Sustainable barrier paper coating based on alpha-1,3 glucan and natural rubber latex.

There is an increasing interest in utilizing more sustainable and inherently biodegradable materials alternatives ideally derived from renewable resources for modern material applications, especially in the area of packaging materials. This work employed the polysaccharide alpha-1,3-glucan derived from an enzymatic polymerization process as a functional additive for natural rubber (NR) latex-based coating films. Coating formulations containing NR and 9-50 wt% alpha-1,3 glucan were prepared and then applied to paper substrates at different thicknesses. The effect of coating formulations on the barrier properties (e.g., oxygen, oil, water vapor barrier), the viscosity, and dry and wet tensile properties were investigated. The NR/glucan coatings exhibited outstanding tensile properties and balanced oxygen and oil barrier performance. However, higher glucan loading could be detrimental to moisture barrier. Overall, this study indicated that the NR/glucan coating films are comparable in performance to commercial coating formulations while providing a renewable, potential to be recycled with paper, and biodegradable alternative.

Enzymatic polymerization designed alpha-1,3 glucan particle morphology as reinforcing fillers of dipped and casted rubber films.

In this work, enzymatic polymerization derived microcrystalline glucan (MCG) polysaccharides fillers were employed as novel sustainable fillers of natural rubber (NR) films. MCG has a designed platelet morphology, with high crystallinity and colloidal stability in aqueous media and rubber lattices. NR films composed of 0-10 phr MCG were then fabricated using dipping and casting processes. The incorporation of MCG in the NR led to a remarkable enhancement in the tear strength, tensile properties, toughness, and an increase in water vapor permeability but a decrease in ethanol permeation. This behavior is appealing in gloves, where high sweat permeation from hands to the environment and limited to no solvent penetration from the environment to the skin is desired. The study indicated that the enzymatically polymerized MCG are effective reinforcing fillers for NR latex and potentially other elastomers offering the potential for appealing physical property improvements.

Elucidating the effect of enzymatic polymerized polysaccharide particle morphology on emulsion properties.

Exploiting the shape of Pickering stabilizers offers the ability to unlock the full potential of nanoparticle-stabilized emulsions for applications in enhanced oil recovery, pharmaceuticals, cosmetics, and coatings. In this work, we utilize engineered polysaccharide particles derived from the enzymatic polymerization of glucose from sucrose with controlled shape for the stabilization of dodecane-in-water emulsions. Altering the particle shape (spherical aggregates, fibrids, or platelets), while maintaining a neutral surface charge allows for a systematic examination of the role of particle shape in the stabilization of emulsions. We find that platelet-shaped particles reduce the interfacial tension and result in the smallest droplet size, while emulsions stabilized by aggregates and fibrids are governed by a network of particles in the continuous phase. Exploiting the synergy between these particles allowed for the tuning of their microstructure and rheological signature which allows us to map and tailor these emulsions for a wider variety of applications.

Enzymatic polymerization derived engineered polysaccharides as reinforcing fillers of ethylene vinyl acetate composites.

A novel monomer based, controlled enzymatic polymerization was employed to produce an engineered alpha-1,3 glucan polysaccharide. The structure and material properties of the engineered polysaccharide were characterized using various techniques. The use of such engineered polysaccharide as a reinforcing filler of polymers was evaluated using model polymers. For this, the alpha-1,3 glucan was incorporated into ethylene vinyl acetate co-polymer (EVA) matrices with vinyl acetate content of 32% and 40% via a melt processing fabrication process. Various mechanical and rheological properties of the fabricated composites were evaluated. The effect of vinyl acetate content of the EVA resin on the interaction with alpha-1,3 glucan that result in various performances attributes was also investigated and reported. The incorporation of alpha-1,3 glucan in these EVA composites resulted in the improvement of key composite properties, such as toughness, modulus, wear resistance, and hardness showing the reinforcing potential of these engineered polysaccharides.

Scope and mechanism of the intermolecular addition of aromatic aldehydes to olefins catalyzed by Rh(I) olefin complexes.

Rhodium (I) bis-olefin complexes Cp*Rh(VTMS)(2) and CpRh(VTMS)(2) (Cp* = C(5)Me(5), Cp = C(5)Me(4)CF(3), VTMS = vinyl trimethylsilane) were found to catalyze the addition of aromatic aldehydes to olefins to form ketones. Use of the more electron-deficient catalyst CpRh(VTMS)(2) results in faster reaction rates, better selectivity for linear ketone products from alpha-olefins, and broader reaction scope. NMR studies of the hydroacylation of vinyltrimethylsilane showed that the starting Rh(I) bis-olefin complexes and the corresponding Cp*/Rh(CH(2)CH(2)SiMe(3))(CO)(Ar) complexes were catalyst resting states, with an equilibrium established between them prior to turnover. Mechanistic studies suggested that CpRh(VTMS)(2) displayed a faster turnover frequency (relative to Cp*Rh(VTMS)(2)) because of an increase in the rate of reductive elimination, the turnover-limiting step, from the more electron-deficient metal center of CpRh(VTMS)(2). Reaction of Cp*/Rh(CH(2)CH(2)SiMe(3))(CO)(Ar) with PMe(3) yields acyl complexes Cp*/Rh[C(O)CH(2)CH(2)SiMe(3)](PMe(3))(Ar); measured first-order rates of reductive elimination of ketone from these Rh(III) complexes established that the Cp ligand accelerates this process relative to the Cp* ligand.

Structure and Reactivity of a Cobalt(I) Phthalaldehyde Complex with Both σ- and π-Bonded Aldehyde Groups.

A bidentate phthalaldehyde ligand with both σ and π coordination of the aldehyde groups is found in [(C5 Me5 )Co{(C(O)H)2 C6 H4 }] (structure depicted). This complex is the "resting state" of the catalyst in the ring closure of the dialdehyde to give the lactone. Interchange of coordination modes occurs with a barrier of 70 kJ mol-1 at 35°C. Investigation of other CoI chelate complexes with a single aldehyde group shows that the coordination mode of the aldehyde is dictated by the nature of the bonding of the other ligating group.