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The use of ionic liquids (ILs) as lubricants or additives has been studied extensively over the past few decades. However, the ILs considered for lubricant applications have been part of a limited structural class of phosphonium- or imidazolium-type compounds. Here, new pyrylium- and pyridinium-based ILs bearing long alkyl chains were prepared and evaluated as friction- and wear-reducing additives in naphthenic greases. The physical properties of the synthetic ILs and additized naphthenic grease were measured. The tribological performance of the greases was measured by using standard benchtop tests. The addition of ILs was detrimental to wear, causing an increase in the amount of material removed by sliding relative to the base greases in most cases. In contrast, the friction performance improved under nearly all conditions tested due to the IL additives. The compatibility of the synthetic ILs with the naphthenic greases and its potential influence upon miscibility and tribological performance are tentatively proposed to be a result of the molecular structure.

The alkylation of 3‐/4‐bromo‐ and ‐iodopyridine with methyl triflate smoothly affords the corresponding N‐methylpyridinium triflate salts. An anion exchange with NaI or [PPh4]Y (Y=Cl, Br, I) yields the corresponding halide salts. Most of them could be structurally characterized and their strong halogen bonds were investigated. While the halogen atom of 4‐halogenopyridinium is susceptible to nucleophilic substitution, 3‐halogenopyridinium ions are far more stable against nucleophilic attacks. Due to the comparable interaction strength of halogen bonds and hydrogen bonds, the latter of which is widely used in chromatography, the potential of 3‐halogenopyridinium moieties for an application in chromatography is obvious and was successfully employed in affinity chromatography of different proteins. [ABSTRACT FROM AUTHOR]

The extent to which electrophores covalently bridged by a saturated linker are electrochemically independent was investigated considering the charge/spin duality of the electron and functionality of the electrophore as a spin carrier upon reduction. By combining computational modeling with electrochemical experiments, we investigated the mechanism by which tethered electrophores react together within 4,4′‐oligo[n]methylene‐bipyridinium assemblies (with n=2 to 5). We show that native dicationic electrophores (redox state Z=+2) are folded prior to electron injection into the system, allowing the emergence of supra‐molecular orbitals (supra‐MOs) likely to support the process of the reductive σ bond formation giving cyclomers. Indeed, for Z=+2, London Dispersion (LD) forces contribute to flatten the potential energy surface such that all‐trans and folded conformers are approximately isoenergetic. Then, upon one‐electron injection, for radical cations (Z=+1), LD forces significantly stabilize the folded conformers, except for the ethylene derivative deprived of supra‐MOs. For radical cations equipped with supra‐MOs, the unpaired electron is delocalized over both heterocycles through space. Cyclomer completion (Z=0) upon the second electron transfer occurs according to the inversion of redox potentials. This mechanism explains why intramolecular reactivity is favored and why pyridinium electrophores are not independent. [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]

Abstract Unfortunately, oil reservoirs are complex considering the fluids (e.g., crude oil composition) and rock properties making it hard to propose a simple enhanced oil recovery (EOR) method for higher oil production. Besides, most of the investigations had focused on crude oil which is a complex mixture of thousands of components making it hard to extract any reliable conclusions with respect to the crude oil type. So, the current study is focused on the application of ionic liquids from different families of pyridinium and imidazolium, titanium oxide nanoparticles, and salts (MgCl2 and CaCl2) in the presence of resinous synthetic oil for the first time. The obtained results using the central composite design (CCD) approach revealed the positive effect of resin fraction on the IFT reduction by 27% considering the initial value (34.9%). Using the CCD approach revealed that using pH = 7, MgCl2 concentration = 21,000 ppm, CaCl2 concentration = 21,000 ppm, resin fraction of 9wt%t and 500 ppm of [C12mim][Cl] concentration reduces the IFT to minimum value of 0.62 mN/m while the minimum IFT value for optimum conditions of solution includes [C12py][Cl] led to minimum IFT value of 2.2 mN/m. But, the contact angle measurements revealed better synergy between [C12py][Cl] and TiO2-NPs (0–200 ppm) for better wettability alteration toward water-wet condition (27.3°) than [C12mim][Cl] (33.2°). Moreover, the IFT measurements revealed that the presence of TiO2-NPs is effective in reducing the IFT of the optimum formulations to 0.55 and 0.84 mN/m for [C12mim][Cl], and [C12py][Cl], respectively. According to the results, it seems that the obtained optimum formulations for [C12mim][Cl], and [C12py][Cl] are applicable for EOR purposes as new hybrid solutions.

Unfortunately, oil reservoirs are complex considering the fluids (e.g., crude oil composition) and rock properties making it hard to propose a simple enhanced oil recovery (EOR) method for higher oil production. Besides, most of the investigations had focused on crude oil which is a complex mixture of thousands of components making it hard to extract any reliable conclusions with respect to the crude oil type. So, the current study is focused on the application of ionic liquids from different families of pyridinium and imidazolium, titanium oxide nanoparticles, and salts (MgCl2 and CaCl2) in the presence of resinous synthetic oil for the first time. The obtained results using the central composite design (CCD) approach revealed the positive effect of resin fraction on the IFT reduction by 27% considering the initial value (34.9%). Using the CCD approach revealed that using pH = 7, MgCl2 concentration = 21,000 ppm, CaCl2 concentration = 21,000 ppm, resin fraction of 9wt%t and 500 ppm of [C12mim][Cl] concentration reduces the IFT to minimum value of 0.62 mN/m while the minimum IFT value for optimum conditions of solution includes [C12py][Cl] led to minimum IFT value of 2.2 mN/m. But, the contact angle measurements revealed better synergy between [C12py][Cl] and TiO2-NPs (0–200 ppm) for better wettability alteration toward water-wet condition (27.3°) than [C12mim][Cl] (33.2°). Moreover, the IFT measurements revealed that the presence of TiO2-NPs is effective in reducing the IFT of the optimum formulations to 0.55 and 0.84 mN/m for [C12mim][Cl], and [C12py][Cl], respectively. According to the results, it seems that the obtained optimum formulations for [C12mim][Cl], and [C12py][Cl] are applicable for EOR purposes as new hybrid solutions. [ABSTRACT FROM AUTHOR]

Efficient water-solubilization of nanocarbons is desirable for both their biological and material applications, but so far has mainly relied on covalent modifications or amphiphiles featuring ionic side-chains. Here, we report a facile 2–4-step synthesis of pyridinium-based, bent aromatic amphiphiles with modular nonionic side-chains (i.e., CH3 and CH2CH2(OCH2CH2)2–Y (Y = OCH3, OH, and imidazole)). The new amphiphiles quantitatively self-assemble into ≈2 nm-sized aromatic micelles in water independent of the side-chain. Importantly, efficient water-solubilization and nonionic surface modification of various nanocarbons (e.g., fullerene C60, carbon nanotubes, and graphene nanoplatelets) are achieved through noncovalent encircling with the bent amphiphiles. The resultant imidazole-modified nanocarbons display a pH-responsive surface charge, as evidenced by NMR and zeta-potential measurements. In addition, solubilization of a nitrogen-doped nanocarbon (i.e., graphitic carbon nitride) in the form of 10–30 nm-sized stacks is also demonstrated using the present amphiphiles.

A library of N-benzylpyridinium-based compounds, 7a-j and 8a-j, was designed and synthesised as potential acetylcholinesterase) AChE (inhibitors. An in vitro assay for the synthesised compounds showed that most compounds had significant AChE inhibitory activities at the nanomolar and submicromolar levels. The benzyl (8a) and fluoro (8b) derivatives were the most active, with IC50 values ≤56 nM. Compound 7f, which had a benzyl moiety, showed the highest potency among all the target compounds, with an IC50 value of 7.5 ± 0.19 nM against AChE, which was higher than that of the activities of tacrine (IC50 = 30 ± 0.2 nM) and donepezil (IC50 = 14 ± 0.12 nM). Compounds with vanillin moieties exhibited antioxidant activity. Among the tested compounds, four derivatives (7f, 7 g, 8f, and 8 g) exhibited superior AChE inhibitory activity, with Ki values of 6–16 nM, which were potent in the same range as the approved drug, donepezil. These compounds showed moderate antioxidant activities, as indicated by the results of the ABTS assay. [ABSTRACT FROM AUTHOR]

Investigation on the hybrid enhanced oil recovery solutions and methods is gaining attention during the last decade since they can activate multiple mechanisms such as viscosity reduction, interfacial tension (IFT) reduction, and wettability alteration. So, the current work is concentrated on the application of 1-octyl-3-methyl pyridinium chloride ([C8py][Cl]) and 1-dodecyl-3-methyl pyridinium chloride ([C12py][Cl]) as novel surfactants in the absence and presence of SiO2 nanoparticles (SiO2-NPs) for the first time for possible IFT reduction and rock wettability change (contact angle (CA) measurement). In this way, the concentration of ionic liquids (ILs) and SiO2-NPs ranged between 0–2000 ppm and 0–1000 ppm, respectively, to see the influence of these chemicals on the wettability change and IFT reduction. The point is that the higher concentrations of these chemicals were not examined since using higher concentrations makes it expensive and uneconomic for field-scale applications. The obtained results revealed that as the pH increases from 3 to 11 in the absence of different chemicals (formation brine/basic crude oil), the IFT experiences an increase from 20.3 to 31.2 mN/m, while the situation for CA is more complicated. In detail, the results revealed that increasing the pH in the range of 3–11 leads to an increase in the CA from 103.2° to 121.3° (increasing pH from 3 to 7) while a further increase in the pH leads to a reduction in CA value from 121.3° to 118.3°. Moreover, the results revealed that increasing the concentration of [C8py][Cl] from 0 to 2000 ppm led to a reduction in IFT value from 20.3 to 0.95 mN/m for pH of 3, from 27.3 to 2.2 mN/m for pH of 7 and from 31.2 to 5.4 mN/m for pH of 11. Besides, the measurements for [C12py][Cl] revealed that increasing the concentration from 0 to 2000 ppm leads to IFT reduction from 20.3 to 0.74 mN/m for pH of 3, from 27.3 to 0.9 for pH of 7, and from 31.2 to 1.4 mN/m for pH of 11. The results demonstrated a higher influence of [C12py][Cl] on the IFT reduction compared with the [C8py][Cl] due to the longer alkyl chain length of [C12py][Cl] which means more detergency power. Furthermore, the effects of these two ILs are examined on the wettability change which showed that both of the examined ILs are capable to manipulate the wettability of the rock surface toward water-wet conditions (53.3°) from oil-wet conditions (121.3°). Also, the influence of SiO2-NPs in the range of 0–1000 ppm is investigated on the IFT reduction and wettability change while the concentration of ILs is held constant at 2000 ppm since the concentration of 2000 ppm leading to the lowest CA and IFT values for both examined ILs. The obtained results reveal that not only the presence of SiO2-NPs with a maximum concentration of 1000 ppm leads to a reducing trend on the IFT in particular for the pH of 11 regardless of the used IL but also it changes the surface wettability to strongly water-wet condition with minimum CA value of 28.5°. In the last stage, the efficiency of the optimum chemical formulations was examined through core flooding experiments using conventional core flooding procedure and the core flooding experiments concomitant with the soaking time (30 days). The experiments revealed that the chemical formulation under a pH of 3 leads to the highest oil recovery factors while the lowest oil recovery factors are obtained under a pH of 11. Besides, the core flooding experiments followed by soaking reveal the ultimate oil recovery of 10.1 and 13.3% based on the original oil in place (OOIP) due to better activation of the wettability change mechanism which was 46% higher than the situation no soaking was performed. The findings of this study can help for a better understanding of the feasibility and applicability of using new hybrid surfactant-NPs-based EOR methods to activate wettability alteration and IFT reduction, especially with a main focus on one specific fraction of crude oil (resin fraction) instead of crude oil. [ABSTRACT FROM AUTHOR]

Abstract Investigation on the hybrid enhanced oil recovery solutions and methods is gaining attention during the last decade since they can activate multiple mechanisms such as viscosity reduction, interfacial tension (IFT) reduction, and wettability alteration. So, the current work is concentrated on the application of 1-octyl-3-methyl pyridinium chloride ([C8py][Cl]) and 1-dodecyl-3-methyl pyridinium chloride ([C12py][Cl]) as novel surfactants in the absence and presence of SiO2 nanoparticles (SiO2-NPs) for the first time for possible IFT reduction and rock wettability change (contact angle (CA) measurement). In this way, the concentration of ionic liquids (ILs) and SiO2-NPs ranged between 0–2000 ppm and 0–1000 ppm, respectively, to see the influence of these chemicals on the wettability change and IFT reduction. The point is that the higher concentrations of these chemicals were not examined since using higher concentrations makes it expensive and uneconomic for field-scale applications. The obtained results revealed that as the pH increases from 3 to 11 in the absence of different chemicals (formation brine/basic crude oil), the IFT experiences an increase from 20.3 to 31.2 mN/m, while the situation for CA is more complicated. In detail, the results revealed that increasing the pH in the range of 3–11 leads to an increase in the CA from 103.2° to 121.3° (increasing pH from 3 to 7) while a further increase in the pH leads to a reduction in CA value from 121.3° to 118.3°. Moreover, the results revealed that increasing the concentration of [C8py][Cl] from 0 to 2000 ppm led to a reduction in IFT value from 20.3 to 0.95 mN/m for pH of 3, from 27.3 to 2.2 mN/m for pH of 7 and from 31.2 to 5.4 mN/m for pH of 11. Besides, the measurements for [C12py][Cl] revealed that increasing the concentration from 0 to 2000 ppm leads to IFT reduction from 20.3 to 0.74 mN/m for pH of 3, from 27.3 to 0.9 for pH of 7, and from 31.2 to 1.4 mN/m for pH of 11. The results demonstrated a higher influence of [C12py][Cl] on the IFT reduction compared with the [C8py][Cl] due to the longer alkyl chain length of [C12py][Cl] which means more detergency power. Furthermore, the effects of these two ILs are examined on the wettability change which showed that both of the examined ILs are capable to manipulate the wettability of the rock surface toward water-wet conditions (53.3°) from oil-wet conditions (121.3°). Also, the influence of SiO2-NPs in the range of 0–1000 ppm is investigated on the IFT reduction and wettability change while the concentration of ILs is held constant at 2000 ppm since the concentration of 2000 ppm leading to the lowest CA and IFT values for both examined ILs. The obtained results reveal that not only the presence of SiO2-NPs with a maximum concentration of 1000 ppm leads to a reducing trend on the IFT in particular for the pH of 11 regardless of the used IL but also it changes the surface wettability to strongly water-wet condition with minimum CA value of 28.5°. In the last stage, the efficiency of the optimum chemical formulations was examined through core flooding experiments using conventional core flooding procedure and the core flooding experiments concomitant with the soaking time (30 days). The experiments revealed that the chemical formulation under a pH of 3 leads to the highest oil recovery factors while the lowest oil recovery factors are obtained under a pH of 11. Besides, the core flooding experiments followed by soaking reveal the ultimate oil recovery of 10.1 and 13.3% based on the original oil in place (OOIP) due to better activation of the wettability change mechanism which was 46% higher than the situation no soaking was performed. The findings of this study can help for a better understanding of the feasibility and applicability of using new hybrid surfactant-NPs-based EOR methods to activate wettability alteration and IFT reduction, especially with a main focus on one specific fraction of crude oil (resin fraction) instead of crude oil.

A library of N-benzylpyridinium-based compounds, 7a-j and 8a-j, was designed and synthesised as potential acetylcholinesterase) AChE (inhibitors. An in vitro assay for the synthesised compounds showed that most compounds had significant AChE inhibitory activities at the nanomolar and submicromolar levels. The benzyl (8a) and fluoro (8b) derivatives were the most active, with IC50 values ≤56 nM. Compound 7f, which had a benzyl moiety, showed the highest potency among all the target compounds, with an IC50 value of 7.5 ± 0.19 nM against AChE, which was higher than that of the activities of tacrine (IC50 = 30 ± 0.2 nM) and donepezil (IC50 = 14 ± 0.12 nM). Compounds with vanillin moieties exhibited antioxidant activity. Among the tested compounds, four derivatives (7f, 7 g, 8f, and 8 g) exhibited superior AChE inhibitory activity, with Ki values of 6–16 nM, which were potent in the same range as the approved drug, donepezil. These compounds showed moderate antioxidant activities, as indicated by the results of the ABTS assay.

A comprehensive analysis of the transport properties of solutions of three pyridinium-based ionic liquids, 2-chloro-1-methylpyridinium iodide [o-mpy][I]; 3-chloro-1-methylpyridinium iodide [m-mpy][I], and 4-chloro-1-methylpyridinium iodide, [p-mpy][I], has been derived utilising conductometric data at temperatures ranging from 298.15 to 313.15 K (in steps of 5 K) in 10%, 30%, and 50% W/W mixtures of MeOH–H2O and DMF–H2O. On the basis of conductometric data, the limiting molar conductance and ion-pair association were evaluated and re-evaluated using a computer-programmed Fuoss-Edelson strategy, and the acquired results were evaluated in terms of the influence of temperature, the solvent's nature, ion-ion, ion–solvent interactions, and substituent positions on the transport characteristics. Using conductance-based data, the Λ ∘ η ∘ , R H , activation energy of the transport process and association's thermodynamic functions values of these ILs were computed and thoroughly analysed. Surprisingly, the "positioning" of the substituent (Cl) in the ortho, meta, or para-position had a minor impact on the ion pair association of three ILs in the chosen solvents, with the K A values for para-substituted [p-mpy][I] being about 1.07-fold lower than [m-mpy][I] and [o-mpy][I], respectively. This article's results supplied critical data about the transport properties of pyridinium-based ionic liquids, which is essential and beneficial for the diverse fields of such ionic liquids that are currently being utilised. [ABSTRACT FROM AUTHOR]

Two pyridinium salt based tricationic surfactants were synthesized using quarternization reaction. The characterization of the surfactants were done by spectroscopic methods (FT-IR and NMR). Some pysicochemical properties like critical micelle concentration, surface tension at critical micelle concentration, Gibbs free energy of micelization, foam height, foam stability and emulsion stability were measured. The anticorrosion properties of the synthesized compounds were investigated by gravimetric measurements. In corrosion tests, where both compounds showed inhibitory activity against the corrosion of carbon steel in 1.0 M HCl environment, while the inhibition efficiency of the compound containing 6 carbon atoms in the long chain was determined in the range of 62–76%, those of the compound containing 8 carbon atoms in the long chain was found in the range of 85–93%. On the other hand, density functional theory (DFT) calculations were applied to arrive at basic molecular/electronic level scale details about the synthesized compounds, in addition to the surface images of the metal obtained by scanning electron microscopy to support the corrosion prevention results. [ABSTRACT FROM AUTHOR]

Two NIR-emitting donor-π-acceptor (D-π-A) type regioisomeric styryl pyridinium dyes (1a–1b) were synthesized and studied for their photophysical performance and environment sensitivity. The two regioisomers, 1a and 1b, exhibited interesting photophysical properties including, longer wavelength excitation (λex ≈ 530–560 nm), bright near-infrared emission (λem ≈ 690–720 nm), high-fluorescence quantum yields (ϕfl ≈ 0.24–0.72) large Stokes' shift (∆λ ≈ 150–240 nm) and high-environmental sensitivity. Probe's photophysical properties were studied in different environmental conditions such as polarity, viscosity, temperature, and concentration. Probes (1a–1b) exhibited noticeable changes in absorbance, emission and Stokes' shift while responding to the changes in physical environment. Probe 1b exhibited a significant bathochromic shift in optical spectra (∆λ ≈ 20–40 nm) compared to its isomer 1a, due to the regio-effect. Probes (1a–1b) exhibited an excellent ability to visualize bacteria (Bacillus megaterium, Escherichia coli), and yeast (Saccharomyces cerevisiae) via fluorescence microscopy. [ABSTRACT FROM AUTHOR]

N‐(difluoromethyl)amino (−NCF2H) compounds are of great interest given their unique and underexplored physiochemical properties. The lack of structural diversity in NCF2H compounds is likely due in part to the shortage of protocols for efficient installation. Presented herein is a new shelf‐stable pyridinium reagent that enables the direct installation of the N‐(difluoromethyl)sulfonamide moiety [N(Ts)CF2H)] onto (hetero)arenes and alkenes for the diversification of aryl and alkyl NCF2H compounds. The described protocol utilizes blue light photoredox catalysis and displays broad functional group tolerance with excellent chemoselectivity. Additional transformations and applicability towards a photoredox continuous flow protocol are also demonstrated. [ABSTRACT FROM AUTHOR]

Steel surfaces treated with synthesized ionic liquid (ILs) namedly 4-methyl-1-(3-phenoxypropyl) pyridinium bromide (Pyr1), 4-(dimethylamino)-1-(2-phenoxyethyl) pyridinium bromide (Pyr2) and4-(dimethylamino)-1-(3-phenoxypropyl) pyridinium bromide (Pyr3) were investigated in HCl acid media (1 M) using several techniques. Surfaces were analyzed by SEM and FESEM microscopy and by XPS spectroscopy, while the inhibition process was studied by electrochemical impedance (EIS) measurements. The results obtained by EIS demonstrated a higher charge transfer resistance that led to a high inhibition performance. According to Langmuir isotherm model and the activation parameters, these ILs can be adsorbed onto the mild steel surface through physical and chemical bonds. This study was supported by DFT and Monte Carlo calculations approach which confirms the adsorption behavior of the studied ILs. [ABSTRACT FROM AUTHOR]

An efficient and facile synthesis of highly substituted pyridinium salts through the annulation of enamines with alkynes is reported herein. A Ag2CO3/HNTf2 synergistically acting catalyst system was developed and used in a condensation reaction between carbonyl substrates and propargylamine to afford structurally diverse pyridinium salts. A mechanistic investigation shows that this one‐pot transformation proceeded via selective 6‐endo‐dig cyclization of the in situ generated propargylenamine and protonolysis of the resulting vinyl–silver intermediate. The reaction conditions are mild, and the substrate scope is broad. During the cyclization, an unusual inversion of the normal reactivity of α,β‐unsaturated carbonyl systems was observed. [ABSTRACT FROM AUTHOR]

Heteroarene 1, n-zwitterions are powerful and versatile building blocks in the construction of heterocycles and have received increasing attention in recent years. In particular, pyridinium and quinolinium 1,4-zwitterions have been widely studied and used in a variety of cyclization reactions due to their air stability, ease of use, and high efficiency. Sulfur- and nitrogen-based pyridinium and quinolinium 1,4-zwitterions, types of emerging heteroatom-containing synthons, have attracted much attention from chemists. These 1,4-zwitterions, which contain multiple reaction sites, have been successfully used in the synthesis of three- to eight-membered cyclic compounds over the last decade. In this review, we present the exciting progress made in the field of cyclization reactions of sulfur- and nitrogen-based pyridinium and quinolinium 1,4-zwitterions. Moreover, the mechanistic insights, the transition states, some synthetic applications, and the challenges and opportunities are also discussed. We hope to provide an overview for synthetic chemists who are interested in the heterocycle synthesis from cyclization reaction with pyridinium and quinolinium 1,4-zwitterions pyridinium and quinolinium 1,4-zwitterions. [ABSTRACT FROM AUTHOR]

[Display omitted] • Covalent organic polymer functionalized by photoactive pyridinium units was developed as a heterogeneous photocatalysis. • The transformation of hydrocarbon into ketone was without any additives or stoichiometric oxidants except for atmospheric. • Photoinduced proton-coupled electron transfer, and 1O 2 and O 2 − play a key role in the photocatalytic reaction. Using oxygen in the air as the sole oxidant to oxidize hydrocarbons into high value-added compounds is a highly promising synthesis strategy with economic advantages. However, the oxidation of hydrocarbons with molecular oxygen under mild conditions is challenging due to the large C–H bond energy in hydrocarbons. Herein, a metal-free two-dimensional covalent organic polymers (COP) functionalized by photoactive pyridinium units has been developed for heterogeneous photocatalytic oxidation of hydrocarbons. This is the first kind of COPs material that can achieve photocatalytic oxidation of hydrocarbons without any additives or stoichiometric oxidants except for the oxygen in the air. [ABSTRACT FROM AUTHOR]

This paper studied the effect of pyridinium-based ionic liquids as cosolvents in a methanol-water solvent system on the hydrolytic activity of Candida rugosa lipase. These ionic liquids were successfully synthesized using imidazolium-based ionic liquid synthesizing methods with a certain adjustment. The hydrolytic activity of Candida rugosa lipase was analyzed using 4-nitrophenol acetate (pNPA) and 4-nitrophenol palmitate (pNPP) as substrates. The addition of ionic liquids had no significant effect on the hydrolytic activity of lipase in a water solvent, and it had a greater effect in methanol. The addition of [C6Py] Br ionic liquid as a methanol cosolvent (methanol: ionic liquid, 10:5) could increase the hydrolytic activity of lipase. The use of ionic liquid as a cosolvent could increase the hydrolytic activity of lipase by about 15.61% while using pNPP as a substrate in the methanol system. A molecular dynamics study for the interaction between lipase and ionic liquids supported the experimental results. The ionic liquid using bromide as an anion provided more stability on lipase conformation. It tends to form the short-range interaction between the lipase and bromide anion. [ABSTRACT FROM AUTHOR]

The reaction of lanthanide (Ln) chloride hydrates ([Ln(H2O)n(Cl)3]) with pyridine (py) yielded a set of dehydrated pyridinium (py-H) Ln-polychloride salts. These species were crystallographically characterized as [[py-H-py][py-H]2[LnCl6]] (Ln-6; Ln = La, Ce, Pr, Nd, Sm, Eu, Gd) or [[py-H]2[LnCl5(py)]] ((Ln-5; Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu). The Ln-6 metal centers adopt an octahedral (OC-6) geometry, binding six Cl ligands. The −3 charge is off-set by two py-H moieties and a di-pyridinium (py-H-py) ion. For the Ln-5 species, an OC-6 anion is formed by the Ln cation binding a single py and five Cl ligands. The remaining −2 charge is offset by two py-H+ cations that H-bond to the anion. Significant H-bonding occurs between the various cation/anion moieties inducing the molecular stability. The change in structure from the Ln-6 to Ln-5 is believed to be due to the Ln-contraction producing a smaller unit cell, which prevents formation of the py-H-py+ cation, leading to the loss of the H-bonding-induced stability. Based on this, it was determined that the Ln-5 structures only exist when the lattice energy is small. While dehydrated polychloride salts can be produced by simply mixing in pyridine, the final structures adopted result from a delicate balance of cation size, Coulombic charge, and stabilizing H-bonding. [ABSTRACT FROM AUTHOR]

A practical protocol for the first regiodivergent asymmetric addition of aryl and alkenyl organometallic reagents to substituted N‐alkyl pyridinium heterocycles is described. The couplings proceed with high regiochemical and stereochemical selectivities, and provide access to chiral 1,2,3‐ and 1,3,4‐trisubstituted dihydropyridine products, controlled by judicious choice of nitrogen activating agent. To this end, a correlation was found between the parameterized size of the activating group and the C2/C4 regioselectivity in the couplings. The utility of the described chemistry was demonstrated in two concise asymmetric syntheses of (+)‐N‐methylaspidospermidine and (−)‐paroxetine. [ABSTRACT FROM AUTHOR]

Densities, refractive indices, viscosities, surface tensions and speeds of sounds were measured and discussed for [Cnpy][[NTf2] (n=2,4,6) and [Cnmpy][[NTf2] (n=2,3,4) as a function of temperature and atmospheric pressure. As expected, all properties decrease with increasing temperature, with viscosity being the property most affected by temperature, while surface tension and refractive index being the properties least affected by temperature. Linear correlation was used to calculate the density, speed of sound, surface tension and refractive index as a function of temperature. The viscosity is correlated using Vogel-Flutcher-Tamman (VFT) equation. From the experimental density data, the coefficients of thermal expansion and the isentropic compressibility coefficients were calculated. The Guggenheim equation was used to calculate the critical temperatures. Moreover, the effect of the alkyl chain length of the investigated ionic liquids on the measured thermophysical properties is discussed.

Ionic liquids (ILs) have emerged as active pharmaceutical ingredients because of their excellent antibacterial and biological activities. Herein, we used the green-chemistry-synthesis procedure, also known as the metathesis method, to develop three series of ionic liquids using 1-methyl-3-butyl imidazolium, butyl pyridinium, and diethyldibutylammonium as cations, and bromide (Br−), methanesulfonate (CH3SO3−), bis(trifluoromethanesulfonyl)imide (NTf2−), dichloroacetate (CHCl2CO2−), tetrafluoroborate (BF4−), and hydrogen sulfate (HSO4−) as anions. Spectroscopic methods were used to validate the structures of the lab-synthesized ILs. We performed an agar well diffusion assay by using pathogenic bacteria that cause various infections (Escherichia coli; Enterobacter aerogenes; Klebsiella pneumoniae; Proteus vulgaris; Pseudomonas aeruginosa; Streptococcus pneumoniae; Streptococcus pyogenes) to scrutinize the in vitro antibacterial activity of the ILs. It was established that the nature and unique combination of the cations and anions were responsible for the antibacterial activity of the ILs. Among the tested ionic liquids, the imidazolium cation and NTf2− and HSO4− anions exhibited the highest antibacterial activity. The antibacterial potential was further investigated by in silico studies, and it was observed that bis(trifluoromethanesulfonyl)imide (NTf2−) containing imidazolium and pyridinium ionic liquids showed the maximum inhibition against the targeted bacterial strains and could be utilized in antibiotics. These antibacterial activities float the ILs as a promising alternative to the existing antibiotics and antiseptics. [ABSTRACT FROM AUTHOR]

A synthesis of a cationic moiety and fluorescent moieties containing amphiphilic 1,4-dihydropyridine (1,4-DHP) derivatives was performed starting with the Hantzsch-type cyclization of dodecyl acetoacetate, phenylaldehyde and ammonium acetate. Bromination of the 2,6-dimethyl groups of a parent 1,4-DHP compound, followed by nucleophilic substitution of bromine with 4-(anthracen-9-yl)pyridine, produced the desired 1,1′-{[3,5-bis((dodecyloxycarbonyl)-4-phenyl-1,4-dihydropyridine-2,6-diyl]bis(methylene)}bis[4-(anthracen-9-yl)pyridin-1-ium] dibromide. The obtained target compound was fully characterized by the IR, 1H NMR, 13C NMR and HRMS data. Studies of the self-assembling properties and characterization of the nanoparticles obtained by the ethanol injection method were performed using dynamic light scattering (DLS) measurements. DLS measurement data showed that 1,1′-{[3,5-bis((dodecyloxycarbonyl)-4-phenyl-1,4-dihydropyridine-2,6-diyl]bis(methylene)}bis[4-(anthracen-9-yl)pyridin-1-ium] dibromide produced liposomes that had average diameters of 200 nm when the samples were freshly prepared, and 140 nm after 7 days or 1 month storage. The PDI values of the samples were approximately 0.50 and their zeta-potential values were approximately 41 mV when the samples were freshly prepared, and 33 mV after storage. The obtained nanoparticles were stored at room temperature for one month and remained stable during that period. The mean molecular area of the cationic 1,4-DHP-anthracene hybrid 4 was 118 Å2, while the mean molecular area of the cationic 1,4-DHP 5 without anthracene substituents was only 83 Å2. The photoluminescence quantum yield (PLQY) value for the EtOH solution of the 1,4-DHP derivative 4 was 10.8%, but for the 1,4-DHP derivative 5 it was only 1.8%. These types of compounds could be used as synthetic lipids in the further development of prospective theranostic delivery systems. [ABSTRACT FROM AUTHOR]

A synthesis of 3-(3,5-difluoro-3,5-bis((alkoxy)carbonyl)-2,6-dioxoheptan-4-yl)-1-methylpyridin-1-ium iodides with ethyl or nonyl ester groups at positions 3 and 5 was performed. Treatment of the corresponding 2',6'-dimethyl-1',4'-dihydro-[3,4'-bipyridine]-3',5'-dicarboxylates with Selectfluor® followed by quaternization of pyridine moiety in the obtained dialkyl 2,4-diacetyl-2,4-difluoro-3-(pyridin-3-yl)pentanedioates with methyl iodide gave the desired 3-(3,5-difluoro-3,5-bis((alkoxy)carbonyl)-2,6-dioxoheptan-4-yl)-1-methylpyridin-1-ium iodides. This type of compound would be useful as synthetic lipids for further development of the delivery systems. The obtained target compounds were fully characterized by 1H NMR, 19F NMR, 13C NMR, HRMS, IR and UV data. The estimation of self-assembling properties and characterization of the nanoparticles obtained by ethanol solution injection in an aqueous media were performed by dynamic light scattering (DLS) measurements. DLS measurement data showed that 3-(3,5-difluoro-3,5-bis((nonyloxy)carbonyl)-2,6-dioxoheptan-4-yl)-1-methylpyridin-1-ium iodide created liposomes with the average diameter of 300–400 nm and polydispersity index (PDI) value around 0.30–0.40, while 3-(3,5-difluoro-3,5-bis((ethyloxy)carbonyl)-2,6-dioxoheptan-4-yl)-1-methylpyridin-1-ium iodide formed a heterogeneous sample with PDI value 1, which was not prospective for delivery system development. [ABSTRACT FROM AUTHOR]

Nowadays, covalent-organic frameworks (COFs) integrated with the electrochemiluminescence (ECL) behavior are highly desired owing to the significant advantages including multifunctionality, high sensitivity, and low background noise. Here, two ionic COFs (iCOFs) consisting of the anthryl-extended viologen as the backbone were designed and synthesized via the Zincke reaction. It is found for the first time that the as-prepared iCOFs accompanied by potassium persulfate as the coreactant can provide a clear ECL response in a water-bearing medium. The maximum ECL emissions of the iCOFs were in agreement with the photoluminescence spectra. Besides, cyclic voltammetry and electron paramagnetic resonance measurements reveal that the pyridinium unit was electrochemically reduced to afford the free radical. Then, it reacted with SO 4 ·- to generate the excited-state [iCOF]*. Finally, [iCOF]* quickly returned to its ground state coupled with a clear ECL emission, yielding a maximum ECL quantum efficiency of 23.4% compared with tris(2,2'-bipyridyl) ruthenium(II) as the benchmark. In brief, the current study opens a way to develop a kind of ECL emitter that holds great potential in sensing, imaging, and light-emitting devices.

Efficient electrochemical energy storage has been identified as one of the most pressing needs for a sustainable energy economy. Inorganic battery materials have traditionally been the center of attention, with the current state-of-the-art device being the lithium-ion battery. Recent pursuits have led to organic materials for their beneficial chemistry and properties, but suitable materials for organic batteries are still few and far between. This Spotlight on Applications highlights two intriguing pyridinium-based organic materials, modified viologens and carbonylpyridiniums, that have both been successfully employed in electrode materials for solid-state Li-ion-type organic batteries (LOBs). We first provide an overview of the inherent electronic properties of each building block and how they can effectively be modified while maintaining or enhancing their desirable electrochemical properties for practical applications. We then describe a range of different material designs for a battery context and their application in various organic device settings, with some examples showing competitive performance with traditional Li-ion batteries.

A synthesis of a cationic moiety and fluorescent moieties containing amphiphilic 1,4-dihydropyridine (1,4-DHP) derivatives was performed starting with the Hantzsch-type cyclization of dodecyl acetoacetate, phenylaldehyde and ammonium acetate. Bromination of the 2,6-dimethyl groups of a parent 1,4-DHP compound, followed by nucleophilic substitution of bromine with 4-(anthracen-9-yl)pyridine, produced the desired 1,1′-{[3,5-bis((dodecyloxycarbonyl)-4-phenyl-1,4-dihydropyridine-2,6-diyl]bis(methylene)}bis[4-(anthracen-9-yl)pyridin-1-ium] dibromide. The obtained target compound was fully characterized by the IR, 1H NMR, 13C NMR and HRMS data. Studies of the self-assembling properties and characterization of the nanoparticles obtained by the ethanol injection method were performed using dynamic light scattering (DLS) measurements. DLS measurement data showed that 1,1′-{[3,5-bis((dodecyloxycarbonyl)-4-phenyl-1,4-dihydropyridine-2,6-diyl]bis(methylene)}bis[4-(anthracen-9-yl)pyridin-1-ium] dibromide produced liposomes that had average diameters of 200 nm when the samples were freshly prepared, and 140 nm after 7 days or 1 month storage. The PDI values of the samples were approximately 0.50 and their zeta-potential values were approximately 41 mV when the samples were freshly prepared, and 33 mV after storage. The obtained nanoparticles were stored at room temperature for one month and remained stable during that period. The mean molecular area of the cationic 1,4-DHP-anthracene hybrid 4 was 118 Å2, while the mean molecular area of the cationic 1,4-DHP 5 without anthracene substituents was only 83 Å2. The photoluminescence quantum yield (PLQY) value for the EtOH solution of the 1,4-DHP derivative 4 was 10.8%, but for the 1,4-DHP derivative 5 it was only 1.8%. These types of compounds could be used as synthetic lipids in the further development of prospective theranostic delivery systems.

Synthesis and Characterization of six novel N,N-dioctylsuccinamate based room temperature ionic liquids (RTILs) bearing imidazolium, pyridinium, ester imidazolium, and quaternary ammonium cations is reported. Extraction of Pb(II) and Co(II) by these RTILs has been investigated. Ionic liquids (ILs) synthesized were [C4mim][N88SA], [C8mim][N88SA], [C4Py][N88SA], [C8Py][N88SA], [α-mim-ester][N88SA] and [N2244][N88SA] termed as L1, L2, L3, L4, L5 and L6 respectively. Liquid-liquid extraction was performed and all the six systems showed excellent extractability results for both Pb(II) and Co(II). During the process of extraction several factors i.e., nature of cation, pH of the aqueous phase, equilibration time, and initial metal ion concentration were investigated. The extraction efficiency of above 98 % for all types of extractants was observed. The nature of cation its concentration, equilibration time, and pH of the aqueous phase significantly influenced the extraction efficiency. Maximum extraction was observed at pH values between 4 and 8 and optimum contact time was observed to be 40–45 min. Increasing the metal ion concentration decreased the extraction efficiency. The extraction efficiency of both metal ions decreased in the order [N88SA][C8mim] (L2) > [α-mim-Ester][N88SA] (L5) > [N88SA][C4mim] (L1). This is evident from the order of extraction behaviour that increasing the bulkiness of cation, results in stronger complexation, hence increasing extraction.

Two NIR-emitting donor-π-acceptor (D-π-A) type regioisomeric styryl pyridinium dyes (1a–1b) were synthesized and studied for their photophysical performance and environment sensitivity. The two regioisomers, 1a and 1b, exhibited interesting photophysical properties including, longer wavelength excitation (λex ≈ 530–560 nm), bright near-infrared emission (λem ≈ 690–720 nm), high-fluorescence quantum yields (ϕfl ≈ 0.24–0.72) large Stokes’ shift (∆λ ≈ 150–240 nm) and high-environmental sensitivity. Probe’s photophysical properties were studied in different environmental conditions such as polarity, viscosity, temperature, and concentration. Probes (1a–1b) exhibited noticeable changes in absorbance, emission and Stokes’ shift while responding to the changes in physical environment. Probe 1b exhibited a significant bathochromic shift in optical spectra (∆λ ≈ 20–40 nm) compared to its isomer 1a, due to the regio-effect. Probes (1a–1b) exhibited an excellent ability to visualize bacteria (Bacillus megaterium, Escherichia coli), and yeast (Saccharomyces cerevisiae) via fluorescence microscopy.

Carbon materials have shown great promise as cost‐effective electrocatalysts for H2O2 electrochemical production. In this work, we prepare a series of well‐defined pyridinium‐conjugated graphite sheets via nucleophilic substitution reaction of graphite with pyridine derivatives in anodic oxidation process. A combination of experimental and computational investigations confirm that the pyridine derivatives are electrochemically grafted onto the armchair‐type edges of graphitic layers, where the adjacent carbon atoms show the positively charged state by the intramolecular charge transfer. The strong charge delocalization on pyridinium‐conjugated graphite sheets leads to the enhanced electrocatalytic performance for oxygen reduction in terms of both activity and selectivity (above 97 %) for H2O2 production. Moreover, we find that the yield of H2O2 is also affected by the H2O2 decomposing capabilities of functional groups on pyridinium. As one kind of pyrolysis‐free strategies, the proposed electrochemical grafting can serve as a molecularly precise regulation to develop nitrogen doped carbon materials for more applications. [ABSTRACT FROM AUTHOR]

Boron dipyrromethene (BODIPY) dyes bearing a pyridyl moiety have been used as metal ion sensors, pH sensors, fluorescence probes, and as sensitizers for phototherapy. A comparative study of the properties of the three structural isomers of meso-pyridyl-BODIPYs, their 2,6-dichloro derivatives, and their corresponding methylated cationic pyridinium-BODIPYs was conducted using spectroscopic and electrochemical methods, X-ray analyses, and TD-DFT calculations. Among the neutral derivatives, the 3Py and 4Py isomers showed the highest relative fluorescence quantum yields in organic solvents, which were further enhanced 2-4-fold via the introduction of two chlorines at the 2,6-positions. Among the cationic derivatives, the 2catPy showed the highest relative fluorescence quantum yield in organic solvents, which was further enhanced by the use of a bulky counter anion (PF6−). In water, the quantum yields were greatly reduced for all three isomers but were shown to be enhanced upon introduction of 2,6-dichloro groups. Our results indicate that 2,6-dichloro-meso-(2- and 3-pyridinium)-BODIPYs are the most promising for sensing applications. Furthermore, all pyridinium BODIPYs are highly water-soluble and display low cytotoxicity towards human HEp2 cells. [ABSTRACT FROM AUTHOR]

A solvent‐free method for the synthesis of quaternary ammonium salts (QAS) by iodoquaternization of alkenes with N‐heteroarenes was reported. Its advantages lie in energy‐saving and clean production by using iodine as the oxidant and manual grinding the starting materials, together with the complete atom economy and low process mass intensity (PMI) value. Demonstrated by 50 examples, the generated QAS was proved to be able to produce valuable chemicals, such as biological protease inhibitors, anti‐cancer agents, and organic fluorescent materials. [ABSTRACT FROM AUTHOR]

A synthesis of 3-(3,5-difluoro-3,5-bis((alkoxy)carbonyl)-2,6-dioxoheptan-4-yl)-1-methylpyridin-1-ium iodides with ethyl or nonyl ester groups at positions 3 and 5 was performed. Treatment of the corresponding 2’,6’-dimethyl-1’,4’-dihydro-[3,4’-bipyridine]-3’,5’-dicarboxylates with Selectfluor® followed by quaternization of pyridine moiety in the obtained dialkyl 2,4-diacetyl-2,4-difluoro-3-(pyridin-3-yl)pentanedioates with methyl iodide gave the desired 3-(3,5-difluoro-3,5-bis((alkoxy)carbonyl)-2,6-dioxoheptan-4-yl)-1-methylpyridin-1-ium iodides. This type of compound would be useful as synthetic lipids for further development of the delivery systems. The obtained target compounds were fully characterized by 1H NMR, 19F NMR, 13C NMR, HRMS, IR and UV data. The estimation of self-assembling properties and characterization of the nanoparticles obtained by ethanol solution injection in an aqueous media were performed by dynamic light scattering (DLS) measurements. DLS measurement data showed that 3-(3,5-difluoro-3,5-bis((nonyloxy)carbonyl)-2,6-dioxoheptan-4-yl)-1-methylpyridin-1-ium iodide created liposomes with the average diameter of 300–400 nm and polydispersity index (PDI) value around 0.30–0.40, while 3-(3,5-difluoro-3,5-bis((ethyloxy)carbonyl)-2,6-dioxoheptan-4-yl)-1-methylpyridin-1-ium iodide formed a heterogeneous sample with PDI value 1, which was not prospective for delivery system development.

N -(sodium 2-hydroxypropylsulfonate) chitosan (HSCS), N -sulfonate chitosan (SCS) and N -isonicotinic sulfonate chitosan (ISCS) were prepared. The structures of the prepared chitosan derivatives were characterized by nuclear magnetic resonance (1H NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, ultraviolet–visible (UV–vis) spectroscopy and elemental analysis (EA). Antibacterial and antibiofilm activities of these chitosan derivatives were evaluated in vitro. The minimum inhibitory concentration (MIC) of HSCS and SCS against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were 0.625 mg/mL and 0.156 mg/mL, respectively. ISCS exhibited MIC values of 0.313 mg/mL and 0.078 mg/mL against E. coli and S. aureus , respectively. ISCS demonstrated superior antibacterial and antibiofilm properties compared to SCS and HSCS. These findings suggest that the incorporation of a pyridine structure into sulfonate chitosan enhances its antibacterial and antibiofilm activities, and the prepared ISCS has a promising application prospect for controlling the reproduction of microorganisms in the field of food packaging. [Display omitted] • The N -isonicotinic sulfonate chitosan was synthesized. • The antibacterial and antibiofilm activities of chitosan derivatives were evaluated. • They showed better antibacterial and antibiofilm activities than chitosan. • The antibacterial properties of chitosan are related to the positive charge density. [ABSTRACT FROM AUTHOR]

[Display omitted] • Metameric impacts showed conformations to be twisted for Reichardt's and planar for Brooker's types. • Metameric impacts showed clear differences in molecular dipole moments for these zwitterions. • Aromatic p -phenylene bridge cases showed 2-fold enhanced dipole moments than non-bridged cases. • Despite the twisted vs planar conformations, dipole moments were found to be unidirectional. • HF, MP2 and CASSCF showed similar behaviours, and DFT methodologies showed very different characteristics. In this contribution, molecular structures, and dipole moments (using self-consistent and linear response theories) were reported for two p -phenylene bridged mesomeric betaines, using AM1, HF, B3LYP, B3PW91, M06-2X, LC-ωPBE, CAM-B3LYP, MP2 and CASSCF methodologies. In this work (1) metameric influences on molecular conformations, and (2) molecular electric dipole moments , and then (3) impact of bridge by comparing with unbridged derivatives , are investigated. Metameric influence on conformational preference was observed and p -phenylene bridge was found to be acting like a facilitator. While most of the methodologies predicted only reasonable impacts of metamerism on molecular dipole moments ; the CASSCF method predicted around 2-fold enhanced dipole moment for Reichardt's type than Brooker's type. p -phenylene bridge effectively enhanced the dipole moments (∼2-fold) than non-bridged zwitterions. Linear response theory-based (field-dependent) results were found to be similar to the static (field-independent) dipole moments. HF, MP2 and CASSCF exhibited similar behaviors, and DFT-based methodologies very different characteristics. [ABSTRACT FROM AUTHOR]

Heteroarene 1, n-zwitterions are powerful and versatile building blocks in the construction of heterocycles and have received increasing attention in recent years. In particular, pyridinium and quinolinium 1,4-zwitterions have been widely studied and used in a variety of cyclization reactions due to their air stability, ease of use, and high efficiency. Sulfur- and nitrogen-based pyridinium and quinolinium 1,4-zwitterions, types of emerging heteroatom-containing synthons, have attracted much attention from chemists. These 1,4-zwitterions, which contain multiple reaction sites, have been successfully used in the synthesis of three- to eight-membered cyclic compounds over the last decade. In this review, we present the exciting progress made in the field of cyclization reactions of sulfur- and nitrogen-based pyridinium and quinolinium 1,4-zwitterions. Moreover, the mechanistic insights, the transition states, some synthetic applications, and the challenges and opportunities are also discussed. We hope to provide an overview for synthetic chemists who are interested in the heterocycle synthesis from cyclization reaction with pyridinium and quinolinium 1,4-zwitterions pyridinium and quinolinium 1,4-zwitterions.

In this study, the solubility of carbon dioxide gas in a series of 1-alkyl-4-methyl pyridinium and 1-alkyl-3-methylimidazolium-based ionic liquids with various anions, viz. thiocyanate ([SCN]−), chloride ([Cl]−) and bromide ([Br]−) was investigated using a quartz crystal microbalance at 298.15 K and pressures up to 0.4 MPa. CO2 solubility in the ionic liquids correlates well with the non-random two-liquid (NRTL) model. The results indicate that the cation alkyl chain length and the type of anion have the main effects on the solubility of carbon dioxide in ionic liquids. CO2 solubility in both 1-alkyl-4-methyl pyridinium and 1-alkyl-3-methylimidazolium-based ionic liquids increased with increasing alkyl chain length of the cation. Also, CO2 solubility was strongly dependent on the selection of the anion. CO2 solubility in both 1-alkyl-4-methyl pyridinium and 1-alkyl-3-methylimidazolium-based ionic liquids increased as follows: [SCN]− > [Cl]− > [Br]−. The solubility of CO2 in some of ionic liquids (ILs) was measured. CO2 solubility in ILs with different alkyl chain lengths in the cation increased with increasing alkyl chain length. Also, CO2 solubility increased with increasing anion basicity. [ABSTRACT FROM AUTHOR]

A pyridinium‐based complex with environment‐friendly and earth‐abundant ZnII ion was synthesized and explored as a green catalyst applied in activating molecular oxygen for the simple and efficient photooxidation of alcohols into aldehydes under additive‐free and mild conditions. The metal coordination was conducive to promoting the electron transfer efficiency and introducing the heavy‐atom effect for the increased generation of ⋅O2− and 1O2. Accordingly, improved photocatalytic performance of this complex compared to its precursor, no matter activity or selectivity, was obtained, facilitating the transformation of alcohols into aldehydes in a sustainable way. [ABSTRACT FROM AUTHOR]

Antibacterial activity is an essential property of ionic liquids. In this work, a comprehensive study has been performed on the antibacterial activity of ionic liquids to be utilized for further research and applications. Eighteen ionic liquids viz. Octyl Imidazolium, octyl Pyridinium, quaternary phosphonium-based cations containing bromide, sodium methane sulphonates, bis(trifluoromethane sulfonyl) imide, dichloroacetate, tetrafluoroborate, hydrogen sulfate were prepared and characterized with the help of different spectroscopic techniques. All these samples of ionic liquids were tested for their antibacterial activity against the most commonly occurring bacteria in the environment, i.e., Enterobacter aerogenes (E. aerogenes), Proteus vulgaris (P. vulgaris), Klebsiella pneumoniae (K. pneumoniae), Pseudomonas aeruginosa (P. aeruginosa), Escherichia coli (E. coli), and Streptococcus pyogenes (S. pyogenes). Most of the ionic liquids show good antibacterial properties, and imidazolium-based ionic liquids were even more antibacterial as compared to positive control. It was observed that a unique combination of cation and anion is essential to achieve desired antibacterial properties. The mechanism of antibacterial activity was further investigated using density functional theory calculations. A good correlation was found between experimental and theoretical studies.

Abstract Dearomative heterocyclic [4+2] cycloaddition between the N‐(2,4‐dinitrophenyl)pyridinium ion of nicotinamide and an enol ether was analyzed by Density Functional Theory (DFT) calculations. The calculation revealed that the reaction undergoes stepwise bond formation rather than occurring in a concerted manner. The experimental products were found to be both kinetically and thermodynamically favored. The calculated transition states and intermediate suggested that the high diastereoselectivity is derived from the electrostatic interaction between the 2‐nitro group of the pyridinium ion and the hydrogen of the enol ether.

The synergistic functioning of redox‐active components that emerges from prototypical 2,2′‐di(N‐methylpyrid‐4‐ylium)‐1,1′‐biphenyl is described. Interestingly, even if a trans conformation of the native assembly is expected, due to electrostatic repulsion between cationic pyridinium units, we demonstrate that cis conformation is equally energy‐stabilized on account of a peculiar LUMO (SupLUMO) that develops through space, encompassing the two pyridiniums in a single, made‐in‐one‐piece, electronic entity (superelectrophoric behavior). This SupLUMO emergence, with the cis species as superelectrophore embodiment, originates in a sudden change of electronic structure. This finding is substantiated by insights from solid state (single‐crystal X‐ray diffraction) and solution (NOE NMR and UV‐vis‐NIR spectroelectrochemistry) studies, combined with electronic structure computations. Electrochemistry shows that electron transfers are so strongly correlated that two‐electron reduction manifests itself as a single‐step process with a large potential inversion consistent with inner creation of a carbon‐carbon bond (digital simulation). Besides, absence of reductive formation of dimers is a further indication of a preferential intramolecular reactivity determined by the SupLUMO interaction (cis isomer pre‐organization). The redox‐gated covalent bond, serving as electron reservoir, was studied via atropisomerism of the reduction product (VT NMR study). The overall picture derived from this in‐depth study of 2,2′‐di(N‐methylpyrid‐4‐ylium)‐1,1′‐biphenyl proves that trans and cis species are worth considered as intrinsically sharply different, that is, as doubly‐electrophoric and singly‐superelectrophoric switchable assemblies, beyond conformational isomerism. Most importantly, the through‐space‐mediated SupLUMO may come in complement of other weak interactions encountered in Supramolecular Chemistry as a tool for the design of electroactive architectures. [ABSTRACT FROM AUTHOR]

In the crystal structure of the title compound, (C5H6N)[Cr(NCS)4(C5H5N)2]·C5H5N, the CrIII ions are octahedrally coordinated by four N-bonding thiocyanate anions and two pyridine ligands into discrete negatively charged complexes, with the CrIII ion, as well as the two pyridine ligands, located on crystallographic mirror planes. The mean planes of the two pyridine ligands are rotated with respect to each other by 90°. Charge balance is achieved by one protonated pyridine molecule that is hydrogen bonded to one additional pyridine solvent molecule, with both located on crystallographic mirror planes and again rotated by exactly 90°. The pyridinium H atom was refined as disordered between both pyridine N atoms in a 70:30 ratio, leading to a linear N—H...N hydrogen bond. In the crystal, discrete complexes are linked by weak C—H...S hydrogen bonds into chains that are connected by additional C—H...S hydrogen bonding via the pyridinium cations and solvent molecules into layers and finally into a three-dimensional network.

Full-visible color-tunable new fluorophores are essential in bioimaging research. However, it is significantly challenging to design fluorophores with the desired optical and biological properties owing to their structural complexity. We report a unified design of an interesting molecular framework, IndiFluors , based on the principle of a donor-acceptor-donor (D 1 -A-D 2 ) system. The IndiFluors comprise pyrylium, pyridinium, and pyridine derivatives, which exhibit full-visible emission color (375-700 nm) by varying donor and acceptor strengths of the core scaffolds. With a minimal change of structure, the bright fluorophores (Φ: 0.96) can be tuned to become nonfluorescent (Φ: 0.01), which is well explained by time-dependent density functional theory (TD-DFT/PCM) by oscillator strengths in the S1 state. Within IndiFluors , pyridinium offers several advantages, including a large Stokes shift (∼154 nm) and excellent stability, compared to pentacyclic pyrylium fluorophores. Especially, the designed probe, PM-Mito-OH , demonstrated specific colocalization in mitochondria and a monitored ratiometric pH change during mitochondrial damage, autolysosomes, and the mitophagy process. Hence, IndiFluors and the derived probe show great potential for cellular pH imaging in live cells while exhibiting minimal cytotoxicity.

The reaction of lanthanide (Ln) chloride hydrates ([Ln(H2O)n(Cl)3]) with pyridine (py) yielded a set of dehydrated pyridinium (py-H) Ln-polychloride salts. These species were crystallographically characterized as [[py-H-py][py-H]2[LnCl6]] (Ln-6; Ln = La, Ce, Pr, Nd, Sm, Eu, Gd) or [[py-H]2[LnCl5(py)]] ((Ln-5; Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu). The Ln-6 metal centers adopt an octahedral (OC-6) geometry, binding six Cl ligands. The −3 charge is off-set by two py-H moieties and a di-pyridinium (py-H-py) ion. For the Ln-5 species, an OC-6 anion is formed by the Ln cation binding a single py and five Cl ligands. The remaining −2 charge is offset by two py-H+ cations that H-bond to the anion. Significant H-bonding occurs between the various cation/anion moieties inducing the molecular stability. The change in structure from the Ln-6 to Ln-5 is believed to be due to the Ln-contraction producing a smaller unit cell, which prevents formation of the py-H-py+ cation, leading to the loss of the H-bonding-induced stability. Based on this, it was determined that the Ln-5 structures only exist when the lattice energy is small. While dehydrated polychloride salts can be produced by simply mixing in pyridine, the final structures adopted result from a delicate balance of cation size, Coulombic charge, and stabilizing H-bonding.