bloom dynamics depend principally on the impact of consumers, a long-recognized control of phytoplankton abundance (30). Our findings for Synechococcus agree with those of Behrenfeld and Boss in so far as division rates (and, by inference, loss rates) are roughly 10 times the accumulation (net growth) rates. Our results differ, however, in that we find a significant positive correlation between division and accumulation rates over the course of the spring bloom (Fig. 4, B and C). This correlation was not detected by Behrenfeld and Boss, and perhaps should not be expected to be evident in the satellite-based observations of chlorophyll concentration that they analyzed (29). Those observations aggregate the entire phytoplankton community over a relatively large region of the ocean and mask individual responses of different taxa.Our observations, made at a much smaller spatial scale and with much finer taxonomic and temporal resolution than that of satellite data, reveal a connection between division rates and the bloom dynamics of Synechococcus. Consumers (including grazers, viruses, and parasites) certainly play a major role in shaping the bloom's trajectory, but the bloom is triggered by an environmental factor, the seasonal temperature rise, which leads to increases in the Synechococcus division rate (Fig. 3). The bloom persists until the division rate plateaus (Fig. 4B), at which point losses overtake division and the bloom begins to decline.We were able to diagnose the importance of temperature in regulating the dynamics of a ubiquitous marine primary producer, Synechococcus, by exploiting a 13-year time series comprising data on millions of individual cells and their traits. This allowed us to not only quantify the relationship between temperature and cell division in a natural population, but also to document how that relationship is the basis for a dramatic phenological shift affecting both Synechococcus and their consumers. It remains to be seen whether this ecological coupling will hold as warming trends continue in the decades to come.
Protection groups were introduced during biomass pretreatment to stabilizel ignins a,g-diol group during its extraction and prevent its condensation. Acetaldehyde and propionaldehyde stabilized the a,g-diol without any aromatic ring alkylation, whichs ignificantly increased final product selectivity.T he subsequent hydrogenolysis catalyzedb yP d/C generated lignin monomers at near-theoretical yields based on Klason lignin (48 %from birch,20% from spruce,70% from high-syringyl transgenic poplar), and with high selectivity to asingle 4-n-propanolsyringol product (80 %) in the case of the poplar.U nlike direct hydrogenation of native wood, hydrogenolysis of protected lignin with Ni/C also led to high selectivity to this single product (78 %), paving the way to highselectivity lignin upgrading with base metal catalysts.T he use of extracted lignin facilitated valorization of polysaccharides, leading to high yields of all three major biomass polymers to asingle major product.
Lignin is one of the most promising sources of renewable aromatic hydrocarbons. Current methods for its extraction from lignocellulosic biomass-which include the kraft, sulfite, and organosolv processes-result in the rapid formation of carbon-carbon bonds, leading to a condensed lignin that cannot be effectively depolymerized into its constituent monomers. Treatment of lignocellulosic biomass with aldehydes during lignin extraction generates an aldehyde-stabilized lignin that is uncondensed and can be converted into its monomers at near-theoretical yields. Here, we outline an efficient, reproducible, and scalable process for extracting and purifying this aldehyde-stabilized lignin as a solid, which can easily be re-dissolved in an organic solvent. Upon exposure to hydrogenolysis conditions, this material provides near-theoretical yields of aromatic monomers (~40-50% of the Klason lignin for a typical hardwood). Cellulose and hemicellulose are also efficiently fractionated. This protocol requires 6-7 h for the extraction of the stabilized lignin and a basic proficiency in synthetic chemistry.
Polysaccharide depolymerization is an essential step for valorizing lignocellulosic biomass. In inexpensive systems such as pure water or dilute acid mixtures, carbohydrate monomer degradation rates exceed hemicellulose-and especially cellulose-depolymerization rates at most easily accessible temperatures, limiting sugar yields. Here, we use a reversible stabilization of xylose and glucose by acetal formation with formaldehyde to alter this kinetic paradigm, preventing sugar dehydration to furans and their subsequent degradation. During a harsh organosolv pretreatment in the presence of formaldehyde, over 90% of xylan in beech wood was recovered as diformylxylose (compared to 16% xylose recovery without formaldehyde). The subsequent depolymerization of cellulose led to carbohydrate yields over 70% and a final concentration of ~5 wt%, whereas the same conditions without formaldehyde gave a yield of 28%. This stabilization strategy pushes back the longstanding kinetic limits of polysaccharide depolymerization and enables the recovery of biomass-derived carbohydrates in high yields and concentrations.
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