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Plastics are an extremely important class of materials that are prevalent in all facets of society; however, their widespread use over time, combined with limited end-of-life strategies, has led to increasing levels of waste accumulation. Although currently considered a burden, plastics waste is potentially an untapped feedstock for numerous chemical and manufacturing processes. In this review, we discuss the state of the art of approaches for valorization of plastics waste from a materials research perspective, including previous efforts to utilize plastics waste and recent innovations that have opportunities to add significant value. Although additional progress is necessary, we present several diverse capabilities and strategies for valorization that, when brought together, address end-of-life challenges for plastics at every stage of design and product consumption. In short, a materials research–based framework offers a unique perspective to address the urgent issues posed by plastics, unlocking the potential of polymers and plastics waste.

To better incentivize the collection of plastic wastes, new chemical transformations must be developed that add value to plastic deconstruction products. Polyethylene terephthalate (PET) is a common plastic whose deconstruction through chemical or biological means has received much attention. However, a limited number of alternative products have been formed from PET deconstruction, and only a small share could serve as building blocks for alternative materials or therapeutics. Here, we demonstrate the production of useful mono-amine and diamine building blocks from known PET deconstruction products. We achieve this by designing one-pot biocatalytic transformations that are informed by the substrate specificity of an ω-transaminase and diverse carboxylic acid reductases (CAR) towards PET deconstruction products. We first establish that an ω-transaminase fromChromobacterium violaceum(cvTA) can efficiently catalyze amine transfer to potential PET-derived aldehydes to form the mono-aminepara-(aminomethyl)benzoic acid (pAMBA) or the diaminepara-xylylenediamine (pXYL). We then identified CAR orthologs that could perform the bifunctional reduction of TPA to terephthalaldehyde (TPAL) or the reduction ofmono-(2-hydroxyethyl) terephthalic acid (MHET) to its corresponding aldehyde. After characterizing 17 CARsin vitro, we show that the CAR fromSegniliparus rotundus(srCAR) had the highest observed activity on TPA. Given these newly elucidated substrate specificity results, we designed modular enzyme cascades based on coupling srCAR and cvTA in one-pot with enzymatic co-factor regeneration. When we supply TPA, we achieve a 69 ± 1% yield of pXYL, which is useful as a building block for materials. When we instead supply MHET and subsequently perform base-catalyzed ester hydrolysis, we achieve 70 ± 8% yield of pAMBA, which is useful for therapeutic applications and as a pharmaceutical building block. This work expands the breadth of products derived from PET deconstruction and lays the groundwork for eventual valorization of waste PET to higher-value chemicals and materials.GRAPHICAL ABSTRACT

Highly enantioenriched benzylic and allylic amines and alcohols are readily available via asymmetric synthesis and in complex natural products. The development of mild, nickel-catalyzed cross-couplings of their derivatives has advanced the tools available for the preparation of a range of highly enantioenriched products, including those with quaternary stereocenters. This perspective focuses on cross-couplings with convenient and functional group-tolerant organoboron reagents and highlights the discoveries of activating groups and conditions that have led to high-yielding and highly stereospecific reactions. Emphasis is placed on mechanistic understanding, particularly with regards to controlling inversion vs. retention pathways. Limitations and opportunities for future developments are also highlighted.

This work reports the synthesis of a triethylsilyl-substituted Fe-Cu complex that provided cyclohexane solubility to conduct time-resolved UV-IR studies. These studies suggest that UV light induces a photochemically active heterodinuclear species for arene borylation catalysis.

This work reports the synthesis of a triethylsilyl-substituted Fe-Cu complex that provided cyclohexane solubility to conduct time-resolved UV-IR studies. These studies suggest that UV light induces a photochemically active heterodinuclear species for arene borylation catalysis.

The identification of Yb(OTf)3 through a multivariable high-throughput experimentation strategy has enabled a unified protocol for the direct conversion of enantioenriched N-acyloxazolidinones to the corresponding chiral esters, amides, and carboxylic acids. This straightforward and catalytic method has shown remarkable chemoselectivity for substitution at the acyclic N-acyl carbonyl for a diverse array of N-acyloxazolidinone substrates. The ionic radius of the Lewis acid catalyst was demonstrated as a key driver of catalyst performance that led to the identification of a robust and scalable esterification of a pharmaceutical intermediate using catalytic Y(OTf)3.

Cross couplings between simple allylic alcohols and aryl and vinyl boronic acids are efficiently catalyzed by nickel(0) catalysts and bidentate N-heterocyclic carbene/phosphine ligands. The bidentate nature of the ligand is shown to extend catalyst lifetime and enable high yields of the corresponding cross coupling products. X-ray crystallography confirms the bidentate nature of the ligand scaffold. Multistep cross coupling-alkene/alkyne insertions reactions are also conducted and the bidentate nature of the substrate makes the pendant phosphine of the ligand unnecessary.

A nickel-catalyzed reductive cross-coupling of alkylpyridinium salts and aryl bromides has been developed using Mn as the reductant. Both primary and secondary alkylpyridinium salts can be used, and high functional group and heterocycle tolerance is observed, including for protic groups. Mechanistic studies indicate the formation of an alkyl radical, and controlling its fate was key to the success of this reaction.

In situ formation of heterobimetallic Pt–Ti catalysts enables rapid room temperature catalysis in enyne cycloisomerization reactions. The Lewis acidic titanium atom in the ligand framework is shown to be essential for fast catalysis. A range of enyne substrates are efficiently cyclized to carbocycles and heterocycles in high yield.

There are a number of factors that must be considered in any attempt to control animal drug residues in milk and milk products. Dairy herds vary greatly in number of cows. Milk from individual cows and farms is pooled, diluting drug residues that may be present in the milk from a single treated cow. Management techniques, including the handling, administration, and record keeping of animal drugs, vary greatly from one dairy to another. It is important that both veterinarians and nonveterinarians adhere to adequate milk discard times for animal drugs used to treat dairy animals. Observance of appropriate safeguards at the farm level, such as record keeping and clearly identifying treated animals, is critical for controlling and preventing the presence of illegal animal drug residues. Within the framework of the Federal Food, Drug, and Cosmetic Act and the Public Health Service Act, the FDA is working with state and other regulatory agencies and industry to better ensure the absence of illegal animal drug residues in milk and milk products. Preventive measures concentrate on minimizing the need to administer animal drugs to lactating cows, and diverting milk containing drug residues from the human food supply. Monitoring programs concentrate on screening milk and tracing violations to the individual producer. Minimizing illegal drug residues in milk and milk products requires close cooperation between farmers, veterinarians, the dairy industry, the pharmaceutical industry, and regulators.