Synthesis of High-Molecular-Weight Poly(ether-alt-ester) by Selective Double Ring-Opening Polymerization of Spiroorthoesters.

We report the selective double ring-opening polymerization of presequenced spiroorthoester monomers to form high-molecular-weight (≈90 kDa) poly(ether-alt-ester)s with a simple cationic alkyl gallium catalyst. The selective formation of double ring-opened polymer units was confirmed by NMR and IR spectroscopies. Thermal and rheological properties of homo- and copolymers were further characterized by differential scanning calorimetry, thermogravimetric analysis, and stress-controlled rotational rheometry. Linear viscoelastic moduli show that these systems are well entangled (plateau modulus), thereby possessing nearly terminal relaxation at long time scales (low frequencies) and Rouse segmental dynamics at short time scales (high frequencies) with characteristic slopes. These are the highest-molecular-weight poly(ether-alt-ester)s reported to date.

Impact of counterion valency on the rheology of sulfonated cellulose nanocrystal hydrogels.

A systematic rheological study on the influence of valency of different counterions on the properties of CNC hydrogels was carried out. Rheo-polarized microscopy was used to prove that preshear of 500 s-1 for 1 min is adequate to completely breakdown agglomerates in the suspension. Furthermore, a rest period of 30 min is sufficient to recover the equilibrium structure of hydrogels. Changing counterions from monovalent (Na+, K+, Li+), to divalent (Mg2+, Ca2+) and to trivalent (Al3+) influenced the network formation. CNC suspensions with monovalent counterions are isotropic at 3 wt%, anisotropic with chiral nematic structures at 5 wt% and form birefringent gels at 7 wt%. Conversely, divalent and trivalent counterions facilitate network formation, leading to gel like behavior at all concentrations. Sonication of CNC samples with monovalent counterions lowers the viscosity by two orders of magnitude while the opposite is true for multivalent counterions due to the formation of strong networks. The varying rheological properties displayed from CNCs with different counter ions may influence the use of CNC as rheological modifiers in fluid-based applications.

Photocross-Linked Antimicrobial Amino-Siloxane Elastomers.

Mechanically robust bulk antimicrobial polymers are one way to address disease transmission via contaminated surfaces. Here, we demonstrate the visible light photo-oxidative cross-linking of amine-containing PDMS using a single-component, solvent-free system where amines have a dual role as antimicrobial functionalities and cross-linking sites. Rose Bengal, a xanthene dye used as a fluorescent stain, is thermally reacted with the polymer to give a solvent-free liquid siloxane that can generate reactive singlet oxygen upon aerobic green light irradiation, coupling the amine functionalities into imine cross-links. Photorheological experiments demonstrate that light intensity is the largest kinetic factor in the photo-oxidative curing of these polymers. Room temperature irradiation under an ambient atmosphere results in free-standing elastic materials with mechanical properties that depend on the amount of Rose Bengal present. An ultimate elongation strain of 117% and Young's modulus of 2.15 MPa were observed for the highest dye loading, with both mechanical properties found to be higher than those for the same solution-based dye amounts. We demonstrate that the solvent-free nature of the material can be exploited to generate 3D structures using low-temperature deposition as well as direct-write patterning and photolithography on glass substrates. The antimicrobial activity was investigated, with the cross-linked material demonstrating greater efficacy against E. coli (Gram negative) compared with MRSA (Gram positive) bacterial strains and inducing complete cell lysis of incubated CHO-K1 mammalian cells, demonstrating applicability as a mechanically robust single-component antimicrobial elastomer.

Rheological characterization of CNC-CTAB network below and above critical micelle concentration (CMC).

The network of Cellulose Nanocrystal (CNC) suspension is explored below and above the critical micelle concentration (CMC), in the presence of cetyltrimethylammonium bromide (CTAB) with a positively charged head using TEM imaging and rheological characterization. CNC-CTAB gels show shear thinning behavior, complex relationship between strain amplitudes and CTAB concentration, diminishing thixotropic behavior as a function of CTAB and single and two yielding stress maxima as a function of CTAB, resulting from different microstructure below and above the critical Micelle Concentration (CMC) of CTAB. Comparing the flow curves of CNC-CTAB suspension/gel revealed the role played by CTAB content, CNC concentration and sonication energy in strengthening of the network. We analyzed and obtained yield stress from steady shear, creep testing and oscillatory experiments and compared them.

Rheological Properties Related to Extrusion of Polyolefins.

Rheological properties related to the extrusion of polyolefins are the shear viscosity, the elongational viscosity, the slip velocity and their temperature- and pressure-dependencies. These properties are measured in the rheology lab mainly via a parallel-plate rheometer and a capillary rheometer. Then appropriate rheological models have to be used to account for all these properties. Such models are either viscous (e.g, the Cross model) or viscoelastic (e.g, the K-BKZ model). The latter gives the best fitting of the experimental data and offers excellent results in numerical simulations, especially in extrusion flows. Wall slip effects are also found and measured by rheometric flows. Modeling of extrusion flows should make use of appropriate slip models that take into effect the various slip parameters, including the effects of shear stress, molecular characteristics, temperature and pressure on the slip velocity. In this paper the importance of these properties in extrusion are discussed.

Toward Biodegradable Electronics: Ionic Diodes Based on a Cellulose Nanocrystal-Agarose Hydrogel.

Bioderived cellulose nanocrystals (CNCs) are used to create light, flexible, biocompatible, and biodegradable electronic devices. Herein, surface modification of cellulose nanocrystals was employed to fabricate cationic and anionic CNCs. Subsequently, we demonstrated rectification behavior from a fixed junction between two agarose hydrogels doped with cationic and anionic cellulose nanocrystals. The current rectification ratio reaches 70 reproducibly, which is significantly higher than that for analogous diodes generated with microfibrillated cellulose (∼15) and the first polyelectrolyte gel diode (∼40). The current-voltage characteristics of the CNC-hydrogel diode are influenced by concentration, gel thickness, scanning frequency, and applied voltage. The high surface area of CNC resulted in high charge density after surface modification, which in turn resulted in good rectification behavior from only small amounts of dopant material.

Effect of Ionic Surfactants on the Viscoelastic Properties of Chiral Nematic Cellulose Nanocrystal Suspensions.

The gelation of cellulose nanocrystal (CNC) suspensions is explored in the presence of two ionic surfactants, namely, sodium dodecyl sulfate (SDS) with a negatively charged head and cetyltrimethylammonium bromide (CTAB) with a positively charged head. The viscosity profile of pure CNC suspensions indicated that at concentrations greater than 5 wt %, they exhibit gel-like behavior, where the viscosity shows a single shear-thinning profile. However, at concentrations lower than 1 wt %, the suspension shows isotropic behavior and experiences a transition to chiral nematic biphasic domains at increasing CNC concentration. In addition, the effect of CTAB, SDS, and NaCl on the surface charge of CNCs is analyzed and coupled with rheological measurements in order to study the relative importance of surfactants and ionic strength on the viscoelastic properties of the CNC suspensions. The mechanism of CNC/surfactants and CNC/CNC interactions leading to the gelation of CNC suspensions is also investigated. It was found that the addition of both ionic surfactants results in the gelation of biphasic chiral nematic CNC suspensions by fostering cross-linking between individual CNCs at smaller concentrations. In the case of CTAB, a gradual and ongoing increase in the viscoelastic moduli was observed with the increase of surfactant concentration, implying the induction of dominant attractive forces between CNCs by surfactant molecules. However, the presence of SDS stimulates both attractive and repulsive forces whose relative dominance controls the viscoelastic properties and gelation.

Poisson-Boltzmann modeling and molecular dynamics simulations of polyelectrolyte gel diodes in the static regime.

We present molecular dynamics (MD) simulations of a model polyelectrolyte gel diode formed by a junction of two oppositely charged crosslinked polyelectrolyte networks, and compare the ion densities and electrostatic field to a corresponding continuum Poisson-Boltzmann (PB) model. At low electrostatic coupling strength (i.e. low Bjerrum lengths), the PB model reproduces the MD simulation results for density and electric field throughout the gel very well. At higher electrostatic coupling (i.e. large Bjerrum lengths) and higher degrees of ionization, the standard PB fails to predict the MD profiles at the diode interface due to counterion condensation, network collapse and field-induced gel deformation. In fact MD simulations predict that the rectifying behavior of diodes operating in such regimes will be much reduced. We develop a modified PB model that accounts for these effects, and show that it produces better agreement with the MD results. The updated PB model can be used for improved modeling of experimental results on PE gel diodes.

Freeze-Thaw Gelation of Cellulose Nanocrystals.

Gels are attractive for applications in drug delivery, tissue engineering, and 3D printing. Here, physical colloidal gels were prepared by freeze-thaw (FT) cycling of cellulose nanocrystal (CNC) suspensions. The aggregation of CNCs was driven by the physical confinement of CNCs between growing ice crystal domains. FT cycling was employed to form larger aggregates of CNCs without changing the surface chemistry or ionic strength of the suspensions. Gelation of CNC suspensions by FT cycling was demonstrated in water and other polar solvents. The mechanical and structural properties of the gels were investigated using rheometry, electron microscopy, X-ray diffraction, and dynamic light scattering. We found that the rheology could be tuned by varying the freezing time, the number of FT cycles, and concentration of CNCs in suspension.

The sol-gel transition of ultra-low solid content TEMPO-cellulose nanofibril/mixed-linkage ß-glucan bionanocomposite gels.

We present the preparation, morphological analysis, and rheological characterization of ultra-low solid content gels prepared by physically cross-linking TEMPO-oxidized cellulose nanofibrils (TEMPO-CNF) with the soluble plant-cell-wall polysaccharide, mixed-linkage ß-glucan (MLG). Of particular note, gel formation was rapidly induced by very small amounts of MLG (e.g. 0.125% w/v) at extremely low TEMPO-CNF concentration (0.05% w/v), which independently were otherwise fluid and thus easily handled. Rheology of these bionanocomposite gel systems as a function of MLG and TEMPO-CNF concentrations revealed that the critical gel concentration of MLG and TEMPO-CNF followed a power-law relation of the concentration of the other component. Surprisingly, these systems also exhibited an additional transition to thick gels at high TEMPO-CNF and MLG concentrations that was visible only at low frequencies. Cryogenic scanning electron microscopy (cryo-SEM) imaging of admixture solutions and gels revealed increased network crowding with increasing MLG amounts. The data are consistent with the hypothesis that non-covalent cellulose-MLG interactions, analogous to those occurring within plant cell walls, drive gel formation. The ability to tune gel physical properties simply by controlling CNF (a promising forest bioproduct) and MLG (a readily available agricultural polysaccharide) fractions at very low solid and polymer content opens new possibilities for material applications in diverse industries.

Molecular simulations of the piezoionic effect.

We present a molecular dynamics study of two polyelectrolyte gels with different degrees of ionization coupled in a slab geometry. Our simulations show that a pressure gradient emerges between the two gels that results in the buildup of a Nernst-Donnan potential. This methodology is reverse to experiments of the piezoionic or mechanoelectric effect, in which an electric potential gradient appears upon application of a pressure gradient to a hydrogel. The Nernst-Donnan potential at the interface is found to scale linearly with temperature with the coefficient of proportionality given by the fraction of concentrations of the uncondensed counterions. We show that the potential difference can also be expressed as a linear function of the lateral pressure, thus providing a molecular interpretation of the piezoionic effect.

A stimulus-responsive, in situ-forming, nanoparticle-laden hydrogel for ocular drug delivery.

Most medications targeting optic neuropathies are administered as eye drops. However, their corneal penetration efficiencies are typically < 5%. There is a clear, unmet need for novel transcorneal drug delivery vehicles. To this end, we have developed a stimulus-responsive, in situ-forming, nanoparticle-laden hydrogel for controlled release of poorly bioavailable drugs into the aqueous humor of the eye. The hydrogel is formulated as a composite of hyaluronic acid (HA) and methylcellulose (MC). The amphiphilic nanoparticles are composed of poly(ethylene oxide) (PEO) and poly(lactic acid) (PLA). Experimental design aided the identification of hydrogel composition and nanoparticle content in the formulation, and the formulation reliably switched between thixotropy and temperature-dependent rheopexy when it was tested in a rheometer under conditions that simulate the ocular surface, including blinking. These properties should ensure that the formulation coats the cornea through blinking of the eyelid and facilitate application of the medication as an eye drop immediately prior to the patient's bedtime. We subsequently tested the efficacy of our formulation in whole-eye experiments by loading the nanoparticles with cannabigerolic acid (CBGA). Our formulation exhibits over a 300% increase in transcorneal penetration over control formulations. This work paves the way for the introduction of novel products targeting ocular diseases to the market.

Antifouling Biomimetic Liquid-Infused Stainless Steel: Application to Dairy Industrial Processing.

Fouling is a widespread and costly issue, faced by all food-processing industries. Particularly, in the dairy sector, where thermal treatments are mandatory to ensure product safety, heat-induced fouling represents up to 80% of the total production costs. Significant environmental impacts, due the massive consumption of water and energy, are also to deplore. Fouling control solutions are thus desperately needed, as they would lead to substantial financial gains as well as tremendous progress toward eco-responsible processes. This work aims at presenting a novel and very promising dairy fouling-mitigation strategy, inspired by nature, and to test its antifouling performances in real industrial conditions. Slippery liquid-infused surfaces were successfully designed directly on food grade stainless steel, via femtosecond laser ablation, followed by fluorosilanization and impregnation with an inert perfluorinated oil. Resulting hydrophobic surfaces (water contact angle of 112°) exhibited an extremely slippery nature (contact angle hysteresis of 0.6°). Outstanding fouling-release performances were obtained for these liquid-infused surfaces as absolutely no trace of dairy deposit was found after 90 min of pasteurization test in pilot-scale equipment followed by a short water rinse.

Slip of polymer melts over micro/nano-patterned metallic surfaces.

The slip behavior of high-density polyethylenes (HDPEs) is studied over surfaces of different topology and surface energy. Laser ablation has been used to micro/nano-pattern the surface of dies in order to examine the effect of surface roughness on slip. In addition, fluoroalkyl silane-based coatings on smooth and patterned substrates were used to understand the effect of surface energy on slip. Surface roughness and surface energy effects were incorporated into the double reptation slip model (Ebrahimi et al., J. Rheol., 2015, 59, 885-901) in order to predict the slip velocity of studied polymers on different substrates. It was found that for dies with rough surfaces, polymer melt penetrates into the cavities of the substrate (depending on the depth and the distance between the asperities), thus decreasing wall slip. On the other hand, silanization of the surface increases the slip velocity of polymers in the case of smooth die, although it has a negligible effect on rough dies. Interestingly, the slip velocity of the studied polymers on various substrates of different degrees of roughness and surface energy, were brought into a mastercurve by modifying the double reptation slip velocity model.

The Role of Nitrogen Donors in Zinc Catalysts for Lactide Ring-Opening Polymerization.

The electronic effects of nitrogen donors in zinc catalysts for ring-opening polymerization of cyclic esters were investigated. Alkyl and benzyloxy zinc complexes supported by tridentate diamino- and aminoimino phenolate ligands were synthesized, and their solid-state and solution structures characterized. The solution-state structures showed that the alkyl complexes are mononuclear, while the alkoxy complexes are dimeric with the ligands coordinated with different denticities depending on the nature of the ligand donors. The catalytic activities of these compounds toward the ring-opening polymerization of racemic lactide were studied and showed that catalysts with secondary and imine nitrogen donors are more active than analogues with tertiary amines.

Chemical, physical and morphological properties of bacterial biofilms affect survival of encased Campylobacter jejuni F38011 under aerobic stress.

Campylobacter jejuni is a microaerophilic pathogen and leading cause of human gastroenteritis. The presence of C. jejuni encased in biofilms found in meat and poultry processing facilities may be the major strategy for its survival and dissemination in aerobic environment. In this study, Staphylococcus aureus, Salmonella enterica, or Pseudomonas aeruginosa was mixed with C. jejuni F38011 as a culture to form dual-species biofilms. After 4days' exposure to aerobic stress, no viable C. jejuni cells could be detected from mono-species C. jejuni biofilm. In contrast, at least 4.7logCFU/cm2 of viable C. jejuni cells existed in some dual-species biofilms. To elucidate the mechanism of protection mode, chemical, physical and morphological features of biofilms were characterized. Dual-species biofilms contained a higher level of extracellular polymeric substances with a more diversified chemical composition, especially for polysaccharides and proteins, than mono-species C. jejuni biofilm. Structure of dual-species biofilms was more compact and their surface was >8 times smoother than mono-species C. jejuni biofilm, as indicated by atomic force microscopy. Under desiccation stress, water content of dual-species biofilms decreased slowly and remained at higher levels for a longer time than mono-species C. jejuni biofilm. The surface of all biofilms was hydrophilic, but total surface energy of dual-species biofilms (ranging from 52.5 to 56.2mJ/m2) was lower than that of mono-species C. jejuni biofilm, leading to more resistance to wetting by polar liquids. This knowledge can aid in developing intervention strategies to decrease the survival and dispersal of C. jejuni into foods or environment.

Hydrothermal Gelation of Aqueous Cellulose Nanocrystal Suspensions.

We report the facile preparation of gels from the hydrothermal treatment of suspensions of cellulose nanocrystals (CNCs). The properties of the hydrogels have been investigated by rheology, electron microscopy, and spectroscopy with respect to variation in the temperature, time, and CNC concentration used in preparation. Desulfation of the CNCs at high temperature appears to be responsible for the gelation of the CNCs, giving highly porous networks. The viscosity and storage modulus of the gels was shown to increase when samples were prepared at higher treatment temperature. Considering the wide natural abundance and biocompatibility of CNCs, this simple, green approach to CNC-based hydrogels is attractive for producing materials that can be used in drug delivery, insulation, and as tissue scaffolds.

Effect of Extreme Wettability on Platelet Adhesion on Metallic Implants: From Superhydrophilicity to Superhydrophobicity.

In order to design antithrombotic implants, the effect of extreme wettability (superhydrophilicity to superhydrophobicity) on the biocompatibility of the metallic substrates (stainless steel and titanium) was investigated. The wettability of the surface was altered by chemical treatments and laser ablation methods. The chemical treatments generated different functionality groups and chemical composition as evident from XPS analysis. The micro/nanopatterning by laser ablation resulted in three different pattern geometry and different surface roughness and consequently wettability. The patterned surface were further modified with chemical treatments to generate a wide range of surface wettability. The influence of chemical functional groups, pattern geometry, and surface wettability on protein adsorption and platelet adhesion was studied. On chemically treated flat surfaces, the type of hydrophilic treatment was shown to be a contributing factor that determines the platelet adhesion, since the hydrophilic oxidized substrates exhibit less platelet adhesion in comparison to the control untreated or acid treated surfaces. Also, the surface morphology, surface roughness, and superhydrophobic character of the surfaces are contributing factors to platelet adhesion on the surface. Our results show that superhydrophobic cauliflower-like patterns are highly resistant to platelet adhesion possibly due to the stability of Cassie-Baxter state for this pattern compared to others. Our results also show that simple surface treatments on metals offer a novel way to improve the hemocompatibility of metallic substrates.

Enhanced Barrier Performance of Engineered Paper by Atomic Layer Deposited Al2O3 Thin Films.

Surface modification of cellulosic paper is demonstrated by employing plasma assisted atomic layer deposition. Al2O3 thin films are deposited on paper substrates, prepared with different fiber sizes, to improve their barrier properties. Thus, a hydrophobic paper is created with low gas permeability by combining the control of fiber size (and structure) with atomic layer deposition of Al2O3 films. Papers are prepared using Kraft softwood pulp and thermomechanical pulp. The cellulosic wood fibers are refined to obtain fibers with smaller length and diameter. Films of Al2O3, 10, 25, and 45 nm in thickness, are deposited on the paper surface. The work demonstrates that coating of papers prepared with long fibers efficiently reduces wettability with slight enhancement in gas permeability, whereas on shorter fibers, it results in significantly lower gas permeability. Wettability studies on Al2O3 deposited paper substrates have shown water wicking and absorption over time only in papers prepared with highly refined fibers. It is also shown that there is a certain fiber size at which the gas permeability assumes its minimum value, and further decrease in fiber size will reverse the effect on gas permeability.

Slip mechanisms in complex fluid flows.

The classical no-slip boundary condition of fluid mechanics is not always a valid assumption for the flow of several classes of complex fluids including polymer melts, their blends, polymer solutions, microgels, glasses, suspensions and pastes. In fact, it appears that slip effect in these systems is the rule and not the exemption. The occurrence of slip complicates the analysis of rheological data, although it provides new opportunities to understand their behavior in restricted environments delineating additional molecular mechanisms i.e. entropic restrictions due to limitations in the number of molecular conformations. This article discusses these complexities and provides future research opportunities.