Ion-Exchange equilibria in cationic polyelectrolytes

A method which allows the evaluation of phenomenological ion exchange constants K_ex is proposed and tested in a cationic polyelectrolyte system. Results for nitrate/chloride exchange are nearly constant over the entire concentration range studied. However, for nitrate/bromide exchange, the results depend on the polyelectrolyte concentration, with K_ex following the same trend as the mean activity coefficient for the polyion bromide. For polyion fluoride, a conformational change is probably induced as nitrate is added to the solution and the result deviates from the linear relationship predicted by the method. Benzene sulfonate behaves like a hydrophilic anion, whereas tosylate and ethylbenzene sulfonate also induce conformational changes by hydrophobic interactions. These results are supported by viscosity measurements and agree well with those recently reported by Satoh, who considered changes in apparent molar volume. © 1994 John Wiley & Sons, Inc.     

Cascade of coil-globule conformational transitions of single flexible polyelectrolyte molecules in poor solvent

We show that hydrophobic flexible polyelectrolyte molecules of poly(2-vinylpyridine) and poly(methacryloyloxyethyl dimethylbenzylammonium chloride) are trapped and frozen due to adsorption on the mica surface, and the observed AFM single molecule structures reflect the molecular conformation in solution. An increase of the ionic strength of the solution induces the cascade of abrupt conformational transitions due to the intrachain segregation from elongated coil to compact globule conformations through intermediate pearl necklace-globule conformations with different amounts of beads per chain. The length of the necklaces and the number of beads decrease, while the diameter of beads increases with the increase of ionic strength. Coexistence at the same time of extended coils, necklaces with different amounts of beads, and compact globules indicates the cascade of the first-order-type phase transitions.     

Simulation of conformational transitions

Conformational transitions are essential for the functioning of many proteins, and understanding this dynamical behavior is a central goal in molecular biology. Computer simulations are playing an important role towards this aim by providing insights into how the conformational changes are induced, propagated and used. Popular methods for the simulation of conformational transitions will be reviewed, with a focus on atomistic molecular dynamics techniques for the calculation of transition pathways     

Dielectric studies of conformational equilibria in acetylpyridines

Results of both linear and non-linear dielectric studies of the tautomeric equilibria in benzene solutions of 2- and 4-acetylpyridines are presented. The suggestion that 2-acetylpyridine occurs only in its trans conformation has been confirmed. The analysis for 4-acetylpyridine has shown the correctness and specific utility of the dielectric methods (particularly the non-linear) to studies of conformational equilibria.     

Electronic structure and conformational equilibria of phenyl-propylcarbocations

Modified CNDO calculations were performed on different conformations of various phenyl propyl cations and related compounds. Molecular energies and electronic structures are presented and discussed. A substituted secondary benzyl cation, the 1-phenyl-1-propyl carbocation (12) is found to be the most stable isomer. The open chain 1-phenyl-2-propyl carbocation (11b) has a lower energy than the propylene benzenium cation (11d). In contrary, previous calculations of 2-phenyl-1-ethyl cation lead to the result that in this case the ethylene benzenium cation is the most stable structure. Rotational barriers for different substituted 1-propyl and 2-propyl cations were calculated. The results are explained by hyperconjugative stabilization.     

Thermal transitions in and structures of dried polyelectrolytes and polyelectrolyte complexes

Dynamic mechanical analysis (DMA) was used to explore the thermomechanical properties of dried polyelectrolytes and polyelectrolyte complexes (PECs) with different thermal and humidity histories. Although differences in the amount of water remaining in polyelectrolytes and PECs were small for ambient versus dessicator storage, the properties of polyelectrolyte‐based materials were drastically different for different humidity histories. Glass transition temperatures (T_gs) of poly(diallyldimethylammonium chloride) (PDADMAC) were shown to vary by 100 °C, depending on humidity and thermal histories. These parameters also change glassy storage modulus values by 100%. Furthermore, we observe that dried PDADMAC is highly lossy. DMA of dried poly(styrene sulfonate) (PSS) was more complex and did not exhibit a glass transition in the tested range. DMA of a PEC of PDADMAC and PSS revealed a humidity history‐dependent water melt in the first heating cycle, as well as storage modulus values of dried and annealed PECs that only varied by 17–26% over a 275 °C temperature range. Based on these results, we report for the first time humidity history as controlling structure and properties of polyelectrolyte‐based materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 684–691     

Large concentration effects on conformational equilibria

The conformational equilibrium in $\text{cis}$-3-Hydroxythiane S-oxide (Scheme 1) is strongly concentration dependent, being affected by intermolecular hydrogen bonding at high concentration.     

Ionization equilibria of rauwolfia alkaloids in concentrated hydroxide solutions

The ionization equilibria at 25°C in aqueous potassium hydroxide solutions of several Rauwolfia alkaloids and 2,3-dimethylindole as model compound have been investigated by U.V. spectrophotometry. Plots of the logarithms of the ionization ratios against the H- acidity function gave straight lines whose slopes are very close to unity. The pKBH values thus obtained are reported.     

Supramolecular structures and conformational transitions in polyelectrolyte gels

Three actual problems connected with the collapse transition of polyelectrolyte gels in poor solvent are reviewed. (i) The first topic is the appearance of microstructures for polyelectrolyte gels in poor enough solvents. Three reasons for microsegregation are discussed: effect of polyelectrolyte – hydrophobic competition, effect of the formation of multiplets from ionic pairs in the ionomer regime and the effect of partial formation of glassy kinetically frozen polymer rich regions. (ii) Second we analyze the interaction of the gels with polymers which are capable to form complexes with the gel chains. Main experimental results are presented for poly(methacrylic acid) gels interacting with poly(ethylene oxide), (iii) Finally, we consider the problem of interaction of polyelectrolyte gels with the sufactants. The micelle formation of surfactants inside the gel and its consequences for the conformational properties of the gel are discussed in detail.     

Fluctuation theory of molecular association and conformational equilibria

General expressions relating the effects of pressure, temperature, and composition on solute association and conformational equilibria using the fluctuation theory of solutions are provided. The expressions are exact and can be used to interpret experimental or computer simulation data for any multicomponent mixture involving molecules of any size and character at any composition. The relationships involve particle-particle, particle-energy, and energy-energy correlations within local regions in the vicinity of each species involved in the equilibrium. In particular, it is demonstrated that the results can be used to study peptide and protein association or aggregation, protein denaturation, and protein-ligand binding. Exactly how the relevant fluctuating properties may be obtained from experimental or computer simulation data are also outlined. It is shown that the enthalpy, heat capacity, and compressibility differences associated with the equilibrium process can, in principle, be obtained from a single simulation. Fluctuation based expressions for partial molar heat capacities, thermal expansions, and isothermal compressibilities are also provided.     

Compensation effect in the thermodynamics of conformational equilibria

The solvent dependence of thermodynamic parameters of conformational equilibria in trans-1,2-dichlorocyclohexane and trans-1,2-bromochlorocyclohexane was investigated by infrared absorption spectra. The results obtained show the existence of a compensation effect in the thermodynamics of conformational equilibria: the enthalpy (ΔH₀) and entropy (ΔS₀) differences change in the same direction when going from one solvent to another. A semi-quantitative estimation of the effect is given on the basis of the equations of statistical thermodynamics. It is shown that the temperature dependence of the ΔS₀ value must be taken into account when determining the enthalpy difference of the conformers. This yields the equality of the true and observed ΔH₀ values.     

Molecular structure and conformational transitions of dichloroacetylchloride

RHF and MP2 techniques in 6–31G(d) basis set have been used to determine the structure of the isolated molecule CHCl₂COCl in two stable conformations (cis-and gosh-), as well as in transition states arising due to the rotary motion of CHCl₂ group around the C—C bond. The energy gap between the conformers and the relevant potential barriers has been calculated using the obtained potential dependence of the internal rotation. Plausible conformation of dichloroacetylchloride is discussed on the basis of ³⁵Cl NQR.     

Multistep mechanism of conformational transitions in metallatranes

The results of an investigation of the spin-spin coupling constants of the protons in the OCH₂CH₂N fragments of asymmetric derivatives of metallatranes and the two-dimensional ¹H NMR (NOESY) spectra of 1-substituted 3,6,10-trimethylsilatranes provide evidence in support of a multistep exchange mechanism for conformational transitions, rather than the synchronous conversion of metallatranes in solution.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 129–133, January, 1987.     

Cooperative conformational transitions of linear biopolymers

Conformational transitions in proteins, nucleic acids, and other biopolymers evidently play a decisive role in many biological processes, particularly in control processes. They often proceed cooperatively, i.e. the elementary process of the transition of an individual segment of these macromolecules in influenced by the state of other segments via intramolecular interactions. In general, the segments favor the same state as their neighbours. The resulting equilibrium properties of cooperative systems, e.g. the sharpness of the transitions and their dependence on the chain length, can be quantitatively explained for linear systems by the linear Ising model. The molecular causes of the cooperativity can be explained for simple model polymers.     

Stereodynamics and conformational equilibria in some chiral pseudo-octahedral tungsten crotyl complexes

The complexes W(CO)₂(η³-crotyl)(diphos)X, where X = Cl and I, and [W(CO)₃(η³-crotyl)(diphos)]SbF₆ were prepared and characterized. The solution dynamics were examined with low temperature NMR experiments, with focus on the effect of the crotyl ligand on controlling the chirality at the metal. A steric influence of halide was also observed which results in different conformational and configurational preferences for the crotyl group. The spontaneous resolution of the neutral complex W(CO)₂(η³-crotyl)(diphos)Cl provides a route for obtaining optically active samples of these compounds. It was found that the conversion to the cationic tricarbonyl complex greatly increases the racemization barrier of the chiral center in the crotyl and also renders the η³-ligand more susceptible to nucleophilic attack.