Targeted particulate adhesion to cellulose surfaces mediated by bifunctional fusion proteins

The adhesion of particles to surfaces is an integral element in many commercial and biological applications. In this article, we report on the direct measurements of protein-mediated deposition and binding of particles to model cellulose surfaces. This system involves a family of heterobifunctional fusion proteins that bind specifically to both a red dye and cellulose. Amine-coated particles were labeled with a red dye, and a fusion protein was attached to these particles at various number densities. The strength of adhesion of a single particle to a cellulose fiber was measured using micropipette manipulation as a function of the specificity of the protein and its surface density and contact time. The frequency and force of adhesion were seen to increase with contact time in fiber experiments. The dynamics of adhesion of the functionalized particles to cellulose-coated glass slides under controlled hydrodynamic flow was explored using a flow chamber for two scenarios: detachment of bound particles and attachment of particles in suspension as a function of the shear rate and surface density of protein. Highly specific adhesion was observed. The critical shear rate for particle detachment was an increasing function of cellulose binding domain (CBD) density on particle surface. A rapid irreversible attachment of particles to cellulose was observed under flow. Using a family of proteins that were divalent for binding either the red dye or cellulose, we found that particle detachment occurred because of the failure of the cellulose-CBD bond. A comparison of fiber binding and particle detachment results suggests that forces of adhesion of particles to cellulose of up to 2 nN can be obtained with this molecular system through multiple interactions. This study, along with the adhesion simulations currently under development, forms the basis of particulate design for specific adhesion applications.     

Effect of filler shape on mechanical properties of rigid polyurethane composites containing plant particles

The effect of types of fillers on mechanical properties of rigid polyurethane composite samples was investigated. Polyurethane (PU) composites were prepared using a molasses polyol (MP, a mixture of molasses and polyethylene glycol, Mw=200) diphenylmethane diisocyanate (MDI) and fillers. The following plant particles, bamboo powder, roast bamboo powder, wood meal, coffee grounds, ground coffee bean parchment and cellulose powder, were used as fillers. The mixture of MP and fillers was reacted with MDI by adding an adequate amount of acetone as a solvent. The content of fillers was defined as the ratio of filler weight to total weight of polyol and fillers. The filler content was varied from 10 to 90 wt%. Polyurethane (PU) composites were prepared using fillers with MP. Lengths of major axis and minor axis for each particle regarded as an ellipse were measured using an optical microscope. Averages of diameter and aspect ratio were derived for each plant particle. The relationships between these average values and the mechanical properties, such as strength and elastic modulus, determined by the compression tests were investigated. The effect of filler content was estimated using the apparent volume ratio which is determined as the ratio of the apparent volume of fillers to the reciprocal values of the apparent density of samples. The master curves of the relationships between the specific values of mechanical properties and the apparent volume ratio were obtained. It was found that the compression strength and the elastic modulus for composite samples with different fillers showed maximum values at average aspect ratio around 3. It was also found that the apparent volume ratio, where the mechanical properties showed maximums, decreases with increasing aspect ratio. Using master curves, it is possible to evaluate the mechanical properties of plant particle filled polyurethane composites are described.     

Novel filled polymer composites prepared from in situ polymerization via a colloidal approach: II. Blends of kaolin/Nylon-6 in situ composites with conventional Nylon-6 and -66

A novel in situ composite comprised of kaolin clay fillers and polyamide 6 (Nylon-6) was synthesized via a colloidal approach by suspending kaolin particles in aqueous caprolactam and then polymerizing the caprolactam under elevated temperature and pressure. This in situ polymerization technique enables the deposition of nylon molecules directly onto the filler surface. It offers a much larger contact surface area for the nylon molecules to interact with the filler particles and enhances filler/matrix interaction through polymer miscibility. The kaolin particles were shown to be uniformly dispersed in Nylon-6 matrix without appreciable agglomeration. In the highly clay-loaded composites such as the 50/50 kaolin/Nylon-6 in situ composite, the deposited nylon molecules probably form a coated layer on the filler particles. This kind of nylon coated fillers may be applied as a reinforcing entity to commercial Nylon-6 or −;66 by improving particle dispersion and melt processability. The 50/50 kaolin/Nylon-6 in situ composites have been used as a masterbatch for blending with commercial Nylon-6 and Nylon-66 to take advantage of their good properties and to reduce cost. Rheology and mechanical properties of the masterbatch/nylon composites have been investigated in comparison with those of the conventional melt-mixed composites. The improvement of rheological and mechanical properties of the in situ composites has been discussed in relation to the composite structure. © 1996 John Wiley & Sons, Inc.     

Mechanism of TiO2 pigment retention on pulp fiber with polyelectrolytes

Pulp fibers and pigment dispersed in water are both negatively charged and, therefore, when a paper sheet is formed on a screen the pigment particles, which are of colloidal dimension, are not retained. Cationic polyelectrolytes are employed to promote pigment retention but the mechanism by which they operate is not well understood.Two cationic polyelectrolytes, based on polyethylenimine and polyacrylamide and used commercially as retention aids were examined to clarify their role in TiO₂ retention. From the comparison of polymer adsorption on both fiber and pigment, their electrophoretic mobility, and the extent of pigment retention it was concluded that the main mechanism is mutual attraction between oppositely charged fiber and pigment. In general, the fibers became positive at a polymer concentration where the pigment was still negative and maximum retention was realized when these negative pigment particles deposited on the already positive fibers. Homoflocculation of the pigment (and mechanical entrapment of pigment flocs in the forming sheet) also contributed to the overall retention and was more pronounced with the polyacrylamide polymer.     

Kinetics of polyelectrolyte adsorption onto polystyrene latex particle studied using electrophoresis: effects of molecular weight and ionic strength

The kinetics of the adsorption of a cationic polymer flocculant onto negatively charged polystyrene latex (PSL) particles were measured by means of electrophoresis as a function of the molecular weight of the polyelectrolyte and the ionic strength of the solution. In the experiment, the dispersion of bare PSL particles was mixed with a polyelectrolyte solution by means of end-over-end rotation in which the mixing intensity was evaluated in terms of the collision frequency between the colloidal particles. The rate of electrophoretic mobility of a PSL particle, which remained as a singlet, was measured against the mixing steps, which was equivalent to the time elapsed after the onset of flocculation. The shape of the kinetic curves is typical: a linear increase for a short period followed by a plateau, implying the saturation of the colloidal surface by the adsorbed polyelectrolyte. In the case of low ionic strength, the plateau value was dependent on the molecular weight of the polyelectrolyte. That is, a lower plateau value was detected when the molecular weight of the polyelectrolyte was smaller and its concentration was lower. However, the amount of adsorption was kinetically controlled only for the case of higher molecular weight. In the case of high ionic strength, the plateau value of electrophoresis was constant, regardless of the polyelectrolyte concentration and molecular weight. These data will ultimately be useful in further analysis of the flocculation behavior of colloidal particles with a polyelectrolyte.     

Biobased contents of biodegradable poly(epsilon-caprolactone) composites polymerized and directly molded using aluminium triflate from caprolactone with cellulose and inorganic filler

Poly(epsilon-caprolactone) (PCL) composite samples were prepared by polymerization and direct molding. The starting compound was epsilon-caprolactone monomer liquid combined with cellulose and inorganic fillers, using aluminium triflate as a catalyst at 80 degrees C, for 6 or 24 h. Cylinder-shaped PCL composite samples with a homogeneously dispersed cellulose filler were prepared with (-)M(n) = 4 600 ((-)M(w)/(-)M(n) = 2.9). The mechanical properties of the PCL composite samples were studied using compression test methods. The strength of a PCL composite with 50 wt.-% cellulose filler (10.8 MPa) was found to be lower than the PCL sample without fillers (19.2 MPa). The biobased content of the PCL composite with 50 wt.-% cellulose filler (51.67%) measured using accelerated mass spectrometry (AMS) was slightly higher than the carbon ratio of cellulose in the starting powder samples (41.3 mol-%). The biobased content of the polymer composite powders by AMS was found not to be affected by the presence of inorganic fillers, such as talc. The rate and extent of biodegradation, caused by Amano Lipase PS, of the PCL composite sample with cellulose filler (40% degradation in 4 d) was the same as that of a PCL sample without the cellulose filler.     

Fuzzy ternary particle systems by surface-initiated atom transfer radical polymerization from layer-by-layer colloidal core-shell macroinitiator particles

We report the synthesis of ternary polymer particle material systems composed of (a) a spherical colloidal particle core, coated with (b) a polyelectrolyte intermediate shell, and followed by (c) a grafted polymer brush prepared by surface-initiated polymerization as the outer shell. The layer-by-layer (LbL) deposition process was utilized to create a functional intermediate shell of poly(diallyl-dimethylammonium chloride)/poly(acrylic acid) multilayers on the colloid template with the final layer containing an atom transfer radical polymerization (ATRP) macroinitiator polyelectrolyte. The intermediate core-shell architecture was analyzed with FT-IR, electrophoretic mobililty (zeta-potential) measurements, atomic force microscopy, and transmission electron microscopy (TEM) techniques. The particles were then utilized as macroinitiators for the surface-initiated ATRP grafting process for poly(methyl methacrylate) polymer brush. The polymer grafting was confirmed with thermo gravimetric analysis, FT-IR, and TEM. The polymer brush formed the outermost shell for a ternary colloidal particle system. By combining the LbL and surface-initiated ATRP methods to produce controllable multidomain core-shell architectures, interesting functional properties should be obtainable based on independent polyelectrolyte and polymer brush behavior.     

Redispergation of TiO2 particles in aqueous solutions

The colloidal stability of TiO2 dispersions in aqueous solutions was studied. Aqueous solutions of ATLAS G-3300 (1.57 x 10(-3) mol/l), TRITON X-100 (5 x 10(-5) mol/l), and PMAA (4 x 10(-6) and 5.81 x 10(-3) mol/l) have been used as medium for redispergation of TiO2 particles. Stability of dispersions was investigated at different pH values by two different methods. By using analytical centrifuge the sedimentation velocity of TiO2 particles was directly measured and by means of light scattering the particle size of dispersed particles has been monitored. Combination of these two methods allowed determination of the aggregation degree of TiO2 particles as well as structure of the aggregates formed in aqueous phase. It has been found that redispergation process does not provide complete separation of virgin TiO2 particles. Even in the case of stable dispersions some aggregates were found, which consisted of 2-4 virgin TiO2 particles. With increasing colloidal stability of dispersions aggregates appear to be spherically shaped. In the system where TRITON X-100 was used, formation of secondary aggregates by fusion of primary ones was observed.     

Cellulose nanofibrils—adsorption with poly(amideamine) epichlorohydrin studied by QCM-D and application as a paper strength additive

In this paper cellulose nanofibrils were used together with a cationic polylelectrolyte, poly(amideamine) epichlorohydrin (PAE), to enhance the wet and the dry strength of paper. The adsorption of nanofibrils and PAE on cellulose model surfaces was studied using quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM). The differences in fibril and polyelectrolyte adding strategies onto cellulose fibres were studied by comparing layer-structures and nano-aggregates formed by the nanofibrils and PAE. The results showed that when PAE was first adsorbed on the model fibre surface a uniform and viscous layer of nanofibrils could be adsorbed. When PAE and nanofibrils were adsorbed as cationic aggregates a non-uniform and more rigid layer was adsorbed. Paper sheets were prepared using both the bi-layer and nano-aggregate adding strategy of the nanofibrils and PAE. When PAE and nanofibrils were adsorbed on pulp fibres as a bi-layer system significant increase in both wet and dry tensile strength of paper could be achieved even at low added amounts of PAE. When the substances were added as nano-aggregates the improvements in paper strength properties were not as significant. Bulk and surface nitrogen content analyses of the paper samples showed that the adding strategy does not affect the total adsorbed amount of PAE but it has a strong effect on distribution of substances in the paper matrix which has a crucial effect on paper wet and dry strength development.     

Biocomposites of plasticized starch reinforced with cellulose crystallites from cottonseed linter

Environmentally friendly starch biocomposites were successfully developed using a colloidal suspension of cottonseed linter cellulose crystallite as a filler to reinforce glycerol plasticized starch (PS). The cellulose crystallites, having lengths of 350 +/- 70 nm and diameters of 40 +/- 8 nm on average, were prepared from cottonseed linters by acid hydrolysis. The dependence of morphology and properties of the PS-based biocomposites on cellulose crystallites content in the range from 0 to 30 wt.-% was investigated by scanning electron microscopy, differential scanning thermal analysis, dynamic mechanical thermal analysis, and measurements of mechanical properties and water absorption. The results indicate that the strong interactions between fillers and between the filler and PS matrix play a key role in reinforcing the resulting composites. The PS/cellulose crystallite composites, conditioned at 50% relative humidity, undergo an increase in both tensile strength and Young's modulus from 2.5 MPa for PS film to 7.8 MPa and from 36 MPa for PS film to 301 MPa. Further, incorporating cottonseed linter cellulose crystallites into PS matrix leads to an improvement in water resistance for the resulting biocomposites. The mechanical behaviors of the starch-based biocomposites as a function of cellulose crystallites content.     

Evaluation of filler particle size within polymer matrix by optical spectroscopy

Polymer composites with inorganic fillers of different nature, concentration, particle size and shape were studied by optical spectroscopy (UV, visible, and IR ranges), optical and electron microscopy, and dynamic light scattering. An experiment to determine the size of the filler particles in aqueous suspension in the polymer matrix of a composite and directly in powders was conducted. It was shown that with increasing concentration aggregation of particles on drying an aqueous slurry occurs to a greater extent than for the filler in the polymer composite. It was demonstrated by examples that the optical spectroscopy can be successfully used for the analysis of sub-micron and micron sized filler particles in a polymer matrix or suspension.     

Interactions and dispersion stability of aluminum oxide colloidal particles in electroless nickel solutions in the presence of comb polyelectrolytes

The effect of comb polyelectrolytes on the dispersion stability of colloidal alumina particles in DI water and commercial electroless nickel (EN) solutions was investigated. Adsorption of polyelectrolytes and major EN components onto colloidal alumina was assessed by TGA, chemical analysis, and zeta potential measurements. Zeta potential measurements were made during titrations of comb-polyelectrolyte-stabilized dispersions with EN solutions to full ionic strength for the first time. The compilation of titration curves made with varying amounts of comb polyelectrolytes provides high resolution and novel insight into the particle/surfactant/EN systems. Continuous decrease in particle/EN components surface interactions with the increase in comb polyelectrolyte coverage is observed. Laser diffraction measurements reveal steric stabilization of nano- and submicronmeter alumina dispersions in both DI water and EN solutions with >7 wt% and >2 wt% comb polyelectrolyte, respectively.     

IR spectroscopic study of polymer blends and composites: A new approach

The particle size distributions of fillers in the films of polymer composites and blends have been investigated by IR spectroscopy and optical and electron microscopy. A new effective spectroscopic technique is proposed for determining the particle concentration, average size, and size distribution of the filler and the character of aggregation of these particles in the bulk of the polymer matrix. The proposed technique is based on the analysis of IR radiation intensity attenuation due to light scattering on filler particles in the polymer matrix. The spectroscopic data are in good agreement with the results of microscopic experiments.     

碳酸钙与碳化硅对室温硫化硅橡胶的补强作用

在有关硅橡胶补强的研究中,人们已经对ＳｉＯ２ 等补强性填料对硅橡胶的补强作用进行了深入的研究,但对非补强填料对室温硫化硅橡胶的补强作用则相对涉及较少．作者研究了ＣａＣＯ３ 和ＳｉＣ 两类非补强性填料以及填料的粒径与分布对室温硫化硅橡胶拉伸强度、断裂伸长率和耐温性能等的影响,发现合适粒径的非补强性填料对室温硫化硅橡胶有较好的补强效果,且在填料粒径及分布匹配时有最好的补强效果,选用ＳｉＣ时还可以有效提高室温硫化硅橡胶的热稳定性．     

The Impact of Filler Geometry on Polylactic Acid-Based Sustainable Polymer Composites

Recently, biocomposites have emerged as materials of great interest to the scientists and industry around the globe. Among various polymers, polylactic acid (PLA) is a popular matrix material with high potential for advanced applications. Various particulate materials and nanoparticles have been used as the filler in PLA based matrix. One of the extensively studied filler is cellulose. However, cellulose fibres, due to their hydrophilic nature, are difficult to blend with a hydrophobic polymer matrix. This leads to agglomeration and creates voids, reducing the mechanical strength of the resulting composite. Moreover, the role of the various forms of pure cellulose and its particle shape factors has not been analyzed in most of the current literature. Therefore, in this work, materials of various shapes and shape factors were selected as fillers for the production of polymer composites using Polylactic acid as a matrix to fill this knowledge gap. In particular, pure cellulose fibres (three types with different elongation coefficient) and two mineral nanocomponents: precipitated calcium carbonate and montmorillonite were used. The composites were prepared by a melt blending process using two different levels of fillers: 5% and 30%. Then, the analysis of their thermomechanical and physico-chemical properties was carried out. The obtained results were presented graphically and discussed in terms of their shape and degree of filling.     

Dispersion evaluation of microcrystalline cellulose/cellulose nanofibril-filled polypropylene composites using thermogravimetric analysis

Microcrystalline cellulose-filled polypropylene (PP) composites and cellulose nanofiber-filled composites were prepared by melt blending. The compounded material was used to evaluate dispersion of cellulose fillers in the polypropylene matrix. Thermogravimetric analysis (TG) and mechanical testing were conducted on composites blended multiple times and the results were compared with single batch melt blended composites. The residual mass, tensile strength, and coefficient of variance values were used to evaluate dispersion of the microcrystalline cellulose fillers in the PP matrix. The potential of using TG to evaluate cellulose nanofiber-filled thermoplastic polymers was also investigated and it was found that the value and variability of residual mass after TG measurements can be a criterion for describing filler dispersion. A probabilistic approach is presented to evaluate the residual mass and tensile strength distribution, and the correlation between those two properties. Both the multiple melt blending and single batch composites manufactured with increased blending times showed improved filler dispersion in terms of variation and reliability of mechanical properties. The relationship between cellulose nanofiber loading and residual mass was in good agreement with the rule of mixtures. In this article, the authors propose to use a novel method for dispersion evaluation of natural fillers in a polymer matrix using TG residual mass analysis. This method can be used along with other techniques such as scanning electron microscope (SEM), transmission electron microscope (TEM), and X-ray diffraction (XRD) for filler dispersion evaluation in thermoplastic composites.     

Electrophoretic mobility of cylindrical soft particles

 A general theory for the electrophoresis of a cylindrical soft particle (i.e., a cylindrical hard colloidal particle coated with a layer of ion-penetrable polyelectrolytes) in an electrolyte solution in an applied transverse or tangential electric field is proposed. This theory unites two different electrophoresis theories for cylindrical hard particles and for cylindrical polyelectrolytes. That is, the general mobility expression obtained in this paper tends to the mobility expression for a cylindrical hard particle for the case where the polyelectrolyte layer is absent or the frictional coefficient in the poly-electrolyte layer becomes infinity, whereas it tends to that for a cylin-drical polyelectrolyte in the absence of the particle core. Simple approximate analytic mobility expressions are also presented. Received: 29 August 1996 Accepted: 7 November 1996     

Model filled rubber. II. Particle composition dependence of suspension rheology

Monodisperse size colloidal particles varying in chemical composition were synthesized by emulsifier‐free emulsion polymerization. Using a stress‐controlled rheometer, the rheological behavior of colloidal suspensions in a low molecular weight liquid polysulfide was investigated. All suspensions exhibited shear thinning behavior. The shear viscosity, dynamic moduli, and yield stress increased as interactions between particles and matrix increased. The rheological properties associated with network buildup in the suspensions were sensitively monitored by a kinetic recovery experiment. We propose that interfacial interactions by polar and hydrogen bonding between particles and matrix strongly promote affinity of matrix polymer to the filler particles, resulting in adsorption or entanglement of polymer chains on the filler surface. A network structure was formed consisting of particles with an immobilized polymer layer on the particle surface with each particle floc acting as a temporary physical crosslinking site. As the interfacial interaction increases, the adsorbed layer thickness on the filler particles, hence, the effective particle volume fraction, increases. As a result, the rheological properties were enhanced in the order PS < PMMA < PSVP. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 815–824, 1999