Scholarly Works, Chemistry

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The Chemistry of the Defensive Secretions of Three Species of Millipedes in the Genus Brachycybe
Banks, Paige; Funkhouser, Emma M.; Macias, Angie M.; Lovett, Brian; Meador, Shelby; Hatch, Arden; Garraffo, H. Martin; Cartwright, Kaitie C.; Kasson, Matt T.; Marek, Paul E.; Jones, Tappey H.; Mevers, Emily (Springer, 2024-06-10)
Millipedes have long been known to produce a diverse array of chemical defense agents that deter predation. These compounds, or their precursors, are stored in high concentration within glands (ozadenes) and are released upon disturbance. The subterclass Colobognatha contains four orders of millipedes, all of which are known to produce terpenoid alkaloids—spare the Siphonophorida that produce terpenes. Although these compounds represent some of the most structurally-intriguing millipede-derived natural products, they are the least studied class of millipede defensive secretions. Here, we describe the chemistry of millipede defensive secretions from three species of Brachycybe: Brachycybe producta, Brachycybe petasata, and Brachycybe rosea. Chemical investigations using mass spectrometry-based metabolomics, chemical synthesis, and 2D NMR led to the identification of five alkaloids, three of which are new to the literature. All identified compounds are monoterpene alkaloids with the new compounds representing indolizidine (i.e. hydrogosodesmine) and quinolizidine alkaloids (i.e. homogosodesmine and homo-hydrogosodesmine). The chemical diversity of these compounds tracks the known species phylogeny of this genus, rather than the geographical proximity of the species. The indolizidines and quinolizidines are produced by non-sympatric sister species, B. producta and B. petasata, while deoxybuzonamine is produced by another set of non-sympatric sister species, B. rosea and Brachycybe lecontii. The fidelity between the chemical diversity and phylogeny strongly suggests that millipedes generate these complex defensive agents de novo and begins to provide insights into the evolution of their biochemical pathways.
Discovery of Biofilm Inhibitors from the Microbiota of Marine Egg Masses
Kyei, Lois; Piedl, Karla; Miller, Eleanor M.; Mevers, Emily (American Chemical Society, 2024-05-30)
Biofilms commonly develop in immunocompromised patients, which leads to persistent infections that are difficult to treat. In the biofilm state, bacteria are protected against both antibiotics and the host’s immune system; currently, there are no therapeutics that target biofilms. In this study, we screened a chemical fraction library representing the natural product capacity of the microbiota of marine egg masses, namely, the moon snail egg collars. This led to the identification of active fractions targeting both Pseudomonas aeruginosa and Staphylococcus aureus biofilms. Subsequent analysis revealed that a subset of these fractions were capable of eradicating preformed biofilms, all against S. aureus. Bioassay-guided isolation led us to identify pseudochelin A, a known siderophore, as a S. aureus biofilm inhibitor with an IC50 of 88.5 μM. Mass spectrometry-based metabolomic analyses revealed widespread production of pseudochelin A among fractions possessing S. aureus antibiofilm properties. In addition, a key biosynthetic gene involved in producing pseudochelin A was detected on 30% of the moon snail egg collars and pseudochelin A is capable of inhibiting the formation of biofilms (IC50 50.6 μM) produced by ecologically relevant bacterial strains. We propose that pseudochelin A may have a role in shaping the microbiome or protecting the egg collars from microbiofouling.
Design, Synthesis, and Antifungal Activity of 3-substituted-2(5H)-Oxaboroles
Campbell, Rose; Buchbinder, Nicklas W. ; Szwetkowski, Connor; Zhu, Yumeng; Piedl, Karla; Truong, Mindy; Matson, John B.; Santos, Webster L.; Mevers, Emily (American Chemical Society, 2024-02-22)
Next generation antimicrobial therapeutics are desperately needed as new pathogens with multiple resistance mechanisms continually emerge. Two oxaboroles, tavaborole and crisaborole, were recently approved as topical treatments for onychomycosis and atopic dermatitis, respectively, warranting further studies into this privileged structural class. Herein, we report the antimicrobial properties of 3-substituted-2(5H)-oxaboroles, an unstudied family of medicinally relevant oxaboroles. Our results revealed minimum inhibitory concentrations as low as 6.25 and 5.20 μg/mL against fungal (e.g., Penicillium chrysogenum) and yeast (Saccharomyces cerevisiae) pathogens, respectively. These oxaboroles were nonhemolytic and nontoxic to rat myoblast cells (H9c2). Structure-activity relationship studies suggest that planarity is important for antimicrobial activity, possibly due to the effects of extended conjugation between the oxaborole and benzene rings.
Neuromodulating Alkaloids from Millipede Defensive Secretions
Menegatti, Carla; Wood, Jared S.; Banks, Paige; Knott, Kenneth; Briganti, Jonathan S.; Briganti, Anthony J.; McNally, Samuel V. G.; Marek, Paul E.; Brown, Anne M.; Jones, Tappey H.; Williamson, R. Thomas; Mevers, Emily (American Chemical Society, 2024)
Millipedes have long been known to produce structurally diverse chemical defenses, including hydrogen cyanide, terpenoid alkaloids, and oxidized aromatics. Although the hydrogen cyanide and oxidized aromatic producing millipedes have been well studied, less than 10% of the terpenoid alkaloid producers have been chemically investigated. Several previous studies have shown that alkaloids disorient predators, but their biochemical target is currently unknown. Herein, we investigated the defensive secretions of a colobognath millipede, Ischnocybe plicata, and elucidated the constitution, absolute configuration, and conformation of four new highly oxidized terpenoid alkaloids, termed ischnocybines, using a range of analytical techniques. The ischnocybines are actively secreted from the defensive glands and were shown to disorient ants, a likely common predator. Evaluation of the ischnocybines in a panel of neuroreceptors revealed that ischnocybine A possesses potent (Ki 13.6 nM) and selective (100-fold) binding affinity for sigma-1, an orphan neuroreceptor, over sigma-2. These molecules represent the most complex alkaloids to be discovered from millipedes and provide the first potential insights into a biochemical target responsible for their defensive properties.
The microbiota of moon snail egg collars is shaped by host-specific factors
Piedl, Karla; Aylward, Frank O.; Mevers, Emily (American Society for Microbiology, 2024-10-04)
Moon snails (Family: Naticidae) lay eggs using a mixture of mucus and sediment to form an egg mass commonly referred to as an egg collar. These egg collars do not appear to experience micro-biofouling or predation, and this observation led us to hypothesize that the egg collars possess a chemically rich microbiota that protect the egg collars from pathogens. Herein, we sought to gain an understanding of the bacterial composition of egg collars laid by a single species of moon snails, Neverita delessertiana, by amplifying and sequencing the 16S rRNA gene from the egg collar and sediment samples collected at four distinct geographical regions in southwest Florida. Relative abundance and non-metric multidimensional scaling plots revealed distinct differences in the bacterial composition between the egg collar and sediment samples. In addition, the egg collars had a lower α-diversity than the sediment, with specific genera being significantly enriched in the egg collars. Analysis of microorganisms consistent across two seasons suggests that Flavobacteriaceae make up a large portion of the core microbiota (36%-58% of 16S sequences). We also investigated the natural product potential of the egg collar microbiota by sequencing a core biosynthetic gene, the adenylation domains (ADs), within the gene clusters of non-ribosomal peptide synthetase (NRPS). AD sequences matched multiple modules within known NRPS gene clusters, suggesting that these compounds might be produced within the egg collar system. This study lays the foundation for future studies into the ecological role of the moon snail egg collar microbiota. IMPORTANCE Animals commonly partner with microorganisms to accomplish essential tasks, including chemically defending the animal host from predation and/or infections. Understanding animal-microbe partnerships and the molecules used by the microbe to defend the animals from pathogens or predation has the potential to lead to new pharmaceutical agents. However, very few of these systems have been investigated. A particularly interesting system is nutrient-rich marine egg collars, which often lack visible protections, and are hypothesized to harbor beneficial microbes that protect the eggs. In this study, we gained an understanding of the bacterial strains that form the core microbiota of moon snail egg collars and gained a preliminary understanding of their natural product potential. This work lays the foundation for future work to understand the ecological role of the core microbiota and to study the molecules involved in chemically defending the moon snail eggs.
Bokeelamides: Lipopeptides from Bacteria Associated with Marine Egg Masses
Campbell, Rose; Kyei, Lois; Piedl, Karla; Zhang, Zheye; Chen, Ming; Mevers, Emily (American Chemical Society, 2024-11)
Moon snails (family: Naticidae) lay egg masses that are rich in bacterial species distinct from the surrounding environment. We hypothesized that this microbiome chemically defends the moon snail eggs from predation and pathogens. Herein, we report the discovery of bokeelamides, new lipopeptides from the egg mass-associated bacterium, Ectopseudomonas khazarica, which were discovered using mass spectrometry (MS)-based metabolomics. The structures of the bokeelamides were elucidated using two-dimensional (2D) nuclear magnetic resonance (NMR), tandem MS, Marfey’s, and genomic analyses.
Chain-length-controllable upcycling of polyolefins to sulfate detergents
Munyaneza, Nuwayo Eric; Ji, Ruiyang; DiMarco, Adrian; Miscall, Joel; Stanley, Lisa; Rorrer, Nicholas; Qiao, Rui; Liu, Guoliang (Springer Nature, 2024-11-18)
Escalating global plastic pollution and the depletion of fossil-based resources underscore the urgent need for innovative end-of-life plastic management strategies in the context of a circular economy. Thermolysis is capable of upcycling end-of-life plastics to intermediate molecules suitable for downstream conversion to eventually high-value chemicals, but tuning the molar mass distribution of the products is challenging. Here we report a temperature-gradient thermolysis strategy for the conversion of polyethylene and polypropylene into hydrocarbons with tunable molar mass distributions. The whole thermolysis process is catalyst- and hydrogen-free. The thermolysis of polyethylene and polyethylene/polypropylene mixtures with tailored temperature gradients generated oil with an average chain length of ~C14. The oil featured a high concentration of synthetically useful α-olefins. Computational fluid dynamics simulations revealed that regulating the reactor wall temperature was the key to tuning the hydrocarbon distributions. Subsequent oxidation of the obtained α-olefins by sulfuric acid and neutralization by potassium hydroxide afforded sulfate detergents with excellent foaming behaviour and emulsifying capacity and low critical micelle concentration. Overall, this work provides a viable approach to producing value-added chemicals from end-of-life plastics, improving the circularity of the anthropogenic carbon cycle.
CoNST: Code Generator for Sparse Tensor Networks
Raje, Saurabh; Xu, Yufan; Rountev, Atanas; Valeev, Edward F.; Sadayappan, P. (ACM, 2024-08)
Sparse tensor networks represent contractions over multiple sparse tensors. Tensor contractions are higher-order analogs of matrix multiplication. Tensor networks arise commonly in many domains of scientific computing and data science. Such networks are typically computed using a tree of binary contractions. Several critical inter-dependent aspects must be considered in the generation of efficient code for a contraction tree, including sparse tensor layout mode order, loop fusion to reduce intermediate tensors, and the mutual dependence of loop order, mode order, and contraction order. We propose CoNST, a novel approach that considers these factors in an integrated manner using a single formulation. Our approach creates a constraint system that encodes these decisions and their interdependence, while aiming to produce reduced-order intermediate tensors via fusion. The constraint system is solved by the Z3 SMT solver and the result is used to create the desired fused loop structure and tensor mode layouts for the entire contraction tree. This structure is lowered to the IR of the TACO compiler, which is then used to generate executable code. Our experimental evaluation demonstrates significant performance improvements over current state-of-the-art sparse tensor compiler/library alternatives.
Polymer characterization by size-exclusion chromatography with multi-angle light scattering (SEC-MALS): a tutorial review
Matson, John B.; Steele, Anna Q.; Mase, Jonathan D.; Schulz, Michael D. (Royal Society Chemistry, 2024)
This tutorial review presents the theory and application of SEC-MALS with minimal equations and a focus on synthetic polymer characterization, serving as an entry point for polymer scientists who want to learn more about SEC-MALS. We discuss the principles of static light scattering, outline its capability to generate absolute weight-average molar mass values, and extend its application to SEC-MALS. Practical elements are emphasized, enabling researchers to appreciate how values for Mn, Mw, and Đ are determined in an SEC-MALS experiment and how experimental conditions and input values, such as the specific refractive index increment (dn/dc), influence the results. Several illustrative SEC-MALS experiments demonstrate the impact of separation quality on Mn (as opposed to Mw), the appearance of contaminants in SEC chromatograms from sample preparation, the influence of concentration on data quality, and how polymer topology affects molecular weight characterization in SEC. Finally, we address practical considerations, common issues, and persistent misconceptions.
High Modulus, Strut-like poly(ether ether ketone) Aerogels Produced from a Benign Solvent
Spiering, Glenn A.; Godshall, Garrett F.; Moore, Robert B. (MDPI, 2024-04-22)
Poly(ether ether ketone) (PEEK) was found to form gels in the benign solvent 1,3-diphenylacetone (DPA). Gelation of PEEK in DPA was found to form an interconnected, strut-like morphology composed of polymer axialites. To our knowledge, this is the first report of a strut-like morphology for PEEK aerogels. PEEK/DPA gels were prepared by first dissolving PEEK in DPA at 320 °C. Upon cooling to 50 °C, PEEK crystallizes and forms a gel in DPA. The PEEK/DPA phase diagram indicated that phase separation occurs by solid–liquid phase separation, implying that DPA is a good solvent for PEEK. The Flory–Huggins interaction parameter, calculated as χ₁₂ = 0.093 for the PEEK/DPA system, confirmed that DPA is a good solvent for PEEK. PEEK aerogels were prepared by solvent exchanging DPA to water then freeze-drying. PEEK aerogels were found to have densities between 0.09 and 0.25 g/cm³, porosities between 80 and 93%, and surface areas between 200 and 225 m²/g, depending on the initial gel concentration. Using nitrogen adsorption analyses, PEEK aerogels were found to be mesoporous adsorbents, with mesopore sizes of about 8 nm, which formed between stacks of platelike crystalline lamellae. Scanning electron microscopy and X-ray scattering were utilized to elucidate the hierarchical structure of the PEEK aerogels. Morphological analysis found that the PEEK/DPA gels were composed of a highly nucleated network of PEEK axialites (i.e., aggregates of stacked crystalline lamellae). The highly connected axialite network imparted robust mechanical properties on PEEK aerogels, which were found to densify less upon freeze-drying than globular PEEK aerogel counterparts gelled from dichloroacetic acid (DCA) or 4-chlorphenol (4CP). PEEK aerogels formed from DPA were also found to have a modulus–density scaling that was far more efficient in supporting loads than the poorly connected aerogels formed from PEEK/DCA or PEEK/4CP solutions. The strut-like morphology in these new PEEK aerogels also significantly improved the modulus to a degree that is comparable to high-performance crosslinked aerogels based on polyimide and polyurea of comparable densities.
Expanding the Biosynthetic Toolbox: The Potential and Challenges of In Vitro Type II Polyketide Synthase Research
Rivers, Max A. J.; Lowell, Andrew N. (MDPI, 2024-03-07)
Type II polyketide synthase (PKS) systems are a rich source of structurally diverse polycyclic aromatic compounds with clinically relevant antibiotic and chemotherapeutic properties. The enzymes responsible for synthesizing the polyketide core, known collectively as the minimal cassette, hold potential for applications in synthetic biology. The minimal cassette provides polyketides of different chain lengths, which interact with other enzymes that are responsible for the varied cyclization patterns. Additionally, the type II PKS enzyme clusters offer a wide repertoire of tailoring enzymes for oxidations, glycosylations, cyclizations, and rearrangements. This review begins with the variety of chemical space accessible with type II PKS systems including the recently discovered highly reducing variants that produce polyalkenes instead of the archetypical polyketide motif. The main discussion analyzes the previous approaches with an emphasis on further research that is needed to characterize the minimal cassette enzymes in vitro. Finally, the potential type II PKS systems hold the potential to offer new tools in biocatalysis and synthetic biology, particularly in the production of novel antibiotics and biofuels.
Synthesis and Crystallographic Characterization of Heteroleptic Ir(III) Complexes Containing the N-oxide Functional Group and Crystallographic Characterization of Ir(III) N-oxide Precursors
Stumbo, Emily E.; Hodge, Emarald K.; Williams, Matthew; Thornton, Diana A.; McMillen, Colin D.; Pienkos, Jared A. (MDPI, 2024-03-16)
The N-oxide functional group has been exploited for synthetic strategies and drug design, and it has been utilized in imaging agents. Herein, we present rare examples of neutral heteroleptic cyclometallated Ir(III) compounds that contain an uncoordinated N-oxide functional group. These species, along with others described within, were verified by NMR, EA, HRMS, and single-crystal X-ray analysis. N-oxide-containing Ir(III) species were prepared selectively in high yields > 66% from chloro-bridged Ir(III) dimers with Acipimox, a picolinate-type ligand containing the N-oxide functional group. Non-N-oxide analogs were synthesized in a similar fashion (yields > 77%). Electrochemical comparison (cyclic voltammetry) indicates that the presence of an N-oxide functional group anodically shifts the reduction potential, suggesting that the N-oxide is acting as an electron-withdrawing group in these species. Crystallographic studies were pursued to examine the coordination behavior of these N-oxides compared to their non-oxidized congeners. The Ir(III) complexes with Acipimox indeed leave the N-oxide uncoordinated and exposed on the complexes. The uncoordinated N-oxide group is influential in directing the packing structures of these complexes directly through C-H···O and O···π interactions at the N-oxide. The crystallographic characterization of cationic Ir(III) compounds with uncoordinated nitrogen atoms is also presented. The C-H···N interactions between these complexes form a variety of dimers, finite chains, and continuous chains. Future work will focus on functionalizing the cationic Ir(III) species into their corresponding N-oxide derivatives and rigorously characterizing how the N-oxide functional group impacts the optical properties of transition metal compounds in both cationic and neutral complexes.
Additive Manufacturing of Poly(phenylene Sulfide) Aerogels via Simultaneous Material Extrusion and Thermally Induced Phase Separation
Godshall, Garrett F.; Rau, Daniel A.; Williams, Christopher B.; Moore, Robert B. (Wiley-VCH GmbH, 2023-11)
Additive manufacturing (AM) of aerogels increases the achievable geometric complexity, and affords fabrication of hierarchically porous structures. In this work, a custom heated material extrusion (MEX) device prints aerogels of poly(phenylene sulfide) (PPS), an engineering thermoplastic, via in situ thermally induced phase separation (TIPS). First, pre-prepared solid gel inks are dissolved at high temperatures in the heated extruder barrel to form a homogeneous polymer solution. Solutions are then extruded onto a room-temperature substrate, where printed roads maintain their bead shape and rapidly solidify via TIPS, thus enabling layer-wise MEX AM. Printed gels are converted to aerogels via postprocessing solvent exchange and freeze-drying. This work explores the effect of ink composition on printed aerogel morphology and thermomechanical properties. Scanning electron microscopy micrographs reveal complex hierarchical microstructures that are compositionally dependent. Printed aerogels demonstrate tailorable porosities (50.0–74.8%) and densities (0.345–0.684 g cm⁻³), which align well with cast aerogel analogs. Differential scanning calorimetry thermograms indicate printed aerogels are highly crystalline (≈43%), suggesting that printing does not inhibit the solidification process occurring during TIPS (polymer crystallization). Uniaxial compression testing reveals that compositionally dependent microstructure governs aerogel mechanical behavior, with compressive moduli ranging from 33.0 to 106.5 MPa.
NAPE-PLD regulates specific baseline affective behaviors but is dispensable for inflammatory hyperalgesia
Chen, Irene; Murdaugh, Laura B.; Miliano, Cristina; Dong, Yuyang; Gregus, Ann M.; Buczynski, Matthew W. (Elsevier, 2023-06-14)
N-acyl-ethanolamine (NAEs) serve as key endogenous lipid mediators as revealed by manipulation of fatty acid amide hydrolase (FAAH), the primary enzyme responsible for metabolizing NAEs. Preclinical studies focused on FAAH or NAE receptors indicate an important role for NAE signaling in nociception and affective behaviors. However, there is limited information on the role of NAE biosynthesis in these same behavioral paradigms. Biosynthesis of NAEs has been attributed largely to the enzyme N-acylphosphatidylethanolamine Phospholipase D (NAPE-PLD), one of three pathways capable of producing these bioactive lipids in the brain. In this report, we demonstrate that Nape-pld knockout (KO) mice displayed reduced sucrose preference and consumption, but other baseline anxiety-like or depression-like behaviors were unaltered. Additionally, we observed sex-dependent responses in thermal nociception and other baseline measures in wildtype (WT) mice that were absent in Nape-pld KO mice. In the Complete Freund's Adjuvant (CFA) model of inflammatory arthritis, WT mice exhibited sex-dependent changes in paw edema that were lost in Nape-pld KO mice. However, there was no effect of Nape-pld deletion on arthritic pain-like behaviors (grip force deficit and tactile allodynia) in either sex, indicating that while NAPE-PLD may alter local inflammation, it does not contribute to pain-like behaviors associated with inflammatory arthritis. Collectively, these findings indicate that chronic and systemic NAPE-PLD inactivation will likely be well-tolerated, warranting further pharmacological evaluation of this target in other disease indications.
Molecular modeling of Poly(methyl methacrylate-block-acrylonitrile) as Precursors of Porous Carbon Fibers
Hao, Xi; Serrano, Joel; Liu, Guoliang; Cheng, Shengfeng (2023-04-22)
2D Hierarchical Microbarcodes with Expanded Storage Capacity for Optical Multiplex and Information Encryption
Worch, Josh; Xie, Yujie; Tong, Zaizai; Rho, Julia; Dove, Andrew; O'Reilly, Rachel (2023-11-28)
The design of nanosegregated fluorescent tags/barcodes by geometrical patterning with precise dimensions and hierarchies could integrate multilevel optical information within one carrier and enhance microsized barcoding techniques for ultrahigh-density optical data storage and encryption. However, precise control of the spatial distribution in micro/nanosized matrices intrinsically limits the accessible barcoding applications in terms of material design and construction. Here, crystallization forces are leveraged to enable a rapid, programmable molecular packing and rapid epitaxial growth of fluorescent units in 2D via crystallization-driven self-assembly. The fluorescence encoding density, scalability, information storage capacity, and decoding techniques of the robust 2D polymeric barcoding platform are explored systematically. These results provide both a theoretical and an experimental foundation for expanding the fluorescence storage capacity, which is a longstanding challenge in state-of-the-art microbarcoding techniques and establish a generalized and adaptable coding platform for high-throughput analysis and optical multiplexing.
Click Step-Growth Polymerization and E/Z Stereochemistry Using Nucleophilic Thiol-yne/-ene Reactions: Applying Old Concepts for Practical Sustainable (Bio)Materials
Worch, Joshua C.; Dove, Andrew P. (American Chemical Society, 2022-08-25)
Polymer sustainability is synonymous with "bioderived polymers" and the zeitgeist of "using renewable feedstocks". However, this sentiment does not adequately encompass the requirements of sustainability in polymers. In addition to recycling considerations and mechanical performance, following green chemistry principles also needs to be maximized to improve the sustainability of polymer synthesis. The synthetic cost (i.e., maximizing atom economy, reducing chemical hazards, and lowering energy requirements) of producing polymers should be viewed as equally important to the monomer source (biomass vs petrol platform chemicals). Therefore, combining the use of renewable feedstocks with efficient syntheses and green chemistry principles is imperative to delivering truly sustainable polymers. The high efficiency, atom economy, and single reaction trajectories that define click chemistry reactions position them as ideal chemical approaches to synthesize polymers in a sustainable manner while simultaneously expanding the structural scope of accessible polymers from sustainably sourced chemicals.Click step-growth polymerization using the thiol-yne Michael addition, a reaction first reported over a century ago, has emerged as an extremely mild and atom-efficient pathway to yield high-performance polymers with controllable E/Z stereochemistry along the polymer backbone. Building on studies of aromatic thiol-yne polymers, around 10 years ago our group began investigating the thiol-yne reaction for the stereocontrolled synthesis of alkene-containing aliphatic polyesters. Our early studies established a convenient path to high-molecular-weight (>100 kDa) E-rich or Z-rich step-growth polymers by judiciously changing the catalyst and/or reaction solvent. This method has since been adapted to synthesize fast-degrading polyesters, high-performance polyamides, and resilient hydrogel biomaterials. Across several systems, we have observed dramatic differences in material properties among polymers with different alkene stereochemistry.We have also explored the analogous thiol-ene Michael reaction to create high-performance poly(ester-urethanes) with precise E/Z stereochemistry. In contrast to the stereoselective thiol-yne polymerization, here the use of monomers with predefined E/Z (geometric) isomerism (arising from either alkenes or the planar rigidity of ring units) affords polymers with total control over stereochemistry. This advancement has enabled the synthesis of tough, degradable materials that are derived from sustainable monomer feedstocks. Employing isomers of sugar-derived isohexides, bicyclic rigid-rings possessing geometric isomerism, led to degradable polymers with fundamentally opposing mechanical behavior (i.e., plastic vs elastic) simply by adjusting the stereochemistry of the isohexide. In this Account, we feature our investigation of thiol-yne/-ene click step-growth polymers and efforts to establish structure-property relationships toward degradable materials with practical mechanical performance in the context of sustainable polymers and/or biomaterials. We have paid attention to installing and controlling geometric isomerism by using these click reactions, an overarching objective of our work in this research area. The exquisite control of geometric isomerism that is possible within polymer backbones, as enabled by convenient click chemistry reactions, showcases a powerful approach to creating multipurpose degradable polymers.
Installing a Single Monomer within Acrylic Polymers Using Photoredox Catalysis
Baker, Jared G.; Zhang, Richard; Figg, C. Adrian (American Chemical Society, 2023-12-21)
Incorporating exactly one monomer at a defined position during a chain polymerization is exceptionally challenging due to the statistical nature of monomer addition. Herein, photoinduced electron/energy transfer (PET) enables the incorporation of exactly one vinyl ether into polyacrylates synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Near-quantitative addition (>96%) of a single vinyl ether is achieved while retaining >99% of the thiocarbonylthio chain ends. Kinetic studies reveal that performing the reactions at 2 °C limits unwanted chain breaking events. Finally, the syntheses of diblock copolymers are reported where molecular weights and dispersities are well-controlled on either side of the vinyl ether. Overall, this report introduces an approach to access acrylic copolymers containing exactly one chemical handle at a defined position, enabling novel macromolecular architectures to probe structure-function properties, introduce sites for de/reconstruction, store information, etc.
Spatially-Encoding Hydrogels With DNA to Control Cell Signaling
Ramani, Namrata; Figg, C. Adrian; Anderson, Alex J.; Winegar, Peter H.; Oh, EunBi; Ebrahimi, Sasha B.; Samanta, Devleena; Mirkin, Chad A. (Wiley, 2023-09)
Patterning biomolecules in synthetic hydrogels offers routes to visualize and learn how spatially-encoded cues modulate cell behavior (e.g., proliferation, differentiation, migration, and apoptosis). However, investigating the role of multiple, spatially defined biochemical cues within a single hydrogel matrix remains challenging because of the limited number of orthogonal bioconjugation reactions available for patterning. Herein, a method to pattern multiple oligonucleotide sequences in hydrogels using thiol-yne photochemistry is introduced. Rapid hydrogel photopatterning of hydrogels with micron resolution DNA features (≈1.5 µm) and control over DNA density are achieved over centimeter-scale areas using mask-free digital photolithography. Sequence-specific DNA interactions are then used to reversibly tether biomolecules to patterned regions, demonstrating chemical control over individual patterned domains. Last, localized cell signaling is shown using patterned protein-DNA conjugates to selectively activate cells on patterned areas. Overall, this work introduces a synthetic method to achieve multiplexed micron resolution patterns of biomolecules onto hydrogel scaffolds, providing a platform to study complex spatially-encoded cellular signaling environments.
Operando characterization and regulation of metal dissolution and redeposition dynamics near battery electrode surface
Zhang, Yuxin; Hu, Anyang; Xia, Dawei; Hwang, Sooyeon; Sainio, Sami; Nordlund, Dennis; Michel, F. Marc; Moore, Robert B.; Li, Luxi; Lin, Feng (Nature Portfolio, 2023-07)
Mn dissolution has been a long-standing, ubiquitous issue that negatively impacts the performance of Mn-based battery materials. Mn dissolution involves complex chemical and structural transformations at the electrode–electrolyte interface. The continuously evolving electrode–electrolyte interface has posed great challenges for characterizing the dynamic interfacial process and quantitatively establishing the correlation with battery performance. In this study, we visualize and quantify the temporally and spatially resolved Mn dissolution/redeposition (D/R) dynamics of electrochemically operating Mn-containing cathodes. The particle-level and electrode-level analyses reveal that the D/R dynamics is associated with distinct interfacial degradation mechanisms at different states of charge. Our results statistically differentiate the contributions of surface reconstruction and Jahn–Teller distortion to the Mn dissolution at different operating voltages. Introducing sulfonated polymers (Nafion) into composite electrodes can modulate the D/R dynamics by trapping the dissolved Mn species and rapidly establishing local Mn D/R equilibrium. This work represents an inaugural effort to pinpoint the chemical and structural transformations responsible for Mn dissolution via an operando synchrotron study and develops an effective method to regulate Mn interfacial dynamics for improving battery performance.

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