Structural Transformations, Composition Anomalies and a Dramatic Collapse of Linear Polymer Chains in Dilute Ethanol-Water Mixtures

Water-ethanol mixtures exhibit many interesting anomalies, such as negative excess partial molar volume of ethanol, excess sound absorption coefficient at low concentrations, and positive deviation from Raoult's law for vapor pressure, to mention a few. These anomalies have been attributed to different, often contradictory origins, but a quantitative understanding is still lacking. We show by computer simulation and theoretical analyses that these anomalies arise from the sudden emergence of a bicontinuous phase that occurs at a relatively low ethanol concentration of x(eth) approximate to 0.06-0.10 (that amounts to a volume fraction of 0.17-0.26, which is a significant range!). The bicontinuous phase is formed by aggregation of ethanol molecules, resulting in a weak phase transition whose nature is elucidated. We find that the microheterogeneous structure of the mixture gives rise to a pronounced nonmonotonic composition dependence of local compressibility and nonmonotonic dependence in the peak value of the radial distribution function of ethyl groups. A multidimensional free energy surface of pair association is shown to provide a molecular explanation of the known negative excess partial volume of ethanol in terms of parallel orientation and hence better packing of the ethyl groups in the mixture due to hydrophobic interactions. The energy distribution of the ethanol molecules indicates additional energy decay channels that explain the excess sound attenuation coefficient in aqueous alcohol mixtures. We studied the dependence of the solvation of a linear polymer chain on the composition of the water-ethanol solvent. We find that there is a sudden collapse of the polymer at x(eth) approximate to 0.05-a phenomenon which we attribute to the formation of the microheterogeneous structures in the binary mixture at low ethanol concentrations. Together with recent single molecule pulling experiments, these results provide new insight into the behavior of polymer chain and foreign solutes, such as enzymes, in aqueous binary mixtures.

Ultrasonic propagation through binary mixtures containing acetic acid

Ultrasonic absorption has been studied by the pulse technique in the binary mixtures of acetic acid in water, methyl and ethyl alcohols and covers a range of 2 to 26 Mc/s. The mixtures are studied from 0 to 100% by weight of the acid. In all the three mixtures, two relaxation processes are observed, the first occurring below the frequency range of the study. The second one occurs near 20 Mc/s in the acid-water mixtures and at much higher frequencies in the other cases. It is qualitatively explained that the monomer-dimer reaction of the acetic acid giving a relaxation near 1 Mc/s has shifted to a higher frequency when mixed in a solvent thus giving rise to a second relaxation in the mixtures.

Coadsorption of Dioxygen and Water on the Ni(110) Surface: Role of O1--Type Species in the Dissociation of Water

While the adsorption of dioxygen at a clean Ni(110) surface gives rise to two O(1s) features at 531 and 530 eV assigned to O-(a) and O2-(a) type species respectively, coadsorption of dioxygen and water mixtures result in the additional formation of hydroxyl species characterized by an O(1s) peak at 532.3 eV. The latter is attributed to the oxygen induced dissociation of water via a low energy pathway involving the O-(a)-type species. The proportions of the O-(a) and the hydroxyl species are greater for small O-2/H2O ratios and lower temperatures (120 K). With increase in temperature, the relative surface concentrations of the O-(a) and the hydroxyl species decrease while there is an increase in the concentration of the oxidic O2-(a) species. Thus, the surface concentrations of both the hydroxyl and the O2-(a) species depend critically on the presence of O- type species. Above 300K the surface chemistry in the main involves the conversion of O- to O2- species via the hydroxyl species.

Helix-sheet interconversion in a synthetic pore lining peptide derived from a designed ion channel

We have designed a four-helix protein that is expected to tetramerize in the membrane to form an ion channel with a structurally well defined pore. A synthetic peptide corresponding to the channel lining helix facilitates ion transport across liposomal membranes and largely helical in membranes. Detailed circular dichroism studies of the peptide in methanol, water and methanal-water mixtures reveal that it is helical in methanol, beta-structured in 97.5% water and a combination of these two structures at intermediate compositions of methanol and water. A fluorescence resonance energy transfer study of the peptide shows that the peptide is monomeric in methanol but undergoes extensive anti-parallel aggregation in aqueous solution.

Fluctuating micro-heterogeneity in water-tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

Water-tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with x(TBA) approximate to 0.03-0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at x(TBA) approximate to 0.05. We note that ``islands'' of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak nonlinearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, x(TBA) approximate to 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level. (C) 2014 AIP Publishing LLC.

Modification of crosslinked chitosan membrane using NaY zeolite for pervaporation separation of water-isopropanol mixtures

The blocked diisocyanate crosslinked chitosan membrane was modified by incorporating different mass% of NaY zeolite. The physico-chemical properties of resulting composite membranes were studied using Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The mechanical properties of the membranes were studied using universal testing machine (UTM). After measuring the equilibrium swelling, membranes were subjected to pervaporation for separation of water-isopropanol mixtures. Both flux and selectivity were increased with increasing NaY zeolite content in the membranes. The membrane containing 40 mass% of NaY zeolite exhibited the highest separation selectivity of 11,241 with a flux of 11.37 x 10(-2) kg/m(2) h for 10 mass% of water in the feed. The total flux and flux of water are almost overlapping each other, suggesting that these membranes could be effectively used to break the azeotropic point of water-isopropanol mixture. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. All the composite membranes exhibited lower activation energy compared to crosslinked membrane, indicating that the permeants require less energy during the process because of molecular sieving action attributed to the presence of sodalite and super cages in the framework of Nay zeolite. The Henry's mode of sorption dominates the process, giving an endothermic contribution. (C) 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Index properties of illite-bentonite mixtures in electrolyte solutions

Bentonite, commonly used for liner constructions in waste containment systems, possesses many limitations. Illite or illite containing bentonite has been proposed as an alternative material for liner construction. Their properties in different types of pore fluids are important to assess the long-term performance of the liner. Further, the illite-bentonite interaction occurs and changes their properties. The effect of these interactions is known when the pore fluid is only water. How their properties are modified in electrolyte solutions has been brought out in this paper. The index properties have been studied since they give an indication of their engineering properties. Due to reduction in the thickness of the diffused double layer and consequent particle aggregation in bentonite, the effect of clay-clay interaction reduces in electrolyte solutions. In electrolyte solutions, the liquid limit, the plasticity index, and free swell index of bentonite are lower than illite. The plasticity index of bentonite is further reduced in KCI solution. Clays with a higher plasticity index perform better to retain pollutants and reduce permeability. Hence, the presence of both illite and bentonite ensures better performance of the liner in different fluids.

Identification of alpha- and beta-Hydroxy Acid Containing Cyclodepsipeptides in Natural Peptide Mixtures Using Negative Ion Mass Spectrometry

Natural peptide libraries often contain cyclodepsipeptides containing alpha or beta hydroxy residues. Extracts of fungal hyphae of Isaria yield a microheterogenous cyclodepsipeptide mixture in which two classes of molecules can be identified by mass spectral fragmentation of negative ions. In the case of isaridins, which contain an alpha-hydroxy residue and a beta-amino acid residue, a characteristic product ion corresponding to a neutral loss of 72 Da is obtained. hi addition, neutral loss of water followed by a 72 Da loss is also observed. Two distinct modes of fragmentation rationalize the observed product ion distribution. The neutral loss of 72 Da has also been obtained for a roseotoxin component, which is also an alpha-hydroxy residue containing cyclodepsipeptide. In the case of isariins, which contain a beta-hydroxy acid residue, ring opening and subsequent loss of the terminal residue as an unsaturated ketene fragment, rationalizes the observed product ion formation. Fragmentation of negative ions provide characteristic neutral losses, which are diagnostic of the presence of alpha-hydroxy or beta-hydroxy residues.

Theoretical and Computational Analysis of Static and Dynamic Anomalies in Water-DMSO Binary Mixture at Low DMSO Concentrations

Experiments have repeatedly observed both thermodynamic and dynamic anomalies in aqueous binary mixtures, surprisingly at low solute concentration. Examples of such binary mixtures include water-DMSO, water-ethanol, water-tertiary butyl alcohol (TBA), and water-dioxane, to name a few. The anomalies have often been attributed to the onset of a structural transition, whose nature, however, has been left rather unclear. Here we study the origin of such anomalies using large scale computer simulations and theoretical analysis in water-DMSO binary mixture. At very low DMSO concentration (below 10%), small aggregates of DMSO are solvated by water through the formation of DMSO-(H2O)(2) moieties. As the concentration is increased beyond 10-12% of DMSO, spanning clusters comprising the same moieties appear in the system. Those clusters are formed and stabilized not only through H-bonding but also through the association of CH3 groups of DMSO. We attribute the experimentally observed anomalies to a continuum percolation-like transition at DMSO concentration X-DMSO approximate to 12-15%. The largest cluster size of CH3-CH3 aggregation clearly indicates the formation of such percolating clusters. As a result, a significant slowing down is observed in the decay of associated rotational auto time correlation functions (of the S = O bond vector of DMSO and O-H bond vector of water). Markedly unusual behavior in the mean square fluctuation of total dipole moment again suggests a structural transition around the same concentration range. Furthermore, we map our findings to an interacting lattice model which substantiates the continuum percolation model as the reason for low concentration anomalies in binary mixtures where the solutes involved have both hydrophilic and hydrophobic moieties.

Thermal Lipid Order−Disorder Transitions in Mixtures of Cationic Cholesteryl Lipid Analogues and Dipalmitoyl Phosphatidylcholine Membranes

Two types of cationic cholesteryl amphiphiles, one where the headgroup is attached to the steroid by an ester linkage and the second by an ether linkage, were synthesized. A third type of cholesteryl lipid bearing an oligoethylene glycol segment was also prepared. Each of these synthetic lipids generated vesicle-like aggregates with closed inner aqueous compartments from their aqueous suspensions. We examined their interaction with L-α-dipalmitoyl phosphatidylcholine (DPPC) membranes using fluorescence anisotropy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). When included in membranes, the synthetic cholesteryl lipids were found to quench the chain motion of the acyl chains of DPPC. This suggests that these cationic cholesteryl derivatives act as filler molecules despite modification at the headgroup level from the molecular structure of natural cholesterol. Careful analyses of DSC and fluorescence anisotropy data suggest that the nature of perturbation induced by each of these cationic cholesterol derivatives is dependent on the details of their molecular structure and provides significant information on the nature of interaction of these derivatives with phospholipid molecules. In general, amphiphiles that support structured water at the interfacial region tend to rigidify the fluid phase more than others. Importantly, these cholesteryl amphiphiles behave less like cholesterol in that their incorporation in DPPC not only abolishes the phase transition but also depresses the phase transition temperature.

Fluctuation quench and hydrophobic collapse of polymers and biopolymers in water-DMSO binary mixture at low DMSO concentration

Binary mixtures have strong influence on activities of polymers and biopolymers even at low cosolvent concentration. Among the several aqueous binary mixtures studied, water-DMSO especially stands out for its unusual behavior at certain specific concentrations of DMSO. In the present work, we study the effect of water-DMSO binary mixture on polymers and biopolymers by taking a simple linear hydrocarbon chain of intermediate length (n = 30) and the protein lysozyme, respectively. We find that at a mole fraction of 0.05 of DMSO (x(DMSO) = 0.05) in aqueous solution, the hydrocarbon chain adopts the collapsed conformation as the most stable and rigid state. In this case of 0.05 mole fraction of DMSO in bulk, the DMSO concentration in the first hydration layer around the polymer is found to be as large as 17%. Formation of such hydrophobic environment around the polymer is the reason for the collapsed state gaining so much stability. Interestingly, similar quench of conformational fluctuation is also observed for the protein investigated. It is observed that in the case of alkane polymer chains, long wavelength fluctuation gets easily quenched, the polymer being purely hydrophobic. However, in case of the protein, quench of fluctuation is prominent only at the hydrophobic surface, and quench of long wavelength fluctuation becomes insignificant for the full protein. As protein contains both hydrophobic and hydrophilic moieties, the extent of quench of conformational fluctuation with respect to that in pure water is almost half for the biopolymer complex (16.83%) than the same for pure hydrophobic polymer chain (32.43%).

Solvation dynamics of tryptophan in water-dimethyl sulfoxide binary mixture: In search of molecular origin of composition dependent multiple anomalies

Experimental and simulation studies have uncovered at least two anomalous concentration regimes in water-dimethyl sulfoxide (DMSO) binary mixture whose precise origin has remained a subject of debate. In order to facilitate time domain experimental investigation of the dynamics of such binary mixtures, we explore strength or extent of influence of these anomalies in dipolar solvation dynamics by carrying out long molecular dynamics simulations over a wide range of DMSO concentration. The solvation time correlation function so calculated indeed displays strong composition dependent anomalies, reflected in pronounced non-exponential kinetics and non-monotonous composition dependence of the average solvation time constant. In particular, we find remarkable slow-down in the solvation dynamics around 10%-20% and 35%-50% mole percentage. We investigate microscopic origin of these two anomalies. The population distribution analyses of different structural morphology elucidate that these two slowing down are reflections of intriguing structural transformations in water-DMSO mixture. The structural transformations themselves can be explained in terms of a change in the relative coordination number of DMSO and water molecules, from 1DMSO:2H(2)O to 1H(2)O:1DMSO and 1H(2)O:2DMSO complex formation. Thus, while the emergence of first slow down (at 15% DMSO mole percentage) is due to the percolation among DMSO molecules supported by the water molecules (whose percolating network remains largely unaffected), the 2nd anomaly (centered on 40%-50%) is due to the formation of the network structure where the unit of 1DMSO:1H(2)O and 2DMSO:1H(2)O dominates to give rise to rich dynamical features. Through an analysis of partial solvation dynamics an interesting negative cross-correlation between water and DMSO is observed that makes an important contribution to relaxation at intermediate to longer times.