Search Results (27)

We report a rare family of pyridine-coordinated iodobismuthate(III) salts supported by alkyltriphenylphosphonium and tetraphenylphosphonium cations. Reactions of BiI₃ with Ph₃PR⁺I⁻ (R = Me, Et, ⁿPr, ⁿBu, Ph) in neat pyridine, followed by crystallization, yield structurally tunable bismuth-halide-pyridine anions dictated by reagent stoichiometry. Combination of BiI₃ and Ph₃PR⁺I⁻ in 2:1 ratio produced [Ph₃PR]₂[BiI₅Py], 1 (R = Me, Et, ⁿPr, Ph), while combination in 1:1 ratio resulted in three compounds: [Ph₃PR][cis-BiI₄Py₂], 2 (R = ⁿPr, Ph), [Ph₃PR][trans-BiI₄Py₂], 3 (R = Me, Et, Ph), and [Ph₃PR]₂[transoid-Bi₂I₈Py₂], 4 (R = Me, Et, ⁿPr, ⁿBu, Ph). In many cases, the compounds were isolated as Py or Et₂O solvates, and in some cases, multiple degrees of solvation or polymorphism were encountered. Hirshfeld analysis of 1–4 showed the major anion–cation/anion/solvent interactions to be H⋯I, H⋯H, and C⋯H. Diffuse reflectance measurements of representative compounds, all of which were yellow-orange to red-orange, revealed bandgaps in the range of 1.9–2.2 eV, where density-of-states KS-DFT calculations attribute the absorption to metal-centered charge transfer within the anionic unit. NLMO and QTAIM analyses further indicate predominantly ionic Bi(III)–I/pyridine bonding with robust inner-sphere coordination that is insensitive to anion speciation. Full article

This work explores a novel and efficient synthetic approach to a new class of boron cluster derivatives via the nucleophilic addition of stabilized phosphorus ylides, Ph₃P=CHR² (R² = COOEt, CN), to a series of nitrilium salts of the closo-decaborate anion, [2-B₁₀H₉NCR¹]⁻ (R¹ = Me, Et, ⁿPr, ⁱPr, Ph). The reaction proceeds regio- and stereospecifically, affording a diverse range of iminoacyl phosphorane derivatives, [2-B₁₀H₉NH=C(R¹)C(PPh₃)R²]⁻, in high isolated yields (up to 95%). The obtained compounds (10 examples) were isolated as tetrabutylammonium or tetraphenylphosphonium salts and thoroughly characterized by multinuclear NMR (¹¹B, ¹H, ¹³C, ³¹P), high-resolution mass spectrometry, and single-crystal X-ray diffraction. The reaction feasibility was found to be strongly influenced by the steric hindrance of the R¹ group. Furthermore, the practical utility of these novel hybrids was demonstrated by employing the [2-B₁₀H₉NH=C(CH₃)C(COOC₂H₅)=PPh₃]⁻ anion as a highly effective membrane-active component in ion-selective electrodes. The developed tetraphenylphosphonium (TPP⁺) sensor exhibited a near-Nernstian response, a low detection limit of 3 × 10⁻⁸ M, and excellent selectivity over a range of common inorganic and organic cations, showcasing the potential of closo-borate-based ionophores in analytical chemistry. Full article

The effects of potassium (K⁺) on yeast metabolism were documented as early as 1940. Studies proposing a mechanism for its transport started in 1950, and in 1953, a mechanism for the stimulation of fermentation was suggested. However, it was not until the 1970s that both mechanisms were clarified in Mexico, and the actual internal pH of the cells was measured. The presence of an H⁺-ATPase that generates an electric plasma membrane difference (PMP), which is used by specific transporters to facilitate the influx of K⁺ and other cations into the cells, was discovered. For years, many efforts were made to estimate and measure the value of the PMP; the obtained results were variable and erratic. In the 1980s, a methodology was developed to estimate the plasma membrane potential by following the fluorescence changes in the DiSC₃(3) dye and measuring its accumulation, which provided actual but inaccurate values. Similar values were obtained by measuring the accumulation of tetraphenylphosphonium. The most reliable method of measuring the actual values of the plasma membrane potential was only recently devised using the also fluorescent dye thioflavin T. This review presents the attempts and outcomes of these experiments necessary to clarify the results reported by different research groups. Innovative research with Genetically Encoded Voltage Indicators (GEVIs) is also included. Full article

Hybrid halocuprates (I) with organic cations show great potential for optoelectronic applications due to their tunable luminescence and high thermal stability. In this study, the iodocuprate (I) [PPh₄][Cu₃I₄], featuring unique helical chains of face-sharing tetrahedra, was synthesized and characterized. This compound exhibits a bandgap of 3.1 eV and orange luminescence at low temperature, attributed to self-trapped exciton emission. [PPh₄][Cu₃I₄] demonstrates exceptional thermal stability among hybrid halocuprates with decomposition above 380 °C, forming a stable melt at ~255 °C without Cu⁺ oxidation in ambient atmosphere. Full article

New derivatives of the closo-decaborate anion [B₁₀H₉–O(CH₂)₂O(CH₂)₃C(O)–L–OCH₃]²⁻ (An) (1: L = Trp; 2: L = His; 3: L = Met; 4: L = Ala(2-oxopyrrolidin-3-yl) (Pld) were synthesized and isolated as tetraphenylphosphonium salts (Ph₄P)₂An. Anions 1²⁻; 2²⁻; 3²⁻, and 4²⁻ contain a pendant functional group from the L-tryptophan methyl ester, L-histidine methyl ester, L-methionine methyl ester, or methyl 2-amino-3-(2-oxopyrrolidin-3-yl)propanoate (-Trp–OCH₃, -His–OCH₃, -Met–OCH₃, or -Pld–OCH₃) residue, respectively, bonded with the boron cluster anion through the oxybis[(ethane-2,1-diyl)oxy] spacer. This pacer is formed as a result of the nucleophilic opening of the attached dioxane molecule in the [B₁₀H₉O(CH₂)₄O]⁻ starting derivative. Sodium salts of the target compounds were isolated and used in biological experiments. It was established that among compounds Na₂An (An = 1–4), not all are capable of inhibiting the cytopathic effect of the virus in vitro. Sodium salts Na₂An have a low toxic effect on a monolayer of continuous canine embryonic kidney (MDCK) cell line. Compounds Na₂1 and Na₂2 had IC₅₀ of 5.0 and 20.0 μg/mL, respectively, while for compounds Na₂3 and Na₂4, IC₅₀ values could not be achieved at the concentrations studied. The studies performed for molecular docking of the anionic part of 1²⁻ and 2²⁻ with the transmembrane domain of viroporin M2 show some differences in the location of these two ligands inside the M2 canal pore. Full article

New iron and cobalt bis(dithiolene) complexes [M(3cbdt)₂] (3cbdt = 3-cyanobenzene-1,2-dithiolate) were prepared as tetraphenylphosphonium (Ph₄P⁺) salts for Fe in the monoanionic state and for Co in both the dianionic and monoanionic states: (Ph₄P)₂[Fe(III)(3cbdt)₂]₂ (1); (Ph₄P)₂[Co(III)(3cbdt)₂]₂ (2); (Ph₄P)₂[Co(II)(3cbdt)₂] (3). These compounds were characterized by single-crystal X-ray diffraction, cyclic voltammetry, EPR, and static magnetic susceptibility. Their properties are discussed in comparison with the corresponding complexes based on the isomer ligand 4-cyanobenzene-1,2-dithiolate (4cbdt) and 4,5-cyanobenzene-1,2-dithiolate (dcbdt), previously described by us. The Fe(III) and the Co(III) compounds (1 and 2) are isostructural, crystallizing in the triclinic $P\overline{1}$ space group, with cis [M(III)(3cbdt)₂] complexes dimerized in a trans fashion, and the transition metal (M = Fe, Co) has a distorted 4+1 square pyramidal coordination geometry. The Co(II) compound (3) crystallizes in the triclinic $P\overline{1}$ space group, with the unit cell containing one cis and three trans inequivalent [Co(II)(3cbdt)₂] complexes with the transition metal (Co) and having a square planar coordination geometry. The Fe(III) complex (1) is EPR-silent, and the static magnetic susceptibility shows a temperature dependence typical of dimers of antiferromagnetically coupled S = 3/2 spins with −J/k_B = 233.6 K and g = 1.8. Static magnetic susceptibility measurements of compound (3) show that this Co(II) complex is paramagnetic, corresponding to an S = ½ state with g = 2, in agreement with EPR spectra showing in solid state a hyperfine structure typical of the I(⁵⁹Co) = 7/2. Static susceptibility measurements of Co(III) complex (2) showed an increase in the paramagnetic susceptibility upon warming above 100 K, which is consistent with strong AFM coupling between dimerized S = 1 units with a constant −J/k_B ~1286 K. Full article

The thermal decomposition of (XMebpyH)₃(H₃O)[W(CN)₈]·3H₂O (where XMebpy denotes 4Mebpy 4,4′-dimethyl-2,2′-bipyridine or 5Mebpy 5,5′-dimethyl-2,2′-bipyridine) in glycerol results in the coordination of XMebpy. Salts of the anion formula [W(CN)₆(XMebpy)]²⁻ were isolated for PPh₄⁺ and/or AsPh₄⁺ cations as well as for K⁺, Rb⁺, and Cs⁺ ones. X-ray single-crystal analyses for tetraphenyl-phosphonium and tetraphenyl-arsonium cations are described. IR, UV-Vis, and cyclic voltammetry data are presented. The results were compared with those for [W(CN)₆(bpy)]²⁻ (bpy = 2,2′-bipyridine) ion salts. Full article

As mitochondria are negatively charged organelles, penetrating cations are used as parts of chimeric molecules to deliver specific compounds into mitochondria. In other words, they are used as electrophilic carriers for such chemical moieties as antioxidants, dyes, etc., to transfer them inside mitochondria. However, unmodified penetrating cations affect different aspects of cellular physiology as well. In this review, we have attempted to summarise the data about the side effects of commonly used natural (e.g., berberine) and artificial (e.g., tetraphenylphosphonium, rhodamine, methylene blue) penetrating cations on cellular physiology. For instance, it was shown that such types of molecules can (1) facilitate proton transport across membranes; (2) react with redox groups of the respiratory chain; (3) induce DNA damage; (4) interfere with pleiotropic drug resistance; (5) disturb membrane integrity; and (6) inhibit enzymes. Also, the products of the biodegradation of penetrating cations can be toxic. As penetrating cations accumulate in mitochondria, their toxicity is mostly due to mitochondrial damage. Mitochondria from certain types of cancer cells appear to be especially sensitive to penetrating cations. Here, we discuss the molecular mechanisms of the toxic effects and the anti-cancer activity of penetrating cations. Full article

A new mixed-valence one-dimensional coordination polymer of formula {[Co^II(MeOH)₂][(μ-NC)₂Co^III(dmphen)(CN)₂]₂}_n·2nH₂O (1) was obtained by reacting the Ph₄P[Co^II(dmphen)(CN)₃] metalloligand (dmphen = 2,9-dimethyl-1,10-phenanthroline and Ph₄P⁺ = tetraphenylphosphonium ion) with cobalt(II) acetate tetrahydrate. The structural analysis shows the formation of a neutral 4,2-ribbon-like chain of vertex-sharing cyanido-bridged {Co^III₂Co^II₂} squares in which the metalloligand underwent an oxidation process and a reorganization to form {Co^III(dmphen)(CN)₄}⁻ linkers that coordinate to the [Co^II(MeOH)₂]²⁺ units through single cyanido ligands. Both cobalt(II) and Co(III) cations are six-coordinated in distorted octahedral environments. The shortest intrachain distance between the paramagnetic cobalt(II) ions is 7.36 Å, a value which is shorter than the shortest interchain one (10.36 Å). Variable-temperature (1.9–300 K) static (dc) magnetic measurements for 1 indicate the occurrence of magnetically isolated high-spin cobalt(II) ions with a D value of +67.0 cm⁻¹. Dynamic alternating current (ac) magnetic measurements between 2.0–13 K reveal that 1 exhibits slow magnetic relaxation under non-zero applied dc fields, being thus a new example of field-induced SIM with easy-plane magnetic anisotropy. Theoretical calculations by CASSCF/NEVPT2 on 1 support the results from magnetometry. The relaxation of the magnetization occurs in the ground state under external dc fields through a two-phonon Raman process and one intra-Kramers mechanism. Full article

Staphylococcus pseudintermedius is the main bacterial cause of skin and soft tissue infections (SSTIs) in companion animals, particularly dogs. The emergence of methicillin-resistant S. pseudintermedius (MRSP) strains, frequently with multidrug resistance phenotypes is a public health concern. This study aimed to evaluate efflux, a resistance mechanism still poorly characterized in S. pseudintermedius, as a contributor to biocide and fluoroquinolone resistance. Susceptibility to the efflux pump substrates ethidium bromide (EtBr), tetraphenylphosphonium bromide (TPP) and ciprofloxacin (CIP) was evaluated by minimum inhibitory concentration (MIC) determination for 155 SSTIs-related S. pseudintermedius in companion animals. EtBr and TPP MIC distributions were analyzed to estimate cut-off (CO_WT) values. The effect of the efflux inhibitors (EIs) thioridazine and verapamil was assessed upon MICs and fluorometric EtBr accumulation assays, performed with/without glucose and/or EIs. This approach detected a non-wild type population towards TPP with increased efflux, showed to be strain-specific and glucose-dependent. Resistance to fluoroquinolones was mainly linked to target gene mutations, yet a contribution of efflux on CIP resistance levels could not be ruled out. In sum, this study highlights the relevance of efflux-mediated resistance in clinical S. pseudintermedius, particularly to biocides, and provides a methodological basis for further studies on the efflux activity on this important pathogen of companion animals. Full article

The mechanism of the phenol–epoxide ring-opening reaction using tetraphenylphosphonium-tetraphenylborate (TPP-K) was investigated using the density functional theory (DFT) method. The reaction was initiated by breaking the P-B bond of TPP-K. The generated tetraphenylborate (TetraPB⁻) reacted with phenol to form a phenoxide ion, which combined with tetraphenylphosphonium (TPP⁺) to produce the active species, i.e., tetraphenylphosphonium phenolate (TPP-OPh). The phenoxide ion in TPP-OPh nucleophilically attacked the epoxide. Simultaneously, the H atom in the phenolic OH group moved to the O atom of the ring-opened epoxide. The formed phenoxide ion bound to TPP⁺ again, and TPP-OPh was regenerated. The rate-determining steps in the reaction were the cleavage of the P-B bond and the triphenylborane-forming reaction. The free energies of activation were calculated to be 36.3 and 36.1 kcal/mol, respectively. It is also suggested that these values in the rate-determining steps could be manipulated by substituents introduced on the Ph group of TetraPB⁻. Based on these results, it is possible to construct new design guidelines for latent hardening accelerators such as TPP-K. Full article

Multidrug transporters (MDTs) are major contributors to microbial drug resistance and are further utilized for improving host phenotypes in biotechnological applications. Therefore, the identification of these MDTs and the understanding of their mechanisms of action in vivo are of great importance. However, their promiscuity and functional redundancy represent a major challenge towards their identification. Here, a multistep tolerance adaptive laboratory evolution (TALE) approach was leveraged to achieve this goal. Specifically, a wild-type E. coli K-12-MG1655 and its cognate knockout individual mutants ΔemrE, ΔtolC, and ΔacrB were evolved separately under increasing concentrations of two lipophilic cations, tetraphenylphosphonium (TPP⁺), and methyltriphenylphosphonium (MTPP⁺). The evolved strains showed a significant increase in MIC values of both cations and an apparent cross-cation resistance. Sequencing of all evolved mutants highlighted diverse mutational mechanisms that affect the activity of nine MDTs including acrB, mdtK, mdfA, acrE, emrD, tolC, acrA, mdtL, and mdtP. Besides regulatory mutations, several structural mutations were recognized in the proximal binding domain of acrB and the permeation pathways of both mdtK and mdfA. These details can aid in the rational design of MDT inhibitors to efficiently combat efflux-based drug resistance. Additionally, the TALE approach can be scaled to different microbes and molecules of medical and biotechnological relevance. Full article

An experimentally simple method for the direct determination of single-ion partition coefficients between water and a PVC membrane plasticized with o-NPOE is suggested. The method uses the traditional assumption of equal single-ion partition coefficients for some reference cation and anion, in this case tetraphenylphosphonium (TPP⁺) and tetraphenylborate (TPB⁻). The method is based on an integrated approach, including direct study of some salts’ distribution between water and membrane phases, estimation of ion association constants, and measurements of unbiased selectivity coefficients for ions of interest, including the reference ones. The knowledge of distribution coefficients together with ion association constants allows for direct calculation of the multiple of the single-ion partition coefficients for the corresponding cation and anion, while the knowledge of unbiased selectivity coefficients together with ion association constants allows for immediate estimation of the single-ion partition coefficients for any ion under study, if the corresponding value for the reference ion is known. Both potentiometric and extraction studies are inherently equilibrium-based techniques, while traditionally accepted methods such as voltammetry and diffusion are kinetical. The inner coherent scale of single-ion partition coefficients between water and membrane phases was constructed. Full article

To elucidate the oxidation behavior of the 2,2′-azobisphenolate (azp) ligand, a series of homoleptic 1:2 Al^III complexes of four azp derivatives (L1) with 5,5′-dichloro-, 5,5′-dimethyl-, 5,5′-di-t-butyl-, 3,3′,5,5′-tetramethyl-substituents and of one imino derivative (L2) were synthesized and obtained as TPP[Al(L)₂]·solvent (TPP = tetraphenylphosphonium ion). The X-ray crystal structure analyses showed that the two ONO-tridentate ligands were meridionally coordinated to a central Al^III ion in an almost perpendicular manner to give a homoleptic octahedral coordination structure in all the Al^III complexes. The proton nuclear magnetic resonance spectra suggested that all the Al^III complexes retained the homoleptic coordination structure in solution. From the cyclic voltammetry measurements in dichloromethane solutions, all the Al^III complexes with the azp ligands showed two partially reversible oxidation waves, and an additional reversible or partially reversible reduction wave. The substitution effects on the first oxidation and reduction peak potentials were revealed in the Al^III complexes with the azp ligands. On the other hand, the imino complex showed a partially reversible oxidation wave accompanying a film deposition. The density functional theory (DFT) calculations indicated that the molecular orbital (MO) coefficients of the frontier MOs in the Al^III complexes were present on the ligands and were absent on the Al^III ion. These results confirmed that the azp ligands are susceptible to oxidation and can give a relatively stable oxidation species depending upon substituent effects. Full article

Pioglitazone (PIO) is an insulin-sensitizing antidiabetic drug, which normalizes glucose and lipid metabolism but may provoke heart and liver failure and chronic kidney diseases. Both therapeutic and adverse effects of PIO can be accomplished through mitochondrial targets. Here, we explored the capability of PIO to modulate the mitochondrial membrane potential (ΔΨ_m) and the permeability transition pore (mPTP) opening in different models in vitro. ΔΨ_m was measured using tetraphenylphosphonium and the fluorescent dye rhodamine 123. The coupling of oxidative phosphorylation was estimated polarographically. The transport of ions and solutes across membranes was registered by potentiometric and spectral techniques. We found that PIO decreased ΔΨ_m in isolated mitochondria and intact thymocytes and the efficiency of ADP phosphorylation, particularly after the addition of Ca²⁺. The presence of the cytosolic fraction mitigated mitochondrial depolarization but made it sustained. Carboxyatractyloside diminished the PIO-dependent depolarization. PIO activated proton transport in deenergized mitochondria but not in artificial phospholipid vesicles. PIO had no effect on K⁺ and Ca²⁺ inward transport but drastically decreased the mitochondrial Ca²⁺-retention capacity and protective effects of adenine nucleotides against mPTP opening. Thus, PIO is a mild, partly ATP/ADP-translocase-dependent, uncoupler and a modulator of ATP production and mPTP sensitivity to Ca²⁺ and adenine nucleotides. These properties contribute to both therapeutic and adverse effects of PIO. Full article