wt % BA nicotine salts were studied at the following nicotine to acid ratios: 1:2 (pH 4), 1:1 (pH 7), and 2:1 (pH 8), in comparison with freebase nicotine (pH 10). Radical yields were quantified by spin-trapping and electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra of free radicals in the nicotine salt aerosol matched those generated from the Fenton reaction, which are primarily hydroxyl (OH) radicals and other reactive oxygen species (ROS). Although the aerosol mass formation was not significantly different for most of the tested nicotine salts and acid concentrations, notable ROS yields were observed only from BA, CA, and TA under the study conditions. The e-liquids with SLA, LA, LVA, SA, and MA produced less ROS than the 2 wt % freebase nicotine e-liquid, suggesting that organic acids may play dual roles in the production and scavenging of ROS. For BA nicotine salts, it was found that the ROS yield increased with a higher acid concentration (or a lower nicotine to acid ratio). The observation that BA nicotine salts produce the highest ROS yield in aerosol generated from a fourth-generation vape device, which increases with acid concentration, has important implications for ROS-mediated health outcomes that may be relevant to consumers, manufacturers, and regulatory agencies.

Solid-state [2+2] photodimerization of eniminium ions oriented in a head-to-tail manner controlled by cation–π interactions produced synHT dimers in high yields. As the resulting dimer is readily converted to 1,3-diacetylcyclobutane, the iminium serves as a removable orientation-controlling group for the conjugated ketones. [ABSTRACT FROM AUTHOR]

We report the implementation of a consecutive photoinduced electron transfer (conPET) strategy for the functionalization of white phosphorus (P4) with inexpensive and widely available aryl bromides and chlorides. By employing a well-known acridinium-based photocatalyst under near-UV irradiation, this protocol gives direct access to valuable triarylphosphines and tetraarylphosphonium salts. The reaction mechanism is elucidated by NMR spectroscopic studies and model reactions. [ABSTRACT FROM AUTHOR]

Herein, an operationally simple and mild protocol for defluorinative alkylation and arylation between thianthrenium salts and α-trifluoromethyl alkene with visible light to afford gem-difluoroolefins has been developed. The main feature of this method is avoiding the use of a metal photocatalyst, and an organic photocatalyst is unnecessary for the arylation reaction. In addition, thianthrene can also be recycled and transformed to thianthrenium salts without affecting the efficiency of these reactions. The protocol demonstrates excellent tolerance of functional groups and viable functionalization of late-stage natural products and pharmaceutically relevant molecules. [ABSTRACT FROM AUTHOR]

Isotopically labeled alkanes play a crucial role in organic and pharmaceutical chemistry. While some deuterated methylating agents are readily available, the limited accessibility of other deuteroalkyl reagents has hindered the synthesis of corresponding products. In this study, we introduce a nickel‐catalyzed system that facilitates the synthesis of various deuterium‐labeled alkanes through the hydrodeuteroalkylation of d2‐labeled alkyl TT salts with unactivated alkenes. Diverging from traditional deuterated alkyl reagents, alkyl thianthrenium (TT) salts can effectively and selectively introduce deuterium at α position of alkyl chains using D2O as the deuterium source via a single‐step pH‐dependent hydrogen isotope exchange (HIE). Our method allows for high deuterium incorporation, and offers precise control over the site of deuterium insertion within an alkyl chain. This technique proves to be invaluable for the synthesis of various deuterium‐labeled compounds, especially those of pharmaceutical relevance. [ABSTRACT FROM AUTHOR]

Pyrylium salts based on a cationic oxygen heterocycle are a key class of chromophores. However, synthesis of these salts generally requires use of harsh acids, copious organic solvents, and in many cases, hazardous conditions. This work provides a two-pot synthesis for substituted triphenyl pyrylium salts wherein chalcone intermediates are first prepared and then mild methanesulfonic acid is used in combination with a dehydrating agent to drive pyrylium cyclization. Purification is achieved through a simple, aqueous workup involving counterion metathesis which avoids the need for environmentally unfriendly organic solvents. This mild, green approach has been applied to synthesize a collection of known pyryliums as well as a new family of red-shifted pyrylium chromophores bearing p -pyrrolidinylphenyl substituents. The synthesis of the latter group demonstrates that unlike other current methods, our approach offers enhanced functional group tolerance as well as finer control over substituent placement. [ABSTRACT FROM AUTHOR]

Environmental pollution significantly challenges human health, ecosystems, and the planet's sustainability. Widespread air, water, and soil contamination from various pollutants requires effective and sustainable solutions to reduce or eliminate pollution and its impacts. In this work, we designed novel magnesium oxide and graphene oxide (MgO@GO) composite free-standing membranes for nanofiltration. The membranes were characterized with the help of Fourier-transform infrared spectroscopy, X-ray diffraction, field-emission scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Further, free-standing MgO@GO composite membranes with different thicknesses were used to measure the water permeance. 410 nm-thick membranes showed high water permeance up to 480 ± 5 Lm−2 h−1 bar−1. Further, the rejection efficiency of the membrane was measured against NaCl, CaCl2, Pb(NO3)2, CdCl2, and amoxicillin. The MgO@GO membrane (410 ± 10 nm) showed 100% rejection for amoxicillin and 99% for Pb(NO3)2, respectively. Additionally, the membranes were stable under acidic and neutral conditions for approximately ∼80 days and may used on an industrial scale to ensure water is clean and free from harmful substances. [ABSTRACT FROM AUTHOR]

A copper‐catalyzed C4‐selective addition of silicon nucleophiles released from an Si−B reagent to prochiral pyridinium triflates is reported. The dearomatization proceeds with excellent enantioselectivity using Cu(CH3CN)4PF6 as the precatalyst and (R,R)‐Ph‐BPE (1,2‐bis[(2R,5R)‐2,5‐diphenylphospholan‐1‐yl]ethane) as the chiral ligand. A carbonyl group at C3 is required for this, likely acting a weak donor group to preorganize and direct the nucleophilic attack towards C4. The resulting 4‐silylated 1,4‐dihydropyridines can be further converted into functionalized piperidine derivatives. [ABSTRACT FROM AUTHOR]

The Kröhnke Pyridine Synthesis has been discovered about six decades ago (1961), by Fritz Kröhnke and Wilfried Zecher at the University of Giessen. The original method involved the reaction of α‐pyridinium methyl ketone salts with α,β‐unsaturated carbonyl compounds in the presence of a nitrogen source, frequently ammonium acetate. Since its discovery, the Kröhnke methodology has been demonstrated to be suitable for the preparation of mono‐, di‐, tri‐ and tetra‐pyridines, with important applications in several research fields. Over the years, a number of modifications to the original approach have been developed and reported, enabling for the broad applicability of these methods even in modern days, also for the synthesis of non‐pyridine compounds. In this critical and tutorial review, we will thoroughly explore and discuss the potential of the original method, the refinements that have been made over the years, as well as some applications arising from each type of pyridine and/or non‐pyridine compounds produced by Kröhnke's approach. [ABSTRACT FROM AUTHOR]

The interactions of salts with polyampholytes are well established using the Hofmeister series. However, the effect of these salts on the diffusivities of polyampholytes is unknown. This article discusses these electrostatically driven physical interactions using two developed prediction models. Sodium and Potassium salts are considered with 3 chaotropic anions and 2 kosmotropic anions. A dimensionless parameter has been developed to predict the trend for these salt interactions. Another model has been developed to predict these interactions for different salt mixtures. The effect of these salts and the mixtures on the second virial coefficient is also studied, and statistical clustering using the k‐means method has been defined, which can provide insight towards the changes in the solution properties of polyampholytes with these salt mixtures. At lower pH, the salt first screens the repulsions in the polyampholytes followed by a re‐expansion phenomenon. [ABSTRACT FROM AUTHOR]

The tetracyanoborate anion [B(CN)4]− (TCB) was utilized as a building block for the synthesis of polynuclear chromium carbonyl compounds upon photolytic reaction with [Cr(CO)6]. Up to four κN-coordinated cyano groups of TCB can be involved in binding to chromium, giving mixtures of [B(CN)4−x{CN–Cr(CO)5}x]− (x = 1–4; 1–4) and [{Cr(CO)4(B(CN)4)}2]2− (5). The reaction of [B(CN)4]− with fac-[Cr(CO)3(MeCN)3] led to isolation of salts of the tetraanionic heterocubane cage [{Cr(CO)3(B(CN)4)}4]4−. [ABSTRACT FROM AUTHOR]

The tetracyanoborate anion [B(CN)4]− (TCB) was utilized as a building block for the synthesis of polynuclear chromium carbonyl compounds upon photolytic reaction with [Cr(CO)6]. Up to four κN-coordinated cyano groups of TCB can be involved in binding to chromium, giving mixtures of [B(CN)4−x{CN–Cr(CO)5}x]− (x = 1–4; 1–4) and [{Cr(CO)4(B(CN)4)}2]2− (5). The reaction of [B(CN)4]− with fac-[Cr(CO)3(MeCN)3] led to isolation of salts of the tetraanionic heterocubane cage [{Cr(CO)3(B(CN)4)}4]4−. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Although various routes have been reported for haloazidation, unavoidable problems exist, such as environmentally unfriendly monomer halogen, the need for in situ generation of unstable halogen azides (XN3), applicability to one type of haloazidation and inability to precisely control selectivity. Herein, we developed a universal strategy for haloazidation of alkenes through controlling the reactivity of IBA‐N3 by switching halogen salts, allowing for the synthesis of a diversity of halogen azide products. Mechanistic studies have shown that by tuning the reactivity of IBA‐N3 via switching halogen salts, different intermediates can be controllably produced to achieve regioselectivity and chemoselectivity in the haloazidation of alkenes. [ABSTRACT FROM AUTHOR]

Water adsorption capacities of various adsorbents reported in the literature were investigated to define a hydrophobicity index that was plotted vs. water capacity. In this plot, logarithmic curves were proposed to be used as indicators of performance limits of adsorbents, especially for adsorption heat pumps. In spite of their useful adsorption properties, zeolites generally exhibited quite low hydrophobicity, remaining well below the logarithmic curve. In this study, the use of composites of zeolite NaY was examined both theoretically and experimentally for improvements in the water capacity and hydrophobicity. Salt impregnation and hydrothermal synthesis experiments were performed to prepare composites of zeolite NaY with LiCl/MgCl2 salts and activated carbon, respectively. Water capacity and hydrophobicity of zeolite NaY composites were generally superior to those of pure zeolite. Zeolite composites may be advantageous for enhancing adsorption capacity and hydrophobicity of zeolites while eliminating low stability and slow adsorption kinetics of other adsorbents. Interface between two different phases might indicate another opportunity to provide improved adsorption properties for zeolite composites. [ABSTRACT FROM AUTHOR]

Several tetrahydroxidohexaoxidopentaborate(1-) salts of N-substituted diimidazolium cations or N-substituted dipyrrolidinium cations linked through N-C6-N chains have been synthesized and characterized spectroscopically (NMR, IR) and by single-crystal XRD studies: [R(NC3H3N)(CH2)6(NC3H3N)R][B5O6(OH)4]2·xH2O (R = Me, x = 0 (1); R = Et, x = 3 (2); [Me(NC3H3N)(CH2(C6H4)CH2)(NC3H3N)Me][B5O6(OH)4]2 (3), [(C4H8N)(R)(CH2)6(R)(NC4H8)][B5O6(OH)4]2·xB(OH)3 (R = Me, x = 0 (4, two polymorphs); R = Et, x = 0 (5); R = Bu, x = 4 (6); R = allyl, x = 0 (7)). Representative samples (1 and 7) were also characterized by thermal (TGA/DSC) studies; compounds are thermally decomposed to B2O3 in air. Numerous anion-anion H-bonding interactions are present in the solid-state structures of 1–5 and 7 as giant anionic networks. Unusually, in 6 there are no R22(8) anion-anion interactions as the co-crystallized B(OH)3 bridges between all pentaborate anions. H-bonding interactions in 1–7 have been examined using Etter graph set analysis; C(8), C33(18), R22(8), R22(12) and R44(12) motifs have been identified. [ABSTRACT FROM AUTHOR]

In this study, the protein and salts distribution (Ca, P, Na and Mg) in processed cheese (PC) samples prepared with 180 or 360 mEq/kg of the calcium sequestering salts (CSS) disodium phosphate (DSP), disodium pyrophosphate (DSPP), sodium hexametaphosphate (SHMP) and trisodium citrate (TSC) was studied. For this purpose, a water-soluble extract (WSE) of PC samples was prepared. All PC samples contained 45–46% moisture, 26–27% fat and 20–21% protein and had a pH of 5.2 or 5.7. Ultracentrifugation slightly reduced the protein content of the WSE of PC, indicating that most protein in the WSE was non-sedimentable. At equal concentration of CSS, the protein content of the WSE was higher for PC at pH 5.7 compared to PC at pH 5.2. Approximately 55–85% of the Ca and P in the WSE of samples was 10 kDa-permeable for PC prepared with DSPP and SHMP. This suggests that the formation of non-permeable Ca–polyphosphate–casein complexes. For PC prepared with TSC, >90% of Ca in the WSE was 10 kDa-permeable, indicating that micellar disruption arises from sequestration of micellar Ca. These results indicate that the WSE method is an appropriate method to understand how salts present in PC are distributed. However, the WSE and ultracentrifugal supernatant of the WSE can include both soluble and protein-associated salts. Therefore, determining levels of salts in 10 kDa permeate of ultracentrifugal supernatant of the WSE is most appropriate. [ABSTRACT FROM AUTHOR]

Dynamic control of the motion in a catenane remains a big challenge as it requires precise design and sophisticated well‐organized structures. This paper reports the design and synthesis of a donor‐acceptor [2]catenane through mechanical interlocking, employing a crown ether featuring two dibenzylammonium salts on its side arms as the host and a cyclobis(paraquat‐p‐phenylene) (CBPQT ⋅ 4PF6) ring as the guest molecule. By addition of external acid or base, the catenane can form self‐complexed or decomplexed compounds to alter the cavity size of the crown ether ring, consequently affecting circumrotation rate of CBPQT ⋅ 4PF6 ring of the catenane. This study offers insights for the design and exploration of artificial molecular machines with intricate cascading responsive mechanisms. [ABSTRACT FROM AUTHOR]

The photoresponsive behavior of both mono- and dicationic bromide salts incorporated with 4-styrylpyridine was investigated. Upon exposure to UV light, the crystals showed dynamic changes, forming new organic salts by the [2 + 2] photodimerization process, which was elucidated by single crystal X-ray analysis and 1H NMR spectroscopy. [ABSTRACT FROM AUTHOR]

A method for the construction of 2-fluoropyrazolo[1,5-a]pyridines through base-promoted [3+2] cycloaddition of N-aminopyridinium salts with gem-difluorostyrenes has been established. A range of N-heterocycles with 2-fluorinated pyrazo[1,5-a]pyridines were efficiently obtained in moderate to good yields. The impact of different substituents on the reaction was discussed in detail. The protocol shows great potential for the synthesis of valuable fluorinated compounds by utilizing gem-difluorostyrenes as fluoride-containing building blocks. [ABSTRACT FROM AUTHOR]

Tris(pentafluoroethyl)indane dihydrate, [In(C2F5)3(OH2)2], and the gallium analog, [Ga(C2F5)3(OH2)2], serve as transfer reagents for the In(C2F5)3 and Ga(C2F5)3 units, as illustrated by the preparation of salts of (pseudo)halogenotris(pentafluoroethyl)indate and ‐gallate anions, [M(C2F5)3)X]− (M=Ga, In; X=F, Cl, Br, I, CN, SCN). Due to the water tolerance and water solubility of [In(C2F5)3(OH2)2] and [Ga(C2F5)3(OH2)2], reactions can be performed in the presence of water or even in an aqueous medium. [ABSTRACT FROM AUTHOR]

A series of nine new soft salts based on two platinum(II) complexes, namely ([Pt(C^N)(CN)2]−[Pt(C^N)(en)]+) (en = ethane-1,2-diamine), has been developed and synthesized. Their photophysical properties in both solution and the solid state were described. All soft salt complexes exhibit phosphorescence emission with PLQY in the solid state up to 0.36. Most of these materials displayed aggregation-induced emission (AIE) or aggregation-induced emission enhancement (AIEE) in water/DMSO solutions as the water ratio increased. Structure–property relationships were analyzed in relation to emission properties. The presence of the free nitrogen atoms in soft salt complexes with a C^N pyrimidine-based ligand allowed for reversible sensitivity to acidic vapors, resulting in the quenching of phosphorescence emission. Additionally, for selected soft salts, we described reversible vapochromism behaviour, making these new materials interesting for multi-detection purposes in anti-counterfeiting applications. [ABSTRACT FROM AUTHOR]

Producing sp3‐hybridized carbon‐enriched molecules is of particular interest due to their high success rate in clinical trials. The installation of aliphatic chains onto aromatic scaffolds was accomplished by nickel‐catalyzed C(sp2)−C(sp3) cross‐electrophile coupling with arylsulfonium salts. Thus, simple non‐prefunctionalized arenes could be alkylated through the formation of aryldibenzothiophenium salts. The reaction employs an electrochemical approach to avoid potentially hazardous chemical redox agents, and importantly, the one‐pot alkylation proved also viable, highlighting the robustness of our approach. [ABSTRACT FROM AUTHOR]

A photoinduced three‐component reaction of thianthrenium salts, DABCO ⋅ (SO2)2, and benzyl ether substituted alkenes is developed, affording δ‐hydroxylsulfones with good functional group tolerance. This transformation proceeds through an anti‐Markovnikov hydrosulfonylation of alkenes under a mild reaction condition. Mechanism studies indicates that this reaction undergoes a radical pathway involving sulfur dioxide insertion and 1,5‐hydrogen transfer processes. [ABSTRACT FROM AUTHOR]

The morphological adjustments of euhalophytes are well-known to be influenced by the soil-soluble salt variation; however, whether and how these changes in morphological traits alter the biomass allocation pattern remains unclear, especially under different NaCl levels. Therefore, an allometric analysis was applied to investigate the biomass allocation pattern and morphological plasticity, and the carbon (C), nitrogen (N), and phosphorus (P) stoichiometric characteristics of the euhalophyte Suaeda Salsa (S. salsa) at the four soil-soluble salt levels of no salt (NS), light salt (LS), moderate salt (MS), and heavy salt (HS). The results showed that soil-soluble salts significantly change the biomass allocation to the stems and leaves (p < 0.05). With the growth of S. salsa, the NS treatment produced a downward leaf mass ratio (LMR) and upward stem mass ratio (SMR); this finding was completely different from that for the salt treatments. When S. salsa was harvested on the 100th day, the HS treatment had the highest LMR (61%) and the lowest SMR (31%), while the NS treatment was the opposite, with an LMR of 44% and an SMR of 50%. Meanwhile, the soil-soluble salt reshaped the morphological characteristics of S. salsa (e.g., root length, plant height, basal stem diameter, and leaf succulence). Combined with the stoichiometric characteristics, N uptake restriction under salt stress is a vital reason for inhibited stem growth. Although the NS treatment had the highest biomass (48.65 g root box−1), the LS treatment had the highest salt absorption (3.73 g root box−1). In conclusion, S. salsa can change its biomass allocation pattern through morphological adjustments to adapt to different saline–alkali habitats. Moreover, it has an optimal biological desalting effect in lightly saline soil dominated by NaCl. [ABSTRACT FROM AUTHOR]

The in situ generation of active photoredox organic catalysts upon anion‐binding co‐catalysis by making use of the ionic nature of common photosensitizers is reported. Hence, the merge of anion‐binding and photocatalysis permitted the modulation of the photocatalytic activity of simple acridinium halide salts, building an effective anion‐binding – photoredox ion pair complex able to promote a variety of visible light driven transformations, such as anti‐Markovnikov addition to olefins, Diels‐Alder and the desilylative C−C bond forming reactions. Anion‐binding studies, together with steady‐state and time‐resolved spectroscopy analysis, supported the postulated ion pair formation between the thiourea hydrogen‐bond donor organocatalyst and the acridinium salt, which proved essential for unlocking the photocatalytic activity of the photosensitizer. [ABSTRACT FROM AUTHOR]

We here describe a visible-light photooxidation of sulfinate salts with common alkenes to yield β-hydroxy sulfones on DNA. This process demonstrates a broad substrate compatibility and achieves conversion rates ranging from moderate to excellent. Most importantly, it presents a straightforward, efficient, and metal-free approach for synthesizing Csp3-rich DNA-encoded libraries. [ABSTRACT FROM AUTHOR]

We demonstrate (1) detectable halogen bonding is not critical for enabling light-driven radical generation from diaryliodonium salts and (2) radicals generated by this route can be captured by transition-metals for C–H arylation reactions. These results are the first step toward developing new metal-catalyzed aryl radical couplings without exogenous photocatalysts. [ABSTRACT FROM AUTHOR]

Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is a widely used lithium (Li) salt that is extensively studied in the field of electrolytes for Li‐ion batteries (LIBs) to improve their performance. A thorough understanding of its underlying mechanisms in LIBs is crucial for gaining deeper insights into its future development. This paper provides an extensive review of the role of LiTFSI in enhancing battery performance, including its benefits for negative electrode protection, the facilitation of fast charging capabilities, and the promotion of battery operation across a wide temperature range. It also highlights the specific drawbacks of LiTFSI in the electrolyte domain and examines potential solutions. By leveraging the unique properties of LiTFSI, the strategies for its effective utilization in current research are outlined. Finally, the paper discusses the lack of research into the mechanism of LiTFSI in interface protection, particularly the evolution mechanisms of multi‐component Li salts at the positive and negative electrode interfaces, and it reasonably anticipates the potential applications of LiTFSI in the realm of non‐liquid batteries. This study not only provides a more comprehensive and profound understanding of LiTFSI but also aids in the exploration of novel electrolyte systems. [ABSTRACT FROM AUTHOR]

A visible‐light‐mediated radical heteroarylation of 2‐mercaptothiazolinium salts with N‐heteroarenes is reported, furnishing the corresponding functionalized N‐heteroarenes in good to high yields. Various alkyl bromides were converted conveniently into redox‐active thiazolinium salts and subsequently into alkyl radicals by reaction with an excited‐state photocatalyst. This mild protocol permits efficient functionalization of various N‐heteroarenes with a wild range of cyclic and acyclic primary and secondary alkyl groups. [ABSTRACT FROM AUTHOR]

The separation of chloride and chlorate ions in the case of a significant excess of chloride ions in a sample is studied by capillary electrophoresis. It is found that under standard separation conditions using a chromate background electrolyte, the signal-to-noise ratio for the chlorate ion peak at c() = 0.1 mM sharply decreases at the concentration ratio c(Cl–)/c() > 100. A number of approaches are considered to eliminate this phenomenon. The most effective approach was to introduce a solution containing acetate ions into the capillary after the sample zone to create conditions for transient isotachophoresis. Optimal parameters for the electrophoretic separation of chloride and chlorate ions are selected at a chloride ion content of 35 mM in the sample. The limit of detection is 0.01 mM chlorate ions (0.03−0.06% based on the mass of dry potassium, sodium, or lithium chlorides). The calibration curve is linear in the range of 0.01−1 mM . The selected conditions allow the determination of chlorate ions at a molar ratio of chloride to chlorate ions of 35−3500. The stacking efficiency factors are 10−70. Perchlorate ions do not interfere with the determination of chlorate ions at the concentrations of both ions of 0.1 mM or lower. The procedure is tested by analysis of table salt. [ABSTRACT FROM AUTHOR]

A [3+2]/[2+1] domino annulation reaction of cyclohexadienones and α‐aryl vinylsulfonium salts has been reported. A range of cyclopropane fused tricyclic enones bearing four contiguous stereocenters were obtained as a single diastereomer in 44–93% yields. The synthetic utility was demonstrated with the gram‐scale reactions and further transformations of the products. [ABSTRACT FROM AUTHOR]

Molecular, crystal, and electronic structures of a series of 3-arylidene-1-pyrrolinium salts are studied. Trifluoroacetates and nitrates of a number of arylidene pyrrolines containing various substituents in the para-position of the arylidene fragment are analyzed. It is shown that the organic cations have a virtually planar molecular structure that is quite easily distorted due to the mobility of the C–C single bond. Varying the substituent in the arylidene pyrroline structure affects insignificantly the geometric and electronic characteristics of the studied compounds. The nature of the anion has almost no effect on the molecular and electronic structure. In all cases, the crystal packing of the studied compounds is mainly due to the hydrogen bonds and non-covalent interactions involving the π-system and the presence of halogen atoms. [ABSTRACT FROM AUTHOR]

The salts bis(2‐amino‐3‐methylpyridinium) fumarate dihydrate, 2C6H9N2+·C4H2O22−·2H2O (I), and 2‐amino‐3‐methylpyridinium 5‐chlorosalicylate, C6H9N2+·C7H4ClO3− (II), were synthesized from 2‐amino‐3‐methylpyridine with fumaric acid and 5‐chlorosalicylic acid, respectively. The crystal structures of these salts were characterized by single‐crystal X‐ray diffraction, revealing protonation in I and II by the transfer of a H atom from the acid to the pyridine base. In the crystals of both I and II, N—H...O interactions form an R22(8) ring motif. Hirshfeld surface analysis distinguishes the interactions present in the crystal structures of I and II, and the two‐dimensional (2D) fingerprint plot analysis shows the percentage contribution of each type of interaction in the crystal packing. The volumes of the crystal voids of I (39.65 Å3) and II (118.10 Å3) have been calculated and reveal that the crystal of I is more mechanically stable than II. Frontier molecular orbital (FMO) analysis predicts that the band gap energy of II (2.6577 eV) is lower compared to I (4.0035 eV). The Quantum Theory of Atoms In Molecules (QTAIM) analysis shows that the pyridinium–carboxylate N—H...O interaction present in I is stronger than the other interactions, whereas in II, the hydroxy–carboxylate O—H...O interaction is stronger than the pyridinium–carboxylate N—H...O interaction; the bond dissociation energies also confirm these results. The positive Laplacian [∇2ρ(r) > 0] of these interactions shows that the interactions are of the closed shell type. An in‐silico ADME (Absorption, Distribution, Metabolism and Excretion) study predicts that both salts will exhibit good pharmacokinetic properties and druglikeness. [ABSTRACT FROM AUTHOR]

In this work, vanadium-substituted cesium phosphomolybdate salts were evaluated as catalysts in glycerol furfural condensation reactions, an attractive route to produce fuel-green bioadditives. Molybdenum atoms of phosphomolybdic acid were substituted with vanadium and precipitated as cesium salts generating catalysts with general formulae Cs3+nPMo12-nVnO40 (n = 1–3). Among the salts evaluated, Cs4PMo11V1O40 was the most active and selective catalyst toward the glyceryl furfural acetals, isomers (dioxolane: dioxane) were obtained at 2: 1 molar ratio with 90% conversion after a 2 h reaction at room temperature. The effect of main reaction parameters such as the glycerol: furfural molar ratio, the catalyst load, solvent, vanadium load, and the temperature were studied. The use of a solid, active, and easily synthesizable catalyst makes this an attractive route to produce fuel bioadditives from renewable raw materials at room temperature. [ABSTRACT FROM AUTHOR]

Palladium‐catalyzed carbonylation of aryl sulfonium salts with CO2 as a CO surrogate has been successfully developed via a one‐pot two‐step procedure. Thus, by merging thianthrenation and the carbonylation, site‐selective aromatic C−H carbonylation of a plethora of readily available arenes can be realized with CO2, providing access to a variety of structurally diverse and useful benzamides, esters and carboxylic acids. Simple operation, broad substrate scope, good functional group tolerance and mild reaction conditions are the attractive features of the method. Late‐stage functionalization of complex bioactive molecules as well as the precise synthesis of pharmaceuticals 1‐BCP and butoxycaine demonstrated the potential application of the established protocol. [ABSTRACT FROM AUTHOR]

N-Phenyl-, 1- and 2-naphthyl-N¹-2- and 4-pyridylthioureas were synthesized via the reaction of phenyl-, 1- and 2-naphthylisothiocyanates with 2- and 4-aminopyridines, and the corresponding pyridine salts were prepared by benzylation of the latter. The anticorrosive properties of the synthesized compounds were studied by the gravimetric method in 3 M HCl at 80°C using the 08 kp steel samples. The introduction of a benzyl fragment into the structure of N-aryl-N¹-pyridylthioureas led to the emergence of a new adsorption ammonium center, which increased the overall anti-corrosion efficiency of the obtained compounds. When using N-aryl-N¹-pyridylthioureas, the corrosion inhibition coefficient had the values of 4.5 to 59.0, whereas it increased to 90.8-629.0 for their salts. To explain the different anti-corrosion activity of N-aryl-N¹-pyridylthioureas and their pyridine salts, quantum-chemical calculations of the energy parameters EHOMO, ELUMO and ΔE=ELUMO-EHOMO were carried out and the dependences of the corrosion inhibition coefficients on EHOMO and ΔE, eΔE were obtained. A correlation was established between the inhibitory efficiency and energy parameters of the studied compounds. [ABSTRACT FROM AUTHOR]

Hypersaline brines provide excellent opportunities to study extreme microbial life. Here, we investigated anabolic activity in nearly 6000 individual cells from solar saltern sites with water activities (aw) ranging from 0.982 to 0.409 (seawater to extreme brine). Average anabolic activity decreased exponentially with aw, with nuanced trends evident at the single-cell level: The proportion of active cells remained high (>50%) even after NaCl saturation, and subsets of cells spiked in activity as aw decreased. Intracommunity heterogeneity in activity increased as seawater transitioned to brine, suggesting increased phenotypic heterogeneity with increased physiological stress. No microbial activity was detected in the 0.409-aw brine (an MgCl2-dominated site) despite the presence of cell-like structures. Extrapolating our data, we predict an aw limit for detectable anabolic activity of 0.540, which is beyond the currently accepted limit of life based on cell division. This work demonstrates the utility of single-cell, metabolism-based techniques for detecting active life and expands the potential habitable space on Earth and beyond.

The Stebnytsy deposit of potash salts is located in the inner Boryslav-Pokut subzone of the Precarpathian depression, Ukrainian Carpathians. The hydrogeological conditions of the Stebnytsky deposit are difficult, therefore mining operations are not carried out at the deposit, and only environmental protection measures are carried out. The mines are under conservation. During the period of operation of the deposit, about 30 million m3 of unfilled man-made voids were formed. To date, the suffusion and diffusion processes of the Stebnytskyi salt deposit have gone beyond the limits of the mine drainage of the deposit, and the deformation of the earth's surface threatens critical infrastructure facilities and residential buildings. As a result of the systematic regular observations of brine manifestations in the Stebnytsky deposit and studies of the processes of interaction of brines with the host rock, an idea was obtained about the peculiarities and regularities of the formation of the modern hydrochemical situation in the deposit, which in turn will allow to assess the degree of danger of individual areas in relation to the penetration of aggressive waters into underground workings salt mine. This article presents ideas about the nature of brines, the samples of which were taken from the revealed brine manifestations in the mine workings of the deposit. These ideas boil down to the fact that the vast majority of studied brines are brines of sedimentary origin and only a small part of them to one degree or another formed their composition due to salt leaching processes. Some regularities of changes in the chemical composition of solutions of sedimentary origin, which are formed in the conditions of deposits of sulfated potassium-magnesium salts, are considered. Research was conducted to study the interaction of brines with kainite rock, the results of the research allow us to establish the parameters characteristic of these solutions, and at the same time, to find out the secondary mineral formation that accompanies this process.

A novel and efficient method has been developed for synthesizing benzothioamide from benzonitrile in supercritical CO2, which could be used to synthesize various benzothioamide derivatives efficiently with yields of up to 98% without the need for organic solvent. Notably, some H2S-based salts were designed and prepared, and they were found to be effective catalysts in promoting the thiolysis of benzonitrile to produce benzothioamide in an excellent yield. Furthermore, the utilization of supercritical CO2 as a solvent has demonstrated a remarkable increase in the yield of the desired product compared to conventional solvents for promoting benzonitrile thiolysis. Additionally, the investigation of the reaction mechanism has revealed that the acid–base properties of the reaction solution played a crucial role in the thiolysis of benzonitrile mediated by the H2S-based salts. [ABSTRACT FROM AUTHOR]

A novel and efficient method has been developed for synthesizing benzothioamide from benzonitrile in supercritical CO2, which could be used to synthesize various benzothioamide derivatives efficiently with yields of up to 98% without the need for organic solvent. Notably, some H2S-based salts were designed and prepared, and they were found to be effective catalysts in promoting the thiolysis of benzonitrile to produce benzothioamide in an excellent yield. Furthermore, the utilization of supercritical CO2 as a solvent has demonstrated a remarkable increase in the yield of the desired product compared to conventional solvents for promoting benzonitrile thiolysis. Additionally, the investigation of the reaction mechanism has revealed that the acid–base properties of the reaction solution played a crucial role in the thiolysis of benzonitrile mediated by the H2S-based salts. [ABSTRACT FROM AUTHOR]

Crystal engineering is emerging as an important approach to design functional materials. In this work, we explore the scope of a sulfonate–pyridinium supramolecular synthon to design the organic salt [(TPT-H)2+(NDSA-H)2−·4H2O] (1), based on 1,5-naphthalenedisulfonic acid (NDSA-2H) and 2,4,6-tris(2-pyridyl)-s-triazine (TPT). Structural studies of 1 establish proton transfer between crystal formers and their aggregation through the water-masked sulfonate–pyridinium synthon to form one-dimensional hydrogen bonded tapes, which further aggregate through weak π–π and C–H⋯O interactions to form a three-dimensional layered solid. The greenish solid 1 exhibits mild charge transfer interactions in the solid-state, as indicated by the red-shift of the absorption beyond 400 cm−1 in the diffuse reflectance spectrum. Interestingly, 1 exhibit mild brownish emission (λmax = 550 nm), which undergoes remarkable blue-shifting on exposure to ammonia fumes (λmax = 450 nm), heat (λmax = 494.8 nm), and grinding (λmax = 542.9 nm). This multi-stimuli responsive behavior of 1 has been investigated in detail, with the help of diffuse reflectance, fluorescence, thermal, spectroscopic, and diffraction studies, and a plausible commentary of the behavior in light of its structure is provided. The intriguing multi-stimuli response behavior of 1 indicates the potential scope of sulfonate–pyridinium based organic salts in applications as sensors and intelligent materials. [ABSTRACT FROM AUTHOR]

Two coordinate boron cations are rare. Herein we report the synthesis of [RNSiMe2CH2]2BF (R = Dipp 3, 1-Ad 5) (Dipp = C6H3(iPr)2, Ad = C10H15) via the reaction of BF3 with the corresponding dilithiated diamides. Subsequent abstraction of fluoride provided the corresponding borinium salts, [(RNSiMe2CH2)2B][B(C6F5)4] (R = Dipp 6, 1-Ad 8). While the former was generated, the latter proved isolable and was crystallographically characterized. [ABSTRACT FROM AUTHOR]

The process of synthesizing 2,5‐diformylfuran (DFF) from sucrose involves three sequential steps: hydrolyzing sucrose into fructose and glucose, dehydrating fructose into 5‐hydroxymethylfurfural (HMF), and subsequently converting HMF into DFF. In this study, various potassium salts and metal bromides, as well as carbohydrates and solvents, were screened for the production of DFF. It was found that KBr was the optimal catalyst for the one‐pot, one‐step conversion of sucrose to DFF. The influences of reaction time, temperature, reactant/solvent ratio, and reactant/catalyst ratio were also completely investigated for process optimization. HMF from the sucrose hydrolysis and fructose dehydration was oxidized thoroughly to DFF. The maximum DFF yield of 62.5 % was achieved after 6 h at 140 °C in dimethyl sulfoxide (DMSO) with sucrose/KBr weight ratio=5.75 and sucrose/DMSO weight ratio=0.104 as the catalyst in the absence of any additives. The large‐scale process was also tested, the main product was isolated by column chromatography and structurally characterized. By comparing the results of this study to previous ones, the process was proved to have benefits, including the utilization of accessible biomass material, available low‐cost catalyst, energy‐saving method, no oxidants or additives, short reaction time, and high DFF yield with 100 % HMF conversion. [ABSTRACT FROM AUTHOR]

Today, rechargeable batteries are omnipresent and essential for our existence. In order to improve the electrochemical performance of electric fields, the introduction of electrolytes with fluorine (F)‐based inorganic elemental compositions is a direction of exploration. However, most fluorocarbons have a high global warming potential and ozone depletion potential, which do not meet the sustainability requirements of the battery industry. Therefore, developing sustainable electrolytes is a viable option for future battery development. Although researchers have made much progress in electrolyte optimization, little attention has been paid to developing low‐toxic and safe electrolytes. This review aims to elucidate the design principles and recent advances in this direction for solvents and salts. It concludes with a summary and outlook on future research directions for the molecular design of green electrolytes for practical high‐voltage rechargeable batteries. [ABSTRACT FROM AUTHOR]

The in situ‐formed polymer electrolytes provide a vital solution for improving both safety and performance in the high‐voltage lithium metal batteries. This study reports new poly(ester‐alt‐acetal) (PEA) electrolytes, synthesized through in situ alternating copolymerization of glutaric anhydride and 1,3‐dioxane. In the presence of 25 wt.% lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), three lithium salts, lithium difluoro(oxalate)borate (LiDFOB), lithium hexafluorophosphate (LiPF6), and lithium tetrafluoroborate (LiBF4) are employed as the catalysts for the copolymerization. These lithium salts can modulate the compositions of the solid‐electrolyte interphase (SEI) layer. PEA‐LiPF6 exhibits outstanding SEI chemistry, with observing the highest LiF content, thereby achieving a remarkable critical current density of up to 2.5 mA cm−2, a Li+ transference number of 0.81, and an expansive electrochemical stability window of 6.0 V. Furthermore, PEA‐LiPF6 demonstrates noteworthy capacity retention rates of 96.6% (0.5 C, 200th/first cycle in LiFePO4||Li), 95.6% (0.5 C, 100th/first cycle in LiMn0.6Fe0.4PO4||Li), 95.1% (1 C, 100th/first cycle in LiCoO2||Li), and 87.0% (1 C, 100th/first cycle in LiNi0.6Co0.2Mn0.2O2||Li full‐cells). This work demonstrates a facile in situ route to fabricate polymer electrolytes for high‐voltage lithium‐metal batteries with balanced and comprehensive performance. [ABSTRACT FROM AUTHOR]