Thermodynamic Data for Complex Formation Between Cucurbituril and Alkali and Alkaline Earth Cations in Aqueous Formic Acid Solution

Complex formation, between alkali and alkaline earth cations and the macrocyclic ligands cucurbituril and 18-crown-6, was studied by calorimetric titration in aqueous formic acid solution (50 vol.%). The solubility of cucurbituril strongly depends on the concentration of formic acid. At low and very high formic acid concentrations, the solubility of cucurbituril is low. For both ligands the formation of proton complexes influence the complexation reactions with cations. Thus, the complex formation in most cases is favored by entropic contributions. Only in the case of the Ba²⁺ ion stability constants and reaction enthalpies could be measured at lower formic acid concentrations. Using a highly sensitive calorimeter, the stability constants and reaction enthalpies for the reaction of Na⁺ and Ba²⁺ with cucurbituril in aqueous solution could be determined.     

Cucurbituril and β-Cyclodextrin as Hosts for the Complexation of Organic Dyes

The complexation of neutral organic molecules by cucurbituril and-cyclodextrin in formic acid was studied by means ofspectrophotometric titrations. In the case of -cyclodextrin thecomposition of the solvent has almost no influence upon the stability of thecomplexes formed. This situation is completely different for cucurbituril.Due to its interactions with protons the measured stability constants of thecomplexes formed with organic molecules increase with decreasing acidconcentration. At low acid concentrations cucurbituril forms more stablecomplexes with organic molecules than -cyclodextrin.     

Synthesis of 2-hydrazino- and 2-amino-1,3,4-thiadiazines containing polyhydric phenol residues in the 5 position

2-Hydrazino-1,3,4-thiadiazines containing polyhydric phenol residues in the 5 position were obtained by reaction of 3,4-dihydroxy-, 2,5-dihydroxy-, and 2,3,4-trihydroxyphenacyl -halides with thiocarbohydrazide. 2-Amino-1,3,4-thiadiazines were obtained by reaction of 3,4-dihydroxy-and 2,5-dihydroxyphenacyl -halides with thiosemicarbazide in acidic and alcoholic media. In contrast to the dihydroxy derivatives, 2,3,4-trihydroxyphenacyl halide forms a 2-amino derivative only in strongly acidic media, whereas the isomeric thiazole compound with a hydrazine group in the 2 position of the thiazole ring is formed in alcoholic media.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1051–1055, August, 1976.     

Mikrotitrationen mit äthylendiamintetraessigsäure. vii

Zusammenfassung Durch Umsetzung von Palladiumsalzen mit Kaliumnickeltetracyanid wird eine dem Palladium äquivalente Nickelmenge in Freiheit gesetzt und kann in ammoniakalischer Lösung gegen Murexid titriert werden. Bei Verwendung von 0,01-m Komplexonlösungen ergeben sich maximale Fehler von±20g Palladium.

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Summary By treating palladium salts with potassium nickel tetracyanide, a quantity of nickel equivalent to the palladium is liberated and can be titrated in an ammoniacal solution with murexide. Maximum errors of±20 g palladium are obtained when 0.01 M solutions of complexone are used.

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Résumé En traitant des sels de palladium avec le nickelotétracyanure de potassium une quantité de nickel équivalente au palladium est mise en liberté et peut être titrée en solution ammoniacale avec la murexide comme indicateur. Par emploi d'une solution 0,01 m de complexone, on obtient une erreur maximum de±20g sur le palladium.

     

Ion-pair extraction of tetracyclines

Summary Ion-Pair Extraction of Tetracyclines Tetracyclines form ion-pair complexes with dyes that can be extracted into chloroform and re-extracted into 0.1N hydrochloric acid and finally quantified by spectrophotometry. Of the dyes studied methyl red, methyl orange, bromophenol blue and bromothymol blue form complexes with cationic form of tetracycline (pH 8–9) and crystal violet with the anionic form (pH 9–10). 98% of tetracycline can be extracted from the body fluids and solution containing 10g/ml of tetracycline can be conveniently analyzed.     

Leaching of the Anthraquinone Dye Solvent Blue 59 Incorporated into Organically Modified Silica Xerogels

The effects of preparation method and precursor composition on the leaching behavior of the anthraquinone dye Solvent Blue 59 incorporated into silica based xerogels have been studied. Xerogels were prepared under acidic conditions from mixtures of 20 mol% of organically modified silicon alkoxides, R–Si(OR)3, in Si(OR)4 (R = methyl or ethyl, R = methyl, vinyl, phenyl). The dye was added at the beginning of the sol-gel reaction. The reaction was carried out by either hydrolysis under acidic conditions or acidolysis by formic acid. The dye incorporated was leached with refluxing ethanol using a Soxhlet extraction procedure to simulate the long-term stability of the samples prepared. With increasing size of organic substituent (methyl < vinyl < phenyl), the amount of dye leached decreases. Results from nitrogen adsorption experiments show that all samples characterized have about the same average pore diameter, but they differ in total pore volume and BET surface area. With increasing size of the organic residue, the pore volume decreases by an order of magnitude. Therefore, it is concluded that the microstructure of the xerogels prepared determines the retention behavior of dyes incorporated during the sol-gel reaction.     

m-Aminophenylarsonic Acid as an Analytical Form for the Photometric Determination of Phenol in Water

The azocoupling reaction of diazonium salts of o- and m-aminophenylarsonic acids with phenol was studied. On the basis of quantum-chemical calculations of the reagents, conformation analysis of resulting azo compounds, and experimental data, it was found that the meta isomer of aminophenylarsonic acid is of practical interest as an analytical reagent for the determination of phenol. The advantage of the proposed reagent is a high stability of the diazonium salt. A procedure was developed for the spectrophotometric determination of phenol in water at a level of 0.06 g/mL. The error in the determination is no higher than 5.5%.     

Evaluation of proton activity in microemulsions by a kinetic probe

The decomposition reaction of the purple dye murexide in acidic media is used as a probe indicator for protons in nonionic microemulsions. The reaction kinetics primarily rely on the proton concentration and permit assessment of the proton activity in the nonionic microemulsions of water/cyclohexane/Igepal and water/heptane/Igepal. The experiments performed in the two microemulsions covered a wide range of water-to-oil mass fraction for the two systems. The kinetic runs were monitored under pseudo-first order conditions by the stopped-flow technique. The equilibrium constants for the formation of purpuric acid and the kinetic constants for the ensuing decomposition reaction fulfill a trend consistent with the micro compartmentalized nature of the multicomponent medium, and support the use of murexide as an indicator of the proton activity in microemulsions.     

Inclusion complexes of proteins: Interaction of cyclodextrins with peptides containing aromatic amino acids studied by competitive spectrophotometry

The stability constants were measured of inclusion complexes formed from aromatic amino acids and their oligopeptides with - and-cyclodextrin, hydroxypropyl-cyclodextrin, and partially methylated-cyclodextrin. The method of competitive spectrophotometry withp-nitrophenol as a competing reagent was used, and measurements were made at pH 7.4-Cyclodextrin formed complexes of higher stability than the other hosts. The stability of complexes of oligopeptides containing L-phenylalanine was invariably higher than that of L-phenylalanine itself. A model for interaction of proteins with cyclodextrins is proposed, in which the most stable complexes are formed when the native functional form of proteins is unfolded and the nonpolar residues that are buried inside the structure are exposed to water. The complexation of the unfolded structure favors its formation; thus thermal denaturation of proteins is easier in the presence of cyclodextrins. On the other hand, this complexation prevents the intermolecular association of unfolded structures by noncovalent hydrophobic bonding between the exposed nonpolar residues; furthermore, the unfolded complexed forms may revert to the native functional form. This prevention of intermolecular association may explain the stabilizing effect of cyclodextrins on solutions of proteins: a return to the native form is achieved more easily from the complexed, unfolded form than from the unfolded, aggregated forms.Dedicated to Professor József Szejtli.     

The nature of active centers in cyclotrimerization of isocyanates catalyzed by the tertiary amine—α-oxide—proton donor system 1. The role of the proton donor

The rate of cyclotrimerization of phenyl isocyanate in chlorobenzene at 120 °C in the presence of the tertiary amine--oxide-proton donor (PD) ternary catalytic system has been studied using a dual calorimeter and a series of phenols with various acidities as the PD. In the presence of weakly acidic phenols, complexes of quaternary ammonium type bases are formed in the ternary catalytic systems. Acidic phenols afford salt complexes with the transfer or a proton from phenol to the tertiary amine in a quantitative yield, while the -oxide present remains unaffected. The structures of the complexes were studied by IR and by IR and¹H NMR spectroscopy.DeceasedTranslated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1382–1385, lune, 1996.     

Synthesis,spectra and redox behavior of copper(II) complexes of curcumin diketimines as models for blue copper proteins

Several new Cu^II complexes, having positive reduction potentials in an in situmanner, were synthesized by reaction of the Knoevenagel condensate, 4-salicylidene-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (from curcumin) with 4-X-anilines and CuCl₂. The solution electronic spectra of these complexes show intense absorption around 530 nm with unusual high extinction values (, 1600--3600 m^-1 cm^-1) due to the low symmetry L--d (Cu) LMCT transition. The e.s.r. spectral features with g _|| > g _|| > 2.0 having four g _|| values and a broadening of the g _||component with moderately low A _|| (110 × 10^-4 cm^-1) also suggest a lower symmetry around Cu^II. The cyclic voltammetric studies of the Cu^II complexes in MeCN show a positive reduction potential (E _pc=502--138 mV) with high peak-to-peak separation (E _p=87--335 mV). The higher and low A _||values together with positive reduction potentials for these Cu^II complexes suggest that they can mimic the functional properties of blue copper proteins, but have poor redox stability.     

Spectrophotometric determination of the stability constant of the Eu(III)-murexide complex

The values of the stability constants of the Ca(II) and lanthanide(III) complexes of murexide reported in the literature were determined without proper correction for binding of buffer ions to the metal ion. The constants are best determined without a buffer present. Accurate values of conditional stability constants for the Eu(III)—murexide complex (relative standard deviation better than 3%), of the differential molar absorptivity of the Eu(III)—murexide complex with respect to murexide at 480 nm (relative standard deviation better than 0.5%) and of the molar absorptivity of murexide at 520 and at 506 nm (precision better than 0.4%) at pH 5.0 and 6.5 at 15, 25 and 35° are reported. The accuracy and precision of the concentration of metal ion solution determined by using these conditional stability constants are discussed.     

Spectral Studies on the Cyclodextrin Inclusion Complexes of Toluidine Blue O and Meldola's Blue in Aqueous Solution

The absorption and emission spectral properties of toluidine blue O (TBO) and Meldola's blue (MDB) in the presence of cyclodextrins (CDs) were studied. Formation of 1 : 1 and 1 : 2 (CD-Dye) inclusion complexes were observed with -CD and -CD, respectively. An increase in the emission intensity was noticed in the presence of -CD due to the formation of 1 : 1 (CD-Dye) inclusion complexes. However, a decrease in the emission intensity was observed in the presence of -CD due to the formation of 1 : 2 (CD-Dye) inclusion complexes. Dimerization of dye molecules in the presence of -CD lead to a decrease in the emission intensity. The formation constants for the 1 : 1 and 1 : 2 (CD-Dye) inclusion complexes were calculated.     

Crown Ether Complexes of Six-Membered N-heteroaromatic Cations

Crown ether complexes of six-membered N-heteroaromatic cations and the closely related bicyclic purinium cation (6) have been studied by ¹H NMR, mass spectrometric and crystallographic methods. The stability constants for the complexes were determined by ¹H NMR titration in acetonitrile solution and the complexation stoichiometry by ¹H NMR and ESI mass spectrometric methods. Altogether six crystal structures of complexes were determined to study the complexation in the solid state. Hydrogen bonding was observed to be the most important interaction for the complexation both in solution and in the solid state but – interactions also contribute to it. All crystal structures of the DB18C6 complexes with six-membered N-heteroaromatic cations, except for 4-hydroxypyridinium, are isomorphous to previously studied five-membered N-heteroaromatic cations and pyridinium complexes. Such a close resemblance is not observed in B18C6 and 18C6 complexes or DB18C6purinium (6).     

UV/H2O2/草酸铁络合物光降解偶氮蓝染料的研究

光氧化法是近年来日益受人们重视的一种治理染料废水的新方法,而现有方法光量子效率低、光能耗大、处理费用高。已有研究表明草酸铁络合物有较高的光降解效率。而在到达地面的太阳辐射中,紫外辐射只占4％左右,所以研究弱紫外辐射下光降解染料废水意义重要。本文用6W低压汞灯光源,过氧化氢．草酸铁络合物光降解水溶液中的偶氮蓝染料,考察pH值、H2O2浓度、染料浓度及光强等因素对降解结果的影响,探讨以自然光为光源催化降解偶氮蓝染料的可行性。     

Spectrophotometric flow injection analysis of formaldehyde in aqueous solutions using 3-methyl-2-benzthiazolinone hydrazone

Summary A flow injection method for the determination of formaldehyde was developed. It is based on its reaction with 3-methyl-2-benzthiazolinone hydrazone (MBTH) to yield a blue formazan anion. Typically 180 l samples are injected into a buffered carrier stream with a frequency of 30 per hour. This sample line merges with the reagent stream containing MBTH, whereupon an azine is formed. After merging with a second stream containing an acidic solution of FeCl₃ as reagent, MBTH is oxidized to an intermediate that attacks the azine yielding the formazan dye with an _max at 635 nm. The method was applied to formaldehyde concentrations in the range from 0.15 mg/l to 15 mg/l. The relative standard deviation was 2.3% for 3 mg/l formaldehyde, and 5.1% for 0.3 mg/l, respectively. Strong reducing agents like nitrite interfere seriously. Out of the family of carbonyl compounds only acetaldehyde and propionaldehyde cause strong positive interference.     

Stability of Copper(II), Nickel(II) and Zinc(II) Binary and Ternary Complexes of Histidine,Histamine and Glycine in Aqueous Solution

The binary and mixed-ligand complexes formed between ligands (histidine (His), histamine (Him) and glycine (Gly)) and some transition metals (Cu(II), Ni(II) and Zn(II)) were studied potentiometrically in aqueous solution at (25.0 ± 0.1) C and I = 0.10 M KCl in order to determine the protonation constants of the free ligands and stability constants of binary and ternary complexes. The complexation model for each system has been established by the software program BEST from the potentiometric data. The most probable binding mode for each binary species of histidine and for all mixed species was also discussed based upon derived equilibrium constants and stability constants related to the binary species. The ambidentate nature of the histidine ligand, i.e. the ability to coordinate histamine-like, imidazolepropionic acid-like and glycine-like modes was indicated from the results obtained. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters, log K, log X and ₁₁₁₀. The concentration distributions of various species formed in solution were also evaluated. In terms of the nature of metal ion, the complex stability follows the trend Cu(II) > Ni(II) > Zn(II), which is in agreement with the Irving-Williams order of metal ions. Thus, the results obtained were compared and evaluated with those in the literature.     

Thermodynamics of surfactant-dye complex formation in aqueous solutions II. Sodium dodecyl sulfate and some azo oil dye systems

Spectrophotometric and thermodynamic investigations are reported of the interactions between anionic surfactant (sodium dodecyl sulfate) and six azo oil dyes (benzene azo naphthalene type) which have an amino group at 4-position of naphthalene. A pronounced spectral change in the dye solution occurs on addition of surfactant. For increasingly surfactant concentrations (below the CMC), the interaction between dye and surfactant is so sharp that the systems may be said to exhibit an isosbestic point; then a new absorption band appears at longer wavelengths. The spectral data can be quantitatively interpreted in terms of a complex formation. The equilibrium coefficients of the complex formation are determined at different temperatures. The thermodynamic parameters of the complex formations (the free energy change (G), enthalpy change (H) and change in entropy (S) are also calculated. The reaction of complex formation is exothermic (H negative).G is dependent on the hydrophobic nature andpKa of the dye. These complexes will form due to hydrophilic-hydrophilic interaction and will become more stable due to hydrophobic-hydrophobic interaction.With increasing amounts of complex, the infinite adsorption, the exhaustion and the rate constant of dyeing for nylon decrease.     

Synthesis of N,O-heterocyclic carbene and coordination to rhodium(I) and copper(I)

5,7-Di-tert-butyl-3-phenyl benzoxazolium tetrafluoroborate 1 could be prepared by simple reaction of the corresponding aminophenol with triethyl orthoformate under acidic conditions. Both rhodium(I) and copper(I) complexes with benzoxazol-2-ylidene ligand were then efficiently synthesised in a straightforward and smooth manner involving the reaction of benzoxazolium salt 1 with metal precursor and an external base. The complexes have been fully characterised and used in metal-catalysed hydrosilylation of ketones, where they showed poor catalytic activity, presumably due to low stability of the complexes under those conditions.     

A Spectroscopic and Molecular Modelling Study of the Nature of the Association Complexes of Nile Red with Cyclodextrins

The polarity-sensitive fluorescent dye Nile Red forms association complexes with various cyclodextrins in aqueous solution. The formation of such association complexes has a significant effect on the Nile Red fluorescence, with the largest effect being observed in -cyclodextrin solution. When -cyclodextrin is used to increase the Nile Red concentration in solution, the absorption spectrum shows a large blue shift indicating the formation of an inclusion complex, but surprisingly the Nile Red fluorescence is strongly suppressed. A proposed explanation for this observation involves the formation of 1:2 host:guest complexes, in which the Nile Red guests are included as relatively non-fluorescent dimers. When the solutions were prepared by adding -cyclodextrinto a near-saturated aqueous solution of Nile Red (so that 1:1 or 2:1 complexation shouldbe favoured), significant fluorescence enhancement was observed. Analysis of thefluorescence enhancement as a function of host concentration indicated the formationof 2:1 host:guest complexes in these solutions. However, electrospray mass spectroscopic studies show no evidence for the formation of any such inclusion complexes. Furthermore, molecular modelling shows that the formation of a complex involving full insertion of Nile Red in the -cyclodextrin cavity is not stable, and will quickly eject the Nile Red guest molecule. These modelling results suggest that an association complex involving capping (via the association of Nile Red parallel to the cavity opening, or by partial insertion into the cavity) of the -cyclodextrin cavity by one or two Nile Red molecules is much more likely.