Search for: All records

Summary statement Tree weatherproofing during senescence is imprinted in trees' stemflow chemistry.We supply novel data on stemflow neutral sugars leaching and propose a conceptual model to explain the interplay between higher stemflow neutral sugar concentrations during senescence and ecophysiological changes in bark/wood chemistry that initiate cold hardiness. 

Abstract We investigate solvent effects in the hydrodeoxygenation of 4-propylguaiacol (4PG, 166 amu), a key lignin-derived monomer, over Ru/C catalyst by combinedoperandosynchrotron photoelectron photoion coincidence (PEPICO) spectroscopy and molecular dynamics simulations. With and without isooctane co-feeding, ring-hydrogenated 2-methoxy-4-propylcyclohexanol (172 amu) is the first product, due to the favorable flat adsorption configuration of 4PG on the catalyst surface. In contrast, tetrahydrofuran (THF)—a polar aprotic solvent that is representative of those used for lignin solubilization and upgrading—strongly coordinates to the catalyst surface at the oxygen atom. This induces a local steric hindrance, blocking the flat adsorption of 4PG more effectively, as it needs more Ru sites than the tilted adsorption configuration revealed by molecular dynamics simulations. Therefore, THF suppresses benzene ring hydrogenation, favoring a demethoxylation route that yields 4-propylphenol (136 amu), followed by dehydroxylation to propylbenzene (120 amu). Solvent selection may provide new avenues for controlling catalytic selectivity. 

Abstract Stemflow is a conduit for the transport of canopy-derived dissolved organic matter (DOM) to the forest floor. This study examined the character of stemflow DOM for four tree species over four phenophases (leafless, emergence, leafed, and senescence for deciduous species and leafed-winter, emergence, leafed- spring/summer, and senescence for coniferous species) occurring in temperate forests; namely,Betula lentaL. (sweet birch),Fagus grandifoliaEhrh. (American beech),Liriodendron tulipiferaL. (yellow poplar), andPinus rigidaMill. (pitch pine). American beech exhibited the lowest average specific UV absorbance at 254 nm (SUVA₂₅₄) values, while yellow poplar displayed the highest values. SUVA₂₅₄values were largest in senescence and smallest in emergence. The spectral slope ratio was lower for pitch pine than the deciduous tree species. Humification index (HIX) values decreased across all species during the emergence phenophase. The developed and validated stemflow-specific four-component parallel factor analysis (PARAFAC) model demonstrated the combined influence of interspecific and temporal fluctuations on the composition of humic and protein-like substances within stemflow. By separating and examining stemflow DOM independent of throughfall, our study provides fresh insights into the spatiotemporal dynamics of stemflow inputs to near-trunk soils that may inform hot spots and hot moments theories. 

Abstract Biomass supply chain performance is heavily affected by uncertainties stemming from supply, demand, or unexpected disruptions. Unlike petrochemical plants that use crude oil, biorefineries often have to deal with the uneven spatial‐temporal distribution of feedstock supply. The modular production strategy provides more flexibility in chemical manufacturing by allowing fast capacity expansion and unit movement. However, modeling and optimizing modular biomass supply chain under uncertainties becomes challenging due to high dimensionality and the existence of discrete decisions. This work optimizes the multiperiod biomass supply chain using the rolling horizon planning and two‐stage stochastic programming framework. We then applied generalized Benders decomposition to reduce the computational complexity of the stochastic mixed integer nonlinear programming supply chain optimization. Furthermore, the solution of the stochastic programming could be used to quantitatively describe the life‐cycle assessment uncertainties of the biomass supply chain performance, demonstrating seasonality and random variability. 

Abstract The hydrogenolysis of polymers is emerging as a promising approach to deconstruct plastic waste into valuable chemicals. Yet, the complexity of plastic waste, including multilayer packaging, is a significant barrier to handling realistic waste streams. Herein, we reveal fundamental insights into a new chemical route for transforming a previously unaddressed fraction of plastic waste – poly(ethylene‐co‐vinyl alcohol) (EVOH) and related polymer blends – into alkane products. We report that Ru/ZrO₂is active for the concurrent hydrogenolysis, hydrogenation, and hydrodeoxygenation of EVOH and its thermal degradation products into alkanes (C₁−C₃₅) and water. Detailed reaction data, product analysis, and catalyst characterization reveal that the in‐situ thermal degradation of EVOH forms aromatic intermediates that are detrimental to catalytic activity. Increased hydrogen pressure promotes hydrogenation of these aromatics, preventing catalyst deactivation and improving alkane product yields. Calculated apparent rates of C−C scission reveal that the hydrogenolysis of EVOH is slower than low‐density polyethylene. We apply these findings to achieve hydrogenolysis of EVOH/polyethylene blends and elucidate the sensitivity of hydrogenolysis catalysts to such blends. Overall, we demonstrate progress towards efficient catalytic processes for the hydroconversion of waste multilayer film plastic packaging into valuable products. 

Abstract The selective introduction of amine groups within deconstruction products of lignin could provide an avenue for valorizing waste biomass while achieving a green synthesis of industrially relevant building blocks from sustainable sources. Here, we built and characterized enzyme cascades that create aldehydes and subsequently primary amines from diverse lignin‐derived carboxylic acids using a carboxylic acid reductase (CAR) and an ω‐transaminase (TA). Unlike previous studies that have paired CAR and TA enzymes, here we examine multiple homologs of each of these enzymes and a broader set of candidate substrates. In addition, we compare the performance of these systems in cell‐free and resting whole‐cell biocatalysis formats using the conversion of vanillate to vanillyl amine as model chemistry. We also demonstrate that resting whole cells can be recycled for multiple batch reactions. We used the knowledge gained from this study to produce several amines from carboxylic acid precursors using one‐pot biocatalytic reactions, several of which we report for the first time. These results expand our knowledge of these industrially relevant enzyme families to new substrates and contexts for environmentally friendly and potentially low‐cost synthesis of diverse aryl aldehydes and amines. 

Harvest optimization offers an effective strategy for maximizing lignin valorization yields and overall biorefinery production of fuels, chemicals, and materials. 

The development of vitrimers with dynamic covalent bonds enables reprocessability in crosslinked networks, offering a sustainable alternative to conventional thermosets. In this work, a thiol-acrylate vitrimer was synthesized from lignin-derivable (bis)phenols (guaiacol and bisguaiacol F) and compared to a control derived from petroleum-based precursors (phenol and bisphenol F) to investigate the effect of structural differences on network properties and thermal reprocessing. The presence of methoxy groups in the lignin-derivable vitrimer promoted intermolecular interactions by serving as additional hydrogen bonding acceptors during curing, leading to a denser network, as evidenced by a higher rubbery storage modulus (∼2.4 MPa vs. ∼1.4 MPa) and glass transition temperature (∼34 °C vs. ∼28 °C). The lignin-derivable vitrimer exhibited a slightly higher elongation-at-break (∼170% vs. ∼130%) and improved mechanical robustness, including a nearly two-fold increase in Young's modulus (∼6.9 MPa vs. ∼3.4 MPa) and toughness (∼750 kJ m−3vs. ∼390 kJ m−3). The similar stress relaxation behavior and activation energy of viscous flow indicated comparable bond exchange dynamics between the two vitrimers, while the lignin-derivable system demonstrated higher thermal healing efficiency with improved recovery of tensile properties after reprocessing. These findings highlight the potential of lignin-based aromatics in designing mechanically robust and sustainable vitrimers, aligning with efforts to develop renewable and reprocessable polymeric materials.