Gel point in CNC dispersion from FT Rheology

A non-linear analysis via Fourier-Transform Rheology (FT-Rheology) and Large Ampli- tude Oscillatory Shear (LAOS) of cellulose nanocrystals (CNC) dispersions is presented. Dynamic frequency and strain sweep measure- ments were performed for different CNC con- centrations with various parameters (w , g ). The relevance of nonlinear material rheological pa- rameters on flow-field-CNC interactions are initially investigated. This preliminary analy- sis is mainly formed on the magnitude of the stress response nonlinearities. Dependence of concentration on phase transition in CNC while applying strain was investigated. A comparison between the linear viscoelastic dynamic moduli and nonlinearities a steep increase in nonlinear response around the gel point

Can intestinal absorption of dietary protein be improved through early exposure to plant-based diet?

Nutritional Programming (NP) has been studied as a means of mitigating the negative effects of dietary plant protein (PP), but the optimal timing and mechanism behind NP are still unknown. The objectives of this study were: 1) To determine whether zebrafish (Danio rerio) can be programmed to soybean meal (SBM) through early feeding and broodstock exposure to improve SBM utilization; 2) To determine if NP in zebrafish affects expression of genes associated with intestinal nutrient uptake; 3) To determine if early stage NP and/or broodstock affects gene expression associated with intestinal inflammation or any morphological changes in the intestinal tract that might improve dietary SBM utilization. Two broodstocks were used to form the six experimental groups. One broodstock group received fishmeal (FM) diet (FMBS), while the other was fed ("programmed with") SBM diet (PPBS). The first ((+) Control) and the second group ((-) Control) received FM and SBM diet for the entire study, respectively, and were progeny of FMBS. The last four groups consisted of a non-programmed (FMBS-X-PP and PPBS-X-PP) and a programmed group (FMBS-NP-PP and PPBS-NP-PP) from each of the broodstocks. The programming occurred through feeding with SBM diet during 13-23 dph. The non-control groups underwent a PP-Challenge, receiving SBM diet during 36-60 dph. During the PP-Challenge, both PPBS groups experienced significantly lower weight gains than the (+) Control group. NP in early life stages significantly increased the expression of PepT1 in PPBS-NP-PP, compared to PPBS-X-PP. NP also tended to increase the expression of fabp2 in the programmed vs. non-programmed groups of both broodstocks. The highest distal villus length-to-width ratio was observed in the dual-programmed group, suggesting an increase in surface area for nutrient absorption within the intestine. The results of this study suggest that NP during early life stages may increase intestinal absorption of nutrients from PP-based feeds

Thixotropy of cellulose nanocrystal suspensions

The thixotropy of cellulose nanocrystal (CNC) water suspensions is intrinsically dependent on the hierarchical structure of the suspension. The diverse hierarchies that comprise individual CNC nanoparticles and mesophase liquid crystalline domains, chiral nematic and nematic structures, contribute selectively to the rheological material response. Here, we combine rheology with polarized light imaging (PLI) to elucidate the thixotropic behavior of CNCs suspended in water. The simultaneous monitoring of PLI and rheological tests enables the observation of mesogens and their orientation dynamics. Creep, dynamic time sweep, ramped hysteresis loop, and thixotropic recovery tests combined with PLI aim to differentiate the contribution of the different hierarchical levels of CNC suspensions to their thixotropy. The range of concentrations investigated comprised biphasic (4 and 5 wt. %) and liquid crystalline phase suspensions (6, 7, and 8 wt. %). The CNC suspensions exhibited complex thixotropy behavior, such as viscosity bifurcations in creep tests and overshoot in ramped hysteresis loop tests. The restructuring and destructuring appeared to correspond to different levels of their hierarchical structure, depending mainly on the phase, in agreement with previous studies. Restructuring was attributed to re-organizations of an individual CNC, e.g., in the isotropic fraction of biphasic suspensions and at the mesogen interfaces in liquid crystalline phase suspensions. However, by increasing liquid crystalline fraction in the biphasic concentrations, restructuring could also involve mesogens, as indicated in the creep tests. For flow conditions above the yield stress, as evidenced by the ramped hysteresis and thixotropy recovery tests, destructuring was dominated by orientation in the flow direction, a process that is readily observable in the form of PLI “Maltese-cross” patterns. Finally, we show that a simple thixotropy model, while unable to capture the finer details of the suspension’s thixotropic behavior, could be employed to predict general features thereof

Isotropic Gels of Cellulose Nanocrystals Grafted with Dialkyl Groups: Influence of Surface Group Topology from Nonlinear Oscillatory Shear

Attractive (non-self-assembling) aqueous cellulose nanocrystal (CNC) suspensions were topologically tailored into isotropic gels through the surface grafting of dialkyl groups. We thus focus on the influence of CNC concentration, including for pristine CNC, surface linker branching, branching degree, and the influence of side group size and branch-on-branch surface-grafted groups. The resulting mobility and strength of interaction in particle-particle interaction mediated by the surface groups was investigated from a rheological point of view. The emphasis is on nonlinear material parameters from Fourier-transform rheology and stress decomposition analysis. The results show that nonlinear material parameters are more sensitive than linear viscoelastic parameters to the onset of weakly interconnected networks in pristine CNC isotropic suspensions. All surface-modified CNC suspensions resulted in isotropic gels. The nonlinear material parameters were found to be broadly sensitive to CNC concentration, branching, degree of branching and surface-grafted linkers’ length. However, the length of the grafted chains and the degree of branching were the primary factors influencing the nonlinear material response. Furthermore, the results showed evidence of two strain amplitude ranges with distinct nonlinear signatures that could be attributed to the disruption of weak network connection points and to distortions of more dense (aggregate) network regions, respectively

Phase transitions of cellulose nanocrystal suspensions from nonlinear oscillatory shear

Cellulose nanocrystals (CNCs) self- assemble in water suspensions into liquid crystalline assemblies. Here, we elucidate the microstructural changes associated with nonlinear deformations in (2–9 wt%) CNC suspensions through nonlinear rheological analysis, that was performed in paral- lel with coupled rheology—polarized light imaging. We show that nonlinear material parameters from Fourier-transform rheology and stress decomposition are sensitive to all CNC phases investigated, i.e. iso- tropic, biphasic and liquid crystalline. This is in con- trast to steady shear and linear viscoelastic dynamic moduli where the three-region behavior and weak strain overshoot cannot distinguish between biphasic and liquid crystalline phases. Thus, the inter-cycle and intra-cycle nonlinear parameters investigated are a more sensitive approach to relate rheological meas- urements to CNC phase behavior

A Novel Approach in the Development of Larval Largemouth Bass Micropterus Salmoides Diets Using Largemouth Bass Muscle Hydrolysates as the Protein Source.

This study’s objectives were to determine the effect of Largemouth Bass (LMB) muscle hydrolysates obtained using same-species digestive enzymes and the degree of LMB muscle hydrolysis when included in the first feeds of growth performance and survival, skeletal development, intestinal peptide uptake, and muscle-free amino acid omposition of larval LMB. LMB muscle was mixed with digestive enzymes from adult LMB, and hydrolyzed for 1.5, 3, and 6 h, respectively. Five diets were produced, the intact diet containing non-hydrolyzed muscle and four diets with 37% muscle hydrolysate inclusion. Those diets were characterized by their level of each hydrolysate (presented as a ratio of 1.5, 3, and 6 Ts hydrolysates): 1:1:1, 1:3:6, 1:3:1, 6:3:1 for diets A, B, C, and D, respectively. To account for gut development, one group of larval LMB was fed a weekly series of diets B, C, and D to provide an increasing molecular weight profile throughout development. This group was compared against others that received either; (1) diets D, C, and B; (2) diet A; or (3) intact diet. The initial inclusion of the hydrolysates significantly improved the total length of the larval LMB; however, neither the hydrolysate inclusion nor the series of dietary molecular weight profiles improved the overall growth of larval LMB. The inclusion of hydrolysates significantly decreased the occurrence of skeletal deformities. The degree of hydrolysis did not have a significant effect on the parameters measured, except for intestinal peptide uptake, which was increased in the group that received the most hydrolyzed diet at the final time of sampling. The lack of overall growth improvement suggests that while the hydrolysates improve the initial growth performance, further research is necessary to determine the optimal molecular weight profile, hydrolysate inclusion level, and physical properties of feeds for larval LMB

In situ monitoring of cellulose etherification in solution: probing the impact of solvent composition on the synthesis of 3-allyloxy-2-hydroxypropyl-cellulose in aqueous hydroxide systems

Etherification of cellulose using allyl glycidyl ether was carried out in aqueous alkaline solutions of benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, NaOH and different mixtures of these bases in order to study the effect of hydroxide base composition on the course of the reaction and the resulting product properties. In situ FTIR spectroscopy and time sweep shear measurements were carried out to monitor the reactions in real time. Infrared Attenuated Total Reflectance Spectroscopy and H-1 NMR confirmed the synthesis of 3-allyloxy-2-hydroxypropyl-cellulose and 2D HSQC NMR confirmed substitution on C2, C3 and C6 in all of the solvents. Quantitative C-13 NMR was used to estimate the molar substitution. Cellulose solutions in these quaternary ammonium hydroxides showed higher stability at 50 degrees C during the course of reaction, faster dissolution and hydrolysis of allyl glycidyl ether and lower molar substitution values compared to NaOH. Even though the highest molar substitution value was obtained in NaOH, the isolated product from this medium had lower solubility in DMSO-d(6) and its C-13 NMR did not differ significantly except for higher intensity of C1 and C6 compared to the other spectra. The obtained results indicated a more pronounced cascade reaction on the substitution itself in NaOH and lower temperature stability of cellulose solutions in this solvent

Percolation and phase behavior in cellulose nanocrystal suspensions from nonlinear rheological analysis

We examine the influence of surface charge on the percolation, gel-point and phase behavior of cellulose nanocrystal (CNC) suspensions in relation to their nonlinear rheological material response. Desulfation decreases CNC surface charge density which leads to an increase in attractive forces between CNCs. Therefore, by considering sulfated and desulfated CNC suspensions, we are comparing CNC systems that differ in their percolation and gel-point concentrations relative to their phase transition concentrations. The results show that independently of whether the gel-point (linear viscoelasticity, LVE) occurs at the biphasic - liquid crystalline transition (sulfated CNC) or at the isotropic - quasi-biphasic transition (desulfated CNC), the nonlinear behavior appears to mark the existence of a weakly percolated network at lower concentrations. Above this percolation threshold, nonlinear material parameters are sensitive to the phase and gelation behavior as determined in static (phase) and LVE conditions (gel-point). However, the change in material response in nonlinear conditions can occur at higher concentrations than identified through polarized optical microscopy, suggesting that the nonlinear deformations could distort the suspensions microstructure such that for example a liquid crystalline phase (static) suspension could show microstructural dynamics similar to a biphasic system