Catalytic carbon-carbon bond cleavage in lignin via manganese-zirconium-mediated autoxidation.

Efforts to produce aromatic monomers through catalytic lignin depolymerization have historically focused on aryl-ether bond cleavage. A large fraction of aromatic monomers in lignin, however, are linked by various carbon-carbon (C-C) bonds that are more challenging to cleave and limit the yields of aromatic monomers from lignin depolymerization. Here, we report a catalytic autoxidation method to cleave C-C bonds in lignin-derived dimers and oligomers from pine and poplar. The method uses manganese and zirconium salts as catalysts in acetic acid and produces aromatic carboxylic acids as primary products. The mixtures of the oxygenated monomers are efficiently converted to cis,cis-muconic acid in an engineered strain of Pseudomonas putida KT2440 that conducts aromatic O-demethylation reactions at the 4-position. This work demonstrates that autoxidation of lignin with Mn and Zr offers a catalytic strategy to increase the yield of valuable aromatic monomers from lignin.

Ni- and Ni/Pd-Catalyzed Reductive Coupling of Lignin-Derived Aromatics to Access Biobased Plasticizers.

Lignin-derived aromatic chemicals offer a compelling alternative to petrochemical feedstocks, and new applications are the focus of extensive interest. 4-Hydroxybenzoic acid (H), vanillic acid (G), and syringic acid (S) are readily obtained via oxidative depolymerization of hardwood lignin substrates. Here, we explore the use of these compounds to access biaryl dicarboxylate esters that represent biobased, less toxic alternatives to phthalate plasticizers. Chemical and electrochemical methods are developed for catalytic reductive coupling of sulfonate derivatives of H, G, and S to access all possible homo- and cross-coupling products. A conventional NiCl2/bipyridine catalyst is able to access the H-H and G-G products, but new catalysts are identified to afford the more challenging coupling products, including a NiCl2/bisphosphine catalyst for S-S and a NiCl2/phenanthroline/PdCl2/phosphine cocatalyst system for H-G, H-S, and G-S. High-throughput experimentation methods with a chemical reductant (Zn powder) are shown to provide an efficient screening platform for identification of new catalysts, while electrochemical methods can access improved yields and/or facilitate implementation on larger scale. Plasticizer tests are performed with poly(vinyl chloride), using esters of the 4,4'-biaryl dicarboxylate products. The H-G and G-G derivatives, in particular, exhibit performance advantages relative to an established petroleum-based phthalate ester plasticizer.

Autoxidation Catalysis for Carbon-Carbon Bond Cleavage in Lignin.

Selective lignin depolymerization is a key step in lignin valorization to value-added products, and there are multiple catalytic methods to cleave labile aryl-ether bonds in lignin. However, the overall aromatic monomer yield is inherently limited by refractory carbon-carbon linkages, which are abundant in lignin and remain intact during most selective lignin deconstruction processes. In this work, we demonstrate that a Co/Mn/Br-based catalytic autoxidation method promotes carbon-carbon bond cleavage in acetylated lignin oligomers produced from reductive catalytic fractionation. The oxidation products include acetyl vanillic acid and acetyl vanillin, which are ideal substrates for bioconversion. Using an engineered strain of Pseudomonas putida, we demonstrate the conversion of these aromatic monomers to cis,cis-muconic acid. Overall, this study demonstrates that autoxidation enables higher yields of bioavailable aromatic monomers, exceeding the limits set by ether-bond cleavage alone.

Measuring Equity From The Start: Disparities In The Health Development Of US Kindergartners.

Racialized disparities in health and well-being begin early in life and influence lifelong health outcomes. Using the Early Development Instrument-a population-level early childhood health measure-this article examines potential health inequities with regard to neighborhood income and race/ethnicity in a convenience sample of 183,717 kindergartners in ninety-eight US school districts from 2010 to 2017. Our findings demonstrate a distinct income-related outcome gradient. Thirty percent of children in the lowest-income neighborhoods were vulnerable in one or more domains of health development, compared with 17 percent of children in higher-income settings. Significantly higher rates of income-related Early Development Instrument vulnerability-defined as children falling below the tenth-percentile cutoff on any Early Development Instrument domain-were demonstrated for Black/African American and Hispanic/Latinx children. These findings underscore the utility of the Early Development Instrument as a way for communities to measure child health equity gaps and inform the design, implementation, and performance of multisector place-based child health initiatives. More broadly, results indicate that for the US to make significant headway in decreasing lifelong health inequities, it is important to achieve health equity by early childhood.

The Kindergarten Early Development Instrument Predicts Third Grade Academic Proficiency.

School readiness skills predict later educational achievement, health, and social-emotional outcomes. Measures of school readiness can provide valuable information to assess both the impact of strategies and policies that prepare children for school as well as informing strategies for improving children's educational trajectories across their school years. The Early Development Instrument (EDI) is a measure of school readiness skills based on teacher-reported observational recall. It has been used extensively in Canada and Australia and is in the early stages of adoption in a number of U.S. cities. The current study uses data from roughly 3,000 children followed longitudinally from kindergarten through third grade from 7 school districts in Orange County, California. The study assesses whether EDI ratings in kindergarten predict third grade proficiency in mathematics and English Language Arts on state assessments. Ratings on the EDI were strongly associated with proficiency in both academic areas, even in the presence of controls for child-level factors and neighborhood fixed effects. Among its components, ratings on the language and cognitive development, communication skills and general knowledge, and social competence domains strongly differentiated children's likelihood of later proficiency in both academic areas. Implications for improving comprehensive early childhood education and schooling policies based on indicators of school readiness are discussed.

Early Child Development, Residential Crowding, and Commute Time in 8 US States, 2010-2017.

OBJECTIVES: To examine relationships of residential crowding and commute time with early child development. METHODS: We used the Early Development Instrument (EDI), a teacher-reported, population-health measure of child development. The sample included child-level observations spanning 8 US states from 2010 to 2017 (n = 185 012), aggregated to the census tract (n= 2793), stratified by percentage of households in poverty. To test the association of commute times, crowding, and child development, we tested overall readiness and 5 EDI domains by using adjusted census tract-level multivariate regression with fixed effects. RESULTS: In the full sample, a 1-standard-deviation increase in crowding was associated with 0.064- and 0.084-point decreases in mean score for cognitive development and communication skills, respectively. For the high-poverty subsample, a 1-standard deviation increase in commute time was associated with 0.081- and 0.066-point decreases in social competence and emotional maturity. CONCLUSIONS: In neighborhoods with increased crowding or commute time, early child development suffers. POLICY IMPLICATIONS: This study suggests a potential relationship between the changing urban landscape and child health. Children would benefit from more multisector collaboration between urban planning and public health.

Measuring the quality of developmental services for young children: a new approach.

Creating a new approach to performance measurement, UCLA researchers propose an initial set of measures that Medicaid and other agencies could use to track the delivery and quality of developmental services for young children. The Developmental Services Quality Performance Measurement (DSQPM) framework, which includes metrics at the individual, provider, county, health plan, and state levels, is implemented through seven discrete measures. The DSQPM measurement set is designed to capture key components of the service-delivery pathway that are typically necessary for screening, identifying, and referring young children who have or are at risk for developmental disabilities. When formally surveyed, a select group of state Medicaid and Maternal and Child Health agencies expressed interest in piloting the DSQPM measurement set. While this particular measurement framework is focused on early childhood health and development, the researchers' multilevel approach is generalizable to other health-related service pathways.

A cost comparison of hospice care in amyotrophic lateral sclerosis and lung cancer.

The authors compare the cost of hospice care provided to 25 amyotrophic lateral sclerosis (ALS) patients and 159 lung cancer patients by the Wissahickon Hospice of the University of Pennsylvania. The mean length of stay was 86.7 days for ALS patients and 35.0 days for patients with lung cancer (P = .011). The mean per patient cost was 5622.93 dollars for the ALS patients and 2658.91 dollars for patients with lung cancer (P = .057) The average operating margin excluding administrative costs was 5293.04 dollars for ALS patients and 2126.74 dollars for patients with lung cancer (P = .008). The longer length of stay (LOS) accounts for this difference. Longer LOS can be accomplished by close clinical monitoring of ALS patients for the development of life threatening respiratory and/or nutritional compromise and by liberalizing the present hospice admission guidelines.