Strings of vesicles: flow behavior in an unusual type of aqueous gel

This is a study of 10 asymmetric gemini surfactants that self-assemble into vesicles which, in turn, self-assemble into gels. The geminis have the following general structure: long-chain/phosphate/2-carbon spacer/quaternary nitrogen/short-chain. Dynamic light scattering and transmission electron microscopy (TEM) demonstrate that in dilute aqueous systems these compounds self-assemble into vesicles. The vesicles are cohesive as proven by cryo-high resolution electron microscopy (cryo-HRSEM) images that reveal a "pearls on a string" morphology. These strings of vesicles create a complex network that rigidifies the water. The one gemini in the study that does not form a gel is also the only vesicle system that, according to cryo-HRSEM and TEM, assembles into clumps rather than chains. It is proposed that the vesicles are cohesive owing to protrusion of short chains from the vesicle surfaces, thereby creating hydrophobic "patches" whose intervesicular overlap supersedes the normal membrane/membrane repulsive forces. Analogous geminis having two long chains, neither of which are thought capable of departing from their bilayers, also form vesicles, but they are noncohesive (as expected from the model). Rheological experiments carried out on the gels show that gelation is mechanically reversible. Thus, if an applied torque breaks a string, the string can rapidly mend itself as long as the temperature exceeds its calorimetrically determined T(m) value. Gel strength, as manifested by the yield stress of the soft material, was shown to be particularly sensitive to the structure of the gemini. All three individual components of the systems (geminis, vesicles, and gels) have widespread practical applications.     

Comment on “Preparation and electrorheological properties of triethanolamine-modified TiO2”

Comments on the recent report of electrorheological (ER) properties of an organic modified titanium dioxide with considerably high yield stress are given based on the analysis of its yield stress data as a function of applied electric field strengths. Using our previously reported universal yield stress equation and critical electric field strengths deduced, it is found that we can collapse their data onto a single curve.     

Combined effects of blockage and yield stress on drag and heat transfer from an in-line array of three spheres

This work reports results on the drag and heat transfer from an in-line array of three isothermal spheres falling in a cylindrical confinement filled with Bingham plastic fluids. The effects of dimensionless parameters, such as the Reynolds number (1 ≤ Re?≤?100), Prandtl number (1 ≤ Pr?≤?100), Bingham number (0 ≤ Bn?≤?100), blockage ratio (2 ≤ β?≤?4) and sphere-to-sphere distance (1.5 ≤ t?≤?6) have been elucidated. The flow and heat transfer characteristics were analysed in terms of yielded/unyielded regions, streamline and isotherm contours, drag coefficient, pressure coefficient, and local and average Nusselt number. Broadly, the drag coefficient shows a positive dependence on Bn and sphere-to-sphere distance (t) while it exhibits an inverse dependence on Re and β. On the other hand, the Nusselt number shows a positive dependence on Re, Pr, Bn and β; and a complex dependence on t for each sphere. Simple predictive expressions for the average Nusselt number for each sphere are formulated, thereby enabling its prediction in a new application.     

Shear and NMR experiments of materials with flow behaviour depending on the deformation history

Oxide ceramic masses react to simple shearing with hardening (peptisation: increase in the shear stress with the shear deformation). In the present study the correlation between the increase in the shear stress and the porosity, agglomeration processes and the type of flow are analysed. For this purpose oxide ceramic masses are tested in a shear device especially developed for pastes and analysed by rheometric experiments, NMR methods and particle size analysis. The results support the hypothesis that structural changes (hardening, increase in the mean porosity) of the material during the peptisation mainly depend on the magnitude and not on the kind of the energy input and thus of the type of flow. The fraction of bound (more generally, the immobilised) water increases with the shear displacement. Also crushing of primary particles could be observed. Both the crushing of solid particles causing an increased solid surface and the formation of a three-dimensional gel structure are microscopic effects capable of resulting in the binding or retaining water. On a macroscopic scale these phenomena cause hardening. Magnetic resonance imaging visualises flow-induced agglomerates, which form owing to the shear flow and increase the porosity averaged over the whole sample. After the shear experiment rolls of paste can be seen which indicate that the general assumption of a plane shear flow in the shear device is not warrantable. Received: 19 July 2001 Accepted: 25 October 2001     

Yield stress and viscoelastic properties of high internal phase ratio emulsions

 The rheology of high internal phase ratio oil-in-water emulsions was investigated using a controlled-stress rheometer. The dispersed-phase (oil) concentration was varied from 71.24 to 89.61% by volume. Three different types of rheological experiments were conducted for each emulsion, namely: steady shear, oscillatory shear, and creep/recovery experiments. All the emulsions investigated in this study possess a yield stress. The yield-stress values obtained from different rheological experiments for the same emulsion show good agreement with each other. The yield-stress value increases exponentially with an increase in the dispersed-phase concentration. The yield-stress data of this study can be described quite well with the Princen and Kiss equation for high internal phase ratio emulsions provided that the thickness of the interdroplet films is taken into account. For any given emulsion, the storage modulus, measured in the linear viscoelastic region, is found to be constant, independent of the frequency, indicating a solid-like behaviour. The value of the storage modulus increases with an increase in the dispersed-phase concentration. The storage modulus data are interpreted in terms of the Princen and Kiss equation. Received: 23 October 1998 Accepted in revised form: 18 February 1999     

Hemodynamics and Wall Shear Stress of Blood Vessels in Aortic Coarctation with Computational Fluid Dynamics Simulation

The purpose of this study was to identify the characteristics of blood flow in aortic coarctation based on stenotic shape structure, stenosis rate, and the distribution of the wall load delivered into the blood vessels and to predict the impact on aneurysm formation and rupture of blood vessels by using a computational fluid dynamics modeling method. It was applied on the blood flow in abdominal aortic blood vessels in which stenosis occurred by using the commercial finite element software ADINA on fluid-solid interactions. The results of modeling, with an increasing stenosis rate and Reynolds number, showed the pressure drop was increased and the velocity was greatly changed. When the stenosis rate was the same, the pressure drop and the velocity change were larger in the stenosis with a symmetric structure than in the stenosis with an asymmetric one. Maximal changes in wall shear stress were observed in the area before stenosis and minimal changes were shown in stenosis areas. The minimal shear stress occurred at different locations depending on the stenosis shape models. With an increasing stenosis rate and Reynolds number, the maximal wall shear stress was increased and the minimal wall shear stress was decreased. Through such studies, it is thought that the characteristics of blood flow in the abdominal aorta where a stenosis is formed will be helpful in understanding the mechanism of growth of atherosclerosis and the occurrence and rupture of the abdominal aortic flow.     

Molecular dynamics and phase behavior of polystyrene/poly(vinyl methyl ether) blend in the presence of nanosilica

The variation of phase morphology, critical temperature of demixing, and molecular dynamics for polystyrene/poly(vinyl methyl ether)(PS/PVME) blends induced by hydrophilic nanosilica(A200) or hydrophobic nanosilica(R974) was investigated. With the phase separation of blend matrix, A200 migrated into PVME-rich phase due to strong interaction between A200 and PVME, while R974 moved into PS-rich phase. The thermodynamic miscibility and concentration fluctuation during phase separation of blend matrix were remarkably retarded by A200 nanoparticles due to the surface adsorption of PVME on A200, verified by the correlation length ξ near the critical region from rheological measurement and the weakened increment of reversing heat capacity(ΔC_p) during glass transition via modulated differential scanning calorimetry(MDSC). The restricted chain diffusion induced by nanosilica still occurred despite no influence of A200 and R974 on the segmental dynamics of homogenous blend matrix. The interactions between nanosilica and polymer components could restrict the terminal relaxation of blend matrix and further manipulate their phase behavior.     

Dynamics of adsorption and desorption of proteins at an air/water interface

Adsorption and desorption dynamics of lysozyme and β-casein at the air/water interface were investigated through stress relaxation experiments. The resulting surface tension changes due to a step-type surface area disturbance, as a function of time, were measured through a capillary wave probe. The adsorption data, obtained after a surface area expansion, can be well fitted to a diffusion-controlled adsorption model. However, desorption relaxation following a surface compression is much slower and cannot be modeled by the diffusion theory. Characteristic diffusion frequency and high-frequency dilational elasticity for protein layers were also obtained and found to be consistent with data reported in the literature.     

Liposomal drugs dispersed in hydrogels. Effect of liposome, drug and gel properties on drug release kinetics

Release of calcein and griseofulvin (GRF) from control (gels in which solutes are dissolved in) and liposomal gels was studied using agarose-assisted immobilization as a technique to separate gels from drug-receptor compartments. Liposomes composed of phosphatidylcholine (PC) or distearoyl-glycero-PC and cholesterol (DSPC/Chol), and incorporating calcein or GRF were prepared by thin film hydration. After cleaning the liposomes they were dispersed in different hydrogels (carbopol 974 [1, 1.5 or 2% (w/w)], hydroxylethyl-cellulose (HEC) [4% (w/w)], or a mixture of the two), and release of calcein or GRF was followed by fluorescence or photometric technique, respectively. Results show that calcein release from liposomal gels is slower compared to control gels, and can be further retarded by using rigid-membrane liposomes (faster release from PC-liposome compared to DSPC/Chol-liposome gels). Additionally, calcein release is not affected by the lipid amount loaded (in the range from 2 to 8 mg/ml), therefore solute loading can be controlled according to needs.

Oppositely, GRF release from liposomal gels is determined by drug loading. At high drug loading levels (compared to GRF aqueous solubility), GRF is released with constant rate from liposomal gels irrespective of liposome type (PC or DSPC/Chol). Thereby, for amphiphilic/lipophilic drugs, drug properties (solubility, log P) determine the system behavior.

Calcein and GRF release from control carbopol gels is faster compared to HEC and mixture gels. The same is true for calcein in liposomal gels. Carbopol gel rheological properties were found to be significantly different (compared to the other gels), implying that these characteristics are important for drug diffusion from gels.     

Synthesis and characterization of carboxymethylcelluloses from non-wood pulps II. Rheological behavior of CMC in aqueous solution

This paper concerns the rheological behavior of carboxymethylcelulloses(CMC) derived after one and two successive steps from different non-woodbleached cellulose pulps. CMC rheological characterization was achieved in0.1M NaCl solution, as a function of polymer concentration. Theevidence of a critical concentration (C* < 1 g/L) is discussedfromsteady shear and dynamic experiments. Rheological properties of the CMC werefound to depend on the cellulose source reactivity and on their degree ofsubstitution (DS). Higher molecular weight of initial cellulose was accompaniedby higher apparent intrinsic viscosity of the CMC produced. Depending on theCMCconcentration and on the degree of etherification, the system behaves as asolution or as a gel. In the case of abaca CMC sample, it is shown that afteronly one step of chemical modification and above a polymer concentration of20 g/L, the system behaves as a gel. The gel behavior was studied asafunction of temperature. In the temperature range from 25 to 45°C, the rheological behavior was found to remain almostconstant due to the existence of dispersed swollen aggregates. This unusualcharacteristic represents an advantage for applications such as oil recovery inthe petroleum industry, where viscosity of the recovered fluid should not diminishwith temperature.     

Rheological behavior of aqueous suspensions containing cationic starch and aluminum magnesium hydrotalcite-like compound in the presence of different electrolytes

The rheological properties of aqueous suspensions consisting of cationic starch (CS) and positively charged aluminum magnesium hydrotalcite-like compound (HTlc) in the presence of different electrolytes (NaCl, CaCl₂ and AlCl₃) were investigated. It is found that the network-like structure of pure CS solution is formed by the interaction between CS molecules. Both the equilibrium viscosities and the elastic response of CS solution decrease with the addition of NaCl, CaCl₂ and AlCl₃. Small amplitude sinusoidal oscillation tests show that a three-dimensional network of the HTlc/CS suspension can be formed through the bridge effect between CS molecules and HTlc particles due to the hydrogen bonding between the ether groups or hydroxyl groups of CS and the hydroxyl groups of HTlc. Both the equilibrium viscosity and dynamic property of the HTlc/CS suspensions indicate that the network-like structural strength of the suspensions increases firstly and then decreases with increasing HTlc content. The equilibrium viscosity and the elastic response of the HTlc/CS suspensions decrease gradually with the addition of NaCl or CaCl₂, but decrease firstly then increase and then decrease with increasing AlCl₃ concentration, i.e., the structural strength of the HTlc/CS suspensions can be strengthened by the addition of appropriate amount of AlCl₃ content.     

Effect of skimming layer in an electroosmotically driven viscoelastic fluid flow over charge modulated walls

We report a numerical study on the effect of the skimming layer in an EOF of Oldroyd-B fluid over charge modulated walls. Three types of flow conditions were identified on the basis of the relative thickness of the skimming layer and the electrical double layer. We observe maximum slip velocity magnitude when the skimming layer thickness is very less than the thickness of the electrical double layer. For higher skimming layer thickness compared to the thickness of electrical double layer, slip velocity magnitude attenuates, and the polymeric stress inside the skimming layer becomes zero. Enhanced fluid elasticity generates asymmetric flow structures inside the microchannel, which can also be achieved by imposing an asymmetric surface charge along the channel walls. Our present analysis highlights the complex flow dynamics of the EOF of biofluids/polymeric fluids with a near-wall region depleted of macro-molecules.     

Temperature‐dependent self‐assembly and rheological behavior of a thermoreversible pmma–PnBA–PMMA triblock copolymer gel

Self‐assembly and mechanical properties of triblock copolymers in a mid‐block selective solvent are of interest in many applications. Herein, we report physical assembly of an ABA triblock copolymer, [PMMA–Pn BA–PMMA] in two different mid‐block selective solvents, n‐butanol and 2‐ethyl‐1‐hexanol. Gel formation resulting from end‐block associations and the corresponding changes in mechanical properties have been investigated over a temperature range of ?80 °C to 60 °C, from near the solvent melting points to above the gelation temperature. Shear‐rheometry, thermal analysis, and small‐angle neutron scattering data reveal formation and transition of structure in these systems from a liquid state to a gel state to a percolated cluster network with decrease in temperature. The aggregated PMMA end‐blocks display a glass transition temperature. Our results provide new understanding into the structural changes of a self‐assembled triblock copolymer gel over a large length scale and wide temperature range. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 877–887     

Microscopic Motion of Atoms in Simple Liquids at Equilibrium and with Shear Flow

Abstract

We investigate the microscopic mechanism of atomic motion and local stress relaxation in Lennard-Jones, LJ liquids using a new class of correlation functions that emphasise the interplay between an abitrary atom in the fluid and its surrounding shells of atoms. We use the linear momenta and stress tensor to characterise the time dependence of this interaction. We consider a series of correlation functions that give complementary information and build a picture of the single particle and small cluster motion. The central particle and first shell undergo a reversal in momentum at different times after the ‘collision’ of the central particle and its first shell of neighbours. This ‘phase difference’ becomes manifest in the subsequent dynamics probed by the new correlation functions. We also consider the effect of a non-newtonian shear flow on this local dynamical relaxation, using profile biased laminar flow equations of motion. In non-newtonian shear flow we find the momentum transfer between particle and cage to be less pronounced and occur over a wider time range.     

Single-chain magnet behavior in an alternated one-dimensional assembly of a Mn(III) Schiff-base complex and a TCNQ radical

An alternated 1:1 chain compound of a Mn(III) salen derivative and the TCNQ monoradical was synthesized: [Mn(5-TMAMsaltmen)(TCNQ)](ClO(4))(2) (1) (TCNQ=tetracyano-p-quinodimethane; 5-TMAMsaltmen=N,N'-(1,1,2,2-tetramethylethylene) bis(5-trimethylammoniomethylsalicylideneiminato)). Compound 1 has a zigzag chain structure packed with adjacent chains with an interchain MnMn distance of over 8 Angatrom. As compound 1 contains no crystallization solvent, the void spaces between chains are occupied only by ClO(4) (-) counter ions. Compound 1 has a structure reminiscent of what has been observed in the family of Mn(III)(porphyrin)-TCNE or -TCNQ compounds reported previously by Miller and co-workers and we demonstrate herein its unique single-chain magnet behavior among this family of compounds. The direct current (dc) magnetic measurements established the one-dimensional nature of compound 1 with an antiferromagnetic exchange coupling, J/k(B) approximately -96 K, between the Mn(III) ion and TCNQ radical and with an activated correlation length (Delta(xi)=26.5 K) at low temperatures (50-15 K). The slow relaxation of the magnetization was shown in compound 1 by the field hysteresis of the magnetization observed below 3.5 K (with a coercive field up to 14 kOe at 1.8 K). Single-crystal magnetization measurements demonstrated the uniaxial symmetry of this compound and allowed an estimation of the anisotropy field, H(a) approximately 97 kOe. The absence of magnetic ordered phase or spin-glass behavior was established by heat-capacity calorimetry measurements that exhibit no abnormality of C(p) between 0.5 K and 10 K. The study of the magnetization relaxation by combined ac (alternating current) and dc techniques showed that compound 1 possesses a single relaxation time (tau). As the consequence of the finite size of the chain, the temperature dependence of tau presents two activated regimes above and below 4.5 K with tau(01)=2.1 x 10(-10) s, Delta(tau1)=94.1 K and tau(02)=6.8 x 10(-8) s and Delta(tau2)=67.7 K, respectively. The detailed analysis of these dynamics properties together with the correlation length, allows an unambiguous demonstration of the single-chain magnet behavior in 1.     

Retention behavior of alkali, alkaline earth and transition metal cations in ion chromatography with an unmodified silica gel column

An unmodified silica gel (Develosil 30-5) column (150×4.6 mm I.D.) has been applied to the ion chromatographic separation of alkali, alkaline earth and transition metal cations. The retention behavior of the above cations on the bare substrate was investigated using a number of weak inorganic and organic acid eluents. During this investigation, several separations were achieved and the most suitable eluent conditions were identified. It was concluded that: (a) 1.5 mM HNO₃-0.5mM pyridine-2,6-dicar☐ylic acid eluent was the most effective for the simultaneous separation of common alkali and alkaline earth metal cations, (b) 1.5 mM oxalic acid eluent resulted in the best separation of alkali, alkaline earth, and transition metal cations, (c) 0.5 mM CuSO₄ eluent could be used for the separation of alkali metal cations alone and (d) 0.5 mM ethylenediamine-oxalic acid eluent at pH 5.5 resulted in themost efficient separation of both alkaline earth and transition metal cations.     

Elastic modulus profiles in the cross sections of drying alkyd coating films: modelling and experiments

The temporal development of the modulus of elasticity and its profile were studied in water-borne alkyd coatings during the drying process of the coating films. Values of the Young’s moduli of elasticity of free coating films were measured using tensile tests. Since the elastic modulus is related to cross-link density, the values of the moduli give information on the advancement of the drying process. A mathematical model was developed to predict the degree of effective cross-linking and the mechanical behaviour of the drying coating films with different thicknesses. This model is based on trends observed by confocal Raman microspectroscopy, which exhibit the profile of the consumption of double bonds and thus can be used to monitor the development of cross-link density as a function of depth from the film surface. The average values of the Young’s measured moduli were successfully described by the numerical model as a function of drying time.     

A Comparison of Simple Rheological Parameters and Simulation Data for Zymomonas mobilis Fermentation Broths with High Substrate Loading in a 3-L Bioreactor

Traditionally, as much as 80% or more of an ethanol fermentation broth is water that must be removed. This mixture is not only costly to separate but also produces a large aqueous stream that must then be disposed of or recycled. Integrative approaches to water reduction include increasing the biomass concentration during fermentation. In this paper, experimental results are presented for the rheological behavior of high-solids enzymatic cellulose hydrolysis and ethanol fermentation for biomass conversion using Solka Floc as the model feedstock. The experimental determination of the viscosity, shear stress, and shear rate relationships of the 10 to 20% slurry concentrations with constant enzyme concentrations are performed with a variable speed rotational viscometer (2.0 to 200 rpm) at 40 °C. The viscosities of enzymatic suspension observed were in range of 0.0418 to 0.0144, 0.233 to 0.0348, and 0.292 to 0.0447 Pa s for shear rates up to 100 reciprocal seconds at 10, 15, and 20% initial solids (w/v), respectively. Computational fluid dynamics analysis of bioreactor mixing demonstrates the change in bioreactor mixing with increasing biomass concentration. The portion-loading method is shown to be effective for processing high-solids slurries.     

The first normal stress difference and viscosity in shear of liquid crystalline solutions of hydroxypropylcellulose: new experimental data and theory

The constitutive equations for liquid crystalline polymers recently proposed by one of us [1] are applied here to interpret the behaviour of the shear viscosity η and the first normal stress difference N₁() measured for liquid crystalline (LC) solutions of hydroxypropylcellulose in acetic acid. N₁( ) is observed to change from positive to negative and again to positive, as the shear rate increases, at lower concentrations, in the LC phase. The -values at which N₁ changes sign depend on the molecular mass (degree of polymerization) and on the concentration. η shows a small Newtonian plateau at low shear rates and a strong shear-thinning at higher values of . The rate of decrease of η in this region shows an “hesitation” similar to one previously observed in LC solutions of poly-γ-benzyl-L-glutamate PBLG. All these observations can be rationalized within the frame-work of Martins' theory. The expressions for N₁() and η derived from this theory fit very well (quantitatively) to the experimental data and some fundamental viscoelastic parameters of the system under study are thereby obtained for the first time.     

载液组成对于卵白蛋白在非对称流场流分离通道中膜吸附和聚集行为的影响

非对称流场流分离技术对于蛋白质等生物大分子的分析具有温和、分离范围广的特点。然而,在场流分离通道中,受载液组成的影响而产生的蛋白质与通道膜的相互作用和蛋白质在通道内的聚集行为,会影响分析物的回收率和尺寸形态,这些现象一定程度上限制了场流分离仪器的进一步应用。该文研究了载液组成对于卵白蛋白在非对称流场流分离中膜吸附和聚集行为的影响。考察了不同pH （6.2、7.4、8.2）、阳离子种类（Na⁺、K⁺、Mg²⁺）及多种离子强度（0~0.1 mol/L）等条件对卵白蛋白洗脱过程的影响。结果表明a）载液的离子强度越大,卵白蛋白的吸附和聚集行为越严重;b） pH和蛋白质的等电点pI的相对大小决定了蛋白质的表面电荷,从而影响蛋白质的吸附聚集行为;c）二价阳离子Mg²⁺更易引发通道中蛋白质的吸附和聚集。这些结果有助于今后使用非对称流场流分离技术分析蛋白质样品时,改善载液组成以获得更高的回收率,降低蛋白质聚集作用,对AF4更广泛地应用于蛋白质生化分析中有较好的参考价值。