The Effect of Cellulose Nanocrystal Reassembly on Latex-Based Pressure-Sensitive Adhesive Performance.

Different cellulose nanocrystal (CNC) forms (dried vs never-dried) can lead to different degrees of CNC reassembly, the formation of nanofibril-like structures, in nanocomposite latex-based pressure-sensitive adhesive (PSA) formulations. CNC reassembly is also affected by CNC sonication and loading as well as the protocol used for CNC addition to the polymerization. In this study, carboxylated CNCs (cCNCs) were incorporated into a seeded, semibatch, 2-ethylhexyl acrylate/methyl methacrylate/styrene emulsion polymerization and cast as pressure-sensitive adhesive (PSA) films. The addition of CNCs led to a simultaneous increase in tack strength, peel strength, and shear adhesion, avoiding the typical trade-off between the adhesive and cohesive strength. Increased CNC reassembly resulted from the use of dried, redispersed, and sonicated cCNCs, along with increased cCNC loading and addition of the cCNCs at the seed stage of the polymerization. The increased degree of CNC reassembly was shown to significantly increase the shear adhesion by enhancing the elastic modulus of the PSA films.

CO2-Switchable colloids.

The development and design of CO2-switchable colloidal particles is described. A presentation of the principles of CO2 switching, especially as they apply to colloids, is followed by recent progress in the preparation of several types of colloidal particles (polymer nanoparticles, metal-organic frameworks (MOFs), quantum dots, graphene, cellulose nanocrystals, carbon nanotubes) for various applications (Pickering stabilizers, catalysts, latexes), and our perspective on future opportunities.

CO2-Responsive Low Molecular Weight Polymer with High Osmotic Pressure as a Draw Solute for Forward Osmosis.

A key challenge in the development of forward osmosis (FO) technology is to identify a suitable draw solute that can generate a large osmotic pressure with favorable water flux while being easy to recover after the FO process with a minimum of energy expenditure. While the CO2- and thermo-responsive linear poly(N,N-dimethylallylamine) polymer (l-PDMAAm) has been reported as a promising draw agent for forward osmosis desalination, the draw solutions sufficiently concentrated to have high osmotic pressure were too viscous to be usable in industrial operations. We now compare the viscosities and osmotic pressures of solutions of these polymers at low and high molecular weights and with/without branching. The best combination of high osmotic pressures with low viscosity can be obtained by using low molecular weights rather than branching. Aqueous solutions of the synthesized polymer showed a high osmotic pressure of 170 bar under CO2 (πCO2) at 50 wt% loading, generating a high water flux against NaCl feed solutions in the FO process. Under air, however, the same polymer showed a low osmotic pressure and a cloud point between 26 and 33 °C (depending on concentration), which facilitates the recovery of the polymer after it has been used as a draw agent in the FO process upon removal of CO2 from the system.

Polysaccharide-Based Nanoparticles as Pickering Emulsifiers in Emulsion Formulations and Heterogenous Polymerization Systems.

Bio-based Pickering emulsifiers are a nontoxic alternative to surfactants in emulsion formulations and heterogenous polymerizations. Recent demand for biocompatible and sustainable formulations has accelerated academic interest in polysaccharide-based nanoparticles as Pickering emulsifiers. Despite the environmental advantages, the inherent hydrophilicity of polysaccharides and their nanoparticles limits efficiency and application range. Modification of the polysaccharide surface is often required in the development of ultrastable, functional, and water-in-oil (W/O) systems. Complex surface modification calls into question the sustainability of polysaccharide-based nanoparticles and is identified as a significant barrier to commercialization. This review summarizes the use of nanocelluloses, -starches, and -chitins as Pickering emulsifiers, highlights trends and best practices in surface modification, and provides recommendations to expedite commercialization.

Polymer Colloids: Synthesis Fundamentals to Applications.

This special issue of Biomacromolecules highlights research from The International Polymer Colloid Group (IPCG), which was founded in 1972 as a forum for the exchange of ideas and emerging research activities for scientists and engineers from both academia and industry who study or use polymer colloids. The increasing relevance of polymeric structures with colloidal dimensions to biomacromolecules research provided the impetus for organizing this special issue. The IPCG is composed of over 120 researchers from over 20 countries who are elected to membership. Activities comprise annual symposia including a biennial International Polymer Colloid Group Research Conference and a semiannual newsletter that incorporates a summary of recent (including unpublished) research results from our members.

Surface Modification of Cellulose Nanocrystals via RAFT Polymerization of CO2-Responsive Monomer-Tuning Hydrophobicity.

Cellulose nanocrystals (CNCs) were converted into a CO2-responsive composite nanomaterial by grafting poly(dimethylaminoethyl methacrylate) (PDMAEMA), poly(diethylaminoethyl methacrylate) (PDEAEMA), and poly(diisopropylaminoethyl methacrylate) (PDPAEMA) onto its surface using both grafting-to and grafting-from approaches. The zeta potential (ζ) of the graft-modified CNC could be reversibly switched by protonation/deprotonation of the tertiary amine groups simply by sparging with CO2 and N2, respectively. Depending on the grafting density and the molecular weight of the polymer grafts, CNC can form stable aqueous dispersions at either mildly acidic pH (under CO2) or mildly basic (under N2) conditions. Moreover, it was also determined that the CNC hydrophobicity, assessed using phase-shuttling experiments at different pH values, was also dependent on both the grafting density and molecular weight of the polymer grafts, thereby making it possible to easily tune CNC dispersibility and/or hydrophobicity.

Graft Modification of Starch Nanoparticles Using Nitroxide-Mediated Polymerization and the "Grafting to" Approach.

Starch nanoparticles (SNP) were modified with synthetic polymers using the "grafting to" approach and nitroxide-mediated polymerization. SG1-capped poly(methyl methacrylate-co-styrene) (P(MMA-co-S)) copolymers with low dispersity and high degree of livingness were first synthesized in bulk. These macroalkoxyamines were then grafted to vinyl benzyl-functionalized SNP to obtain biosynthetic hybrids. The grafted materials, SNP-g-P(MMA-co-S), were characterized by 1H NMR, FTIR, TGA, and elemental analysis. The total amount of grafted polymer and the grafting efficiency were evaluated for different molecular weights (5870-12150 g·mol-1) of the grafted polymer, the polymer addition approach (batch or semibatch) and the initial polymer loading (2.5, 5, or 10 g polymer/g SNP). The proposed approach presented in this work to graft modify SNP allows for a precise surface modification of the nanoparticles, while permitting that the final properties of the resulting biohybrid to be tunable according to the choice of polymer grafted.

Microsuspension Polymerization of Styrene Using Cellulose Nanocrystals as Pickering Emulsifiers: On the Evolution of Latex Particles.

We report a mechanistic study of the microsuspension polymerization of styrene stabilized by cellulose nanocrystals (CNCs) in its native form as well as graft-modified with copolymers of styrene and N-3-(dimethylamino)propyl methacrylamide (DMAPMAm) or N,N-(diethylamino)ethyl methacrylate (DEAEMA). Native CNCs and graft-modified CNCs were shown to form stable styrene emulsions with an average droplet diameter of 18-20 and 5-9 µm, respectively. Initiators of widely varying water solubilities [2,2'-azobisisobutyronitrile (AIBN), 2-2'-azobis(2,4-dimethylvaleronitrile) (Vazo-52), and lauroyl peroxide (LPO)] were employed for the polymerizations. The type of initiator and the type of CNC were shown to directly affect the microsuspension polymerization kinetics, particle size, and molecular weight distribution. Using AIBN and Vazo-52, submicron latex particles were observed in the final latex in addition to the desired 3-20 µm CNC-armored microsuspension particles. The resulting latex and microsuspension polystyrene particles were studied for their CNC coverage and surface charge. We found that the presence of CNCs in the aqueous phase did not lead to Pickering emulsion polymerization by heterogeneous nucleation.

Graft modification of starch nanoparticles using nitroxide-mediated polymerization and the grafting from approach.

Starch nanoparticles (SNP) are attracting increased attention as a renewable bio-based alternative to petroleum-based polymers in the materials community. In this work, we describe the grafting from of SNP with synthetic polymers via nitroxide-mediated polymerization (NMP). Varying amounts of poly(methyl methacrylate-co-styrene) (P(MMA-co-S)), poly(methyl acrylate) (PMA) and poly(acrylic acid) (PAA) were grafted from the surface of SNP in a three-step process. The grafting of synthetic polymers from the surface of SNP was confirmed by FTIR, 1H NMR, elemental analysis and thermogravimetric analysis. These new tailor-made starch-based hybrid materials could find use in paper coatings, adhesives, paints, as well as in polymer latex applications.

Synthesis of Diblock and Triblock Polymers from Cyclooctadiene and Norbornene Via ROMP in Miniemulsion.

The synthesis of diblock and triblock linear polyolefins via ring opening metathesis polymerization (ROMP) in an aqueous nanoparticle dispersion is presented. The different block polyolefins are synthesized from the cyclic olefins 1,5-cyclooctadiene and norbornene (NB), using a water-soluble TEGylated ruthenium alkylidene catalyst, yielding the structures PCOD-b-PNB, PNB-b-PCOD, and PCOD-b-PNB-b-PCOD. High monomer conversion (>90%), monitored by NMR, is achieved in relatively short times (≈1 h) for the polymerization of each block. The livingness of the system, essential to obtain block copolymers, is confirmed by gel permeation chromatography. Latex particles' size during the multiple steps range between 90 and 150 nm. The results demonstrate that it is possible to obtain nanoparticle latexes from ROMP-based monomers with block copolymer architectures, creating the opportunity to copolymerize olefins bearing different functional groups for the synthesis of new materials.

Grafting from Starch Nanoparticles with Synthetic Polymers via Nitroxide-Mediated Polymerization.

Nitroxide-mediated polymerization (NMP) is employed to graft synthetic polymers from polysaccharides. This work demonstrates the first successful polymer grafting from starch nanoparticles (SNPs) via NMP. To graft synthetic polymers from the SNPs' surface, the SNPs are first functionalized with 4-vinylbenzyl chloride prior to reaction with BlocBuilder MA yielding a macroinitiator. Methyl methacrylate with styrene, acrylic acid, or methyl acrylate are then grafted from the SNPs. The polymerizations exhibited linear reaction kinetics, indicating that they are well controlled. Thermal gravimetric analysis and spectroscopic techniques confirmed the synthesis of the precursors materials and the success of the grafting from polymerizations. The incorporation of hydrophobic synthetic polymers on hydrophilic SNPs yields new hybrid materials that could find use in several industrial applications including paper coatings, adhesives, and paints.

Polymerization-Induced Self-Assembly (PISA) of 1,5-Cyclooctadiene Using Ring Opening Metathesis Polymerization.

Ring opening metathesis polymerization (ROMP) is a technique that allows the synthesis of well-defined linear polyolefins. Polymerization-induced self-assembly (PISA) involves the synthesis of amphiphilic block copolymers: a hydrophilic block is first polymerized homogeneously in solution (usually water) followed by polymerization of a second hydrophobic block, resulting in a diblock copolymer that self-assembles. In this communication, preliminary results of the development of PISA for the synthesis of amphiphilic block linear polyolefins via ROMP using a water-soluble PEGylated ruthenium alkylidene catalyst are presented. In the first step, a water-soluble modified-norbornene monomer was polymerized in water, then 1,5-cyclooctadiene was added to the system to produce amphiphilic block polyolefins. By varying the concentrations of hydrophilic versus hydrophobic monomer, stable latexes with final particles of ≈200 nm diameter were prepared.

CO2-Switchable-hydrophilicity membrane (CO2-SHM) triggered by electric potential: faster switching time along with efficient oil/water separation.

We report a membrane that can be reversibly switched between a hydrophilic state and a hydrophobic state simply by alternately bubbling CO2 into and passing electric potential (EP) through a solution in contact with the membrane. The prepared membrane could be effectively used for oil/water separation.

Living Ab Initio Emulsion Polymerization of Methyl Methacrylate in Water Using a Water-Soluble Organotellurium Chain Transfer Agent under Thermal and Photochemical Conditions.

Ab initio emulsion polymerization of methyl methacrylate (MMA) using a water-soluble organotellurium chain transfer agent in the presence of the surfactant Brij 98 in water is reported. Polymerization proceeded under both thermal and visible light-irradiation conditions, giving poly(methyl methacrylate) (PMMA) with controlled molecular weight and low dispersity (D<1.5). Despite the formation of an opaque latex, the photoactivation of the organotellurium dormant species took place efficiently, as demonstrated by the quantitative monomer conversion and temporal control. Control of polymer particle size (PDI<0.030) was also achieved using a semi-batch monomer addition process. The PMMA polymer in the particles retained high end-group fidelity and was successfully used for the synthesis of block copolymers.

Compositional analysis of lignocellulosic biomass: conventional methodologies and future outlook.

The composition and structural properties of lignocellulosic biomass have significant effects on its downstream conversion to fuels, biomaterials, and building-block chemicals. Specifically, the recalcitrance to modification and compositional variability of lignocellulose make it challenging to optimize and control the conditions under which the conversion takes place. Various characterization protocols have been developed over the past 150 years to elucidate the structural properties and compositional patterns that affect the processing of lignocellulose. Early characterization techniques were developed to estimate the relative digestibility and nutritional value of plant material after ingestion by ruminants and humans alike (e.g. dietary fiber). Over the years, these empirical techniques have evolved into statistical approaches that give a broader and more informative analysis of lignocellulose for conversion processes, to the point where an entire compositional and structural analysis of lignocellulosic biomass can be completed in minutes, rather than weeks. The use of modern spectroscopy and chemometric techniques has shown promise as a rapid and cost effective alternative to traditional empirical techniques. This review serves as an overview of the compositional analysis techniques that have been developed for lignocellulosic biomass in an effort to highlight the motivation and migration towards rapid, accurate, and cost-effective data-driven chemometric methods. These rapid analysis techniques can potentially be used to optimize future biorefinery unit operations, where large quantities of lignocellulose are continually processed into products of high value.

CO2-Responsive Graft Modified Chitosan for Heavy Metal (Nickel) Recovery.

Chitosan was chemically functionalized with poly(diethylaminoethyl methacrylate) (PDEAEMA) using a grafting to approach to produce a CO2-responsive material for adsorbing metals from wastewater streams. A need for improved economical and greener approaches to recover heavy metals from wastewater streams exists due to increasing resource scarcity. Chitosan is currently used as an adsorbent for heavy metals but suffers from some properties that can be disadvantageous to its effectiveness; it is difficult to effectively disperse in water (which limits available surface area) and to regenerate. We set out to improve its effectiveness by grafting CO2-responsive tertiary amine containing polymers onto the chitosan backbone, with the goals of preparing and assessing a new type of adsorbent based on a novel concept; using carbon dioxide switchable polymers to enhance the performance of chitosan. PDEAEMA chains prepared by nitroxide-mediated polymerization were grafted onto chitosan functionalized with glycidyl methacrylate. In carbonated water, the grafted chitosan displayed improved dispersibility and exhibited a Ni(II) adsorption capacity higher than several other chemically functionalized chitosan variants reported in the literature with the regenerated material having a higher capacity than all physical and chemical derivatives reported in the literature. The results of this study validate the continued development of this material for applications in heavy metal removal and recovery from wastewater streams.

CO2-responsive polymeric materials: synthesis, self-assembly, and functional applications.

CO2 is an ideal trigger for switchable or stimuli-responsive materials because it is benign, inexpensive, green, abundant, and does not accumulate in the system. Many different CO2-responsive materials including polymers, latexes, solvents, solutes, gels, surfactants, and catalysts have been prepared. This review focuses on the preparation, self-assembly, and functional applications of CO2-responsive polymers. Detailed discussion is provided on the synthesis of CO2-responsive polymers, in particular using reversible deactivation radical polymerization (RDRP), formerly known as controlled/living radical polymerization (CLRP), a powerful technique for the preparation of well-defined (co)polymers with precise control over molecular weight distribution, chain-end functional groups, and polymer architectural design. Self-assembly in aqueous dispersed media is highlighted as well as emerging potential applications.

Microalgae Recovery from Water for Biofuel Production Using CO2-Switchable Crystalline Nanocellulose.

There is a pressing need to develop efficient and sustainable approaches to harvesting microalgae for biofuel production and water treatment. CO2-switchable crystalline nanocellulose (CNC) modified with 1-(3-aminopropyl)imidazole (APIm) is proposed as a reversible coagulant for harvesting microalgae. Compared to native CNC, the positively charged APIm-modified CNC, which dispersed well in carbonated water, showed appreciable electrostatic interaction with negatively charged Chlorella vulgaris upon CO2-treatment. The gelation between the modified CNC, triggered by subsequent air sparging, can also enmesh adjacent microalgae and/or microalgae-modified CNC aggregates, thereby further enhancing harvesting efficiencies. Moreover, the surface charges and dispersion/gelation of APIm-modified CNC could be reversibly adjusted by alternatively sparging CO2/air. This CO2-switchability would make the reusability of redispersed CNC for further harvesting possible. After harvesting, the supernatant following sedimentation can be reused for microalgal cultivation without detrimental effects on cell growth. The use of this approach for harvesting microalgae presents an advantage to other current methods available because all materials involved, including the cellulose, CO2, and air, are natural and biocompatible without adverse effects on the downstream processing for biofuel production.

Oseltamivir-conjugated polymeric micelles prepared by RAFT living radical polymerization as a new active tumor targeting drug delivery platform.

Targeted drug delivery using polymeric nanostructures has been at the forefront of cancer research, engineered for safer, more efficient and effective use of chemotherapy. Here, we designed a new polymeric micelle delivery system for active tumor targeting followed by micelle-drug internalization via receptor-induced endocytosis. We recently reported that oseltamivir phosphate targets and inhibits Neu1 sialidase activity associated with receptor tyrosine kinases such as epidermal growth factor receptors (EGFRs) which are overexpressed in cancer cells. By decorating micelles with oseltamivir, we investigated whether they actively targeted human pancreatic PANC1 cancer cells. Amphiphilic block copolymers with oseltamivir conjugated at the hydrophilic end, oseltamivir-pPEGMEMA-b-pMMA (oseltamivir-poly(polyethylene glycol methyl ether methacrylate)-block-poly(methyl methacrylate), were synthesized using reversible addition-fragmentation chain transfer (RAFT) living radical polymerization. Oseltamivir-conjugated micelles have self-assembling properties to give worm-like micellar structures with molecular weight of 80 000 g mol(-1). Oseltamivir-conjugated water soluble pPEGMEMA, dose dependently, both inhibited sialidase activity associated with Neu1, and reduced viability of PANC1 cells. In addition, oseltamivir-conjugated micelles, labelled with a hydrophobic fluorescent dye within the micelle core, were subsequently internalized by PANC1 cells. Blocking cell surface Neu1 with anti-Neu1 antibody, reduced internalization of oseltamivir-conjugated micelles, demonstrating that Neu1 binding linked to sialidase inhibition were prerequisite steps for subsequent internalization of the micelles. The mechanism of internalization is likely that of receptor-induced endocytosis demonstrating potential as a new nanocarrier system for not only targeting a tumor cell, but also for directly reducing viability through Neu1 inhibition, followed by intracellular delivery of hydrophobic cytotoxic chemotherapeutics.

Polymerization Induced Self-Assembly of Alginate Based Amphiphilic Graft Copolymers Synthesized by Single Electron Transfer Living Radical Polymerization.

Alginate-based amphiphilic graft copolymers were synthesized by single electron transfer living radical polymerization (SET-LRP), forming stable micelles during polymerization induced self-assembly (PISA). First, alginate macroinitiator was prepared by partial depolymerization of native alginate, solubility modification and attachment of initiator. Depolymerized low molecular weight alginate (∼12 000 g/mol) was modified with tetrabutylammonium, enabling miscibility in anhydrous organic solvents, followed by initiator attachment via esterification yielding a macroinitiator with a degree of substitution of 0.02, or 1-2 initiator groups per alginate chain. Then, methyl methacrylate was polymerized from the alginate macroinitiator in mixtures of water and methanol, forming poly(methyl methacrylate) grafts, prior to self-assembly, of ∼75 000 g/mol and polydispersity of 1.2. PISA of the amphiphilic graft-copolymer resulted in the formation of micelles with diameters of 50-300 nm characterized by light scattering and electron microscopy. As the first reported case of LRP from alginate, this work introduces a synthetic route to a preparation of alginate-based hybrid polymers with a precise macromolecular architecture and desired functionalities. The intended application is the preparation of micelles for drug delivery; however, LRP from alginate can also be applied in the field of biomaterials to the improvement of alginate-based hydrogel systems such as nano- and microhydrogel particles, islet encapsulation materials, hydrogel implants, and topical applications. Such modified alginates can also improve the function and application of native alginates in food and agricultural applications.