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  1. Abstract

    Bacterial natural product biosynthetic genes, canonically clustered, have been increasingly found to rely on hidden enzymes encoded elsewhere in the genome for completion of biosynthesis. The study and application of lanthipeptides are frequently hindered by unclustered protease genes required for final maturation. Here, we establish a global correlation network bridging the gap between lanthipeptide precursors and hidden proteases. Applying our analysis to 161,954 bacterial genomes, we establish 5209 correlations between precursors and hidden proteases, with 91 prioritized. We use network predictions and co-expression analysis to reveal a previously missing protease for the maturation of class I lanthipeptide paenilan. We further discover widely distributed bacterial M16B metallopeptidases of previously unclear biological function as a new family of lanthipeptide proteases. We show the involvement of a pair of bifunctional M16B proteases in the production of previously unreported class III lanthipeptides with high substrate specificity. Together, these results demonstrate the strength of our correlational networking approach to the discovery of hidden lanthipeptide proteases and potentially other missing enzymes for natural products biosynthesis.

  2. Abstract

    Self‐assembling peptides are a popular vector for therapeutic cargo delivery due to their versatility, tunability, and biocompatibility. Accurately predicting secondary and supramolecular structures of self‐assembling peptides is essential for de novo peptide design. However, computational modeling of such assemblies is not yet able to accurately predict structure formation for many peptide sequences. This review identifies patterns in literature between secondary and supramolecular structures, primary sequences, and applications to provide a guide for informed peptide design. An overview of peptide structures, their applications as nanocarriers, and analytical methods for characterizing secondary and supramolecular structure is examined. A top‐down approach is then used to identify trends between peptide sequence and assembly structure from the current literature, including an analysis of the drivers at work, such as local and nonlocal sequence effects and solution conditions.

  3. Abstract

    Cytochrome P450 OleT is a fatty acid decarboxylase that catalyzes the production of olefins with biofuel and synthetic applications. However, the relatively sluggish catalytic efficiency of the enzyme limits its applications. Here, we report the application of a novel class of benzene containing small molecules to improve the OleT activity. The UV‐Vis spectroscopy study and molecular docking results confirmed the high proximity of the small molecules to the heme group of OleT. Up to 6‐fold increase of product yield has been achieved in the small molecule‐modulated enzymatic reactions. Our work thus sheds the light to the application of small molecules to increase the OleT catalytic efficiency, which could be potentially used for future olefin productions.

  4. Abstract

    To produce multi-dopant ferrite nanoparticles, the ‘Extended LaMer’ and seed-mediated growth techniques were combined by first utilizing traditional thermal decomposition of metal acetylacetonates to produce seed particles, followed by a continuous injection of metal oleate precursors to increase the volume of the seed particles. With the choice of precursors for the seeding and dripping stage, we successfully synthesized particles with manganese precursor for seeding and cobalt precursor for dripping (Mn0.18Co1.04Fe1.78O4, 17.6 ± 3.3 nm), and particles with cobalt precursors for seeding and manganese precursors for dripping (Mn0.31Co0.74Fe1.95O4, 19.0 ± 1.9 nm). Combining transmission electron microscopy, energy-dispersive x-ray spectroscopy, x-ray diffraction, and vibrating sample magnetometry, we conclude that the seed-mediated drip method is a viable method to produce multi-dopant ferrite nanoparticles, and the size of the particles was mostly determined by the seeding stage, while the magnetic properties were more affected by the dripping stage.

  5. Abstract

    Although dipolar forces between copolymer chains are relatively weak, they result in ubiquitous inter‐ and/or intramolecular interactions which are particularly critical in achieving the mechanical integrity of polymeric materials. In this study, a route is developed to obtain self‐healable properties in thermoplastic copolymers that rely on noncovalent dipolar interactions present in essentially all macromolecules and particularly fluorine‐containing copolymers. The combination of dipolar interactions between C─F and C═O bonds as well as CH2/CH3entities facilitates self‐healing without external intervention. The presence of dipole‐dipole, dipole‐induced dipole, and induced‐dipole induced dipole interactions leads to a viscoelastic response that controls macroscopic autonomous multicycle self‐healing of fluorinated copolymers under ambient conditions. Energetically favorable dipolar forces attributed to monomer sequence and monomer molar ratios induces desirable copolymer tacticities, enabling entropic energy recovery stored during mechanical damage. The use of dipolar forces instead of chemical or physical modifications not only eliminates additional alternations enabling multiple damage‐repair cycles but also provides further opportunity for designing self‐healable commodity thermoplastics. These materials may offer numerous applications, ranging from the use in electronics, ion batteries, H2fuel dispense hoses to self‐healable pet toys, packaging, paints and coatings, and many others.

  6. Abstract

    Known for their adaptability to surroundings, capability of transport control of molecules, or the ability of converting one type of energy to another as a result of external or internal stimuli, responsive polymers play a significant role in advancing scientific discoveries that may lead to an array of diverge applications. This review outlines recent advances in the developments of selected commodity polymers equipped with stimuli‐responsiveness to temperature, pH, ionic strength, enzyme or glucose levels, carbon dioxide, water, redox agents, electromagnetic radiation, or electric and magnetic fields. Utilized diverse applications ranging from drug delivery to biosensing, dynamic structural components to color‐changing coatings, this review focuses on commodity acrylics, epoxies, esters, carbonates, urethanes, and siloxane‐based polymers containing responsive elements built into their architecture. In the context of stimuli‐responsive chemistries, current technological advances as well as a critical outline of future opportunities and applications are also tackled.

  7. Abstract

    A non‐volatile conjugated polymer‐based electrochemical memristor (cPECM), derived from sodium 4‐[(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐2‐yl)methoxy]butane‐2‐sulfonate (S‐EDOT), is fabricated through roll‐to‐roll printing and exhibited neuromorphic properties. The 3‐terminal device employed a “read” channel where conductivity of the water‐soluble, self‐doped S‐PEDOT is equated to synaptic weight and was electrically decoupled from the programming electrode. For the model system, a +2500 mV programming pulse of 100 ms duration resulted in a 0.136 μS resolution in conductivity change, giving over 1000 distinct conductivity states for one cycle. The minimum programming power requirements of the cPECM was 0.31 pJ mm−2and with advanced printing techniques, a 0.1 fJ requirement for a 20 μm device is achievable. The mathematical operations of addition, subtraction, multiplication, and division are demonstrated with a single cPECM, as well as the logic gates AND, OR, NAND, and NOR. This demonstration of a printed cPECM is the first step toward the implementation of a mass produced electrochemical memristor that combines information storage and processing and may allow for the realization of printable artificial neural networks.


    Cobaltocenium‐containing polyelectrolyte block copolymer nanoparticles were prepared via polymerization‐induced self‐assembly (PISA) using aqueous dispersion RAFT polymerization. The cationic steric stabilizer was a macromolecular chain‐transfer agent (macro‐CTA) based on poly(2‐cobaltocenium amidoethyl methacrylate chloride) (PCoAEMACl), and the core‐forming block was poly(2‐hydroxypropyl methacrylate) (PHPMA). Stable cationic spherical nanoparticles were formed in aqueous solution with low dispersity without adding any salts. The chain extension of macro‐CTA with HPMA was efficient and fast. The effects of block copolymer compositions, solid content, charge density, and addition of salts were studied. It was found that the degree of polymerization of both the stabilizer PCoAEMACl and the core‐forming PHPMA had a strong influence on the size of nanoparticles. © 2019 Wiley Periodicals, Inc. J. Polym. Sci.2020,58, 77–83

  9. Abstract

    Recent advances of supramolecular chemistry utilized in the development of self‐healing polymers have revealed that the rate and equilibrium constants of bond dissociation/re‐association, bonding directionality, chain relaxation time, decay rate of chain relaxation after damage, and cluster formation may impact the healing efficiency in a given environment. This review provides an assessment of supramolecular chemistries responsible for self‐healing using H‐bonding, metal–ligand, host–guest, ionic, π–π, and hydrophobic interactions. The impact of these chemistries on self‐healing is examined for various polymeric systems with multifunctional applications which are unique to supramolecular networks. This review also discusses the driving forces leading to physical damage closure in the context of supramolecular bond dynamics, providing insights into the design principles to achieve efficient recovery.

  10. Abstract

    The predictive self‐assembly of tunable nanostructures is of great utility for broad nanomaterial investigations and applications. The use of equilibrium‐based approaches however prevents independent feature size control. Kinetic‐controlled methods such as persistent micelle templates (PMTs) overcome this limitation and maintain constant pore size by imposing a large thermodynamic barrier to chain exchange. Thus, the wall thickness is independently adjusted via addition of material precursors to PMTs. Prior PMT demonstrations added water‐reactive material precursors directly to aqueous micelle solutions. That approach depletes the thermodynamic barrier to chain exchange and thus limits the amount of material added under PMT‐control. Here, an ex situ hydrolysis method is developed for TiO2that mitigates this depletion of water and nearly decouples materials chemistry from micelle control. This enables the widest reported PMT range (M:T = 1.6–4.0), spanning the gamut from sparse walls to nearly isolated pores with ≈2 Å precision adjustment. This high‐resolution nanomaterial series exhibits monotonic trends where PMT confinement within increasing wall‐thickness leads to larger crystallites and an increasing extent of lithiation, reaching Li0.66TiO2. The increasing extent of lithiation with increasing anatase crystallite dimensions is attributed to the size‐dependent strain mismatch of anatase and bronze polymorph mixtures.