Polymer Size Distribution Research Articles

Comparison of Small and Large Deformation Rheological Properties of Wheat Dough and Gluten

ABSTRACTThe rheological properties of dough and gluten are important for end‐use quality of flour but there is a lack of knowledge of the relationships between fundamental and empirical tests and how they relate to flour composition and gluten quality. Dough and gluten from six breadmaking wheat qualities were subjected to a range of rheological tests. Fundamental (small‐deformation) rheological characterizations (dynamic oscillatory shear and creep recovery) were performed on gluten to avoid the nonlinear influence of the starch component, whereas large deformation tests were conducted on both dough and gluten. A number of variables from the various curves were considered and subjected to a principal component analysis (PCA) to get an overview of relationships between the various variables. The first component represented variability in protein quality, associated with elasticity and tenacity in large deformation (large positive loadings for resistance to extension and initial slope of dough and gluten extension curves recorded by the SMS/Kieffer dough and gluten extensibility rig, and the tenacity and strain hardening index of dough measured by the Dobraszczyk/Roberts dough inflation system), the elastic character of the hydrated gluten proteins (large positive loading for elastic modulus [G′], large negative loadings for tan δ and steady state compliance [Je0]), the presence of high molecular weight glutenin subunits (HMW‐GS) 5+10 vs. 2+12, and a size distribution of glutenin polymers shifted toward the high‐end range. The second principal component was associated with flour protein content. Certain rheological data were influenced by protein content in addition to protein quality (area under dough extension curves and dough inflation curves [W]). The approach made it possible to bridge the gap between fundamental rheological properties, empirical measurements of physical properties, protein composition, and size distribution. The interpretation of this study gave indications of the molecular basis for differences in breadmaking performance.

Experimental observation and prediction of interfacial tension and viscoelastic emulsion model behavior in novel phosphate glass–polymer hybrids

The interfacial tension of hybrids composed of a tin-based phosphate glass (Pglass) and thermoplastic polymers, low-density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) was investigated using pendant drop and droplet deformation methods. High surface tension values were determined for the pure Pglass and subsequently used to obtain interfacial tension values that were found to be greater than that of most polymer blends reported in the literature. Small amplitude oscillatory shear data were fitted to the Choi–Schowalter and Palierne emulsion models in order to estimate the interfacial tension and to validate the accuracy (or lack thereof) of using a polymer emulsion model on the special Pglass–polymer systems. Although some of the hybrids showed satisfactory agreement with the emulsion models, wide ranges of interfacial tensions were obtained, suggesting that a more complicated theory that explicitly takes the Pglass–polymer interactions, shape factor, and size distributions of the dispersed Pglass phase into account may be necessary for more accurate modeling of these special hybrid systems with enhanced benefits.

Colloid-induced polymer compression

We consider a model mixture of hard colloidal spheres and nonadsorbing polymerchains in a theta solvent. The polymer component is modelled as a polydispersemixture of effective spheres, mutually noninteracting but excluded from thecolloids, with radii that are free to adjust to allow for colloid-inducedcompression. We investigate the bulk fluid demixing behaviour of this modelsystem using a geometry-based density functional theory that includesthe polymer size polydispersity and configurational free energy, obtainedfrom the exact radius-of-gyration distribution for an ideal (random-walk)chain. Free energies are computed by minimizing the free energy functionalwith respect to the polymer size distribution. With increasing colloidconcentration and polymer-to-colloid size ratio, colloidal confinement is found toincreasingly compress the polymers. Correspondingly, the demixing fluidbinodal shifts, compared to the incompressible-polymer binodal, to higherpolymer densities on the colloid-rich branch, stabilizing the mixed phase.

Quantitative Variation of HMW Glutenin Subunits from Hard Red Spring Wheats Grown in Different Environments

ABSTRACTThe objective of this study was to investigate the quantitative variation of HMW glutenin subunits in relation to glutenin polymers and hence breadmaking quality across different environments. Six genotypes of hard red spring (HRS) wheat were grown at seven locations in North Dakota in 1998 in a randomized complete‐block experimental design with three replicates at each location. Unreduced SDS‐soluble glutenins of flour were fractionated by multistacking SDS‐PAGE into different sized glutenin polymers, followed by SDS‐PAGE and imaging densitometry to determine the quantitative variation of HMW glutenin subunits. SDS‐insoluble glutenin polymers also were examined for their quantitative composition of HMW glutenin subunits. The results showed that the percentage of HMW glutenin subunits was significantly affected by growing locations. The quantity of HMW glutenin subunits in SDS‐insoluble glutenins was significantly and positively correlated with loaf volume. SDS‐insoluble glutenin polymers had a higher percentage of HMW glutenin subunits than did SDS‐soluble glutenins. SDS‐insoluble glutenin polymers in flour were positively and significantly correlated in proportions of both total and individual HMW glutenin subunits in total SDS glutenins. SDS‐insoluble glutenin polymers also were positively and significantly correlated with the combined proportion of HMW glutenin subunits 2* + 5. The results of this study indicated that either subunit 2* or 5 might be more important in forming a greater quantity of larger SDS‐insoluble glutenin polymers than other subunits. SDS‐insoluble glutenin polymers from different cultivars or locations could have different quantities of HMW glutenin subunits in their composition. SDS‐insoluble glutenin polymers with more HMW glutenin subunits might be larger sized than those with less HMW glutenin subunits. Environment significantly influenced the quantitative variation of HMW glutenin subunits, which in turn affected the size distribution of glutenin polymers, and hence breadmaking quality.

Heterogeneity in bacterial surface polysaccharides, probed on a single-molecule basis.

The heterogeneity in bacterial surface macromolecules was probed by examining individual macromolecules on the surface of Pseudomonas putida KT2442 via single-molecule force spectroscopy (SMFS). Using an atomic force microscope (AFM), the silicon nitride tip was brought into contact with biopolymer molecules on bacterial cells and these macromolecules were stretched. Force-extension measurements on different bacterial cells showed a range of adhesion affinities and polymer lengths. However, substantial heterogeneity was also observed in the force-extension curves on a single bacterium. A given bacterium has biopolymers that range in size from tens to hundreds of nanometers, with adhesion affinities for the AFM tip from nearly zero to greater than 1 nN. A distribution of polymer sizes was confirmed by size-exclusion chromatography. The freely jointed chain (FJC) model for polymer elasticity was applied to individual force-extension curves in order to estimate the contour lengths and segment lengths of the polymer chains. A range of segment lengths was obtained using the FJC model, from 0.154-0.45 nm in water, 0.154-0.32 nm in 0.01 M KCl, and 0.154-0.65 nm in 0.1 M KCl. The modeling confirms that the heterogeneity in biopolymers is more than a matter of differences in molecular weights, since a range of stiffnesses (segment lengths) was also observed. The effect of salt concentration on biopolymer conformation and adhesion was also explored. While the biopolymers were flexible in all solvents, they were slightly more extended in water than in either of the salt solutions (0.01 and 0.1 M KCl). The adhesion of polysaccharides with the AFM tip was not dependent on salt concentration, because the polymers were not highly charged and heterogeneity overwhelmed any trends that could be observed in adhesion with respect to solution ionic strength. These experiments indicate that heterogeneity in biopolymer properties on an individual bacterium and within a population of bacterial cells may be much greater than previously believed and should be incorporated into models of bacterial adhesion.

Effects of inert volume-excluding macromolecules on protein fiber formation. I. Equilibrium models

The equilibrium Oosawa–Asakura model for nucleated assembly of rod-like protein fibers is recast in terms of dimensionless (scaled) quantities. The model is then generalized to treat arbitrarily large deviations from thermodynamic ideality arising from high fractional volume occupancy by an inert protein or polymer. Each state of association of the self-associating protein is modeled as an equivalent rigid convex particle (sphere or spherocylinder) and the crowding species is modeled either as an equivalent sphere or cylindrical rod. The resulting conservation of mass relation is readily solved to yield the fractional abundance of monomer, from which the entire equilibrium distribution of oligomeric species can be calculated, either directly or through the use of an additional scaling relationship. Results indicating the potential effect of volume occupancy on the equilibrium solubility of the self-associating protein and upon the equilibrium distribution of polymer size are presented. It is found that the fractional (logarithmic) change in both solubility and in the breadth of the polymer size distribution scale almost linearly with the fractional (logarithmic) change in the thermodynamic activity of monomer.

Preparation and characterization of poly ( N -isopropylacrylamide- co -dimethylaminoethyl methacrylate) microgel latexes

Monodisperse cationic thermosensitive latex microgels have been prepared by radical-initiated precipitation polymerization of N-isopropylacrylamide, methylene bisacrylamide using 2,2′-azobis(2-amidinopropane hydrochloride) as an initiator and dimethylaminoethyl methacrylate (DMAEMA) as a cationic monomer. The final microgel latexes were characterized with respect to water-soluble polymer formation, particle size and size distribution. Adding cationic monomer (DMAEMA) was found to drastically affect the particle size, but not the size distribution as observed both by transmission electron microscopy and quasielastic light scattering (QELS). However, too high a DMAEMA concentration in the feed composition led to enhanced formation of water-soluble polymer. The volume phase-transition temperature of cleaned microgels examined by QELS (particle size versus temperature) was found to be around 32 °C and was slightly dependent on the concentration of the cationic monomer. The volume phase-transition temperature range becomes broader with increasing cationic monomer concentration. In addition, the pH of the polymerization medium was found to affect the final particle size and amount of water-soluble polymer formed.

Preparative Method for In Vitro Production of Functional Polymers from Glutenin Subunits of Wheat

ABSTRACTAn in vitro method for preparative‐scale production of artificial glutenin polymers utilizes a controlled environment for the oxidation of glutenin subunits (GS) isolated from wheat flour to achieve high polymerization efficiency. The functionality of in vitro polymers was tested in a 2‐g model dough system and was related to the treatment of the proteins before, during, and after in vitro polymerization. When added as the only polymeric component in a reconstituted model dough (built up from gliadin, water solubles, and starch fractions), in vitro polymers could mimic the behavior of native glutenin, demonstrating properties of dough development and breakdown. Manipulating the high molecular weight (HMW)‐GS to a low molecular weight (LMW)‐GS ratio altered the molecular weight distribution of in vitro polymers. In functional studies using the 2‐g mixograph, simple doughs built up from homopolymers of HMW‐GS were stronger than those using homopolymers of LMW‐GS. These differences may be accounted for, at least in part, by different polymer size distributions. The ability to control the size and composition of glutenin polymers shows the potential of this approach for investigating the effects of glutenin polymer size on dough function and flour end‐use quality.

Size Characterisation of Glutenin Polymers by HPSEC-MALLS

The use of an on-line coupling of a new high-performance size exclusion chromatography (HPSEC) phase characterised by a very high exclusion limit and a multiangle laser light scattering detection (MALLS) for the size characterisation of wheat glutenin polymer was examined. Flour glutenin polymers which were extracted and purified by differential solubility in aqueous 50 and 70% propan-1-ol were solubilised with or without sonication in combination with a surfactant, 2% SDS. The glutenin polymers of the two genotypes studied, Soissons (5+10, Glu-1D) and Thésée (2+12, Glu-1D), were characterised by large polydispersity and by significant differences of size distribution of total polymers. The molecular size distribution of the total polymers, which can be used to differentiate the two genotypes, was highly correlated with the percentage of high-molecular glutenin subunits (HMW-GS) in glutenins. Furthermore, the results obtained for both the SDS-soluble and SDS-insoluble glutenin polymers from the two varieties revealed significant differences in size distribution, and also in molecular conformation (dependence of size upon mass). The molecular dimensions of SDS-insoluble polymers increased more slowly with the molecular weight than SDS-soluble polymers, which suggested a more compact structure. To conclude, the method appears to be a viable procedure to obtain rapid size characterisation of unreduced glutenin.

Changes in protein composition during grain development in wheat

Changes in glutenin, gliadin, glutenin subunit composition, and polymer size distribution were monitored for 4 cultivars of wheat (Triticum aestivum L.) throughout grain filling in an irrigated and non-irrigated environment over 2 seasons. The synthesis of glutenin and gliadin was modelled using a logistic function to determine the rate and duration of synthesis in response to environmental conditions. The maximum rate of synthesis of glutenin occurred approximately 6–8 days after the maximum rate of gliadins, with the duration extended by a similar period. High molecular weight glutenin subunits (HMWGS) were detected earlier than low molecular weight glutenin subunits (LMWGS). After the initial synthesis of HMWGS, there was a period at approximately mid grain filling when the rate of synthesis was reduced, followed by a period of more rapid synthesis in the latter stages of grain filling. In contrast, once detected, LMWGS increased at a faster rate than, and were in excess with respect to, HMWGS. Cultivar and environmental differences were observed, but in all cases the average molecular weight of polymeric glutenin increased throughout grain filling. Large polymers (>400 kD) increased continuously during grain filling, whereas polymers in the range 150–400 kD remained relatively constant and smaller polymers <150 kD decreased. As grain filling approached physiological maturity, there was a rapid increase in the synthesis of large polymers. The gliadin to glutenin ratio was almost the same in grain from adjacent irrigated and non-irrigated environments subjected to high temperatures at mid grain f illing, but the proportion of highly polymeric glutenin was greater from the non-irrigated environment.

Direct Evidence that the Number and Location of Cysteine Residues affect Glutenin Polymer Structure

In this study, the possible roles of three well-characterised model prolamins in the structure of the glutenin macropolymer were examined. Model prolamins were labelled with fluorescein isothiocyanate (FITC), and incorporated into the glutenin macropolymer of a base flour using a partial reduction-oxidation scheme. The effect of incorporation of the model prolamins on dough behaviour was determined by assessing differences in polymer size distribution, mixing properties, and distribution of the model prolamins in a dough after incorporation. Using this approach, the prolamins capable of forming inter-chain disulphide bonds were shown to be incorporated into the glutenin macroÍpolymer, while prolamins that were not capable of forming inter-chain disulphide bonds were retained as monomers. The distribution of fluorescently-labelled prolamins after their incorporation into the glutenin macropolymer of the dough was examined by confocal light scanning microscopy, in order to determine the possible roles of ω-gliadins and glutenin-like subunits with varied cysteine residue compositions in the structural organisation. The role of the model prolamins was a function of the disulphide-bonding capabilities of the polypeptides. Model ω-gliadins were retained as monomers and functioned as space fillers; model glutenin-like subunits containing a single cysteine residue incorporated into the glutenin macropolymer but functioned as chain terminators; and model glutenin-like subunits containing two cysteine residues incorporated into the glutenin macropolymer and acted as chain extenders.

Temperature‐Induced Changes in the Dynamic Rheological Behavior and Size Distribution of Polymeric Proteins for Glutens from Wheat Near‐Isogenic Lines Differing in HMW Glutenin Subunit Composition

ABSTRACTViscoelasticity of hydrated gluten depends on composition of HMW gluten subunits (GS), size distribution of glutenin polymers, and proteinprotein interactions. Glutens extracted from four near‐isogenic lines with differing HMW‐GS were analyzed. Rheological properties were studied by dynamic assay in shear. Size distribution of prolamins was determined by sequential extraction and size‐exclusion HPLC. Assays performed at 20°C confirmed that viscoelasticity was determined by large glutenin polymers. The abundance of large glutenin polymers depended on the HMW‐GS composition of the lines. Difference of functionality linked to subunit structure was highlighted by comparing the behaviors of the 1A/1B null and 1A/1D null lines. Glutens were submitted to heating and cooling cycles, with or without an SH‐blocking agent (N‐ethylmaleimide [NEMI]). At 20–40°C, no irreversible changes of the mechanical properties occurred. Thermal treatment affected chain mobility, and possibly H bonds, but not the chemical structure of the network. At >40°C, irreversible rheological changes were observed without NEMI. Irreversibility was mainly due to chemical modifications affecting the polymer size distribution through SH‐SS exchange reactions. The sensitivity of gluten to temperature depended on subunit composition.

A study of dual polymer flocculation

Flocculation of alumina fines with combinations of the anionic form of a polyacrylic acid (PAA) and a high molecular weight cationic copolymer of acrylamide and quaternary acrylate salt (Percol) was investigated. Effects of PAA and Percol molecular weights as well as Percol charge density on the rate of flocculation were also investigated. In order to determine the role of the polymer conformation and changes in it due to the presence of another polymer, the fluorescence label method was employed to monitor PAA conformation at the alumina ∣ water interface under different polymer addition modes, such as the sequential addition of the two polymers vs. co-addition. Importantly, polymer size distribution was found to have a marked effect depending on the polymer type: in the case of PAA, a broader distribution yielded better flocculation; no such effect was observed with Percol. Based on the results, an overall mechanistic picture of dual polymer flocculation is proposed.

Phase transitions of colloid-polymer systems in two dimensions.

Phase transitions of systems consisting of colloidal particles and non-adsorbing polymer in a solvent are studied theoretically in two dimensions. The colloids are modeled as hard spheres and the polymer as an ideal gas. The imbalance in osmotic pressure induced by the depletion effect gives rise to an effective attraction tail for the colloid-colloid interaction. For a monodisperse polymer, liquid-liquid separation is predicted to occur for appropriate colloid concentrations when the ratio s of the radius of gyration of the polymer to the radius of the colloidal particle is greater than 0.31, while solid-liquid separation is predicted to occur for all colloid concentrations when s is smaller than 0.31. Polydispersity of polymer is found to increase the extent of liquid-liquid coexistence, and when the average s is smaller than 0.31, and for appropriate colloid concentrations, liquid-liquid coexistence occurs provided the polymer size distribution is broad enough. Partitioning and size distribution of polymer in coexisting phases are also predicted.

The kinetics of proteinase K digestion of linear prion polymers.

Transmissible spongiform encephalopathies such as scrapie are caused by a protein-only infectious agent, known as a prion. It is not clear how a protein can be capable of replicating itself, and the mechanism remains controversial. One influential model hypothesizes that prions are nucleated, macroscopically linear polymers. We investigated the theoretical kinetics of this model and derived predictions which could be used to test the model. In the model, the polymerization and depolymerization rates are independent polymer size. This leads to an exponential size distribution at equilibrium. In agreement with a prediction stemming from this size distribution, the average size of PrP-res polymers was proportional to the square root of the concentration of PrP-res in a published study of in vitro conversion. Prion digestion by proteinase K (PK) is predicted to be biphasic. The second phase of digestion should be virtually independent of the PK concentration and should depend on the initial size distribution of prion polymers. For initially equilibrated polymers with an exponential size distribution, phase two digestion is exponential at a predicted rate. This rate varies in a defined way with the concentration used for equilibration and with other parameters which affect the average polymer size.

Application of the negative staining technique to both aqueous and organic solvent solutions of polymer particles

Transmission electron microscopy (TEM) imaging of several different polymers in aqueous and organic solutions using the negative staining technique is demonstrated, to emphasise the possibilities of this specimen preparation technique for polymer science. Negative stains can readily be prepared in both water and organic solvents (e.g. dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) and tetrahydrofurane (THF)). Polymer particle size, size distribution and shape seen in negative stain correlates well with those of unstained materials. The particle surface and smaller particles (e.g. 10–20 nm) are more clearly defined in the presence of a negative stain. The inherent problems of sample overload, anomalous double-sided sample spreading of the sample on the carbon support film and rapid drying of polymer and negative stain from organic solvents, do not prevent the production and selection of satisfactory specimen regions for TEM study. The presence of metallic clusters within polymer particles is not masked by negative stain and assessment of the number of metallic clusters entrapped within the polymer and/or free in the solvent can be readily made. The cationic negative stain, uranyl actetate (UA), is widely used as the stain of choice for polymer solutions, but the anionic negative stains (phosphotungstic acid (PTA) and ammonium molybdate (AM)) have also been successfully employed in this work.

Quantitative fractionation of grape proanthocyanidins according to their degree of polymerization.

A method was developed for the fractionation of grape (seed or skin) proanthocyanidins according to their degree of polymerization. After precipitation in chloroform/methanol (75:25, v/v), the grape proanthocyanidins were deposited onto an inert glass powder column and sequentially dissolved in several fractions by increasing proportions of methanol in the solvent. Each fraction from each proanthocyanidin source was quantified and characterized after acidic degradation with phenylmethanethiol (i.e., thiolysis). The comparison of data from total extract and successive fractions showed that a quantitative separation was achieved so that estimation of polymer size distribution in relation to other compositional characteristics (proportions of prodelphinidin units, galloylation rate) was thus possible. Mean degree of polymerization of separated proanthocyanidins ranged increasingly from 4.7 to 17.4 in seed (8.1 for total extract) and from 9.3 to 73.8 in skin (34.9 for total extract). The method proposed is very interesting for the study of grape proanthocyanidins according to their degree of polymerization because it gives both qualitative and quantitative information especially on the highly polymerized forms, which were not fractionated by previous techniques.

Correlation of polymer particle size with droplet size in suspension polymerisation of methylmethacrylate in a batch oscillatory-baffled reactor

We report our pioneering experimental investigation of polymer particle size and size distribution in suspension polymerisation of methylmethacrylate (MMA) in a batch 50 mm diameter stainless-steel jacketed oscillatory-baffled reactor. In such a reactor, fluid mixing is achieved by eddies that are generated when fluid passes through a set of equally spaced stationary orifice baffles. Those periodically formed vortices can be controlled by a combination of operational and geometrical parameters, such as oscillation frequency, oscillation amplitude, baffle diameter and baffle spacing. Based on a confidential and scaled-down fcormulation of a proprietary dental-grade MMA resin supplied by the Bonar Polymers, polymerisation reactions were performed under a controlled environment and the effects of the operational conditions on transient droplet size, final polymer particle size and their size distributions are studied. The mean particle size of polymer, d v,0.5 , is compared with the Sauter mean size of droplet, d 32, obtained with no reaction taking place and a correlation between d 32 and d v,0.5 is established, which predicts the final particle sizes of polymer being made in such a reactor with a high degree of accuracy. In addition, a comparison of polymer particle size distribution, molecular weight distribution and residual initiator content is also carried out between our reactor and the traditional stirred-tank reactor.

A comprehensive model for the prediction of particle-size distribution in catalyzed olefin polymerization fluidized-bed reactors

A generalized steady-state population balance model is developed to investigate the particle-size distribution developments in gas-phase fluidized-bed olefin polymerization reactors. The model rigorously accounts for the combined effects of particle growth, attrition, elutriation and agglomeration for both uniform-size and size distributed catalyst feed. Model predictions are found to be in agreement with recent experimental results on particle elutriation and agglomeration in polyethylene fluidized beds. Simulation results show that the rate of particle agglomeration exhibits an exponential increase with the bed temperature. Furthermore, particle elutriation is influenced by the agglomeration process which largely reduces the number of small-size particles. It is also shown that due to the large polymerization rates exhibited in gas-phase olefin polymerization processes and to the near-well-mixed bed behaviour, the feed catalyst size distribution strongly affects the particle-size distribution in the bed. The population balance model developed in this paper proves to be a unique tool for simulating the effects of different process parameters on the polymer size distribution in gas- phase fluidized-bed olefin polymerization reactors.

Self-Association of Linker Histone H5 and of Its Globular Domain: Evidence for Specific Self-Contacts

The ability of avian-specific linker histone H5, and the globular domains of H5 (GH5) and H1(0) (GH1(0), to self-associate either free in solution or when bound to DNA was investigated. All three proteins underwent a salt-dependent increase in turbidity that may be indicative of nonspecific interactions. Dithiobis(succinimidyl propionate) cross-linking was used to measure specific contacts for both H5 and GH5 free in solution and bound to DNA. H5 and GH5 each became cross-linked in solution, with GH5 displaying divalent polymerization interactions, which suggests that two specific surfaces were involved in the assembly process. For GH5-DNA complexes, cross-linking appeared to be largely the consequence of aggregation, but under low concentrations of DSP, cross-linking GH5 was observed to assemble preferentially onto DNA before oligomerizing to form massive aggregates. Both linear and supercoiled DNA facilitated GH5 interactions compared to assembly in solution; differences in the distribution of cross-linked polymer sizes indicates that assembly is dependent on both the presence of DNA and the morphology of the DNA. Finally, on the basis of a technique referred to as quantitative proteolysis, GH5 assembly on DNA appears to involve specific protein-protein contacts involving the C terminus of one partner. Overall, the cumulative results reported here support the premise that linker histones assemble specifically both in solution and on DNA.