Dihydrogen Phosphate Anions Research Articles

Transport of Anions across the Dialytic Membrane Induced by Complexation toward Dendritic Receptors.

A novel approach to inducing anion transport over the dialytic membrane was proposed and successfully tested using the dihydrogen phosphate anion. The anion receptor based on isophthalamide was anchored on a dendritic skeleton, resulting in a macromolecular structure with a limited possibility to cross the dialytic membrane. The dendritic receptor was placed in a compartment separated from a mother anion solution by a membrane. The resulting anion complexation reduced the actual concentration of the anion and induced the anion transfer across the membrane. The anion concentration in mother solution decreased, while it was found to be increased in the compartment with the dendritic receptor. This phenomenon was observed using dendritic receptors with four and eight complexation sites. A detailed analysis of a series of dialytic experiments by 1H NMR spectroscopy enabled an assessment of the complexation behavior of both receptors and an evaluation of the dendritic effect on the anion complexation.

Optical Anion Receptors with Urea/Thiourea Subunits on a TentaGel Support.

Two simple chemosensors with urea (L1) and thiourea (L2) groups were synthesized and studied by different spectroscopic techniques. Both receptors can sense acetate (Ac–), dihydrogen phosphate (H2PO4–), and fluoride (F–) anions, accompanied by changes in UV–vis and 1H NMR spectra, and an optical response is observed as a color change of the solutions due to deprotonation and hydrogen-bonding processes. Also, L1 and L2 were supported on TentaGel resins (R1 and R2), and their fluoride-sensing properties in DMSO and water solutions were studied. Interestingly, R2 can sense fluoride ions in sample solutions of 100% water.

Bioinspired Reactive Interfaces Based on Layered Double Hydroxides-Zn Rich Hydroxyapatite with Antibacterial Activity

This work is focused on the preparation and multi-technique characterization of potentially biocompatible reactive interfaces obtained by combining layered double hydroxides (LDHs) and hydroxyapatite (HA). Antimicrobial and osteoinductive metallic ions as Zn2+ and Ga3+ were chosen as intralayer constituents of LDH to obtain ZnAl and ZnAlGa systems. These LDHs, exchanged with dihydrogenphosphate anions, promoted the precipitation of HA on the LDH surface yielding HA@LDH composites. X-ray diffraction quantitative analysis, through the Rietveld refinement method, coupled with elemental analysis and micro-Raman spectroscopy showed the formation of a mixed Ca-Zn HA phase. Scanning electron microscopy revealed that HA, in the presence of LDH, grew preferentially along its a-axis, thus crystallizing mainly in the form of flake crystals. LDH and HA@LDH composites showed antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa at not cytotoxic concentrations for human osteoblasts (hFob 1.19), especially when Ga cations were present in the LDH structure. The effect of the presence of HA in the composites on the bone-bonding ability and on human osteoblast proliferation was also investigated. The HA seemed to reduce the toxicity of the LDH toward human osteoblast while did not affect the bone-bonding ability. This multidisciplinary study provides the bio-chemical, structural characterization of new LDH and HA@LDH composites, evaluating also their bioactivity to be potentially applicable to titanium-based prostheses.

In Ukrainian

Quantum chemical modeling of orthophosphoric acid adsorption sites on the hydrated surface of anatase was performed by the method of density functional theory (exchange-correlation functional PBE0, basis set 6-31 G(d,p)). The influence of the aqueous medium was taken into account within the framework of the continual solvent model. The work uses a cluster approach. The anatase surface is simulated by a neutral Ti(OH)4(H2O)2 cluster. The results of analysis of the geometry and energy characteristics of all the calculated complexes show that the highest interaction energy is inherent to the intermolecular complex of orthophosphoric acid and hydrated surface of anatase, where the oxygen atom of the phosphoryl group (О=Р≡) forms a hydrogen bond with a hydrogen atom of the coordinated water molecule of Ti(OH)4(H2O)2 cluster and two hydrogen atoms of the hydroxyl groups of the orthophosphoric acid molecule form two hydrogen bonds with two oxygen atoms of the titanol groups. The formation energy effect of this complex is -134.0 kJ/mol. The formation energy effect of the complex with separated charges by the proton transfer from the molecule H3PO4 to the Ti(OH)4(H2O)2 cluster with the formation of dihydrogen phosphate anion and the protonated form of the titanol group (º) is -131.1 kJ/mol, so indicating less thermodynamic probability of such intermolecular interaction. The smallest thermodynamic probability (-123.9 kJ/mol) of complexation between orthophosphoric acid and hydrated anatase surface where a water molecule moves from the coordination sphere of the titanium atom. The calculation results indicate a possible adsorption of the H3PO4 molecule in an aqueous solution on the hydrated anatase surface. Taking into account the effect of the solvent within the polarization continuum insignificantly changes the adsorption energy, which is -44.5 kJ/mol; for vacuum conditions this value is -49.0 kJ/mol.

Renaturation of Lyophilized Concanavalin a Treated in Water Content Controlled Hydrated Ionic Liquids

A fraction of commercially available lyophilized concanavalin A (ConA) shows low mannose binding activity. In this study, we investigated the effects of the component ion and water content of hydrated ionic liquids (ILs) as treatment solvent on the mannose binding ability of lyophilized ConA. While high mannose binding ability was observed treated in hydrated ILs composed of dihydrogen phosphate anion with three water molecules per ion pair, it decreased with increase in water content. In contrast, no increase in mannose binding ability was observed after treatment with hydrated ILs composed of bromide anions. A steady response in mannose binding was observed after treatment with hydrated cholinium dihydrogen phosphate ([ch][dhp]). Following treatment with hydrated [ch][dhp] with three water molecules per ion pair, the mannose binding ability of lyophilized ConA increased twofold, while the low and high mannose binding ConA fraction showed an increase of 3.3 and 1.8 in the binding response, respectively.

Controlled Diffusion of Photoswitchable Receptors by Binding Anti-electrostatic Hydrogen-Bonded Phosphate Oligomers.

Dihydrogen phosphate anions are found to spontaneously associate into anti-electrostatic oligomers via hydrogen bonding interactions at millimolar concentrations in DMSO. Diffusion NMR measurements supported formation of these oligomers, which can be bound by photoswitchable anion receptors to form large bridged assemblies of approximately three times the volume of the unbound receptor. Photoisomerization of the oligomer-bound receptor causes a decrease in diffusion coefficient of up to 16%, corresponding to a 70% increase in effective volume. This new approach to external control of diffusion opens prospects in controlling molecular transport using light.

Synthesis of dihydrogen phosphate-based ionic liquids: Experimental and COSMO-RS based investigation for methane hydrate inhibition

In this study, three novel ionic liquids (ILs) having dihydrogen phosphate anion namely, 1-ethyl-3-methylimidazolium dihydrogen phosphate (EMIMDHP), 1-(3-cyanopropyl)-3-methylimidazolium dihydrogen phosphate (CPMIM DHP) and 1-butyl-3-methylimidazolium dihydrogen phosphate (BMIM DHP) are synthesized through metathesis reaction for their potential application as novel gas hydrate inhibitors. Their structures are confirmed by Nuclear Magnetic Resonance (1H NMR). The ILs effects on the equilibrium methane hydrate dissociation curve and the induction time in a pressure range of 50 to 100 bar are measured in a high-pressure micro-differential scanning calorimeter (HP Micro-DSC). The inhibition ability of these ILs towards hydrate formation are predicted through the analysis of σ-profile, which describe the hydrogen-bond formation properties of the ILs, computed by COSMO-RS software. Prior to that, a standard correlation model for hydrate dissociation of pure water as the baseline for the Hydrate-aqueous Liquid-Vapor Equilibrium (HLVE) curve is successfully developed through experimental and literature data. Hence, this model can be used by any researcher as a baseline for the HLVE curve. Through the Micro-DSC experiments, these ILs are found to perform a dual-functional thermodynamic and kinetic inhibitor behaviour. These ILs simultaneously shift the HLVE curve to a lower temperature and retard the hydrate formation by slowing down the hydrate nucleation rate.

Exploring the Effects of Various Polymeric Backbones on the Performance of a Hydroxyaromatic 1,2,3-Triazole Anion Sensor

Polymeric chemosensors are vital sensing tools because of higher sensitivity compared to their monomeric counterparts and tunable mechanical properties. This study focuses on the incorporation of a hydroxyaromatic 1,2,3-triazole sensor, 2-(4-phenyl 1H-1,2,3-triazol-1-yl)phenol (PTP), into polymers. By itself, the triazole has a selective, fluorometric response to the fluoride, acetate, and dihydrogen phosphate anions, and is most responsive to fluoride. Current investigations probe the suitability of various polymeric backbones for the retention and enhancement of the triazole’s sensing capabilities. Backbones derived from acrylic acid, methyl methacrylate, divinylbenzene, and styrene were explored. UV-illumination, Nuclear Magnetic Resonance (NMR) titration, and ultraviolet-visible (UV-Vis) absorption and fluorescence spectroscopy studies are used to investigate the performance of newly synthesized polymers and the derivatives of PTP that serve as the polymers’ precursors. Among the polymers investigated, copolymers with styrene proved best; these systems retained the sensing capabilities and were amenable to tuning for sensitivity.

Extraction of lignin and quantitative sugar release from biomass using efficient and cost-effective pyridinium protic ionic liquids.

Lignocellulosic biomass is enormously abundant around the globe. It bears huge potential for renewable products as its components can be converted to many useful products via cheaper processes. Recently, the component of biomass that has attracted enormous attention is lignin owing to its several aromatic or phenolic constituents. The utilization of lignin, however, is hindered by its troublesome separation mainly due to the difficult nature of the lignocellulosic biomass. Protic ionic liquids have great potential for extraction of lignin from the lignocellulosic biomass to make it viable for various transformations. In this study, protic ionic liquids comprising a pyridinium cation and a dihydrogen phosphate anion (H2PO4−) were prepared and used for lignin extraction and subsequent saccharification of the cellulose pulp. The ILs exhibited appreciably high lignin yields (optimum 73%) under mild conditions (100 °C) and shorter time (2 h). Fairly good sugar (glucose) yields (77%) verify effective delignification. The analysis of ILs and biomass was accomplished by H-NMR, FT-IR, SEM, HSQC and GPC.

Rationally designed phenanthrene derivatized triazole as a dual chemosensor for fluoride and copper recognition.

A 1,2,3-triazole chemosensor containing phenanthrene and phenol moieties (PhTP) was efficiently synthesized via copper (I)-catalyzed azide-alkyne cycloaddition, "click chemistry". PhTP is a dual analyte sensor for fluoride and copper (II) ions in homogeneous medium. Deprotonation of the phenolic OH proton by the fluoride ion is responsible for a change in fluorescence color from blue (PhTP) to yellowish-orange (PhTP-fluoride adduct), while a charge transfer between the triazole nitrogen of the chemosensor and Cu2+ revealed a turn-off fluorescence output. The detection capability of PhTP was analyzed with a series of anions (F-, Cl-, Br-, I-, H2PO4-, ClO4-, OAc-, BF4-) and cations (Fe3+, Fe2+, Cu2+, Ag+, Cr3+, Al3+, Co2+, Ni2+, Cd2+, Zn2+). With anions, competitive fluorescence responses under UV lamp were observed for acetate and dihydrogen phosphate anions, but maximum response from fluoride ion was substantiated from steady state absorption and fluorescence experiments. With cations, PhTP displayed a selective and sensitive recognition towards Cu2+ ion through spectral modulation in absorption spectroscopy and a turn-off fluorescence response. Nuclear magnetic resonance (NMR) spectroscopic titration studies supported the results obtained through photophysical studies and provided evidence for the ion-binding sites on the probe.

Cast iron corrosion protection with chemically modified Mg[sbnd]Al layered double hydroxides synthesized using a novel approach

Layered double hydroxides (LDHs) intercalated with corrosion inhibitive species are considered as promising additives to protection coatings. However, the conventional method of LDH preparation via co-precipitation followed by anion exchange is a water consuming and slow process hardly applicable to industrial use.In this work, a novel approach to LDH synthesis via hydration of sol-gel prepared mixed metal oxides and two-step anion exchange, all assisted by high-power sonication, was applied. MgAl and Mg-Al-Ce LDH with cations ratios 2:1 and 2:0.9:0.1, respectively, intercalated with corrosion inhibitive dihydrogen phosphate anion were successfully prepared.The obtained LDH were characterized by X-ray diffraction and scanning transmission electron microscopy. Anion release from these LDH in NaCl solutions and their corrosion inhibitive action on cast iron samples were monitored by electrochemical impedance spectroscopy. The results show that the dihydrogen-phosphate-intercalated LDHs produced using the novel technique are efficient in corrosion protection.

A Molecular Cobalt Hydrogen Evolution Catalyst Showing High Activity and Outstanding Tolerance to CO and O2.

There is a demand to develop molecular catalysts promoting the hydrogen evolution reaction (HER) with a high catalytic rate and a high tolerance to various inhibitors, such as CO and O2 . Herein we report a cobalt catalyst with a penta-dentate macrocyclic ligand (1-Co), which exhibits a fast catalytic rate (TOF=2210 s-1 ) in aqueous pH 7.0 phosphate buffer solution, in which proton transfer from a dihydrogen phosphate anion (H2 PO4 - ) plays a key role in catalytic enhancement. The electrocatalyst exhibits a high tolerance to inhibitors, displaying over 90 % retention of its activity under either CO or air atmosphere. Its high tolerance to CO is concluded to arise from the kinetically labile character of undesirable CO-bound species due to the geometrical frustration posed by the ligand, which prevents an ideal trigonal bipyramid being established.

A Molecular Cobalt Hydrogen Evolution Catalyst Showing High Activity and Outstanding Tolerance to CO and O2

AbstractThere is a demand to develop molecular catalysts promoting the hydrogen evolution reaction (HER) with a high catalytic rate and a high tolerance to various inhibitors, such as CO and O2. Herein we report a cobalt catalyst with a penta‐dentate macrocyclic ligand (1‐Co), which exhibits a fast catalytic rate (TOF=2210 s−1) in aqueous pH 7.0 phosphate buffer solution, in which proton transfer from a dihydrogen phosphate anion (H2PO4−) plays a key role in catalytic enhancement. The electrocatalyst exhibits a high tolerance to inhibitors, displaying over 90 % retention of its activity under either CO or air atmosphere. Its high tolerance to CO is concluded to arise from the kinetically labile character of undesirable CO‐bound species due to the geometrical frustration posed by the ligand, which prevents an ideal trigonal bipyramid being established.

Synthesis of Tris-pillar[5]arene and Its Association with Phenothiazine Dye: Colorimetric Recognition of Anions.

A multicyclophane with a core based on tris(2-aminoethyl)amine (TREN) linked by amide spacers to three fragments of pillar[5]arene was synthesized. The choice of the tris-amide core allowed the multicyclophane to bind to anion guests. The presence of three terminal pillar[5]arene units provides the possibility of effectively binding the colorimetric probe N-phenyl-3-(phenylimino)-3H-phenothiazin-7-amine (PhTz). It was established that the multicyclophane complexed PhTz in chloroform with a 1:1 stoichiometry (lgKa = 5.2 ± 0.1), absorbing at 650 nm. The proposed structure of the complex was confirmed by 1H-NMR spectroscopy: the amide group linking the pillar[5]arene to the TREN core forms a hydrogen bond with the PhTz imino-group while the pillararenes surround PhTz. It was established that the PhTz:tris-pillar[5]arene complex could be used as a colorimetric probe for fluoride, acetate, and dihydrogen phosphate anions due to the anion binding with proton donating amide groups which displaced the PhTz probe. Dye displacement resulted in a color change from blue to pink, lowering the absorption band at 650 nm and increasing that at 533 nm.

THE CONTRIBUTION OF LACTATE AND PHOSPHATE ANIONS TO THE BUFFER PROPERTIES OF TISSUE HOMOGENATES OF BREAST ADENOCARCINOMA

The article discusses the role of conjugated lactic acid/ lactate anion (LacH/Lac-) and dihydrogenphosphate anion/ hydrogenphosphate anion (H2PO4-/HPO42-) pairs in the formation of the buffer properties of tissue as a factor determining pH. The buffer properties of homogenates of the tissue of adenocarcinoma of the mammary gland and the adjacent tissue were quantitatively characterized by the buffer capacity which was determined by potentiometric titration. The concentrations of acid anions were determined spectrophotometrically. The material was biopsy specimens of mammary gland adenocarcinoma (T1-4, N0-1, M0) and adjacent tissue of 22 patients aged from 33 to 75 years. It was found that the buffer capacity of tumors is in 2.5 times higher than in normal tissue. It was established that for the tumor tissue, the buffer capacity of the LacH/Lac- system is in 3 times higher, and the buffer capacity of the H2PO4-/HPO42-system is in 2.5 times greater than for normal untransformed tissue. Concentrations of lactate anions (1,93 ± 0,50 vs 0,57 ± 0,22; p <0.001) and phosphate anions (2,54 ± 0,39 vs 0,70 ± 0,19; p <0,001) in homogenates of the tumor tissue were significantly higher in tumor tissue in comparison with the adjacent tissue. A strong correlation was found between the concentration of phosphate anions and the buffer capacity for tumor tissue (r = 0,857; p = 0,002) and for adjacent tissue (r = 0,917; p <0,001). The correlation between the concentration of lactate anions and the buffer capacity for tumor tissues can be estimated as average (r = 0,626; p = 0,053), while it is absent for the adjacent tissue (r = 0,494; p = 0,147). The results suggest that the acid-base properties of homogenates of mammary adenocarcinoma tissues are determined by two buffer systems: LacH/Lac- and H2PO4-/HPO42-, while the intracellular acid-base homeostasis of non-transformed tissues is mainly determined by the H2PO4-/HPO42- system.

Photophysical properties of 1-pyridine-3-phenylpyrazoloquinoline and molecular logic gate implementation

The work demonstrates the photophysical properties of 1-(2-pyridyl)-3-phenyl-pyrazolo[3,4-b]quinoline with the focus on the effect of pyridyl substituent on excited-state deactivation of the pyrazoloquinoline core, and on the molecular logic gate implementation. The deactivation mechanism of the singlet excited state was investigated by means of UV-vis absorption, steady-state and time-resolved fluorescence spectroscopy as well as nanosecond laser flash photolysis. The maximum of absorption (emission) in nonpolar cyclohexane is located at 385 nm (421 nm) and only slightly depends on solvent polarity. The compound exhibits a moderate fluorescence (up to 42%) and a low-temperature phosphorescence (77 K). The studies reveal that the pyridyl group modifies the deactivation mechanism by triggering efficient intersystem crossing. Moreover, the effect of various chemical species: proton, electron-donating amine, and dihydrogenphosphate anion on the absorption and emission of the investigated dye was evaluated. The interpretation of the fluorescence behaviour in the presence or absence of the chemical inputs leads to the realization of unimolecular logic circuits that are able to perform advanced arithmetic operations, such as subtraction (XOR/INH) or IMP/INH logic circuit. The experimental results were supported by quantum-chemical calculations.

Suitability of dihydrogen phosphate anion to salt out cholinium-based ionic liquids

The segregation capacity of cholinium dihydrogen phosphate (N1112OHDHP) in aqueous solutions of two non-ionic surfactants belonging to Triton X family (Triton X-100 and Triton X-102) was explored at different temperatures from T = (298.15 to 333.15) K. The experimental data for each binodal curve have been correlated using three empirical models based on exponential and polynomial equations. The tie-line data were suitably described by applying the Othmer-Tobias and Bancroft models. The data obtained demonstrated the great ability of N1112OHDHP to act as phase promoter in aqueous solutions of non-ionic surfactants in comparison with other ionic liquids like N1112OHCl, N1112OHDHC or C2C1imC2SO4.

Crystal structure of a host-guest complex of the tris-urea receptor, 3-(4-nitro-phen-yl)-1,1-bis-{2-[3-(4-nitro-phen-yl)ureido]eth-yl}urea, that encapsulates hydrogen-bonded chains of di-hydrogen phosphate anions with separate tetra-n-butyl-ammonium counter-ions.

The title compound, C25H25N9O9·C16H36N+·H2PO4 - (I) or (C25H25N9O9)·(n-Bu4N+)·(H2PO4 -) (systematic name: 3-(4-nitro-phen-yl)-1,1-bis-{2-[3-(4-nitro-phen-yl)ureido]eth-yl}urea tetra-butyl-ammonium di-hydrogen phosphate), comprises a tris-urea receptor (R), a di-hydrogen phosphate anion and a tetra-n-butyl-ammonium cation. It crystallizes with two independent formula units in the asymmetric unit. The conformations of the two tris-urea receptors are stabilized by N-H⋯O and C-H⋯O intra-molecular hydrogen bonds. Each di-hydrogen phosphate anion has two O-H⋯O inter-molecular hydrogen-bonding inter-actions with the other di-hydrogen phosphate anion. Inversion-related di-anion units are linked by further O-H⋯O hydrogen bonds, forming a chain propagating along the a-axis direction. Each di-hydrogen phosphate anion makes a total of four N-H⋯O(H2PO4 -) hydrogen bonds with two ureido subunits from two different tris-urea receptors, hence each tris-urea receptor provides the two ureido subunits for the encapsulation of the H2PO4 - hydrogen-bonded chain. There are numerous inter-molecular C-H⋯O hydrogen bonds present involving both receptor mol-ecules and the tetra-n-butyl-ammonium cations, so forming a supra-molecular three-dimensional structure. One of the butyl groups and one of the nitro groups are disordered over two positions of equal occupancy.

Conformational Control of a Pyrrole-Based Amide Pentamer by Dihydrogen Phosphate Anion Binding

Conformational Control of a Pyrrole-Based Amide Pentamer by Dihydrogen Phosphate Anion Binding

Pyrene-Linked Formylated Bis(dipyrromethane): A Fluorescent Probe for Dihydrogen Phosphate.

Anion receptor 1, a pyrene-functionalized tetrakis-(1 H-pyrrole-2-carbaldehyde), binds tetrabutylammonium dihydrogen phosphate in chloroform with high affinity over other test salts. Fluorescence quenching is seen upon the addition of H2PO4- to 1. The limit of detection (LOD) is ca. 46 nM. Anion binding in the solid state was confirmed via X-ray diffraction analysis, which revealed a sandwich-type complex, [1·3TBAH2PO4]2, wherein two separate molecules of 1 are linked via six dihydrogen phosphate anions bound in an S-like fashion.