Kinetics and mechanism of hydrogen peroxide oxidation of chromone-3-carboxaldehydes in aqueous acid and micellar media

Oxidation of chromone-3-carboxaldehyde (CCA) and substituted analogues by H₂O₂ has been carried out in aqueous acid (HCl and H₂SO₄) and micellar media. Reaction kinetics indicated order in [CCA] as well as [H₂O₂] to be unity while it is a fraction (1 > n > O) in [acid]. Reaction rates were found to be faster in the solvents of low-dielectric constant (D). Added salt (KCl or (NH₄)₂SO₄) increased the rate of oxidation marginally. On the basis of observed linearity of Amis plot and marginal positive salt effect, protonated CCA (enol form of CCA, a cation) and H₂O₂ (neutral molecule) were considered as reactive species in the rate limiting step. Reaction rates were found to be enhanced significantly in anionic and nonionic micellar (sodium dodecylsulfate (SDS) and Triton X-100 (Tx), respectively) media. However, cationic micelles [cetyl trimethyl ammonium bromide (CTAB)] indicated marginal retardation effect. Effect of anionic and cationic micelles has been interpreted in terms of electrostatic interactions, while that of nonionic micelles in terms of hydrophobic interactions. Structure-reactivity correlations have been interpreted by Hammett's equation. Negative “ρ” (reaction constant) values indicated cationic transition state. © 1996 John Wiley & Sons, Inc.     

Effect of ionic micellar medium on kinetics and mechanism of oxidation of bovine serum albumin: A pulse radiolysis study

Effect of protein–micelle interaction on bovine serum albumin (BSA) oxidation by trichloromethyl peroxyl radical (CCl₃O₂^·) in anionic sodium dodecyl sulfate (SDS) and cationic cetyltrimethyl ammonium bromide (CTAB) micellar media has been studied using nanosecond pulse radiolysis technique. Viscosity measurement and light scattering studies have suggested that SDS and CTAB micelles produce BSA–micelle aggregates of different sizes and polydispersity. Oxidation kinetics and transients have been affected both by anionic SDS and cationic CTAB micelles but in a different manner. Tryptophanyl-CCl₃O₂^· adduct radical to tyrosyl radical transformation in BSA has been observed in anionic SDS micelles but not in cationic CTAB micelles. Similar studies have also been done with tryptophan and tyrosine amino acids, which undergo oxidation in BSA. The study suggests that Coulombic and hydrophobic interactions between micelles and protein affect the structure of the protein to shield its functional amino acids, like tryptophan and tyrosine, to neutral oxidizing radical.     

Effect of anionic and cationic micelles on the oxidation of <Emphasis Type="SmallCaps">D</Emphasis>-glucose by cerium(IV) in presence of H<Subscript>2</Subscript>SO<Subscript>4</Subscript>

The influence of surfactants (anionic and cationic) on the reactivity of the redox couple cerium(IV) and D-glucose was examined spectrophotometerically. Various kinetic parameters have been determined in the absence and presence of surfactants. The kinetics were followed by monitoring the disappearance of the absorbance of cerium(IV) at 385 nm. The reaction obeyed first-order kinetics with respect to [D-glucose] in both media. No effect of anionic micelles of sodium dodecyl sulfate (SDS) was observed due to electrostatic repulsion between the negative head group of SDS and reactive species of cerium(IV) (Ce(SO₄) ₃ ²⁻ ). A twofold increase in the oxidation rate was observed in the presence of cationic micelles of cetyltrimethylammonium bromide (CTAB). The observed catalytic role has been analyzed in terms of the Menger–Portnoy model. The effects of various inorganic salts (Na₂SO₄, NaNO₃ and NaCl) were also studied in micellar media.     

Mononuclear and binuclear chelates of biacetylmonoxime picolinoylhydrazone

Mononuclear and binuclear chelates of biacetylmonoxime picolinoylhydrazone (H₂BMPcH) with Cr^III, Fe^III, Co^II, Ni^II, Cu^II, Zn^II, Cd^II, Pd^II and UO₂ ²⁺ have been prepared. Elemental analyses, molar conductivities, spectral (u.v., visible, i.r., n.m.r., e.s.r.), thermal (t.g., d.t.g., d.t.a.) and magnetic susceptibility measurements have been used to characterize the chelates. The i.r. spectral data indicate that H₂BMPcH behaves in a bidentate, tridentate and/or tetradentate manner and the hydrazonic azomethine nitrogen constituents the chelating backbone in all chelates. Based on magnetic and spectroscopic data, the structures for the chelates are proposed as follows: tetrahedral for [Co(HBMPcH)(H₂O)]Cl, octahedral for [Co(HBMPcH)₂], [Cr(HBMPcH)Cl(H₂O)]₂Cl₂, [Fe(HBMPcH)Cl-(H₂O)]₂Cl2, [Ni(BMPcH)(H2O)2], square-planar for (Ni(HBMPcH)Cl], [Pd(HBMPcH)Cl], [Cu(HBMPcH)(H2O)]Cl and tetragonally distorted octahedral for [Cu(BMPcH)(H2O)2]2 chelates. Generally, the solid metal acetate complexes have a unique decomposition exotherm profile which can be used as a rapid and sensitive tool for the detection of acetate-containing complexes.     

Bis­[tris(2,2′‐bi­pyridine‐κ2N,N′)­ruthenium(II)] hexa­cyano­ferrate(III) chloride octahydrate

In the title compound, [Ru^II(C₁₀H₈N₂)₃]₂[Fe^III(CN)₆]Cl·8H₂O, the [Ru(bpy)₃]²⁺ (bpy is 2,2′‐bi­pyridine) cations and water mol­ecules afford intriguing microporous honeycomb layers, while the [Fe(CN)₆]³⁻ anions and the remainder of the water mol­ecules form anionic sheets based on extensive hydrogen‐bonding networks. The cationic and anionic layers alternate along the c axis. The Fe atom in [Fe(CN)₆]³⁻ lies on an inversion centre and the axial cyano ligands are hydrogen bonded to the water mol­ecules encapsulated within the micropores [N⋯O = 2.788 (5) Å], giving an unusual interpenetration between the cationic and anionic layers. On the other hand, the in‐plane cyano ligands are relatively weakly hydrogen bonded to the water mol­ecules [N⋯O = 2.855 (7) and 2.881 (8) Å] within the anionic sheets.     

Metallo-guanines and metallo-guanosines

Metallo-guanines of the type [M(G)₂·2H₂O] [M = Ni^II, Fe^II, Cu^II and UO₂ ^II; G = anionic guanine], [M(G)₂(GH)· H₂O] (M = Co^II and Mn^II; GH = neutral guanine), [Pd(G)₂]·2H₂O and [Zn(G)Cl]₂ have been isolated and characterised. Anionic guanine functions as a bidentate ligand and links through N(3) and N(9). E.p.r. data indicate that the Cu^II complex has a highly distorted octahedral structure. The magnetic susceptibility data suggest that the Co^II and Ni^II complexes possess pseudooctahedral geometry. Neutral guanines are probably unidentate and coordinate either through N(3) or N(9). The isolated guanosine complexes are of the types: [M(Gs)₂·H₂O] [M = Ni^II and Cu^II, Gs = anionic guanosine] [Pd(Gs)₂]·2H₂O and [UO₂(Gs)₂]. I.r. data indicate that guanosine also functions as a bidentate ligand, but coordinates through N(1) and C₂ — NH₂. The electronic absorption spectra of the complexes indicate that guanine is a stronger ligand than guanosine.     

Spectrophotometric study of interaction and solubilization of procaine hydrochloride in micellar systems

The interaction of Procaine hydrochloride (PC) with cationic, anionic and non-ionic surfactants; cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and triton X-100, were investigated. The effect of ionic and non-ionic micelles on solubilization of Procaine in aqueous micellar solution of SDS, CTAB and triton X-100 were studied at pH 6.8 and 29°C using absorption spectrophotometry. By using pseudo-phase model, the partition coefficient between the bulk water and micelles, K_x, was calculated. The results showed that the micelles of CTAB enhanced the solubility of Procaine higher than SDS micelles (K_x = 96 and 166 for SDS and CTAB micelles, respectively) but triton X-100 did not enhanced the solubility of drug because of weak interaction with Procaine. From the resulting binding constant for Procaine-ionic surfactants interactions (K_b = 175 and 128 for SDS and CTAB surfactants, respectively), it was concluded that both electrostatic and hydrophobic interactions affect the interaction of surfactants with cationic procaine. Electrostatic interactions have a great role in the binding and consequently distribution of Procaine in micelle/water phases. These interactions for anionic surfactant (SDS) are higher than for cationic surfactant (CTAB). Gibbs free energy of binding and distribution of procaine between the bulk water and studied surfactant micelles were calculated.      

Kinetics of hydrolysis of procaine in aqueous and micellar media

The kinetics of alkaline hydrolysis of procaine under the pseudo–first‐order condition ([OH^?] ? [procaine]) has been carried out. N,N‐Diethylaminoethanol and p‐aminobenzoate anion were obtained as the hydrolysis product. The rate of hydrolysis was found to be linearly dependent upon [NaOH]. The addition of cationic cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DDTAB) and tetradecyltrimethylammonium bromide, and anionic sodium dodecyl sulfate (SDS) micelles inhibited the rate of hydrolysis. The maximum inhibitive effect on the reaction rate was observed for SDS micelles, whereas among the cationic surfactants, CTAB inhibited most. The variation in the rate of hydrolysis of procaine in the micellar media is attributed to the orientation of a reactive molecule to the surfactant and the binding constant of procaine with micelles. The rate of hydrolysis of procaine is negligible in DDTAB micelles. The observed results in the presence of cationic micelles were treated on the basis of the pseudophase ion exchange model. The results obtained in the presence of anionic micelles were treated by the pseudophase model, and the various kinetic parameters were determined. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 45: 1–9, 2013     

Effects of anionic and cationic micelles on the oxidation of d-dextrose by diperiodatoargentate(III)

The oxidative behavior of d-dextrose toward diperiodatoargentate(III) (DPA) has been studied in the absence and presence of anionic and cationic micelles of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB), respectively. The kinetics is based on the reduction of silver(III) to silver(I) by d-dextrose under pseudo-first-order conditions. The monoperiodatoargentate(III) ions act as active oxidants in comparison to that of DPA. The reactions are first- and fractional-order dependence with respect to [DPA] and [d-dextrose], respectively. The reaction rates decrease with [H⁺] and [periodate]. The premicellar environment of SDS and CTAB strongly inhibits the reaction rate. Inhibition is due to favorable thermodynamic/electrostatic binding between the Ag(III) complex and CTAB monomer aggregates. A suitable mechanism involving a one-electron transfer (rate-determining step) from d-dextrose to the silver(III) species has been proposed. Activation parameters have been evaluated and discussed.     

Kinetics of the diazotization and azo coupling reactions of procaine in the micellar media

The kinetics of the diazotization reaction of procaine in the presence of anionic micelles of sodium dodecyl sulfate (SDS) and cationic micelles of cetyltrimethyl ammonium bromide (CTAB), dodecyltrimethyl ammonium bromide (DDTAB) and tetradecyltrimethyl ammonium bromide (TDTAB) were carried out spectrophotometrically at λ_max = 289 nm. The values of the pseudo first order rate constant were found to be linearly dependent upon the [NaNO₂] in the concentration range of 1.0 × 10⁻³ mol dm⁻³ to 12.0 × 10⁻³ mol dm⁻³ in the presence of 2.0 × 10⁻² mol dm⁻³ acetic acid. The concentration of procaine was kept constant at 6.50 × 10⁻⁵ mol dm⁻³. The addition of the cationic surfactants increased the reaction rate and gave plateau like curve. The addition of SDS micelles to the reactants initially increased the rate of reaction and gave maximum like curve. The maximum value of the rate constant was found to be 9.44 × 10⁻³ s⁻¹ at 2.00 × 10⁻³ mol dm⁻³ SDS concentration. The azo coupling of diazonium ion with β-naphthol (at λ_max = 488) nm was found to linearly dependent upon [ProcN₂⁺] in the presence of both the cationic micelles (CTAB, DDTAB and TDTAB) and anionic micelles (SDS). Both the cationic and anionic micelles inhibited the rate of reactions. The kinetic results in the presence of micelles are explained using the Berezin pseudophase model. This model was also used to determine the kinetic parameters e.g. k_m, K_s from the observed results of the variation of rate constant at different [surfactants].     

The preparation and characterization of some new nickel(II), copper(II), zinc(II) and cadmium(II) complexes of the pyrrole-2-carboxaldehyde Schiff bases ofS-alkyl esters of dithiocarbazic acid

Summary New complexes of general formulae [Ni(HL)₂], [ML]·H₂O and [Cu(HL)X] (H₂L = pyrrole-2-aldehyde Schiff bases ofS-methyl- andS-benzyldithiocarbazates; X = Cl or Br; M = Ni^II, Cu^II, Zn^II or Cd^II) were prepared and characterized by a variety of physicochemical techniques. The Schiff bases coordinate as NS bidentate chelating agents in [Ni(HL)₂] and [Cu(HL)X], and as tridentate NNS chelates in [ML] (M = Ni^II, Cu^II, Zn^II or Cd^II). Both the [Ni(HL)₂] and [NiL] complexes are diamagnetic and square-planar. Based on magnetic and spectroscopic evidence, thiolate sulphur-bridged dimeric square-planar structures are assigned to the [Cu(HL)X] and [ML] (M = Ni^II or Cu^II) complexes. The complexes ML (M = Zn^II or Cd^II) are polymeric and octahedral.     

The First Cyclopentadienylalkylphosphane Nickel Chelates: Synthesis,Structures, and Reactions

The first cyclopentadienylalkylphosphane nickel chelate complexes are reported. The anionic ligand obtained by reaction of spiro[2.4]hepta‐4,6‐diene with lithium di‐tert‐butylphosphide was treated with NiCl₂ to yield [η⁵:κ¹‐(di‐tert‐butylphosphanylethyl)cyclopentadienyl]chloronickel(II). From this complex, some acetonitrile‐stabilized cationic complexes were obtained by reaction with the respective silver salts in acetonitrile. Methyl‐ and alkynylnickel chelates were prepared by reaction of the chloronickel complex with methyllithium and by copper‐mediated coupling with terminal alkynes, respectively. Some of the complexes prepared were investigated by X‐ray crystallography or cyclic voltammetry. The alkynylnickel chelates undergo cycloaddition reactions with ethoxycarbonylisothiocyanate or tetracyanoethylene, and the cyclobutenes obtained undergo ring opening to the corresponding dienes. The study includes an NMR spectroscopic investigation of the two conformers of one of these dienes.     

Kinetics of interaction of Histidine and Histidine Methyl Ester with Ninhydrin in micellar media

Kinetics of the interaction of histidine and histidine methyl ester with ninhydrin under varying concentrations of reactants, anionic (sodium dodecyl sulphate, SDS), cationic (cetyltrimethylammonium bromide, CTAB) and non‐ionic (Triton X‐100, TX‐100) micelles have been carried out. Rate of the reaction was found to be independent of the initial concentration of histidine (and histidine methyl ester) but was dependent on [Ninhydrin]. The SDS micelles had no effect on the rate of the reaction. In the presence of the CTAB micelles a small enhancement in the rate was observed. The rate − [CTAB] profile showed that the increase in [CTAB] increased the rate up to a maximum value and a further increase had a decreasing effect on the rate. The rate was enhanced by TX‐100 also but, unlike CTAB micelles, TX‐100 possessed a curve without peak for the rate − [TX‐100] profile. The following rate equation was obeyed by the reaction in CTAB and TX‐100 micelles: Values of k_w, k_m, and K_S were evaluated and are reported herein. ©1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 103–111, 1999     

Iron(II)-8-mercaptoquinoline,iron(II)-5-chloro-8-mercaptoquino-line and iron(II)-5-bromo-8-mercaptoquinoline complexing in the iron(III) hexacyanoferrate(II) gelatin-immobilized matrix systems

Novel complexing processes in the Fe^II-8-mercaptoquinoline, Fe^II-5-chloro-8-mercaptoquinoline and Fe^II-5-bromo-8-mercaptoquinoline systems, not used previously in coordination chemistry, namely complexing as an iron(III)hexacyanoferrate(II) gelatin-immobilized matrix (GIM) in contact with an aqueous solution of the corresponding ligand, have been observed and analysed. Incorporation of these ligands into the inner coordination sphere is preceded by the decomposition of the immobilized compound KFe[Fe(CN)₆] to form hydroxides or oxohydroxides of Fe^II and Fe^III under the action of OH^- ions. It has been shown that Fe^IIFeIII redox process and the formation of FeB₃ chelates (B^- is a singly deprotonated form of the corresponding ligand) take place during complexing under such conditions.     

Lability‐Controlled Syntheses of Heterometallic Clusters

A bulky bidentate ligand was used to stabilize a macrocyclic [Fe^III₈Co^II₆] cluster. Tuning the basicity of the ligand by derivatization with one or two methoxy groups led to the isolation of a homologous [Fe^III₈Co^II₆] species and a [Fe^III₆Fe^II₂Co^III₂Co^II₂] complex, respectively. Lowering the reaction temperatures allowed isolation of [Fe^III₆Fe^II₂Co^III₂Co^II₂] clusters with all three ligands. Temperature‐dependent absorption data and corresponding experiments with iron/nickel systems indicated that the iron/cobalt self‐assembly process was directed by the occurrence of solution‐state electron‐transfer‐coupled spin transition (ETCST) and its influence on reaction intermediate lability.     

Interaction of pyrimethamine and sulfadiazine with ionic and neutral micelles: Electronic absorption and fluorescence studies

The binding of two antitoxoplasmosis drugs, pyrimethamine (PYR) and sulfadiazine (SDZ) to cationic cetyltrimethylammonium chloride (CTAC), anionic sodium dodecylsulfate (SDS), zwiterionic N-hexadecyl-N,N-dimethyl-2-ammonium-1-propanesulfonate (HPS) and neutral polyoxyethylene-dodecyl-ether (Brij-35^®) micelles was studied using absorption and fluorescence spectroscopic methods. The pK_a of PYR changed in the presence of charged anionic, cationic and zwiterionic micelles, indicating that interaction is influenced by the micellar charge. For SDZ, pK_a changes were lower than 1 for all micelles, suggesting the occurrence of low binding constants in addition to a reasonable influence of the micellar charge. The values of binding constants K_b, obtained from fluorescence measurements, for PYR to CTAC micelles were very low at pH 4.0, where the drug is in a complete protonated state, increasing at pH 9.0 to long-chained CTAC and HPS micelles since this factor also favors accomodation of the neutral drug in the hydrophobic compartments. For SDZ the binding constants were determined from optical absorption measurements. Low binding constants were observed to charged surfactant micelles, with influence of micellar charge. It must be stated however that those values can be underestimated due to the relatively low sensitivity of the method based on absorption measurements.     

Regulatory role of surfactants in the kinetics of glucose oxidase-catalyzed oxidation ofd-glucose by ferrocenium andn-butylferrocenium ions

The effect of micelles of different surfactants (cationic, anionic, and neutral) on the kinetics of the glucose oxidase-catalyzed reduction of ferrocenium cations RFc⁺ (R=H, Buⁿ) byd-glucose was studied by spectrophotometry. In micellar media of Triton X-100 and sodium dodecyl sulfate (SDS), the Michaelis dependence of the reaction rate on the HFc⁺ concentration is observed, while this dependence has an extreme character in cationic micelles of cetyltrimethylammonium bromide (CTAB). The nature and concentration of surfactants of all types have a slight effect on the rate of reduction of HFc⁺. The level of enzymatic activity is approximately equal in the case of Triton X-100 and CTAB and is considerably lower in the SDS micelles. On going from HFc⁺ to BuⁿFc⁺, the reaction rate is maximum in the cationic CTAB micelles, the anionic SDS micelles exhibit almost no activity, and the activity has an intermediate value in neutral micelles of Triton X-100. The conditions are presented under which the micellar medium controls the catalytic activity of glucose oxidase with respect to ferrocenium cations. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1795–1801, October, 1997.     

Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines

The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H₂) important. A high-spin (hs) Fe^II complex with o-phenylenediamine (opda) ligands, [Fe^II(opda)₃]²⁺ (hs- [6R] ²⁺), was reported showing photochemical H₂ evolution. In addition, a low-spin (ls) [Fe^II(bqdi)₃]²⁺ (bqdi: o-benzoquinodiimine) (ls- [0R] ²⁺) formation by O₂ oxidation of hs- [6R] ²⁺, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls- [0R] [PF₆]₂ can be reduced by hydrazine giving ls-[Fe^II(opda)(bqdi)₂][PF₆]₂ (ls- [2R] [PF₆]₂) and ls-[Fe^II(opda)₂(bqdi)][PF₆]₂ (ls- [4R] [PF₆]₂) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials.     

Kinetics and mechanism of pentacyanohydroxoferrate(III) formation from the reaction of cyanide ion with [Fe2L(OH)2]2− (L=triethylenetetraaminehexaacetate)

Summary The kinetics and mechanism of the reaction between [Fe₂L(OH)₂]^2– and cyanide ion (L = TTHA, triethylenetetraaminehexaacetate) have been studied spectrophotometrically atpH=11.0±0.1,I=0.1 M(NaClO₄) and T = 25±0.1 °C. The overall reaction consists of three distinct, observable stages. The first stage involves the dissociation of the binuclear complex into a mononuclear complex [FeL(OH)]^4– which then reacts with cyanide to form [Fe(CN)₅OH]^3–. The species [Fe(CN)₅OH]^3– reacts further with an excess of cyanide and forms [Fe(CN)₆]^3– in the second stage of reaction. The last stage involves the reduction of [Fe(CN)₆]^3– formed in the second stage by the TTHA^6– released in the first stage of reaction. The formation of [Fe(CN)₅OH]^3– in the first stage is firstorder in [Fe₂L(OH)₂]^2– and third-order in cyanide over a large range of cyanide concentrations but becomes zero-order in cyanide at [CN^–] < 4×10^–2M.These observations enable us to suggest the presence of a slow step in which [Fe₂L(OH)₂]^2– dissociates into [FeL(OH)]^4– and [FeOH]²⁺ at low cyanide concentrations and a cyanide assisted rapid dissociation of [Fe₂L(OH)₂]^2– to [FeL(OH)(CN)]^5– at higher cyanide concentrations. The species [FeL(OH)(CN)]^5– reacts further with an excess of cyanide to produce [Fe(CN)₅OH]^3– finally.The reverse reaction between [Fe(CN)₅OH]^3– and TTHA^6– follows first-order dependence in each of [Fe(CN)₅OH]^3– and TTHA^6– and inverse first-order dependence on cyanide concentration. A six-step mechanism has been proposed for the first stage of reaction in which the fifth has been identified as the rate-determining step.