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1. Life Cycle Assessment in the Design of Plant Oil-Based Latex Adhesives

   Iryna Bon, Vasylyna Kirianchuk (August 2021, ACS)

   ACS (Ed.)

   Synthetic method for developing plant oil-based monomers (POBMs) using direct transesterification reaction of oil triglycerides with N-(Hydroxyethyl) acrylamide was created and widely used by our group. Resulted acrylic monomers undergo free-radical polymerization, including in emulsion process, to yield latex polymers, suitable for application as adhesives. 

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2. Biobased latex adhesives from isobornyl methacrylate and plant-oil-based acrylic monomers

   https://doi.org/10.1680/jgrma.23.00070  

   Domnich, Bohdan; Shevhcuk, Oleg; Kirianchuk, Vasylyna; Voronov, Andriy (September 2023, Green Materials)

   A range of cross-linkable latex copolymers with biobased content of up to 90% was synthesized from isobornyl methacrylate combined with acrylic monomers based on high-oleic soybean oil (HO-SBM) or camelina oil (CMM) through miniemulsion polymerization. By varying the HO-SBM and CMM macromolecular fractions, the cross-linking density of the resulting materials can be altered due to differences in the fatty acid profiles of the plant-oil-based monomers. The glass transition temperature of the synthesized copolymers correlates very well with the calculated Flory–Fox values. A higher cross-linking density of the biobased copolymer films leads to a notable growth in the modulus of the materials, while the elongation at break decreases due to more restricted macromolecular mobility. Remarkably, the copolymer with the highest unsaturation degree in the investigated range (based on CMM) shows an increase in both the modulus and elongation at break, due perhaps to extended entanglements of fatty-acid-based side chains. The adhesion performance of the cross-linked biobased copolymers was evaluated by performing shear and peel strength measurements on steel and polypropylene. Based on the obtained results, the unsaturation degree of CMM and HO-SBM (determined by plant oil composition) can be applied as a criterion for adjusting adhesion by choosing plant-oil-based monomers (or their mixtures) with different unsaturation degrees to achieve properties and performance required for specific applications. 

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3. Reductive Depolymerization of Lignin to Aromatic Compounds over Promoted Nickel Catalysts in Sub‐ and Supercritical Methanol

   https://doi.org/10.1002/cnma.202400222  

   Parker, Julia; Santillan‐Jimenez, Eduardo; Harman‐Ware, Anne_E; Umenweke, Great_C; Heintz, Olivier; Caboche, Gilles; Crocker, Mark (December 2024, ChemNanoMat)

   Abstract The use of γ‐Al₂O₃‐supported Ni catalysts promoted with either Cu or Fe was investigated for the reductive catalytic fractionation (RCF) of hybrid poplar in methanol at 200 and 250 °C. The effectiveness of lignin depolymerization was quantified in terms of the lignin oil production, the quantity and distribution of identifiable monomers present in the lignin oil, and the yield of residual solids. All of the Ni‐based catalysts tested provided improved yields of lignin oil and monomers, along with reduced char formation, relative to blank (sans catalyst) runs. The highest monomer yield of 51 % was obtained at 250 °C over a 20 wt.% Ni‐5 wt.% Cu/Al₂O₃catalyst, the improved performance obtained through Cu promotion being attributed to the ability of Cu to facilitate NiO reduction, resulting in an increased amount of Ni⁰on the catalyst surface and, consequently, improved hydrogenation activity. The main monomers formed were propanol‐, propyl‐ and propenyl‐substituted guaiacol and syringol, the S/G ratio of the products corresponding closely to that in the native lignin. 

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4. Sustainability and Adhesive Performance of Plant Oil-Based Latexes

   Iryna Bon, Vasylyna Kirianchuk (June 2021, Great Lakes Regional Meeting (GLRM) 2021)

   Sustainability of the adhesives prepared from fossil-based materials has become a growing concern. Thus, replacement of petroleum-based materials by ones derived from renewable resources is pursued as a sustainable strategy for reducing their carbon footprint. Biobased latexes can be widely used as waterborne adhesives if their performance and properties are competitive to those currently available in the market. This work aims to evaluate the performance of latex adhesives with higher biobased content recently developed in our group. For this purpose, plant oil-based vinyl monomers HOSBM and CMM (derived from high oleic soybean oil and camelina oil, respectively) in combination with methyl methacrylate (MMA) and butyl acrylate (BA) were copolymerized using miniemulsion to yield latexes to be tested as adhesives. The MMA (“rigid” fragment) content was kept at 55 wt%, while BA (within remaining 45 wt% of the “soft” fragments) has been gradually replaced by either CMM or HOSBM. The effect of partial substitution of the BA by CMM or HOSBM on adhesive properties was assessed using peel testing (ASTM D 1876-08) on the multiple substrates. Presence of plant oil-based fragments in latex copolymers improves adhesives peel strength on most substrates. Plant oil-based latexes with the maximum content of CMM or HOSBM (up to 45wt %) and their optimal adhesive performance were determined on various carpet and paperboard substrates. Additionally, Life Cycle Assessment (LCA) method was used as a tool to evaluate the environmental performance of the synthesized latex adhesives as well as identify the hotspots in the synthesis of these plant-derived adhesives in their early design stages. LCA of plant oil-based monomers can explain to which extent the sustainability of the biobased latex adhesives can be improved. The authors thank the NSF Industry and University Cooperative Research Center for Bioplastic and Biocomposites for financial support. Thanks to NSF CB2 (1916564) 

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5. Probing protein aggregation at buried interfaces: distinguishing between adsorbed protein monomers, dimers, and a monomer–dimer mixture in situ

   https://doi.org/10.1039/d1sc04300e  

   Lu, Tieyi; Guo, Wen; Datar, Prathamesh M.; Xin, Yue; Marsh, E. Neil; Chen, Zhan (January 2022, Chemical Science)

   Protein adsorption on surfaces greatly impacts many applications such as biomedical materials, anti-biofouling coatings, bio-separation membranes, biosensors, antibody protein drugs etc. For example, protein drug adsorption on the widely used lubricant silicone oil surface may induce protein aggregation and thus affect the protein drug efficacy. It is therefore important to investigate the molecular behavior of proteins at the silicone oil/solution interface. Such an interfacial study is challenging because the targeted interface is buried. By using sum frequency generation vibrational spectroscopy (SFG) with Hamiltonian local mode approximation method analysis, we studied protein adsorption at the silicone oil/protein solution interface in situ in real time, using bovine serum albumin (BSA) as a model. The results showed that the interface was mainly covered by BSA dimers. The deduced BSA dimer orientation on the silicone oil surface from the SFG study can be explained by the surface distribution of certain amino acids. To confirm the BSA dimer adsorption, we treated adsorbed BSA dimer molecules with dithiothreitol (DTT) to dissociate these dimers. SFG studies on adsorbed BSA after the DTT treatment indicated that the silicone oil surface is covered by BSA dimers and BSA monomers in an approximate 6 : 4 ratio. That is to say, about 25% of the adsorbed BSA dimers were converted to monomers after the DTT treatment. Extensive research has been reported in the literature to determine adsorbed protein dimer formation using ex situ experiments, e.g. , by washing off the adsorbed proteins from the surface then analyzing the washed-off proteins, which may induce substantial errors in the washing process. Dimerization is a crucial initial step for protein aggregation. This research developed a new methodology to investigate protein aggregation at a solid/liquid (or liquid/liquid) interface in situ in real time using BSA dimer as an example, which will greatly impact many research fields and applications involving interfacial biological molecules. 

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