ESR studies on hydroxyl radical reactions with glycine

Radicals H₂N? ?H? COOH and H₂N? ?H? COO^? which have different ESR. spectra are observed during the reaction of hydroxyl radicals with glycine in aqueous solution. Rapid and reversible exchange between the different dissociated radicals is induced by addition of phosphoric acid. The pH dependence of the ESR. spectra yields the pK value and rate constants for proton transfer reactions between the radicals and phosphoric acid.     

Synthesis,Structure and Cytotoxicity of N,N and N,O-Coordinated RuII Complexes of 3-Aminobenzoate Schiff Bases against Triple-negative Breast Cancer

Half-sandwich Ru^II complexes, [(YZ)Ru^II(η⁶-arene)(X)]+, (YZ=chelating bidentate ligand, X=halide), with N,N and N,O coordination ( 1 – 9 ) show significant antiproliferative activity against the metastatic triple-negative breast carcinoma (MDA-MB-231). 3-aminobenzoic acid or its methyl ester is used in all the ligands while varying the aldehyde for N,N and N,O coordination. In the N,N coordinated complex the coordinated halide(X) is varied for enhancing stability in solution (X=Cl, I). Rapid aquation and halide exchange of the pyridine analogues, 2 and 3 , in solution are a major bane towards their antiproliferative activity. Presence of free −COOH group ( 1 and 4) make complexes hydrophilic and reduces toxicity. The imidazolyl 3-aminobenzoate based N,N coordinated 5 and 6 display better solution stability and efficient antiproliferative activity (IC₅₀ ca. 2.3–2.5 μM) compared to the pyridine based 2 and 3 (IC₅₀>100 μM) or the N,O coordinated complexes ( 7 – 9 ) (IC₅₀ ca. 7–10 μM). The iodido coordinated, 6 , is resistant towards aquation and halide exchange. The N,O coordinated 7 – 9 underwent instantaneous aquation at pH 7.4 generating monoaquated complexes stable for at least 6 h. Complexes 5 and 6 , bind to 9-ethylguanine (9-EtG) showing propensity to interact with DNA bases. The complexes may kill via apoptosis as displayed from the study of 8 . The change in coordination mode and the aldehyde affected the solution stability, antiproliferative activity and mechanistic pathways. The N,N coordinated ( 5 and 6 ) exhibit arrest in the G2/M phase while the N,O coordinated 8 showed arrest in the G0/G1 phase.     

Tolerance of Aedes aegypti larvae to triorganotins

The effects of triorganotins on the 4th instar stage of Aedes aegypti larvae were evaluated. The most effective of the 15 triorganotins used in the study was tributyltin chloride with an LC₅₀ value of 0.57 ± 0.07 mg dm⁻³. The low LC₅₀ values obtained indicated that this class of compounds is an effective larvicide against the larvae of this species of mosquito. The toxicity of the compounds was found to be primarily dependent on the R group attached to the tin atom. The order of activity for the triorganotins tested was Bu > Ph > Cy > Me. However, a limited order, based on two series of the compounds tested, was also observed for the anionic X group on the tin atom. Copyright ­© 2000 John Wiley & Sons, Ltd.     

Preparation of macroreticular-type oleophilic anion exchange resin membrane and its permselectivity to halides and thiocyanate

Macroreticular-type oleophilic anion exchange resin membranes containing high-molecular-weight ammonium ions such as tri-n-octylbenzylammonium and tri-n-dodecylbenzylammonium as fixed site were freshly prepared. These membranes were wetted well with water-immiscible organic solvents even in aqueous surroundings. The properties of the membrane, i.e. porosity, water and organic solvent content, capacity and conductivity were determined. The permselectivity of the membrane impregnated with nitrobenzene or o-nitrophenyloctylether to halide and thiocyanate ions was evaluated by measurement of bi-ionic membrane potential and electrodialysis. p]The sequence of the permselectivity was Cl^? < Br^? < I^? < SCN^?, and was consistent with the Hofmeister anion series. The value of the permselectivity was 10–100 times larger than that of usual hydrophilic anion exchange membranes. It was found that the permselectivity of the present membrane was strongly dependent on the separation factor, which was in turn affected by the hydrophobicity of the membrane. The effect of the ion association between fixed ion-exchange site and counter ion on the specific conductance of the membrane was also discussed.     

An Ionic Liquid Bulk-Modified Carbon Paste Electrode and Its Electrocatalytic Activity toward p-Aminophenol

An ionic liquid bulk-modified carbon paste electrode （M-CPE） has been fabricated by using 1-heptyl-3-methylimidazolium bromide as a modifier. Cyclic voltammetry （CV） and differential pulse voltammetry （DPV） were used to evaluate the electrocatalytic activity of the proposed electrode by choosing p-aminophenol （p-AP） as a model compound. Both at a bare carbon paste electrode （CPE） and the M-CPE, p-AP yielded a pair of redox peaks in 0.1 mol·L^-1 phosphate buffer solution （PBS, pH 7.0）. At the CPE, the peak-to-peak potential separation （AEp） was 0.233 V, while at the M-CPE the AEp was decreased to 0.105 V. Furthermore, the current response to p-AP at the M-CPE was 10.2 times of that at the CPE by DPV. The electron transfer rate constant （ks） ofp-AP at the M-CPE was 13.3 times of that at the CPE. Under the optimal condition, a linear dependence of the catalytic current versus p-AP concentration was obtained in the range of 2.0× 10^- 6 to 3.0× 10^- 4 mol·L^-1 with a detection limit of 6.0× 10^-7 mol·L^-1 by DPV. In addition, compared to other modified method the proposed electrode exhibited distinct advantages of simple prapartion, surface renewal, good reproducibility and good stability. It has been used to determine p-AP in simulated wastewater samples.     

Ferromagnetically Coupled S=1 Chains in Crystals of Verdazyl-Nitronyl Nitroxide Diradicals

Thermally stable organic diradicals with a triplet ground state along with large singlet-triplet energy gap have significant potential for advanced technological applications. A series of phenylene-bridged diradicals with oxoverdazyl and nitronyl nitroxide units were synthesized via a palladium-catalyzed cross-coupling reaction of iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields. The diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180 °C. For the diradicals, both substantial AF (ΔE_ST≈−64 cm⁻¹) and FM (ΔE_ST≥25 and 100 cm⁻¹) intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para- or meta-phenylene) and by the type of oxoverdazyl block (C-linked or N-linked). Upon crystallization, diradicals with the triplet ground state form unique one-dimensional exchange-coupled chains with strong intra- and weak inter-diradical ferromagnetic coupling.     

Elimination of equivalence point errors in the potentiometric titration of chloride, bromide and iodide mixtures with silver nitrate

When two or more halides are determined in solution by precipitation titration with silver nitrate as the titrant, significant errors can occur at the first equivalence point as a result of coprecipitation. Errors of up to 33% were found for the first equivalence point for solutions containing mixtures of halides at micromolar levels. The addition of a flocculating agent to the solution reduced coprecipitation by increasing the rate of exchange between the precipitated silver halide and the halide ion remaining in solution. A logarithmic relationship was observed between the charge of the flocculating agent and the logarithmic concentration of the agent needed to minimise coprecipitation. Although flocculating agents reduced coprecipitation, they do not, however, completely eliminate equivalence point errors. Here a new method is presented which effectively eliminates the problem of coprecipitation during precipitation titrations for solutions containing two halides. In order to decrease the possibility of coprecipitation, we used selective complexation of the precipitation ion Ag⁺ in order to control the AgX solubility. For example, in the case of CF⁻ plus X⁻ (X=Br⁻ or I⁻), we added sufficient NH₃ to form Ag(NH₃)⁺ so that the free Ag⁺ activity was reduced below that required for theoretical AgCl precipitation in the absence of the other halides. Once the titration of the less soluble halide was completed and the first equivalence point determined, the Ag(NH₃)⁺ complex was destroyed by acidification of the solution to a pH less than 6. The titration is then continued and the second equivalence point determined. Equivalence point errors were reduced to less than 1.5% with careful application of the method.     

Ionic salt permeabilities and membrane potentials of asymmetric polypeptide membrane

Asymmetric membrane potentials and transport properties of polypeptide membrane consisting of two layers with poly(L-glutamic acid) and poly (γ-methylL-glutamate) were studied in the pH range of 2 to 6 at 25 °C. Under the condition adopted, the poly (L-glutamic acid) layer of the membrane underwentα helix to coil transition which was confirmed by ATR-IR measurements. The membrane potentials of the asymmetric membrane between two identical solutions of KCl,Δψ _asym, which is called asymmetric potential, were observed.Δψ _asym values were effected by the structural transition of poly (L-glutamic acid) layer. As a result, the effective charge density of the membrane, which was derived by the asymmetric membrane potential measurements, had a maximum at the transition region of pH=4.8. On the other hand, the permeation coefficient of KCl,P _i, was higher in the direction from poly (L-glutamic acid) side to poly (γ-methylL-glutamate) side, “G →M direction”, than in the oppositeM →G direction. Furthermore,P _i inG →M direction was dependent on the solution pH, that is,P _i decreased when pH was increased to 4.8 and increased on further increasing of pH These membrane behaviors were described in terms of the competition between structural transition and variation of fixed charge density owing to the helix to coil transition of the asymmetric polypeptide membrane.     

Direct detection of singlet oxygen sensitized by nalidixic acid: the effect of pH and melanin

Abstract— Singlet oxygen yields are reported for the antibiotic nalidixic acid in D₂O at pH values above and below its pK., in water. The φ_Δincreases on lowering the pH. The effect of eumelanin on the φ_Δ values is shown to be substantial at pH 4.4, but virtually zero above the pK_n value. Human serum albumin seems to have little effect on the singlet oxygen yield at high pH in the presence of melanin. The results are correlated with the experimental and clinical observations relating to the photosensitizing activity of the drug.     

Role of the activity coefficient in the dissemination of pH: comparison of primary (Harned cell) and secondary (glass electrode) measurements on phosphate buffer considering activity and concentration scales

Despite recent efforts devoted to assessing both the theoretical rationale and the experimental strategy for assignment of primary pH values, these have not yet been accomplished satisfactorily. Traceability and comparability of pH values are achieved only within the constraints of internationally accepted conventions and predefined conditions that cannot account for all possible situations when pH is measured. Critical parameters to be defined are, in particular, the activity coefficients (γ _i) of the ionic species involved in the equilibrium with the hydrogen ions in the solution, which are usually estimated with the approximation typical of the Debye–Hückel theoretical model. For this paper, primary (Harned cell) measurements (traceable to the SI system) of the pH of a phosphate buffer have been considered and the results have been compared with secondary (glass electrode) measurements obtained by considering either the activity (paH) or concentration (pcH) scale of the hydrogen ions. With conventional approaches based on measurements related to activity or concentration scale, discrepancies emerge which have been assigned to incomplete inferences of γ _i arising from chemical features of the solution. It is shown that fitting and comparable paH and pcH results are attainable if evaluation of γ _i is performed using better estimates of the ionic strength, according to an enhanced application of the Debye–Hückel theory.     

Energies of OH⋯X− hydrogen bonds in the gas phase and proton affinities

The energies of hydrogen-bond formation (−ΔH⁰_HX) between hydroxy derivatives and halide ions in the gas phase obey the following relationship: −ΔH⁰_HX = 0 (ΔPA > 0)+32 e^{−0.0156&mid;ΔPA&mid;}, or −ΔH⁰_HX = −ΔPA (ΔPA < 0) + 32 e^{−0.0156∣ΔPA∣}, where ΔPA is the difference between the heterolytic dissociation energy of the -OH and HX bonds. This relation is discussed as a function of the different factors (electrostatic, repulsion, polarization and charge transfer) contributing to the protonation reaction or hydrogen-bond formation.     

Rapid transacylations of activated ester substrates bound to the primary side β-cyclodextrin-cyclen conjugate and its M2+ complexes

The ability of cyclodextrins to effect rapid transacylations of bound substrates has been well studied. One important difference between cyclodextrin and enzyme-mediated transacylation is the pH required. Because the pK _a of a cyclodextrin secondary-side hydroxyl group is about 12, transacylations are accelerated in the presence of cyclodextrin under basic conditions (pH > 10.5). In 1988, our group reported the synthesis of cyclodextrin with attached cyclen-Co(III) complexes; significant acceleration in the reaction withp-nitrophenyl acetate was observed only with the primary side derivative. Of course, metalloenzymes utilize M²⁺ and not M³⁺ catalytic centers; in addition, large rate accelerations in the transacylations of both activated and unactivated substrates have been observed previously in systems utilizing M²⁺ ions (e.g., Zn, Cu, Ni) as well as M³⁺ ions (e.g. Co, Ir, Cr). In this paper, we describe the ability of CD-cyclen-M²⁺ conjugates to transacylate activated esters, amides, and phosphates. In addition, the ability of the apoenzyme mimic to effect transacylations was examined.     

Thermodynamics of Complexation of Tetraalkylammonium and Rare-earth Cations with Two Sulfonatocalix[n]arenes (n=4 and 6) in Aqueous Solution

We report results of a microcalorimetry study of the association of inorganic and organic cations with two p-sulfonatocalix[n]arenes (host 1: n = 4; host 2: n = 6) in aqueous solution at 298.15 K. First, we have determined the thermodynamic parameters for the complexation between the host 2 and a series of quaternary ammonium cations. We have evaluated the influence of the pH on the structure and energetics of these organic complexes. We have also reported the association constant and enthalpy of reaction for the complexation of some rare-earth cations (Sm³⁺, Dy³⁺, Y³⁺ and Sc³⁺ cations) with the two hosts. In all cases we have observed the formation of 1:1 complexes.

Whereas the association is driven by a favourable entropy change for the inorganic cations (ΔH > 0 and TΔS>>0), it is controlled by a favourable enthalpy change for the organic cations (ΔH < < 0 and TΔS < 0 or >0). In acidic solution, the complexes formed between host 2 and tetraalkylammonium cations are weaker than those formed with the cyclic tetramer. In neutral solution this effect is not observed. All the results are in line with a conformational change of host 2 with the pH.     

Chemiluminescence of Cypridina Luciferin Analogs. Part 3. MCLA Chemiluminescence with Singlet Oxygen Generated by the Retro-Diels-Alder Reaction of a Naphthalene Endoperoxide

The chemiluminescence of the Cypridina luciferin analog, 2-methyl-6-(p-methoxyphenyl)-3,7-dihydroirnidazo[1,2-a]pyrazin-3-one (MCLA), with O₂ (¹Δ_g) generated by the retro-Diels-Alder reaction of 3-(4′-methyI-l'-naphthyl)-propionic acid endoperoxide was studied in an aqueous solution with pH 7.12 at 37°C. The retro-Diels-Alder reaction occurs with a first-order rate constant of (4.16 ± 0.13) × 10^?4/s to quantitatively yield O₂ (¹Δ_g) and 3-(4′-methyl-l'-naphthyl (-propionic acid. MCLA consumed equimolar amounts of O₂ (¹Δ_g) with a second-order rate constant (6.96 ± 0.27) × 10⁸/M/s to emit light in an aqueous solution with pH 7.12 at 37°C. The chemiluminescence spectrum was identified as the fluorescence spectrum of 2-acetylamino-5-(p-methoxyphenyl)pyrazine (OMCLA), a major chemiluminescence reaction. Chemiluminescence spectra and product yields for MCLA reactions with O₂¹Δ_g, with O₂ (³Σ^?_g) and with superoxide anion radicals are identical, suggesting that all of these reactions occur via a common MCLA-2-hydrope-roxide intermediate formed by a combination of MCLA radicals and superoxide anion radicals. We have established practical use of NEPO as an O₂ (¹Δ_g) source and MCLA as a biological probe for detecting O₂ (¹Δ_g).     

Electrochemical Investigation of some Flavonoids in Aprotic Media

Cyclic voltammerty data for the oxidation of 15 flavonoids in acetonitrile have been presented. Up to three peaks in different potential regions appear in the CV curves, depending on the structure of a flavonoid. The peak in the first potential region (+0.79÷+1.03 V vs SCE) occurs when a flavonoid molecule has an o-dihydroxy moiety in the ring A or B. From the data in the literature, the formation of o-quinone is responsible for the occurrence of the peak. When the o-dihydroxy moiety is in ring B and the hydroxyl group is at position 3, the second peak in the potential region+1.08÷+1.32 V, is present. It is an agreement that the peak is due to oxidation of benzofuranone derivative formed in reaction of o-quinone with water. Molecules with an o-quinone moiety located in ring A seem to be less reactive, and the peak in the second potential region does not occur. However, the existence of an o-quinone in the ring B is not necessary for the peak in the second potential region to be present. The oxidation of kaempferol and morin, which have hydroxyl groups at positions 3 and 4’, takes place at 0.98 V and 0.97 V, respectively, and leads to the formation of p-quinone methide. We have shown that the peak in the second potential region also appears when the hydroxyl group in the flavonoid molecule is only at position 3 or at position 4’. For 3-hydroxyflavone and apigenin, which are oxidized at +1.10 V and 1.49 V respectively, p-quinone methide was detected after controlled potential bulk electrolysis. A mechanism which includes the reaction of the carbon radical with a trace of water has been proposed. For flavonoids that have an o-dihydroxy moiety in ring B and the hydroxyl group at position 3, two oxidation peaks are observed in the CV curves in the second potential region for low scan rates (below 0.1 V s⁻¹). An explanation of this behavior has been proposed.     

Yields of singlet nitrenes from halogen atom—azide molecule reactions

Chemiluminescence from the a¹Δ and b¹Σ⁺ excited electronic states of nitrogen halide diatomics is observed when HN₃ is allowed to react with mixtures of halogen atoms in a discharge-flow apparatus. Excited NF (a¹Δ) is produced by the F + HN₃ reaction, and NCl (a¹Δ, b¹Σ⁺) and NBr (a¹Δ, b¹Σ⁺) are produced by the F, Cl, + HN₃ and F, Br + HN₃ reactions, respectively. In the low-density limit, the yield of NF(a¹Δ) was found to be near unity. The yields of the b¹Σ⁺ states of NCl and NBr were determined to have a lower limit of ca. 10%. A number of results from these experiments, including direct observation of N₃ radicals in the flow, support a hypothetical mechanism in which N₃ acts as an intermediate. A second possible mechanism proceeding via an HNF intermediate cannot be ruled out.     

Living cationic polymerization of vinyl ethers and styrene derivatives: Design of initiating systems based on added salts with halogen anions

This paper overviews three living cationic polymerization systems (for styrene, p-methoxystyrene, and isobutyl vinyl ether) that are, in common, featured by: (i) specifically in nonpolar solvents, the use of the hydrogen halide/metal halide initiating systems (HX/MX_n; X: I, Br, Cl; MX_n: ZnX₂, SnCl₄), which generate a living growing carbocation stabilized by a nucleophilic counteranion (X⁻…MX_n); (ii) specifically in polar solvents, the use of externally added ammonium salts (nBu₄N⁺Y⁻; Y⁻: I⁻, Br⁻, Cl⁻), which permit the generation of living species from HX/MX_n by providing nucleophilic halogen anions Y⁻, either the same as or different from the halogen X⁻ in HX.     

First Synthesis and Properties of Calix[4]arene with Two Alternately Arranged Phloroglucinols and Two p-tert-Butylphenols

The Calix[4]arene 1 including two alternately arranged phloroglucinols and p-tert-butylphenols was synthesized via the “3+1” coupling procedure, and its pKa values were estimated to be 3–4 and 7.5, while those of the other six phenolic hydroxyls were approximately 11. Its UV–vis spectrum at pH 11 and ¹H and ¹³C NMR spectra in NaOD-D₂O solution (pH 12.8) showed a dramatic change like those of the phloroglucinol when compared to those in acidic or neutral solution, which suggests a change in the phloroglucinol moiety to the keto-form. During the solvent extraction for alkali metal species using 1, Li⁺ was only extracted in the low yield of 15% at pH 11. The cyclic voltammetry study of 1 was used to compare it with the phloroglucinol and p-tert-butylphenol. The redox potential of the corresponding two phloroglucinols was observed in 1.     

Lanthanide‐Based T2ex and CEST Complexes Provide Insights into the Design of pH Sensitive MRI Agents

The CEST and T₁ /T₂ relaxation properties of a series of Eu³⁺ and Dy³⁺ DOTA‐tetraamide complexes with four appended primary amine groups are measured as a function of pH. The CEST signals in the Eu³⁺ complexes show a strong CEST signal after the pH was reduced from 8 to 5. The opposite trend was observed for the Dy³⁺ complexes where the r_2ex of bulk water protons increased dramatically from ca. 1.5 mm ⁻¹ s⁻¹ to 13 mm ⁻¹ s⁻¹ between pH 5 and 9 while r₁ remained unchanged. A fit of the CEST data (Eu³⁺ complexes) to Bloch theory and the T_2ex data (Dy³⁺ complexes) to Swift–Connick theory provided the proton‐exchange rates as a function of pH. These data showed that the four amine groups contribute significantly to proton‐catalyzed exchange of the Ln³⁺‐bound water protons even though their pK _a’s are much higher than the observed CEST or T_2ex effects. This demonstrated the utility of using appended acidic/basic groups to catalyze prototropic exchange for imaging tissue pH by MRI.