The phase transfer mechanism of 18-molybdophosphate anion at the water/nitrobenzene interface

The phase transfer mechanism of 18-molybdophosphate anion at the water/nitrobenzene interface has been investigated by chronopotentiometry with cyclic linear current-scanning (CLC) and cyclic voltammetry (CV). The transfer species is 18-molybdophosphtae anion with a charge number of 4, H₂[P₂Mo₁₈O₆₂]^4-. The transfer process is controlled by diffusion at a slow polarization rate and considerably influenced by pH of the aqueous phase. The stable forms and pH range of the heteropoly anion in the aqueous solution can be directly confirmed through voltammetric behavior. The theoretical analysis of the relationship between the transfer potential and solution pH is identical to the experimental results. The linear concentration relationship with the transfer peak current is suggested to be used in the determination of heteropoly acids (salts).     

TRANSFER MECHANISM OF QUININE DRUG ACROSS THE OIL/WATER (O/W) INTERFACE

The transfer phenomena of quinine drug at the aqueous 1,2- dichloroethane (DCE)interface have been studied by the current- scanning polarography. The relationships be-tween the wave height and pH of aqueous phase, concentration of quinine as well as therate of water drop are discussed. The effect of supporting electrolyte, buffer solution andthe nature of organic solvent on the polarographic wave is studied. The transfer char-acteristics of quinine in aqueous phase and in organic phase are compared, The mono- pro-tonated and diprotonated quinines can both transfer at the interface so as to produce twopolarographic waves. The transfer process of quinine at the interface is simultaneouslycontrolled by diffusion and reestablishment of the disturbed protonated equilibrium ofquinine. A further investigation is made by chronopotentiometry. On the basis of thetheoretical analysis, the formulae of the limiting current are derived and discussed. Thetheoretical results are in agreement with the experimental ones.     

Synergetic extraction of Co3+

The extraction of Co³⁺ from 0.1M aqueous acetate medium buffered to pH 5.3 by thenoyltrifluoroacetone (HTTA) in benzene and by 8-quinolinol (HQ) also in benzene at various temperatures has been studied. The species formed were Co(OH)₂ (TTA)·(HTTA)₂ and Co(Q₃)·2HQ, respectively. 1,10-phenanthroline (Phen) as a base was also mixed with HTTA to form the species Co(OH)₂(TTA)·(HTTA). Phen and Co(OH)₂ (TTA)(HTTA)·2Phen. No synergism was observed upon the addition of Phen to HQ.     

2,2′-Dipyridyl and 1,10-phenanthroline in the synergetic extraction of Eu3+

The thermodynamics of the extraction of Eu³⁺ by thenoyltrifluoroacetone (HTTA) and by mixtures of HTTA and bidentate amine bases such as 2,2-dipyridyl (Dipy) and 1,10-phenanthroline (Phen) in benzene from an aqueous phase fixed to 0.1M ionic strength (NaClO₄), pH 3.9, has been investigated. Phenanthroline forms both the Eu(TTA)₃·Phen and Eu(TTA)₃·2Phen species, which are much stronger than the dipyridyl complexes. The diluent effect on the extraction is also studied.     

Disparity between solution-phase equilibria and charge state distributions in positive-ion electrospray mass spectrometry

Two peptides, bradykinin and gramicidin S, were used to investigate the relationship between protonation in the solution phase and charge state distribution observed in electrospray ionization (ES) mass spectra. The degree of protonation in solution was estimated using acid-base equilibrium calculations where possible. Protonation in solution was varied by adjusting pH, solvent composition and peptide concentration. Major disparities were observed between calculated solution-phase peptide protonation and the charge state distributions observed in ES mass spectra. The [(M + 2H)²⁺]/[(M + H)⁺] ratio calculated in solution was larger than the abundance ratio (M + 2H)²⁺ /(M + H)⁺ in the ES mass spectra of all acidic aqueous (pH < 6.5) and non-aqueous solutions; in basic aqueous solutions (pH > 9.5) the opposite was true. At high pH, electrophoretic droplet charging may reduce the activity of OH^? in positively charged droplets. The results at low pH imply the existence of supplementary factors in the ES ionization process which largely attenuate the degree of charging in the gas phase as compared with solution. Factors such as the increasing intra- and intermolecular coulombic repulsion between charge carriers (protons) and increasing attractive forces between protonated sites and counterions at progressively later stages of charged droplet evaporation were hypothesized to be chiefly responsible for this effect. Non-aqueous solvents of high basicity compete with analytes to some extent for available protons, forming protonated solvent molecules while decreasing the sensitivity and the degree of multiple charging of peptides.     

Electrochemical study of solvent extraction with 8-quinolinols as complexing agent-I. Distribution behavior of 8-quinolinols

The distribution behavior of 8-quinolinols (HQ) in organic and acidic aqueous solutions (or alkaline solutions) was electrochemically examined by current scan polarography and chronopotentiometry. It follows from the results that the half wave potential of the observed polarographic waves, corresponding to the Faradaic transfer of quinolinolium ions (or oxinate ions) formed in the aqueous solution after distribution of quinolinols is dependent on the dissociation constant of H(2)Q(+) (or HQ) and the pH of the aqueous solution, but independent of the distribution constant of 8-quinolinols.     

Ligand displacement-induced fluorescence switch of quantum dots for ultrasensitive detection of cadmium ions

This paper reports the construction of a simple CdTe quantum dots (QDs)-based sensor with 1,10-phenanthroline (Phen) as ligand, and the demonstration of a novel ligand displacement-induced fluorescence switch strategy for sensitive and selective detection of Cd²⁺ in aqueous phase. The complexation of Phen at the surface quenches the green photoluminescence (PL) of QDs dominated by a photoinduced hole transfer (PHT) mechanism. In the presence of Cd²⁺, the Phen ligands are readily detached from the surface of CdTe QDs, forming [Cd(Phen)₂(H₂O)₂]²⁺ in solution, and as a consequence the PL of CdTe QDs switches on. The detection limit for Cd²⁺ is defined as ∼0.01 nM, which is far below the maximum Cd²⁺ residue limit of drinking water allowed by the U.S. Environmental Protection Agency (EPA). Two consecutive linear ranges allow a wide determination of Cd²⁺ from 0.02 nM to 0.6 μM. Importantly, this CdTe QDs-based sensor features to distinctly discriminate between Cd²⁺ and Zn²⁺, and succeeds in real water samples. This extremely simple strategy reported here represents an attempt for the development of fluorescent sensors for ultrasensitive chemo/biodetection.     

液/液界面电子转移研究苯甲酰吡啶-缩氨基硫脲的亲脂性

The ion transfer reaction of 2-benzoylpyridine-thiosemicarbazone (HL), which has antimicrobial and antifungal properties and anticancer activity, has been studied to determine its lipophilicity by cyclic voltammetry at the water/1,2-dichloroethane (1,2-DCE) interface. The physicochemical parameters such as standard partition coefficient (IgP1) and the standard Gibbs energy of transfer (△G0,w→otr,I) of the protonated form of the ligand were measured as a function of pH in aqueous phase. The protonated form of the ligand exhibited reversible or quasi-reversible voltammograms at the 1,2-DCE in the range of pH 1-5. The protonation constants of the ligand, pKal, and pK? were determined spectrophotometrically and were found to be 12.14 and 3.24, respectively. The standard Gibbs energy of transfer (△G0,w→otr,N) and the partition coefficient of neutral species (IgPN) were also determined by the shake-flask method. The standard Gibbs energy of transfer of this compound across the water/1,2-DCE interface was evaluated as the quantitative measure of its lipophilicity. The difference between lgP1 and lgPN was related to the degree of charge delocalization and was used to evaluate qualitatively the lipophilicity of the ligand.     

Utilizing a pH‐Sensitive Dye in the Selective Fluorescent Recognition of Sulfate

A receptor containing amidopyrrole binding subunits and free amino groups, conjugated to a naphthalimide dye, has been designed and synthesized. The intrinsic selectivity of the binding motif for phosphate present in DMSO completely disappears in 10 % DMSO aqueous buffer at pH 3.6, at which the receptor is protonated. The electrostatic interactions between the receptor and an anion start to dominate, thus leading to selectivity for sulfate. The ability of the HSO₄^? anion to transfer the proton to the amino group during the recognition event suppresses the photoinduced electron transfer (PET) on the dye, resulting in a selective turn‐on fluorescent response. The choice of pH of the solution for sensing is dictated by the pK_a value of the dye.     

CONTROLLED/"LIVING" RADICAL POLYMERIZATION OF STYRENE IN AN AQUEOUS DISPERSION SYSTEM

Atom transfer radical polymerization (ATRP) of styrene catalyzed by cuprous (CuX)/1, 10-phenanthroline (Phen)and CuX/CuX_2/Phen was conducted in an aqueous dispersed system. A stable latex was obtained by using ionic surfactantsodium lauryl sulfonate (SLS) or composite surfactants, such as SLS/polyoxyethylene nonyl phenyl ether (OP-10),SLS/hexadecanol and SLS/OP-10/hexadecanol. Among which SLS and SLS/OP-10/hexadecanol systems established betterdispersed effect during the polymerization. It was found that Phen was a more suitable ligand than N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA) to maintain an appropriate equilibrium of the activator Cu(I) and the deactivatorCu(II) between the organic phase and the water phase. The effect of several initiators (such as EBiB, CCl_4 and 1-PEBr) andthe temperature on such a kind of ATRP system was also observed. The number-average molar mass (M_n) of polystyrene (PS)increased with the conversion and the molar mass distribution (M_w/M_n) remained narrow. These experimental data show thatthe polymerization could be controlled except for the quick increase of monomer conversion and the number-average molarmass of PS in the initial stage of polymerization. Furthermore, the initiator efficiency was found to be low (～57%) inCuX/Phen catalyzed system. To overcome this problem, Cu(II)X_2 (20 mol%-50 mol% based on CuX) was introduced intothe polymerization system. In this case, higher initiator efficiency (60%-90%), low M_w/M_n of PS (as low as 1.08) wereachieved and the molar masses of the PS fit with the theoretical ones.     

pH-Controlled selection between one of three guests from a mixture using a coordination cage host

We demonstrate the use of a simple pH swing to control the selection of one of three different guests from aqueous solution by a coordination cage host. Switching between different guests is based on the fact that neutral organic guests bind strongly in the cage due to the hydrophobic effect, but for acidic or basic guests, the charged (protonated or deprotonated) forms are hydrophilic and do not bind. The guests used are adamantane-1,3-dicarboxylic acid (H₂A) which binds at low pH when it is neutral but not when it is deprotonated; 1-amino-adamantane (B) which binds at high pH when it is neutral but not when it is protonated; and cyclononanone (C) whose binding is not pH dependent and is therefore the default guest at neutral pH. Thus an increase in pH can reversibly switch the host between the three different bound states cage·H₂A (at low pH), cage·C (at medium pH), and cage·B (at high pH) in succession.     

Polarographic reduction of benzylidenemalononitrile

The mechanism of reduction of benzylidenemalononitrile (1), C₆H₅CH=C(CN)₂, at the dropping mercury electrode in aqueous solutions containing 50% methanol changes with pH. In acidic solutions the reduction proceeds by a four-electron transfer to the monoprotonated species, yielding an aminomethyl derivative. In alkaline solutions two one-electron steps involving the vinyl double bond reduction are observed. Hydrolysis of dinitrile 1 to form benzaldehyde complicates the study at high pH values. The system is unique in that at pH 5–6 the unprotonated form is reduced at more positive potentials than the protonated form, reflecting a change in the mechanism of the reduction process.     

Multistate properties of 7-(N,N-diethylamino)-4'-hydroxyflavylium. An example of an unidirectional reaction cycle driven by pH

The synthetic flavylium salt 7-(N,N-diethylamino)-4'-hydroxyflavylium tetrafluoroborate gives rise in aqueous solution to a complex network of chemical reactions driven by pH. The system was studied by 1H NMR, single crystal X-ray diffraction, steady state and transient UV-Vis spectrophotometry as well as stopped flow. The crystal structure shows a high degree of coplanarity between the pyrylium system and the phenyl group in position 2. Thermodynamic and kinetic constants for the pH dependent network of chemical reactions were obtained. The introduction of an amino group in position 7 allows formation of protonated species leading, in particular, to a tautomeric form of the protonated cis-chalcone, H+, whose absorption spectra is rather red shifted, in comparison with the correspondent protonated trans-chalcone, H+. The H+ species can be rapidly converted into the flavylium cation through a first order process with lifetime of 0.2 s at pH = 2.35. This new reaction channel confers this compound a peculiar behaviour in acidic media, allowing to define an unidirectional pH driven reaction cycle.     

Effect of complexing agent (1,10-phenanthroline) on ADP and KDP crystals

1,10-Phenanthroline (Phen) as a new additive was added into the solutions of KH₂PO₄ (KDP) and NH₄H₂PO₄ (ADP) in a small amount (∼2.5·10⁻³ M L⁻¹). The crystals were grown from the aqueous solutions of pH ∼4.5 at constant temperature by solvent evaporation technique. It leads to an increase in metastable zone width and assists the bulk growth process. The growth rate of crystals in the presence of Phen decreases considerably with an increase in impurity concentration (∼2.5·10⁻² M L⁻¹). Not much variation is observed in FTIR and XRD of pure and doped ADP/KDP. It appears that the growth promoting effect (GPE) of Phen is caused by the adsorption of the organic additive on the prism faces of ADP/KDP crystals. Higher optical transmittance is observed in the presence of the dopant. Detailed microhardness studies of ADP crystals reveal the anisotropy in the hardness behaviour. Scanning electron microscope (SEM) photographs exhibit the effectiveness of the impurity in changing the surface morphology of ADP/KDP crystals. Contrary to expectations, Phen depresses the NLO efficiency of ADP/KDP, suggesting that the molecular alignments in the presence of Phen results in cancellation effects disturbing the non-linearity.     

Synergistic extraction behavior of samarium(III), europium(III) and dysprosium(III) with 1-nitroso-2-naphthol and 1,10-phenanthroline

The equilibrium extraction behavior of Sm(III), Eu(III) and Dy(III) from aqueous NaClO₄ solutions in the pH range of 4–9 at 0.1 M ionic strength into organic solutions of 1-nitroso-2-naphthol (HA) and 1,10-phenanthroline (Phen) has been studied. The equilibrium concentrations of Eu were assayed through the 344 keV photopeak of the¹⁵²Eu radiotracer used. The concentrations of Sm and Dy were measured by irradiating one mL portions of the organic extract and analyzing the 104 and 108 keV photopeaks of the short-lived neutron activation products,¹⁵⁵Sm and^165mDy, respectively. Quantitative extraction of Eu with 5×10^–2 M HA alone was obtained in the pH range of 6.7–7.8 with n-butanol, 7.4–8.5 with chloroform, 8.0–8.7 with ethyl acetate, 7.7–8.5 with isoamyl alcohol and 6.1–8.0 with methyl isobutyl ketone (MIBK). But, Eu was extracted only to a maximum of 78% and 83% in the pH range of 8.3–8.9 and 7.4–8.1 with carbon tetrachloride and xylene, respectively. The extraction of Sm and Dy were found quantitative in the pH range of 6.3–7.0 and 6.6–7.1, respectively, with 5×10^–2 M HA alone in MIBK solutions. The synergistic extraction of Eu was quantitative in the pH range of 6.6–9.8 with chloroform, 7.8–8.9 with ethyl acetate, 7.7–8.5 with isoamyl alcohol and 6.0–9.6 with MIBK when 1×10^–2 M each of HA and Phen were employed. Sm and Dy were quantitatively extracted into MIBK solutions containing 5×10^–2 M each of HA and Phen in the pH range 6.0–7.5 and 6.1–7.5, respectively. The distribution ratios of these lanthanides (Ln) were determined as a function of pH, and HA and Phen concentrations. The analysis of the data suggests that these Ln are extracted as LnA₃ chelates when HA alone is used. In the presence of HA and Phen, both LnA₃(Phen) and LnA₃(Phen)₂ adducts are formed only in the MIBK system while LnA₃(Phen) complexes are the predominant ones in all other solvent systems studied. The extraction constants and the adduct formation constants of these complexes have been calculated.     

High-resolution determination of H+ by ion chromatography. Application to the simultaneous determination of H+, Na+, NH4+ and K+ in acid rain.

An ion chromatographic (IC) method was developed for the high-resolution determination of a sample's free hydrogen ion concentration (H+). Highly purified lithium dodecyl sulfate was used as the stationary phase, a slightly acidified aqueous LiCl solution was used as the mobile phase and conductivity was used for analyte detection. An electrical double layer (EDL) containing H+ was established on the stationary phase by using a slightly acidified electrolyte solution as the eluent. H+ in the EDL protonated any weak acid groups (i.e., silanols) on the stationary phase so that H+ from the sample could be retained/separated purely by dodecyl sulfate. The optimum molar ratio of H+:Li+ in the EDL for this IC system was obtained by using an aqueous solution containing 40.0 mM LiCl and 0.07 mM H2SO4 as the eluent. After separation, H+ was detected by direct conductimetric measurement. An H+ detection limit of better than 8.2 x 10(-6) M was obtained from the analysis of standard aqueous H2SO4 solutions. Other monovalent cations could also be separated with this method, giving detection limits of 7.4 x 10(-5), 4.3 x 10(-5) and 4.2 x 10(-5) M for Na+, NH4+ and K+, respectively. The method was applied to the simultaneous determination of H+, Na+, NH4+ and K+ in acid rain. The results obtained showed a significant improvement in reproducibility when compared with those from a conventional pH-meter. Acid rain samples with a pH < 5 could be analyzed with this IC system.     

The effect of interfacial mass transfer on steady-state water radiolysis

The effect of aqueous–gas interfacial transfer of volatile species on the γ-radiolysis of water was studied as a function of gas-to-liquid volume ratio at various solution pHs and cover gas compositions. Water samples with cover-gas headspace were irradiated at an absorbed dose rate of 2.5 Gy s^?1 and the radiolytic productions of H₂ in the cover gas and H₂O₂ in the water phase were monitored as a function of irradiation time. The experimental results were compared with computer simulations using a water radiolysis kinetics model that included primary radiolysis, subsequent reactions of the primary radiolysis products in the aqueous phase, and aqueous–gas interfacial transfer of the volatile species H₂ and O₂. This study shows that the impact of the interfacial mass transfer strongly depends on pH. At pH≤8 (lower than the pKa of ?H of 9.6) the effect of aqueous-to-gas phase transfer of the volatile species on the steady-state concentrations of the other radiolysis products is negligible. At higher pHs (≥8), radiolytic production of O₂ is slow but considerable, which results in significant increase in the steady-state concentrations of H₂ and H₂O₂ compared to those at lower pHs. Thus, in the presence of headspace, the interfacial transfer of both H₂ and O₂ becomes significant, and the aqueous concentrations of H₂ and O₂ are no longer independent of the interfacial surface area and water volume. Nevertheless, the accumulated mass of H₂(g) in the headspace is proportional to the aqueous concentration of H₂ at all pHs, and the gaseous concentration of H₂ in the headspace can be used to infer the aqueous concentration of H₂.     

Properties of fluoroantimonates(III) complexes with amino acids

Crystalline complex fluoroantimonates(III) with amino acids (glycine, β-alanine, DL-serine, DL-valine, L-leucine, and L-phenylalanine) have been prepared. The complexes stability in aqueous solutions has been studied with the cementation method. ¹H NMR studies of aqueous solutions of the amino acids complexes with SbF₃ at pH 1–6 and room temperature are reported. Preparation of polycrystalline metal antimony in aqueous solutions of tetrafluoroantimonates(III) complexes with the protonated amino acids has been demonstrated.     

Evidence for intramolecular aromatic-ring stacking in the physiological pH range of the monodeprotonated xanthine residue in mixed-ligand complexes containing xanthosinate 5'-monophosphate (XMP)

The stability constants of the mixed-ligand complexes formed between Cu(Arm)2+ [Arm = 2,2'-bipyridine (Bpy) or 1,10-phenanthroline (Phen)], and the di- or trianion of xanthosine 5'-monophosphoric acid [= XMP(2-) or (XMP - H)(3-)] were determined by potentiometric pH titration in aqueous solution (25 degrees C; I = 0.1 M, NaNO3). Those for the monoanion, i.e., the Cu(Arm)(H;XMP)+ complexes, could only be estimated; for these species it is concluded that the metal ion is overwhelmingly bound at N7 and the proton resides at the phosphate group. Similarly, in the Cu(Arm)(XMP)+/- [= Cu(Arm)(X - H.MP.H)+/-] complexes Cu(Arm)2+ is also at N7 but the xanthine residue has lost a proton whereas the phosphate group still carries one, i.e., stacking plays, if at all, only a very minor role, yet, the N7-bound Cu(Arm)2+ appears to form an outer-sphere macrochelate with P(O)2(OH)-, its formation degree being about 60%. All this is different in the Cu(Arm)(XMP - H)- complexes, which are formed by the (XMP - H)(3-) species, that occur at the physiological pH of 7.5 and for which previously evidence has been provided that in a tautomeric equilibrium the xanthine moiety loses a proton either from (N1)H or (N3)H. In Cu(Arm)(XMP - H)- the phosphate group is the primary binding site for Cu(Arm)2+ and the observed increased complex stability is mainly due to intramolecular stack (st) formation between the aromatic-ring systems of Phen or Bpy and the monodeprotonated xanthine residue of (XMP - H)(3-); e.g., the stacked Cu(Phen)(XMP - H) isomer occurs with approximately 76%. Regarding biological systems the most important result is that at physiological pH the xanthine moiety has lost a proton from the (N1)H/(N3)H sites forming (XMP - H)(3-) and that its anionic xanthinate residue is able to undergo aromatic-ring stacking.