Thermodynamics of Hierarchical Aggregation in Pigment Dispersions.

Many commercially and industrially important materials aggregate to form nanoscale mass-fractal structures. Unlike hard aggregates such as fumed silica, aqueous pigment-based inks consist of weakly bound nanoparticles stabilized by a surfactant. These soft aggregates can easily break apart and re-form balancing mixing energy and the reduction in surface energy with clustering or aggregation. Rapid thermal motion of small elemental crystallites leads to dense clusters or primary particles. The larger primary particles have slower thermal motion and aggregate into ramified mass fractals to form a dual-level hierarchical structure. It is proposed that the hierarchical structure relies on subtle and competitive equilibria between the different hierarchical structural levels. A new hierarchical thermodynamics model by Vogtt is used. Pigment yellow 14 and pigment blue 15:3 as surfactant-stabilized aqueous dispersions were employed to explore the thermodynamics of nanoparticle hierarchical equilibria. It was demonstrated that reversible nanoparticle aggregation can be described solely by the change in free energy of dissociation and the change in free energy of mixing in the context of a subunit being removed from a cluster. The hierarchical thermodynamics is dominated by the solubility of the dispersing surfactant. At the cloud point for the surfactant, primary particles approach the size of an elemental particle and the degree of aggregation becomes very large. The results indicate that subtle and reproducible control over pigment hierarchical structure and size is possible through thermal equilibration, manipulation of the surfactant properties, and elemental crystallite size.

From well-entangled to partially-entangled wormlike micelles.

We combine mechanical rheometry, diffusing wave spectroscopy (DWS), and small angle neutron scattering (SANS) with a simulation model, the "pointer algorithm", to obtain characteristic lengths and time constants for wormlike micelle (WLM) solutions over a range of salt concentrations encompassing the transition from unentangled to entangled solutions. The solutions contain sodium lauryl ethylene glycol sulfate (SLE1S), cocamidopropyl betaine (CAPB), and NaCl. The pointer algorithm is extended to include relaxation of unentangled micelles, allowing micelle parameters to be extracted from the rheology of partially entangled solutions. DWS provides the data at high frequency needed to determine micelle persistence length accurately. From pointer algorithm fits to rheology, we observe a salt-induced rapid change in micellar length as the solution enters the well-entangled regime and a weaker growth with surfactant concentration consistent with mean-field theory. At a lower surfactant concentration, micelle length and persistence length from SANS are roughly consistent with values from rheology once the lower surfactant concentration used in SANS is accounted for. This is, to our knowledge, the first time that quantitative comparisons of structural features including micelle length are made between rheology and SANS. Finally, scaling laws for micelle diffusion and recombination times indicate that micelle kinetics are reaction controlled leading to mean-field recombination with surrounding micelles over the entire range of concentration of interest except at very low and very high surfactant concentrations where either short micelles or branched micelle clusters are dominant.

Enthalpy and Entropy of Scission in Wormlike Micelles.

The free scission energy is the thermodynamic parameter that governs the contour length of wormlike micelles (WLMs). It is the contour length and the propensity to coil and entangle that determine the viscoelastic properties of this commercially important substance class. The free scission energy Δ Fsc and the associated change in enthalpy Δ Hsc and entropy Δ Ssc on scission have been determined for a mixed anionic/zwitterionic surfactant system (sodium laureth sulfate and cocamidopropyl betaine) at various salt concentrations (3-5 wt % NaCl). Both enthalpy Δ Hsc and entropy Δ Ssc changes decrease linearly with increasing NaCl concentration. At NaCl concentrations above 4 wt %, Δ Ssc even adopts negative values. The term TΔ Ssc decreases more rapidly than Δ Hsc around room temperature and causes the observed elongation of WLMs upon addition of NaCl. It is suggested that Δ Ssc is initially positive due to fewer bound counterions per surfactant molecule at end caps compared to the intact, cylindrical parts before scission, leading to a net release of ions upon scission. Negative values of Δ Ssc are attributed to hydrophobic hydration occurring at the end caps at high salt concentrations. 23Na NMR measurements indicate the presence of immobilized ions, supporting a previously proposed ion-cloud model based on neutron scattering results.

The effect of solvent polarity on wormlike micelles using dipropylene glycol (DPG) as a cosolvent in an anionic/zwitterionic mixed surfactant system.

HYPOTHESIS: The behavior/properties of micellar solutions are governed by Coulombic interactions that are influenced by the polarity of the surfactant head groups, hydrophobic tails, and solvent molecules. The addition of co-solvent should have a direct impact on solvent polarity and the size of the micelles are expected to decrease accordingly. EXPERIMENTS: In this study, a mixed surfactant system is studied composed of a common anionic surfactant, sodium laureth sulfate-1, modified by a zwitterionic surfactant, cocamidopropyl betaine in deuterated water. In this system, worm-like micelles (WLMs) are formed. The influence of a co-solvent, dipropylene glycol (DPG) in the present of high salt content, is investigated. DPG primarily modifies the dielectric constant of the solvent. FINDINGS: It was found that the addition of DPG slightly decreased the micelle radius, but dramatically reduced the persistence length as well as the contour length of the micelles. The relative dependence of contour length on salt concentration is not significantly changed. Thus, it is shown that the self-assembled structure can be tuned by adjusting solvent polarity without affecting the relative tunability of the WLM/ellipsoidal structure through counter ion concentration.

Structural Emergence in Particle Dispersions.

Particle dispersions, such as pigment-based inks, comprise weakly bound, milled nanoparticles. The properties of these pigments depend on both their chemical composition and a rather complex structural hierarchy which emerges from these dispersions. The emergence of structure under semidilute conditions is related to the structure of the dilute particles, the particle spacing (mesh size), processing history, and the interaction potential. Kinetic simulations could predict such emergence using these input parameters. In this paper, organic pigments are studied as an example of the importance of emergent structure to predict properties such as brilliance and opacity. Organic pigments are used to impart color to commercial inks, plastics, coatings, and cosmetics. In many cases, dilute pigments are mass fractal structures consisting of aggregated nanoparticles held together by weak van der Waals forces. In water, surfactant is added to create a pigment dispersion (an ink). The final properties of a pigment emerge from a complex interplay between aggregation and dispersion of aggregates as a function of concentration. Samples of the organic pigment yellow 14, PY14, were milled to four primary particle sizes to study the effect on structural emergence. The interaction between surfactant-stabilized PY14 aggregates in an aqueous medium was quantified by the second virial coefficient, A2, which reflects long-range interactions. The degree of aggregation is associated with short-range attractive interactions between primary particles. In this series of pigments, the degree of aggregation increases dramatically with reduction in primary particle size. Concurrently, the second-order virial coefficient, A2, increases reflecting stronger long-range repulsive interactions with particle size. Structural emergence can be understood through the percolation concentration and the filler mesh size. A2 is translated into a repulsive interaction potential for use in dissipative particle dynamics simulations to enable predictive modeling. This description of the interactions between dispersed pigment aggregates allows for a more scientific and predictive approach to understand structural emergence.

Thermodynamic stability of worm-like micelle solutions.

Worm-like micelles (WLMs) are nano-scale self-assemblies widely used for viscosity enhancement, for drug delivery, and in personal care products. The stability of WLMs under variable ionic and surfactant concentrations is important to applications of these fascinating materials. In this work it is demonstrated that a virial approach can be used to understand and predict WLM stability. A mixed surfactant system consisting of sodium laureth sulfate and cocoamidopropyl betaine was examined using small-angle neutron scattering. A linear relationship between the second virial coefficient, A2, and the salt to surfactant ratio, Θs-s, is derived and demonstrated. The Θs-s-dependent term is described via association/dissociation kinetics of salt ions between the bulk and an ion cloud surrounding the WLMs yielding, , where Keq is the association/dissociation constant, nsurf is the molar surfactant concentration, b is the molar excluded volume, M the WLM molar mass, Θs-s is the salt-surfactant ratio and Θ is the salt-surfactant ratio where the interactions are solely determined by the excluded volume. The ratio b/M2 is independent of WLM contour length. The exponent ϑ is found to be approximately 5/4 in agreement with polymer scaling laws for the semi-dilute regime in good solvents.

Free Energy of Scission for Sodium Laureth-1-Sulfate Wormlike Micelles.

Wormlike micelles (WLMs) are nanoscale, self-assembled components of many products from shampoos to fracking fluids due to their viscoelasticity. Their rheological behavior is largely governed by the contour length of the micelles and the concomitant propensity of the micelles to overlap and entangle. The large contour lengths, on the order of micrometers, is the result of a delicate balance between the scission enthalpy of the wormlike micelles on the one hand and entropic factors such as the mixing entropy of dispersion, the ordering of water molecules and counterions, and the mobility of branch points on the other hand. The structure and contour length of wormlike micelles assembled from sodium laureth-1-sulfate was determined at various temperatures using small-angle neutron scattering. The results allow the calculation of the enthalpy and entropy as well as the free energy of scission and are employed to critically evaluate the common methods to determine micellar scission energy from mean-field theory. Interesting behavior is observed when comparing branched and unbranched WLMs that may reflect on mechanistic differences in chain scission.

Scattering Function for Branched Wormlike Chains.

Wormlike or threadlike structures with local cylindrical geometry are abundantly found in nature and technical products. A thorough structural characterization in the bulk for a whole ensemble, however, is difficult. The inherent semiordered nature of the tortuous large-scale structure and especially the quantification of branching renders an assessment difficult. In the present work we introduce a hybrid function expressing the scattering intensities for X-rays, neutrons, or light in the small-angle regime for this system. The function is termed "hybrid" because it employs terms from different approaches. The large-scale structure is described via a Guinier term as well as a concomitant power-law expression in momentum transfer q taken from the so-called unified function. The local cylindrical shape, however, is taken into account through a form factor for cylinders from rigid-body modeling. In principle, the latter form factor can be replaced by an expression for any other regular body so that the new hybrid function is a versatile tool for studying hierarchical structures assembled from uniform subunits. The appropriateness and capability of the new function for cylindrical structures is exemplified using the example of a wormlike micellar system.

Ideal polyethylene nanocrystals.

The water-soluble catalyst precursor [[(2,4,6-(3,5-(CF3)2C6H3)3-C6H2)-N═C(H)-(3-(9-anthryl)-2-O-C6H3)-κ(2)-N,O]Ni(CH3)(TPPTS)] (TPPTS = tri(sodiumphenylsulfonate)phosphine) polymerizes ethylene to aqueous dispersions of highly ordered nanoscale crystals (crystallinity χ(DSC) ≥ 90%) of strictly linear polyethylene (<0.7 methyl-branches/1000 carbon atoms, Mn = 4.2 × 10(5) g mol(-1)). SAXS in combination with cryo-TEM confirms this unusually high degree of order (χ(SAXS) = 82%) and shows the nanoparticles to possess a very thin amorphous layer on the crystalline lamella, just sufficient to accommodate a loop, but likely no entanglements. This ideal chain-folded structure is corroborated by annealing studies on the aqueous-dispersed nanoparticles, which show that the chain can move through the crystal as evidenced by lamella thickening without disturbing the crystalline order as concluded from an unaltered low thickness of the amorphous layers. These ideal chain-folded polyethylene nanocrystals arise from the crystallization in the confined environment of a nanoparticle and a deposition of the growing polymer chain on the crystal growth front as the chain is formed by the catalyst.

Anisotropic nanoparticles of precise microstructure polyolefins.

Nanoparticles of precisely branched polyethylenes possess a distinct oblate shape resulting from a crystalline lamella in the particle as revealed by SAXS and TEM, and display controllable and well-behaved thermal behaviour.

Alcohol induced structural and dynamic changes in ß-lactoglobulin in aqueous solution: a neutron scattering study.

Structural and dynamic properties of ß-lactoglobulin (ß-LG) were revealed as a function of alcohol concentration in ethanol- and trifluoroethanol(TFE)-water mixtures with circular dichroism (CD), small-angle neutron scattering (SANS) and quasi-elastic neutron scattering (QENS). The CD spectra showed that an increase in TFE concentration promotes the formation of the ß-sheet structure of ß-LG. The SANS-intensities were fitted using form factors for two attached spheres for the native and native-like states of the protein. At higher alcohol concentrations, where aggregation takes place, a form factor modelling diffusion limited colloidal aggregation (DLCA) was employed. The QENS-data were analyzed in terms of internal motions for all alcohol concentrations. While low concentrations of TFE (10% (v/v)) lead to an increase of the mean square amplitudes of vibrations and a retention of a native-like structure - but not to an increase of the characteristic radius of proton diffusion processes a. Addition of 20% (v/v) of TFE induces aggregation, going along with a further increase of . Further increase of TFE concentration to 30% (v/v) changes the nanoscale structure of the oligomeric nucleate, but induces no further significant changes in . The present study underlines the necessity of methods sensitive to the dynamics of a system to obtain a complete picture of a molecular process.

Supramolecular Structures of Enzyme Clusters.

The structural characterization of subtilisin mesoscale clusters, which were previously shown to induce supramolecular order in biocatalytic self-assembly of Fmoc-dipeptides, was carried out by synchrotron small-angle X-ray, dynamic, and static light scattering measurements. Subtilisin molecules self-assemble to form supramolecular structures in phosphate buffer solutions. Structural arrangement of subtilisin clusters at 55 °C was found to vary systematically with increasing enzyme concentration. Static light scattering measurements showed the cluster structure to be consistent with a fractal-like arrangement, with fractal dimension varying from 1.8 to 2.6 with increasing concentration for low to moderate enzyme concentrations. This was followed by a structural transition around the enzyme concentration of 0.5 mg mL-1 to more compact structures with significantly slower relaxation dynamics, as evidenced by dynamic light scattering measurements. These concentration-dependent supramolecular enzyme clusters provide tunable templates for biocatalytic self-assembly.

Microdomains in lipid vesicles: structure and distribution assessed by small-angle neutron scattering.

We examined the structure and distribution of microdomains in ternary multilamellar and unilamellar vesicles representing a canonical model raft mixture consisting of dioleoylphosphatidylcholine (DOPC), dipalmitoylphosphatidylcholine (DPPC), and cholesterol via contrast matched small-angle neutron scattering (SANS). The impetus of the work was to reveal the size and distribution of microdomains consistent with the form factor and intermolecular structure factor S(Q) of the scattering pattern of unilamellar and multilamellar vesicles prepared from this ternary lipid system. The data are consistent with the presence of cylindrically shaped microdomains with an average radius of approximately 15 nm assembled in a fractal-like geometry, and with corresponding modeling studies. In the multilamellar vesicle system, coupling of domains across the interlamellar water layer is observed.

Capturing the interaction potential of amyloidogenic proteins.

Experimentally derived static structure factors obtained for the aggregation-prone protein insulin were analyzed with a statistical mechanical model based on the Derjaguin-Landau-Verwey-Overbeek potential. The data reveal that the protein self-assembles into equilibrium clusters already at low concentrations. Furthermore, striking differences regarding interaction forces between aggregation-prone proteins such as insulin in the preaggregated regime and natively stable globular proteins are found.

Protein-protein interactions in complex cosolvent solutions.

The effects of various kosmotropic and chaotropic cosolvents and salts on the intermolecular interaction potential of positively charged lysozyme is evaluated at varying protein concentrations by using synchrotron small-angle X-ray scattering in combination with liquid-state theoretical approaches. The experimentally derived static structure factors S(Q) obtained without and with added cosolvents and salts are analysed with a statistical mechanical model based on the Derjaguin-Landau-Verwey-Overbeek (DLVO) potential, which accounts for repulsive and attractive interactions between the protein molecules. Different cosolvents and salts influence the interactions between protein molecules differently as a result of changes in the hydration level or solvation, in charge screening, specific adsorption of the additives at the protein surface, or increased hydrophobic interactions. Intermolecular interaction effects are significant above protein concentrations of 1 wt %, and with increasing protein concentration, the repulsive nature of the intermolecular pair potential V(r) increases markedly. Kosmotropic cosolvents like glycerol and sucrose exhibit strong concentration-dependent effects on the interaction potential, leading to an increase of repulsive forces between the protein molecules at low to medium high osmolyte concentrations. Addition of trifluoroethanol exhibits a multiphasic effect on V(r) when changing its concentration. Salts like sodium chloride and potassium sulfate exhibit strong concentration-dependent changes of the interaction potential due to charge screening of the positively charged protein molecules. Guanidinium chloride (GdmCl) at low concentrations exhibits a similar charge-screening effect, resulting in increased attractive interactions between the protein molecules. At higher GdmCl concentrations, V(r) becomes more repulsive in nature due to the presence of high concentrations of Gdm(+) ions binding to the protein molecules. Our findings also imply that in calculations of thermodynamic properties of proteins in solution and cosolvent mixtures, activity coefficients may not generally be neglected in the concentration range above 1 wt % protein.

Noninvasive auto-photoreduction used as a tool for studying structural changes in heme-copper oxidases by FTIR spectroscopy.

We demonstrate an efficient Fourier transform infrared (FTIR) spectroscopic method, termed "auto-photoreduction," that uses anaerobic photo-induced internal electron transfer to monitor reaction-initiated changes of heme-copper oxidases. It can be applied without the use of either expensive electrochemical equipment, or caged compounds, which cause significant background signals. At high irradiation power, carbon monoxide is released from high-spin heme a of cytochrome c oxidase and heme o from cytochrome bo(3). Photochemistry is initiated at wavelengths <355 nm, and the photochemical action spectrum has a maximum of 290 nm for cytochrome bo(3), which is consistent with the possible intermediate involvement of tyrosinate or an activated state of tyrosine. We propose that the final electron donors are proton channel water molecules. In the pH range of 4-9, the noninvasive auto-photoreduction method yields highly reproducible FTIR redox difference spectra within a broad range, resolving a number of vibrational changes outside the amide I region (1600-1640 cm(-1)). Furthermore, it provides details of redox-induced changes in the spectral region between 1600 and 1100 cm(-1). The auto-photoreduction method should be universally applicable to heme proteins.

Electron transfer at the low-spin heme b of cytochrome bo(3) induces an environmental change of the catalytic enhancer glutamic acid-286.

Intramolecular proton transfer of heme-copper oxidases is performed via the K- and the transmembrane D-channels. A carboxyl group conserved in a subgroup of heme-copper oxidases, located within the D-channel close to the binuclear center (=glutamic acid-286 in cytochrome bo(3) from Escherichia coli) is essential for proton pumping. Upon electron transfer to the fully oxidized (FO) enzyme, this amino acid has been shown to undergo a cyanide-independent environmental change. The redox-induced environmental transition of glutamic acid-286 is preserved in the site-directed mutant Y288F, which has lost its Cu(B) binding capacity. Furthermore, the mixed-valence (MV) redox state of cytochrome bo(3) (in which Cu(B) and high-spin heme are reduced, whereas the low-spin heme stays oxidized) was prepared by anaerobic exposure of the protein to carbon monoxide. This complex was converted (i) to the FO state by reaction with the caged dioxygen donor mu-peroxo) (mu-hydroxo) bis [bis (bipyridyl) cobalt (III)] and (ii) to the fully reduced (FR) state via caged electron donors; the environmental change of glutamic acid-286 could be observed only upon reduction. Taken together, these results from two different lines of evidence clearly show that the redox transition of the low-spin heme b center alone triggers the change in the chemical environment of this acidic side chain. It is suggested that glutamic acid-286 is a kinetic enhancer of proton translocation, which is energetically favoured in mesophilic oxidases.

Caged O(2). Reaction of cytochrome bo(3) oxidase with photochemically released dioxygen from a cobalt peroxo complex.

We developed the synthesis of the caged oxygen donor (micro-peroxo)(micro-hydroxo)bis[bis(bipyridyl)cobalt(III)] complex (HPBC) as nitrate salt, which has, compared with the perchlorate-form described previously [MacArthur, R., Sucheta, A., Chong, F.F. & Einarsdottir, O. (1995) Proc. Natl Acad. Sci. USA, 92, 8105-8109], greatly enhanced solubility. Now, the quantum efficiency of the photolytical release of dioxygen was determined to be 0.4 per photon at a laser wavelength of 308 nm, which was used to observe biological reactions. The X-ray structure of HPBC has been solved, and the molecular interactions of photochemically generated oxygen with cytochrome oxidase were investigated with optical and FT-IR spectroscopy: it acts as acceptor of electrons transferred from prereduced cytochrome bo(3), the heme-copper oxidase from Escherichia coli. FT-IR spectra revealed typical absorbance difference changes in the carbonyl region of cytochrome bo(3), supported by bandshifts due to solvent isotope exchange and by assignment using site-directed mutants. IR difference spectra of the photooxidation reaction using the caged oxygen compound, and of the photoreduction reaction using the caged electron donor FMN, have inverted shapes. The spectroscopic signals of carboxyl groups are thus equivalent in both reactions: the use of chemically produced oxygen allows the observation of the ongoing molecular changes of cytochrome bo(3) oxidase under quasi-physiological conditions.