Characterization of nutritional and functional properties of "Blanco Sinaloa" chickpea (Cicer arietinum L.) variety, and study of the rheological behavior of hummus pastes.

In this work the preparation of a hummus pastes from a Mexican variety of chickpea (Blanco Sinaloa, BS) was investigated. With this purpose, the nutritional and functional properties of the raw chickpea were evaluated, which revealed a content of protein, fiber and lipids of 19, 1.6 and 10.3%, respectively. Meanwhile the values of hydration capacity, water absorption index, water solubility index, emulsifying activity and foam capability were 0.65 g/seed, 2.26 g/g, 22.3%, 40.7% and 29.2%, respectively. Based on these results this variety of chickpea was considered suitable for the target application. The preparation of the paste was done by further sterilization of the paste promoted a decreased on the activity of lipoxygenase (68%) and starch content (40%). The rheological characterization of the hummus paste showed that the sterilization induced the formation of a tridimensional structure, due to the gelatinization of the starch and protein denaturation. Moreover, the linear viscoelastic zone shifted to higher values of strain (%γ), whereas the storage modulus (G') increased in about two orders of magnitude. The results of frequency sweeps showed that the paste exhibits a solid-like behavior (weak gel). Measurements of shear rate of the paste (unsterilized and sterilized) revealed that the shear viscosity exhibited a shear thickening behavior and a thixotropic behavior.

A master dynamic flow diagram for the shear thickening transition in micellar solutions.

The shear thickening behavior of dilute micellar solutions of hexadecyltrimethylammonium-type surfactants with different counterions (tosylate, 3- and 4-fluorobenzoate, vinylbenzoate and salicylate) and of n-alkyltetradecylammonium bromide (CnTAB), with n = 14, 16 and 18, is examined here. These solutions undergo a shear thickening transition due to the formation of shear-induced structures (SISs) in the shear range studied. Here we report a relationship between the shear thickening intensity and the differences in the hydrophobicity of counterions according to the Hofmeister-like anion series, which leads to a master flow diagram. This master flow diagram is produced by plotting a normalized shear thickening intensity (Iη - 1)/(Imax - 1) versus CD/CD,max, where Iη is the shear-thickening intensity, defined as the largest viscosity obtained in the shear-thickening transition (STT) at a given surfactant concentration CD divided by the Newtonian viscosity η0, and Imax is the largest intensity value obtained in the STT at a surfactant concentration CD,max. The master flow diagram is built using several cetyltrimethylammonium-type surfactants with different counterions, according to a Hofmeister-like series, and by n-alkyltetradecylammonium bromide surfactants with different alkyl chain lengths.

Physicochemical, morphological and rheological properties of canned bean pastes "negro Queretaro" variety (Phaseolus vulgaris L.).

Proximate, thermal, morphological and rheological properties of canned "negro Querétaro" bean pastes, as a function of fat content (0, 2 and 3 %) and temperature (60, 70 and 85 °C), were evaluated. Raw and precooked bean pastes were characterized by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). Well-defined starch granules in the raw bean pastes were observed, whereas a gelatinized starch paste was observed for the canned bean pastes. The DSC analysis showed that the raw bean pastes had lower onset peak temperatures (79 °C, 79.1 °C) and gelatinization enthalpy (1.940 J/g), compared to that precooked bean pastes (70.4 °C, 75.7 °C and 1.314 J/g, respectively) thermal characteristics. Moreover, the dynamic rheological results showed a gel-like behavior for the canned bean pastes, where the storage modulus (G') was frequency independent and was higher than the loss modulus (G″). The non-linear rheological results exhibited a shear-thinning flow behavior, where the steady shear-viscosity was temperature and fat content dependent. For canned bean pastes, the shear-viscosity data followed a power law equation, where the power law index (n) decreased when the temperature and the fat content increased. The temperature effect on the shear-viscosity was described by an Arrhenius equation, where the activation energy (Ea) was in the range from 19.04 to 36.81 KJ/mol. This rheological behavior was caused by gelatinization of the starch during the cooking and sterilization processes, where starch-lipids and starch-proteins complex were formed.

Poly(styrene oxide)-poly(ethylene oxide) block copolymers: From "classical" chemotherapeutic nanocarriers to active cell-response inducers.

Two poly(styrene oxide)-poly(ethylene oxide) (PSO-PEO) triblock copolymers with different chain lengths were analyzed as potential chemotherapeutic nanocarriers, and their ability to inhibit the P-glycoprotein (P-gp) efflux pump in a multidrug resistant (MDR) cell line were measured in order to establish possible cell-responses induced by the presence of the copolymer molecules. Thus, EO33SO14EO33 and EO38SO10EO38 polymeric micelles were tested regarding doxorubicin (DOXO) entrapment efficiency (solubilization test), physical stability (DLS), cytocompatibility (fibroblasts), release profiles at various pHs (in vitro tests), as well as P-gp inhibition and evasion and cytotoxicity of the DOXO-loaded micelles in an ovarian MDR NCI-ADR/RES cell line and in DOXO-sensitive MCF-7 cells. EO33SO14EO33 and EO38SO10EO38 formed spherical micelles (~13nm) at lower concentration than other copolymers under clinical evaluation (e.g. Pluronic®), exhibited 0.2% to 1.8% loading capacity, enhancing more than 60 times drug apparent solubility, and retained the cargo for long time. The copolymer unimers inhibited P-gp ATPase activity in a similar way as Pluronic P85, favoring DOXO accumulation in the resistant cell line, but not in the sensitive cell line. DOXO loaded in the micelles accumulated more slowly inside the cells, but caused greater cytotoxicity than free drug solutions in the NCI-ADR-RES cell line, which overexpressed P-gp. Hence, PSO-PEO block copolymers offer interesting features as new biological response modifiers to be used in the design of efficient nanocarriers for cancer chemotherapy.

Kinetics of the sphere-to-rod like micelle transition in a pluronic triblock copolymer.

The kinetics of the sphere-to-rod transition was studied in aqueous micelle solutions of triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) pluronic P103 (PEO(17)PPO(60)PEO(17)). This transition was triggered by a temperature jump from the sphere phase to the rod phase and monitored with dynamic light scattering. The combination of the scattering intensity and the hydrodynamic radius were used to show that the micelles grow steadily as rods throughout the growth process. The transition was found to exhibit a single exponential behavior even in the case of large deviations from equilibrium. The linear increase in the decay rate with increasing copolymer concentration shows that the transition is dominated by a mechanism involving fusion and fragmentation of proper micelles. The decays of the sphere-to-rod transition were simulated for two pathways: random fusion fragmentation and successive addition of spherical micelles to rods. We show that micelle growth most likely occurs via random fusion-fragmentation. The second order rate constant for fusion and the fragmentation rate are calculated for the case of random fusion-fragmentation.

Aggregation and adsorption behavior of low concentration aqueous solutions of hexadecyltrimethylammonium ortho, meta, and parafluorobenzoate.

The aggregation properties of 2-, 3-, and 4-fluorobenzoic acids (2FBA, 3FBA, and 4FBA, respectively) and their salts with hexadecyltrimethylammonium cations (HTA2FB, HTA3FB, and HTA4FB) in water were studied with a battery of techniques. Their activity at the air/solution interface has been also studied. The position of the fluorine atom in the acid affected the solubility, adsorption, and aggregation in the pure acids solutions. The 4FBA is less water soluble, more hydrophobic, and has the lower critical aggregation concentration of the three isomers. The behavior of the HTA2FB compound in aqueous solution is different from that of HTA3FB and HTA4FB. The critical micelle concentration, critical concentration for sphere-to-rod-like micelle transition, and Krafft point of HTA3FB and HTA4FB are lower than those of the other surfactant but their surface activities are higher. The differences between the HTA2FB and the other two surfactants have been explained on the basis of the regular solution theory of mixed micelles and in light of the analysis of the hydration shell of the acids through molecular dynamic simulations. The results of the present work suggest that the different behaviors are due to a combination of different dehydration tendencies and the steric possibility of inclusion of the counterions in the micelle palisade layer. The formation of rod-like micelles by HTA2FB, while the tetradecyltrimethylammonium 2-fluorobenzoate only forms spherical aggregates, is explained on the basis of the packing parameter. The mentioned factors are complementary to others presented in literature. These conditions may be used in the rational design of micelles by means of molecular dynamics simulations, reducing the trial-and-error approach used to date.

Phase and rheological behavior of the hexadecyl(trimethyl)azanium; 2-hydroxybenzoate/water system.

The phase and rheological behavior of hexadecyl(trimethyl)azanium; 2-hydroxybenzoate (CTAS), and water as a function of surfactant concentration and temperature are investigated here. The critical micellization concentration (cmc(1)) and the concentration at which the structure of aggregates changes (cmc(2)) as well as the Krafft temperature (T(K)) are reported. A large micellar solution region exhibiting high viscosity, as well as hexagonal- and lamellar-phase regions were identified. In the dilute region, below the overlapping entanglement concentration (C*), the micellar solutions exhibit shear thickening. Above C*, wormlike micelles form and the solutions show strong viscoelasticity with Maxwell behavior in the linear regime and shear banding flow in the non-linear regime. The linear viscoelastic regime was analyzed with the Granek-Cates model, showing that the relaxation is controlled by the kinetics of reformation-and-scission of the micelles. The steady response in the non-linear regime is compared with the predictions of the Bautista-Manero-Puig (BMP) and the Giesekus models.

Temporal evolution of the size distribution during exchange kinetics of pluronic P103 at low temperatures.

The micellar dynamics of many (PEO-PPO-PEO) triblock copolymers have been extensively investigated throughout the past decade using ultrasonic relaxation or temperature jump experiments. These methods primarily use the total scattering intensity to quantify the exchange mechanisms, and these results are then interpreted to get an idea about temporal evolution of the micelle size and size distribution. In this paper, we present experiments where we directly measure the size of the micelles and the size distribution during the exchange kinetic of the pluronic triblock copolymer P103. Solutions of the commercial P103 surfactant form premicelle aggregates in the proximity of the critical micelle temperature and proper micelles at high temperatures. The kinetics of evolution from aggregates to proper micelles is investigated using dynamic light scattering after a temperature jump. The temporal evolution of the scattering intensity and the average size as well as the size distribution were used to discuss the possible exchange mechanisms.

Rheology of the Pluronic P103/water system in a semidilute regime: evidence of nonequilibrium critical behavior.

The linear and nonlinear rheological behaviors of semidilute aqueous solutions of the amphiphile triblock polymer Pluronics P103 in water are reported here. For C(surf) < or = 20 wt%, micelles are spherical at temperatures lower than ca. 27 degrees C and grow with increasing temperature to form long polymer-like micelles. These polymer-like micelles exhibit strong viscoelasticity and a shear-banding region that shrinks as the cloud point is approached. Master time-temperature-concentration curves were obtained for the dynamic moduli using traditional shifting factors. In the nonlinear regime, P103 polymer-like micellar solutions follow the master dynamic phase diagram proposed by Berret and colleagues, in which the flow curves overlap in the low-shear-rate homogeneous flow region. Within the nonhomogeneous flow region (confirmed by flow birefringence and small-angle light-scattering measurements), oscillations and overshoots are detected at the inception of shear flow, and two main relaxation mechanisms are apparent after cessation of steady shear flow. Evidence for nonequilibrium critical behavior is presented, in which the order parameter is the difference of critical shear rates that limit the span of the plateau stress. Most of the steady-state and transient features of the nonlinear rheology of the P103 polymer-like micelles are reproduced with the Bautista-Manero-Puig (BMP) model, including the predictions of nonequilibrium critical behavior under flow.

Phase behavior of the Pluronic P103/water system in the dilute and semi-dilute regimes.

The detailed temperature-composition phase diagram of the P103/water system in the dilute and semidilute regions is reported here using density and ultrasound velocity measurements, differential scanning calorimetry (DSC), rheometry and dynamic (DLS) and static light scattering (SLS). These techniques allow a precise determination of the critical micellar temperature (CMT), the sphere-to-rod micellar transition temperature (GMT) and the cloud point temperature (CPT) as a function of concentration. DLS and SLS measurements were employed to gain information on unimers and aggregate sizes and on the transition from spherical-to-rod micelles.

Rheological behavior of surfactant-based precursors of silica mesoporous materials.

The linear and non-linear viscoelastic behaviors of polymer-like micellar solutions of cetyltrimethylammonium tosilate (CTAT) with added NaOH and tetraethyl orthosilicate (TEOS) to produce precursors of mesoporous materials are studied. The effect of TEOS/CTAT (T/C) ratio at fixed CTAT concentration, CTAT concentration at fixed T/C and aging time are reported. The systems show increasingly larger deviations from near-Maxwell behavior upon increasing T/C ratio, CTAT concentration and aging. Moreover, in steady and unsteady shear-flow, shear banding develops between two critical shear rates, which tend to fade as the T/C ratio and aging increase. The Granek-Cates model is employed to analyze linear viscoelastic behavior. The Bautista-Manero-Puig (BMP) model is used here to reproduce the steady and transient nonlinear rheology of these systems. We explain these results in terms of the changes in inter-macromolecular interactions that arise out of the presence of colloidal additives in the viscoelastic gel. The ordered mesoporous materials were identified by X-ray diffractometry (XRD) and high-resolution transmission electron microscopy.

Phase and rheological behavior of the polymerizable surfactant CTAVB and water.

The phase and rheological behaviors of the polymerizable surfactant, cetyltrimethylammonium benzoate (CTAVB), and water as a function of surfactant concentration and temperature are investigated here. The critical micelle concentration (cmc) and the (cmc(2)), as well as the Krafft temperature (T(K)), are reported. A large highly viscous micellar solution region and hexagonal- and lamellar-phase regions were identified. The micellar solutions exhibit shear thickening in the dilute regime, below the overlapping or entanglement concentration. At higher concentrations, wormlike micelles form and the solutions show strong viscoelasticity and Maxwell behavior in the linear regime and shear banding flow in the nonlinear regime. The linear viscoelastic regime is analyzed with the Granek-Cates model, showing that the relaxation is controlled by the kinetics of reformation and scission of the micelles. The steady and unsteady responses in the nonlinear regime are compared with the predictions of the Bautista-Manero-Puig (BMP) model. Model predictions follow the experimental data closely.