The Journal of Physical Chemistry B (J PHYS CHEM B)

Publications in this journal

• Article: Effects of temperature and salt addition on the association behavior of charged amphiphilic diblock copolymers in aqueous solution.

  Solmaz Bayati, Kaizheng Zhu, Loan T T Trinh, Anna-Lena Kjøniksen, Bo Nyström
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  ABSTRACT: Effects of temperature on the association behavior in aqueous solutions of a series of charged thermoresponsive poly(N-isopropylacrylamide)-block-poly((3-acrylamidopropyl) trimethylammonium chloride) (abbreviated as PNIPAAM(n)-b-PAMPTMA(+)(20)) with different lengths of the PNIPAAM block (n = 24, 48, and 65) have been studied with the aid of turbidimetry, zeta sizer, and dynamic light scattering (DLS). The turbidity results show that the transition to high turbidity values is shifted to lower temperatures when the length of the PNIPAAM block increases. It was observed that the value of the cloud point (CP) dropped with increasing polymer concentration, enlarged length of the PNIPAAM block, and augmented salinity. It was found that the decay of the correlation function from DLS is bimodal at temperatures well below CP, where the fast mode represents the motion of the unimers and the slow mode the dynamics of micelles/intermicellar complexes. At higher temperatures, larger particles of the system grow at the expense of the smaller ones in the spirit of Ostwald ripening, and clusters with a narrow size distribution evolve at high temperatures. By adding salt (NaCl), enhanced aggregation occurs at elevated temperatures because of screening of Coulomb repulsions.
  The Journal of Physical Chemistry B 08/2012; 116(36):11386-95.
• Article: Phenylnaphthalenes: Sublimation Equilibrium, Conjugation, and Aromatic Interactions

  Carlos F. R. A. C. Lima, Marisa A. A. Rocha, Bernd Schröder, Lígia R. Gomes, John N. Low, Luís M. N. B. F. Santos
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  ABSTRACT: In this work, the interplay between structure and energetics in some representative phenylnaphthalenes is discussed from an experimental and theoretical perspective. For the compounds studied, the standard molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K, were determined by the measurement of the vapor pressures as a function of T, using a Knudsen/quartz crystal effusion apparatus. The standard molar enthalpies of formation in the crystalline state were determined by static bomb combustion calorimetry. From these results, the standard molar enthalpies of formation in the gaseous phase were derived and, altogether with computational chemistry at the B3LYP/6-311++G(d,p) and MP2/cc-pVDZ levels of theory, used to deduce the relative molecular stabilities in various phenylnaphthalenes. X-ray crystallographic structures were obtained for some selected compounds in order to provide structural insights, and relate them to energetics. The thermodynamic quantities for sublimation suggest that molecular symmetry and torsional freedom are major factors affecting entropic differentiation in these molecules, and that cohesive forces are significantly influenced by molecular surface area. The global results obtained support the lack of significant conjugation between aromatic moieties in the α position of naphthalene but indicate the existence of significant electron delocalization when the aromatic groups are in the β position. Evidence for the existence of a quasi T-shaped intramolecular aromatic interaction between the two outer phenyl rings in 1,8-di([1,1′-biphenyl]-4-yl)naphthalene was found, and the enthalpy of this interaction quantified on pure experimental grounds as −(11.9 ± 4.8) kJ·mol–1, in excellent agreement with the literature CCSD(T) theoretical results for the benzene dimer.
  The Journal of Physical Chemistry B 02/2012; 116:3557.
• Article: Sizing of PDADMAC/PSS complex aggregates by polyelectrolyte and salt concentration and PSS molecular weight

  V. Starchenko, M. Müller, N. Lebovka
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  ABSTRACT: Herein we report on the influence of salt and polyelectrolyte (PEL) concentration, molecular weight, and mixing ratio on the size and size distribution of polyelectrolyte complex (PEC) particles composed of cationic poly(diallyldimethylammonium chloride) and anionic poly(styrene sulfonic acid). The unusual salt concentration dependence of PEC particle sizes was observed. This behavior was explained by competition of two processes both related to the charge screening: swelling/shrinking of the outer shell formed by the excess PEL molecules and increasing/decreasing of the aggregation rate of colloidal PEC particles. The results on the size regulation of PEC particles by varying PEL concentration reflect both competitive processes as well. The regulation of the mixing ratio of PEL allows producing PEC particles with different charges, and it does not affect significantly the PEC particle size regulation by salt concentration. The PEC size dependence on the molecular weight of polymer was shown to be power and an exponent value of a ˜ 0.13 was obtained for the spherical PEC particles. This value is lower than one for polymer particles with a compact globular structure with exponent values of a = 0.33. However, the molecular weight of only one polymer component of a two-component PEC particle was varied.
  The Journal of Physical Chemistry B 01/2012; 116:14961-14967.
• Article: Thermodynamics of Cationic and Anionic Surfactant Interaction

  P. Norvaišas, V. Petrauskas, D. Matulis
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  ABSTRACT: The interaction between positively and negatively charged linear surfactants is an interesting system for the understanding of the fundamental interplay of hydrophobic and ionic forces in lipid membranes and proteins. We used isothermal titration calorimetry to dissect the Gibbs free energies, enthalpies, entropies, and heat capacities of interaction into hydrophobic and ionic contributions for alkylamine interaction with alkyl sulfates and alkane sulfonates. Dependence on aliphatic chain length, surfactant concentration, temperature, and ionic strength provided a detailed thermodynamic description of this interaction. Reactions of surfactants with tails longer than approximately 10 carbon atoms were primarily driven by enthalpy changes arising from solid-phase interactions between aliphatic tails. Entropic contributions were small relative to enthalpic ones. Contributions of methylene groups were additive. The binding reaction can yield a solid or liquid complex, depending on temperature. Thermodynamic dissection yielded the parameters of the phase transition.
  The Journal of Physical Chemistry B 01/2012; 116:2138.
• Article: Effect of Ethylene Glycol and Its Derivatives on the Aggregation Behavior of an Ionic Liquid 1-Butyl-3-methyl Imidazolium Octylsulfate in Aqueous Medium

  Tejwant Singh, † K. Srinivasa Rao, Arvind Kumar
  The Journal of Physical Chemistry B 01/2012; 116:1612.
• Article: The Role of Site-Specific Hydrogen Bonding Interactions in the Solvation Dynamics of N-acetyl-Tryptophanamide

  F. Messina, A.M. El-Zohry, O.F. Mohammed, M. Chergui
  The Journal of Physical Chemistry B 01/2012;
• Article: Temperature-induced aggregation kinetics in aqueous solutions of a temperature-sensitive amphiphilic block copolymer.

  Atoosa Maleki, Anna-Lena Kjøniksen, Kaizheng Zhu, Bo Nyström
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  ABSTRACT: Time effects for the temperature-induced association complexes in solutions of the thermoresponsive poly(N-isopropylacrylamide)-block-poly(ethylene glycol)-block-poly(N-isopropylacrylamide) (PNIPAAM(69)-b-PEG(23)-b-PNIPAAM(69)) copolymer that exhibit a lower critical solution temperature were studied by means of turbidimetry and dynamic light scattering (DLS). The DLS results clearly show that at temperatures below the cloud point (CP) unimers coexist with intermicellar structures, which contract as the CP is approached. At this stage, no time effect was detected. At temperatures above the CP, large association structures are formed, and these aggregates dominate the decay of the correlation functions. A novel time-dependent growth of the aggregates was observed over several hours. The growth of the clusters is strengthened as the temperature rises, and this feature is supported by the turbidity results and the reduced scattered intensity experiments. For a low polymer concentration, an initial growth of the clusters is observed, whereas at longer times the apparent hydrodynamic radius from DLS is virtually constant. The results from this work stress the importance to check possible time effects in solutions of thermosensitive copolymers as the cloud point is approached.
  The Journal of Physical Chemistry B 06/2011; 115(29):8975-80.
• Article: Effects of temperature and salt concentration on the structural and dynamical features in aqueous solutions of charged triblock copolymers.

  Anna-Lena Kjøniksen, Kaizheng Zhu, Manja A Behrens, Jan Skov Pedersen, Bo Nyström
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  ABSTRACT: Effects of temperature and salt addition on the association behavior in aqueous solutions of a series of charged thermosensitive methoxypoly(ethylene glycol)-block-poly(N-isopropylacrylamide)-block-poly(4-styrenesulfonic acid sodium) triblock copolymers (MPEG(45)-b-P(NIPAAM)(n)-b-P(SSS)(22)) with different lengths of the PNIPAAM block (n=17, 48, and 66) have been studied with the aid of turbidity, small-angle X-ray scattering (SAXS), and dynamic light scattering (DLS). Increasing temperature and salinity as well as longer PNIPAAM blocks are all factors that promote the formation of association structures. The SAXS data show that, for the copolymers with n=48 and n=66, increasing temperature and salt concentration induce interchain associations and higher values of the aggregation number, whereas no aggregation was observed for the copolymer with the shortest PNIPAAM chain. However, DLS measurements reveal the presence of larger association clusters. The cloud point is found to decrease with raising salinity and longer PNIPAAM block. The general picture that emerges is the delicate interplay between repulsive electrostatic forces and hydrophobic interactions and that this balance can be tuned by changing the temperature, salinity, and the length of the PNIPAAM block.
  The Journal of Physical Chemistry B 02/2011; 115(10):2125-39.
• Article: Single-molecule behavior of asymmetric thermoresponsive amphiphilic copolymers in dilute solution.

  Ricardo Rodríguez Schmidt, Ramón Pamies, Anna-Lena Kjøniksen, Kaizheng Zhu, José G Hernández Cifre, Bo Nyström, José García de la Torre
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  ABSTRACT: A bead-and-spring model has been used to simulate the behavior of thermoresponsive asymmetric diblock amphiphilic copolymers with aid of Monte Carlo simulations. The alteration of the thermodynamic conditions was mimicked by using a Lennard-Jones potential, which was related to the measured temperatures by comparison with experimental data for aqueous solutions of two sets of diblock copolymers, namely methoxypoly(ethylene glycol)-block-poly(N-isopropylacrylamide), one with different lengths of the hydrophilic block (MPEG(n)-b-PNIPAAM(71)) and one with varying lengths of the hydrophobic block (MPEG(57)-b-PNIPAAM(m)). The influence of the length of both the thermoresponsive and the hydrophilic block on the size and conformation of single molecules at various temperatures was studied by means of simulations. The temperature-induced contraction of the copolymer (MPEG(n)-b-PNIPAAM(71)) entities is only modestly affected by changing the length of the hydrophilic block, whereas for the MPEG(57)-b-PNIPAAM(m) copolymer both the transition temperature and the magnitude of the compression of the molecules are strongly influenced by the length of the thermosensitive block. When the MPEG chain fully covers the hydrophobic core, the copolymer moieties are stabilized, whereas poorly covered cores can promote interchain aggregation at elevated temperatures.
  The Journal of Physical Chemistry B 07/2010; 114(27):8887-93.
• Article: Viscosification in polymer-surfactant mixtures at low temperatures.

  Neda Beheshti, Anna-Lena Kjøniksen, Kaizheng Zhu, Kenneth D Knudsen, Bo Nyström
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  ABSTRACT: Interactions between the anionic surfactant sodium dodecyl sulfate (SDS) and hydroxyethylcellulose (HEC) or its hydrophobically modified analogue (HM-HEC) have been studied over an extended temperature region with the aid of turbidimetry, small-angle neutron scattering (SANS), and shear viscosimetry. Anomalous viscosity enhancements were observed for semidilute HEC/SDS and HM-HEC/SDS solutions at high SDS concentrations at temperatures far below the Krafft point for aqueous solutions of SDS. From the Arrhenius-Frenkel-Eyring (AFE) plots of the temperature dependence of the zero-shear viscosity, the activation energy of chain disengagement (DeltaE(vis)) was found to be on the order of 40 kJ mol(-1) for the HEC/SDS mixtures, whereas for the HM-HEC/SDS system, much higher values of DeltaE(vis) (up to 141 kJ mol(-1)) were reported, and the activation energy increased with an increasing level of SDS addition. Break points in the AFE plots were observed for both the HEC/SDS and HM-HEC/SDS systems at low temperatures and high SDS concentrations. Time evolutions of both the turbidity and the shear viscosity were monitored after quenching of the temperature from 25 to 1 degrees C. The turbidity results revealed in general a less pronounced transition for the HEC/SDS and HM-HEC/SDS systems than for the corresponding polymer-free SDS/water solutions. In the course of time, a significant viscosity enhancement was found for the HEC/SDS system at high levels of SDS addition, and a much stronger viscosification was observed for the HM-HEC/SDS system at the highest surfactant concentration. The overall results suggest that hydrated SDS aggregates act as cross-linkers of the network and generate the substantial viscosification of the systems at low temperature and high levels of SDS addition. For the HM-HEC/SDS system, further strengthening of the network occurs because of the contribution from hydrophobic interactions. The SANS data on HEC/SDS mixtures reveal that some structural reorganization takes place at low temperatures in the presence of high SDS concentrations, and this is ascribed to enhanced polymer-SDS interactions and the formation of clusters that strengthened the cross-links of the network.
  The Journal of Physical Chemistry B 05/2010; 114(19):6273-80.