Adhesive polymer: Intermacromolecular interaction in fluid solution studied by fluorescence depolarization method

The fluorescence depolarization of the anthryl groups attached to poly(styrene-maleic anhydride) [P(St-MA)] has been examined in mixtures of various acrylic adhesive polymers with toluene for weight fractions ranging from 0 to 0.25. It is clear that the relative mean rotational relaxation time of the anthryl groups sharply increases with increasing concentration of poly(2-ethylhexylacrylate) (PEHA) containing about 5% acrylic acid units and 10% vinyl acetate units. It may be concluded that an excellent adhesive polymer is made with acrylic acid units as agents for intra- and interaction and vinyl acetate units as depression agents for acrylic acid units and agents for strong PEHA-P(St-MA) interaction.     

Methylmercuric halide-halide complexation in ethanol solution

The formation constants for CH₃HgCl₂^? at 26°C (0.31 l/mole), and for CH₃HgBr₂^? at 26°C (0.94 l/mole) and at 60°C (0.70 l/mole) in ethanol solution have been determined from the variation of Hg NMR chemical shift (by INDOR) with composition of methylmercuric halide-lithium halide solutions. These data have been employed in a reexamination of the “one-anion” and “two-anion” catalysed reactions of mercuric bromide with alkylmercuric bromides.     

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.     

Intermacromolecular interactions involving linear and network polyacids and nonionic polymers

Interactions between linear and network polymers are studied in the case when one component is a polyacid and the other component is an uncharged polymer. It is shown that, under different reaction conditions, swelling or contraction of the polymer network can be observed for the same pair of reagents. It is found that, during consideration of the formation of an interpolymer complex between network and linear polymers, a distinction should be made between a semi-interpenetrating network and a hydrogel with a modified surface. The latter forms under conditions when the linear polymer practically does not penetrate the network and the complexation occurs predominantly on the sample surface.     

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.     

Poly-N-vinylamides,complexation and conformational changes in aqueous solution

Interaction between small molecules (iodine and 1-anilinonaphthalene-8-sulphonate) and poly-N-methylacetamide (PVMA), poly-N-vinylcaprolactam (PVCL), poly-N-vinylpyrrolidone (PVP) and copolymers of N-vinyleaprolactam with N-vinylpyrrolidone (CP VCL-VP) and with N-vinyl-N-methylacetamide (VMA) were studied. All the polymers formed complexes with the small molecules. The stability constant for the complexes with the probe increases in the series PVMA < PVP < copolymer < PVCL indicating the essential role of hydrophobic interactions in the complex formation. With increasing temperature of aqueous solution from 18 to 33°, the constant decreased for PVP, PVMA and copolymers with low VCL content and increased for PVCL. A folding of PVC coils was observed over the temperature range, demonstrating a relationship between the conformational changes of macromolecules and the polymer complex formation. Addition of PVCL, PVMA and PVP to aqueous I₃^? solution brings about a shift of λ_max from 350 nm for free triiodide ions to 372, 367 and 364 nm respectively. It is explained by different dipole moments of the side substituents. The stability constant for the polymers and I₃^? was estimated as approx. 10⁵ M. The ability of the polymers to form complexes depends on chainlength. The greatest loss of the ability was observed for PVCL with $\text{M}{}_{\mathrm{n}}$ changing from 6 × 10³ to 2 × 10³. Interaction of the polymers with I₃^? is accompanied by a conformational shrinking of coils. In the case of the probe, forces of electrostatic repulsion between negative charges of sulphonate groups result in an unfolding of polimer coils.     

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   

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.     

Dinegative tetrahedral oxoanion complexation; structural and solution phase observations

A structural and solution phase study of complexation of dinegative oxoanionic guests by protonated azacryptand hosts is presented. The interactions involve a complex balance of competing factors: anion free energy of hydration, host basicity and solvation, and complementarity of steric matching between host and guest. The formation constants of dinegatively charged anion cryptates are much larger than the analogous values for the mononegative analogues perchlorate or perrhenate.     

Structure and complexation energy of benzotrifuroxan–benzene molecular complex

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Stability analysis and scattering properties of charged crosslinked blends in solution

The phase behavior and scattering properties of crosslinked charged polymer blends in solution are examined. De Gennes' analogy between the effects of crosslinks in a network and electrostatic charges in a dielectric medium on the scattering properties and the phase behavior of crosslinked polymer blends is used. This analogy is extended to include the effects of screening in order to improve its agreement with the experimental data in the small q range. The excluded volume interactions are explicitely introduced through the blob model. The enhancement of compatibility of the mixture and the increase of its rigidity constant are evaluated in certain cases. The limit of neutral polymers is discussed because it corresponds to the case of charged mixtures in the presence of excess salt. The kinetics of the microphase separation transition is briefly discussed. A dynamical model including the long range hydrodynamic interaction is presented. The relaxation frequency of the stable modes and the growth rate of unstable ones are also considered.     

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.     

Architectural formation of a conjugated bimetallic Pd(II) complex via oxidative complexation and a tetracyclic Pd(II) complex via self-assembling complexation

The conjugated homobimetallic palladium(II) complex [(L1)Pd(qd)Pd(L1)] (qd = quinonediimine) was obtained in a one-pot reaction by the in-situ oxidative complexation of 1,4-phenylenediamine with the palladium(II) complex [(L1)Pd(MeCN)] (H2L1 = N,N'-bis(2-phenylethyl)-2,6-pyridinedicarboxamide) while in the absence of an additional ligand [(L1)Pd(MeCN)] was converted to the amide-bridged macrocyclic tetramer [Pd(L1)]4.     

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.     

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.     

The kinetics and molecular modeling of the complexation of tenoxicam with cyclodextrins in solution

The effect of cyclodextrins on photodegradation of tenoxicam (TEN) was studied at pH 4, 7 and 10. After 60 min of irradiation with UV light, the photodegradation was extensive. All cyclodextrins (alpha, beta, or gamma) stabilize TEN and reduce the rate of photodegradation. The largest effect of cyclodextrins is at pH 7. Molecular modeling results help to explain and manipulate the results. The results are discussed and compared with other results from previous studies.     

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.     

Shear induced mixing/demixing: blends of homopolymers,of homopolymers plus copolymers,and blends in solution

Shear may shift the phase boundary towards the homogeneous state (shear induced mixing, SIM), or in the opposite direction (shear induced demixing, SID). SIM is the typical behavior of mixtures of components of low molar mass and polymer solutions, SID can be observed with solutions of high molar mass polymers and polymer blends at higher shear rates. The typical sequence with increasing shear rate is SIM, then occurrence of an isolated additional immiscible area (SID), melting of this island into the main miscibility gap, and finally SIM again. A three phase line originates and ends in two critical end points. Raising pressure increases the shear effects. For copolymer containing systems SID is sometimes observed at very low shear rates, preceding the just mentioned sequence of shear influences.