Redox-dependent complexation ability of flavin-hosts in aqueous solution

The synthesis of the novel macrocyclic host 1 incorporating an isoalloxazine moiety as model for active sites of flavoenzymes is described. The complexation between oxidized and reduced flavin-host and aromatic guests is analyzed in aqueous solution.     

The conformational features of palytoxin in aqueous solution

Conformational features of palytoxin and acetylated palytoxin were investigated by detailed analyses of NOESY spectra. The conformational differences between palytoxin and acetylated palytoxin may account for the difference in the assembly state of palytoxin, which exists as an associated dimer, and the acetylated derivative, which exists as a monomer in aqueous solution. Two palytoxin units in the dimer may come in contact with each other at the hydrophobic region (C21-40) and the region around two conjugated double bonds (C60-84). The amino group of palytoxin is important for biological activities via Na/K ATPase, but it was not found to be involved in the contact faces of the two palytoxin units. This information should aid in revealing how palytoxin interacts with Na/K ATPase.     

Conformations and complexation abilities of chemically modified cyclodextrins in aqueous solution

Circular dichroism spectral and fluorescence decay methods have been employed to determine the conformations of mono[6-(p-tolylseleno)-6-deoxy]-β-CD(1), mono(6-anilino-6-deoxy) −β -CD (2) and mono[6-(L-tryptophan)-6-deoxy]−β -CD (3) in phosphate buffer solution (pH 7.2, 0.1 mol dm⁻³) at 298.15 K. The results indicate that compounds 2 and 3 formed self-inclusion complexes in aqueous buffer solution, while the substituent of compound 1 was not included into cyclodextrin cavity at all. Furthermore, the complex stability constant (logK _s) and Gibbs free en-ergy change (−ΔAG °) of these three cylcodextrin derivatives with several cycloalkanols have been determined by circular dichroism spectral titration in phosphate buffer solution at 298.15 K. It is found that the location of the substituent affects the stability of host-guest complex in aqueous solution.     

Fluoride ion complexation by a cationic borane in aqueous solution

The phosphonium borane [p-Mes(2)B(C(6)H(4))PMePh(2)](+) complexes fluoride in water containing 10% methanol with a binding constant of 1.0(+/-0.1) x 10(3) M(-1) to afford the zwitterion p-Mes(2)FB(C(6)H(4))PMePh(2).     

Rare earth element complexation by fluoride ions in aqueous solution

Rare earth fluoride stability constants for Ce, Eu, Gd, Tb and Yb at 25°C have been determined by examining the influence of fluoride ions on the distribution of rare earths between tributyl phosphate (TBP) and 0.68M NaClO₄. Our results indicate that rare earth mono and difluoro complexation constants show a steady increase as a function of atomic number from La to Tb but remain relatively constant after Dy. This behavior is similar to that which has been observed for dicarboxylic acids. Stepwise stability constant ratios, K₂/K₁, obtained in our work (where K₁=[MF²⁺][M³⁺]^–1[F^–]^–1 and K₂=[MF ₂ ⁺ ]^–1[MF²⁺]^–1[F^–]^–1) indicated that, for all rare earths, K₂/K₁=0.09±0.03.     

Scandium sulfate complexation in aqueous solution by dielectric relaxation spectroscopy

Ion association in aqueous solutions of scandium sulfate has been investigated at 25 degrees C and at concentrations from 0.01 to 0.8 M by broadband dielectric spectroscopy over the frequency range 0.2 相似文献   

Time-dependent conformational changes of polyelectrolyte complexes in solution

Changes in the conformation of the polyelectrolytes when contacted with oppositely charged polyelectrolytes or when subjected to shifts in solution conditions (pH), have been studied in this work along with reversibility of the changes using fluorescence spectroscopy. While changes due to both of the above are marked, they are measurably different from each other. Thus, the extent of coiling of the complexes formed between the anionic polyelectrolyte, maleicacid anhydride–propene and the cationic polyelectrolytes was much higher than that achieved by the change in pH alone. Also, while the changes due to pH shifts were fast and reversible, that due to complexation between oppositely charged ones involved first a rapid uncoiling followed by slow recoiling to a new structure. Interestingly, shifting the coiled conformation to an even more coiled one resulted in a new reversible state, but shifting to a stretched state by complexation led to a somewhat irreversible structure. Also maximum interaction obtained between the anionic and one cationic polyelectrolyte was markedly higher than that between the former and another cationic polymer. These observations using fluorescence spectroscopy was consistent with that obtained by the potentiometric titration. The study clearly shows the importance of the manner in which the polyelectrolytes are equilibrated to desired solution conditions. These results are interpreted here in terms of deprotonation/protonation of the polyelectroytes upon pH change and complexation with oppositely charged ones resulting in screening of charges as well as stiffening.     

Energetic and conformational changes upon complexation of gelatin with sodium dodecyl sulfate

The effect of sodium bis(2-ethylhexyl)sulfosuccinate/isooctane/water microemulsions on the stability of 2,2-dimethyl-2,3-dihydro-1-benzofuran-7-yl methylcarbamate (carbofuran, CF), 3-hydroxy-2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate (3-hydroxycarbofuran, HCF) and 3-keto-2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate (3-ketocarbofuran, KCF) in basic media has been studied. The presence of these microheterogeneous media implies a large basic hydrolysis of CF and HCF on increasing surfactant concentration and, also, on increasing water content in the microemulsion. The hydrolysis rate constants are approximately 2- and 10-fold higher than those in pure water for HCF and CF, respectively. In contrast, a steep descent in the rate of decomposition for KCF was observed. These behaviours can be ascribed to the presence of CF derivatives both in the hydrophilic phase and in the lipophilic phase, while the hydroxyl ions are only restricted to the water pool of the microemulsion (hydrophilic phase). The kinetic rate constants for the basic hydrolysis in AOT-based microemulsions have been obtained on the basis of a pseudophase model. Taking into account that an important part of soils are colloids, the possibility of the presence of restricted water environments implies that soil composition and its structure will play an important role in the stability of these carbamates. In fact, we observed that the presence of these restricted aqueous media in the environment, in particular in watersheds and in wastewaters, could reduce significantly the half-life of these pesticides (33% and 91% for HCF and CF, respectively).     

Synthesis of water-soluble 2-alkylcyclodextrin-C60 conjugates and their inclusion complexation in aqueous solution

Two β-cyclodextrin-C₆₀ conjugates (3 and 4) with a flexible linker at the secondary face of cyclodextrin are synthesized by a single reaction of 2-(ω-azidoundecanyl)-2-O-heptakis (2,3,6-tri-O-methyl)-β-cyclodextrin (2) and C₆₀, both of which display satisfactory water solubility. Structural analyses show that 3 is a closed [5,6] aziridinofullerene, whereas 4 is a bis-adduct derivative. Using rhodamine B (RhB) as a guest molecule, the inclusion complexation behavior of 3 was investigated in aqueous solution.     

Molecular complexation of the triterpene glycoside hederasaponin C and caffeine in aqueous solution

Molecular complexation of the triterpene glycoside hederasaponin C [hederagenin 3-O-α-L-rhamnopyranosyl-(1→2)-O-β-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ether] and caffeine in aqueous solution was studied by UV spectroscopy for the first time. The complex composition, which included two glycosides and one caffeine, was determined using isomolar series and molar ratios. The ichthyotoxicity of the complex and its components against Poecilia reticulata was studied.     

A molecular dynamics study of alkaline earth metal-chloride complexation in aqueous solution

The relative stability of alkaline earth metals (M2+ = Mg2+, Ca2+, Sr2+, and Ba2+) and their chloride complexes in aqueous solution is examined through molecular dynamics simulations using a flexible SPC water model with an internally consistent set of metal ion force field parameters. For each metal-chloride ion pair in aqueous solution, the free energy profile was calculated via potential of mean force simulations. The simulations provide detailed thermodynamic information regarding the relative stability of the different types of metal-chloride pairs. The free energy profiles indicate that the preference for contact ion pair formation increases with ionic radius and is closely related to the metal hydration free energies. The water residence times within the first hydration shells are in agreement with residence times reported in other computational studies. Calculated association constants suggest an increase in metal-chloride complexation with increasing cation radii that is inconsistent with experimentally observed trends. Possible explanations for this discrepancy are discussed.     

Molecular dynamics and conformational kinetics of mono- and disaccharides in aqueous solution.

Acoustical attenuation spectra between 10 kHz and 2 GHz, complex dielectric spectra between 300 kHz and 40 GHz, and time-resolved non-equilibrium measurements are reported for aqueous solutions of various mono- and disaccharides with and without 2:1 valent salts. The spectra reveal a variety of relaxation regimes with relaxation times between 1 micros and 10 ps. In addition, the time-resolved observations enable the study of the mutarotation with relaxation times on the order of 10(3) s. Variation of the concentration and temperature as well as a careful choice of the saccharides allow a discussion of the relaxation processes in terms of a chair-chair ring inversion, two modes of pseudorotation, an exocyclic hydroxymethyl group rotation, a carbohydrate-carbohydrate association, and, in the disaccharide solutions, a rotation of the rings relative to another. Salt-containing solutions show also relaxation phenomena reflecting different steps cation-carbohydrate association and variations in the carbohydrate conformational isomerizations and associations due to interactions with cations.     

Polymer colloids formed by polyelectrolyte complexation of vinyl polymers and polysaccharides in aqueous solution

The polyelectrolyte complex formed from the polyanion and polycation was studied by turbidimetry, static and electrophoretic light scattering, and elementary analysis. Sodium salts of polyacrylate (PA) and heparin (Hep) were chosen as the polyanion, and hydrochloric salts of poly(vinyl amine) (PVA) and chitosan (Chts) as the polycation. Although these vinyl polymers and polysaccharides have remarkably different backbone chemical structures and linear charge densities, all the four combinations PA-PVA, PA-Chts, Hep-PVA, and Hep-Chts provide almost stoichiometric polyelectrolyte complexes which are slightly charged owing to the adsorption of the excess polyelectrolyte component onto the neutral complex. The charges stabilize the complex colloids in aqueous solution of a non-stoichiometric mixture, and the aggregation number of the complex colloids increases with approaching to the stoichiometric mixing ratio. The mixing ratio dependence of the aggregation number for the four complexes is explained by the model proposed in the previous study.     

Water-soluble calixarenes—self-aggregation and complexation of noncharged aromatic guests in buffered aqueous solution

Water-soluble calix[4]arenes are useful receptors for hydrophobic substrates in aqueous buffered solution. The inclusion of 22 aromatic guests as well as the self-aggregation behavior of amphiphilic hosts was studied by ¹H NMR spectroscopy. The association constants obtained range from 10 to 1000 L mol⁻¹. In all cases, the aromatic moiety is included into the hydrophobic pocket of the calixarenes maximizing hydrophobic contacts. Additionally, substituents such as methyl or chlorine exhibit a preference for inclusion in the pocket of the macrocycles owing to CH/π or Cl/π interactions. In case self-aggregation is observed, millimolar CMC values are to be found.     

Cd(II) complexation in aqueous solution with dipyridine- and phenanthroline-containing polyamine macrocycles

The coordination features toward Cd(II) of four phenanthroline-containing and three dipyridine-containing macrocyclic polyamines have been studied by means of potentiometric and spectrophotometric UV–Vis measurements in aqueous solutions. All ligands form stable 1:1 metal complexes. The stability constants of the Cd(II) are generally lower than those reported for Cd(II) complexes with aliphatic macrocyclic polyamines containing the same number of nitrogen donors. This effect is mainly related to the stiffening of the ligands, due to the insertion of a large and rigid heteroaromatic moiety within the aliphatic polyamine framework. This structural feature does not allow the nitrogen donor to achieve an optimal arrangement around the metal ion. The decreased stability is often accompanied by facile protonation of the complexes, suggesting that some amine groups are not involved in metal binding.     

Thermodynamics of mixed-ligand complexation of gadolinium ethylenediaminetetraacetate with amino acids in aqueous solution

Mixed-ligand complexation of GdEdta⁻ with glycinate, L-glutamate, DL-aspartate, iminodiacetate, and nitrilotriacetate anions in aqueous solutions at 298.15 K and the ionic strength I = 0.5 (KNO₃) was studied. The thermodynamic parameters (logK, Δ _r G, Δ _r H, Δ _r S) of these reactions were determined from calorimetric and pH-metric data. The most probable way of coordination of the amino acids in the heteroleptic complexes is discussed.     

The kinetics of cobalt(II) complexation with o-phthalate in aqueous solution

The rate constants for the formation and dissociation of cobalt(II) complexes with o-phthalate in aqueous solution have been determined by a pressure-jump technique. The forward and reverse rate constants obtained are k_f = 1.1 x 10⁶ M⁻¹ s⁻¹ and k_r = 1.6 x 1O³ s⁻ at 25°C, respectively. The activation parameters of the reaction were also obtained from the temperature variation study. The results indicate that chelate ring closure and rupture are affected by the rigidity of the benzene ring of the ligand, and thus the rate determining step of the reaction is the chelate ring closure process.     

Thermodynamic modeling of CO2 and H2S solubilities in aqueous DIPA solution, aqueous sulfolane-DIPA solution, and aqueous sulfolane-MDEA solution with electrolyte NRTL model

A thermodynamic model developed for CO₂ and H₂S solubilities in aqueous MDEA solution is extended to cover CO₂ and H₂S solubilities in aqueous DIPA solution, aqueous sulfolane-DIPA solution, and aqueous sulfolane-MDEA solution. The model makes use of the 2009 version of the electrolyte NRTL model for liquid phase activity coefficient calculations and the PC-SAFT equation of state for vapor phase fugacity coefficient calculations. The NRTL binary parameters for the molecule-electrolyte pairs required for the H₂O-DIPA-CO₂ ternary and the H₂O-sulfolane-DIPA-CO₂ quaternary are regressed against the solubility data of CO₂ in aqueous DIPA solution and aqueous sulfolane-DIPA solution, respectively. The NRTL binary parameters for the molecule-electrolyte pairs required for the H₂O-DIPA-H₂S ternary and the H₂O-sulfolane-DIPA-H₂S quaternary are regressed against the solubility data of H₂S in aqueous DIPA solution and aqueous sulfolane-DIPA solution simultaneously. The NRTL binary parameters for the electrolyte-electrolyte pairs involved in the H₂O-DIPA-CO₂-H₂S quaternary are regressed against the solubility data of the acid gas mixtures in aqueous DIPA solution. Likewise, the NRTL binary parameters for the sulfolane-electrolyte pairs required for the H₂O-sulfolane-MDEA-CO₂ quaternary and the H₂O-sulfolane-MDEA-H₂S quaternary are regressed against the solubility data of the acid gases in aqueous sulfolane-MDEA solution. The predicted enthalpies of acid gas absorption are compared favorably with the literature data available for the H₂O-DIPA-CO₂ system, the H₂O-DIPA-H₂S system, and the H₂O-sulfolane-MDEA-CO₂ system.     

Mixed-ligand complexation of iron(III) ethylenediaminetetraacetate with iminodiacetate and ethylenediamine in aqueous solution

The formation of the heteroleptic complexes FeEdtaIda³⁻ and FeEdtaEn⁻(Ida²⁻ is the iminodiacetate anion and En is ethylenediamine) was examined by direct calorimetry, pH potentiometry, and spectrophotometry at 298.15 K and the ionic strength I = 0.5 (KNO₃). A possible way of coordination of the ligands in the heteroleptic complexes was discussed.