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1. On the Search of a Silver Bullet for the Preparation of Bioinspired Molecular Electrets with Propensity to Transfer Holes at High Potentials

   https://doi.org/10.3390/biom11030429  

   Derr, James Bennett; Rybicka-Jasińska, Katarzyna; Espinoza, Eli Misael; Morales, Maryann; Billones, Mimi Karen; Clark, John Anthony; Vullev, Valentine Ivanov (March 2021, Biomolecules)

   null (Ed.)

   Biological structure-function relationships offer incomparable paradigms for charge-transfer (CT) science and its implementation in solar-energy engineering, organic electronics, and photonics. Electrets are systems with co-directionally oriented electric dopes with immense importance for CT science, and bioinspired molecular electrets are polyamides of anthranilic-acid derivatives with designs originating from natural biomolecular motifs. This publication focuses on the synthesis of molecular electrets with ether substituents. As important as ether electret residues are for transferring holes under relatively high potentials, the synthesis of their precursors presents formidable challenges. Each residue in the molecular electrets is introduced as its 2-nitrobenzoic acid (NBA) derivative. Hence, robust and scalable synthesis of ether derivatives of NBA is essential for making such hole-transfer molecular electrets. Purdie-Irvine alkylation, using silver oxide, produces with 90% yield the esters of the NBA building block for iso-butyl ether electrets. It warrants additional ester hydrolysis for obtaining the desired NBA precursor. Conversely, Williamson etherification selectively produces the same free-acid ether derivative in one-pot reaction, but a 40% yield. The high yields of Purdie-Irvine alkylation and the selectivity of the Williamson etherification provide important guidelines for synthesizing building blocks for bioinspired molecular electrets and a wide range of other complex ether conjugates. 

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2. What defines biomimetic and bioinspired science and engineering?

   https://doi.org/10.1515/pac-2021-0323  

   Rybicka-Jasińska, Katarzyna; Derr, James B.; Vullev, Valentine I. (June 2021, Pure and Applied Chemistry)

   null (Ed.)

   Abstract Biomimicry, biomimesis and bioinspiration define distinctly different approaches for deepening the understanding of how living systems work and employing this knowledge to meet pressing demands in engineering. Biomimicry involves shear imitation of biological structures that most often do not reproduce the functionality that they have while in the living organisms. Biomimesis aims at reproduction of biological structure-function relationships and advances our knowledge of how different components of complex living systems work. Bioinspiration employs this knowledge in abiotic manners that are optimal for targeted applications. This article introduces and reviews these concepts in a global historic perspective. Representative examples from charge-transfer science and solar-energy engineering illustrate the evolution from biomimetic to bioinspired approaches and show their importance. Bioinspired molecular electrets, aiming at exploration of dipole effects on charge transfer, demonstrate the pintail impacts of biological inspiration that reach beyond its high utilitarian values. The abiotic character of bioinspiration opens doors for the emergence of unprecedented properties and phenomena, beyond what nature can offer. 

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3. Molecular design and engineering of biomimetic, bioinspired and biologically derived materials

   https://doi.org/10.1039/d0me90011g  

   Jayaraman, Arthi; Patel, Amish J. (March 2020, Molecular Systems Design & Engineering)

   Guest Editors Arthi Jayaraman and Amish Patel introduce this themed collection of papers showcasing the latest research on the molecular design and engineering of bioinspired, biological and/or biomimetic materials. 

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4. Classification of Biological and Bioinspired Aquatic Systems: A Review

   https://doi.org/10.1016/j.oceaneng.2017.11.012  

   R. Salazar, V. Fuentes (January 2018, Ocean engineering)

   Robotic systems capable of aquatic movement has increased exploitation in recent years due to the diverse range of missions that can be performed in otherwise hostile environments. These aquatic unmanned vehicles (AUVs) have begun to transition to systems that replicate biological animals as they are already extremely efficient at moving in aqueous environments. The result is the abandonment of inefficient propeller based locomotion for a biological locomotion type suitable for the specific mission. There is a diverse range of biological locomotion's available with animals that give a range of criteria to follow. In this review, existing aquatic animals and found AUVs are classified. How the bioinspired systems compare to the animals in their locomotion is investigated and discussed. Then, it is discussed what makes these systems bioinspired and biomimetic, and the AUVs that fall into these distinctive categories. Limitations and future recommendations on possible improvements for these systems are offered. 

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5. Bioinspired Design Rules for Flipping across the Lipid Bilayer from Systematic Simulations of Membrane Protein Segments

   https://doi.org/10.1039/D5ME00032G  

   Park, ByungUk; Van_Lehn, Reid C (May 2025, Molecular Systems Design & Engineering)

   The orientation of integral membrane proteins (IMPs) with respect to the membrane is established during protein synthesis and insertion into the membrane. After synthesis, IMP orientation is thought to be fixed due to the thermodynamic barrier for “flipping” protein loops or helices across the hydrophobic core of the membrane in a process analogous to lipid flip-flop. A notable exception is EmrE, a homodimeric IMP with an N-terminal transmembrane helix that can flip across the membrane until flipping is arrested upon dimerization. Understanding the features of the EmrE sequence that permit this unusual flipping behavior would be valuable for guiding the design of synthetic materials capable of translocating or flipping charged groups across lipid membranes. To elucidate the molecular mechanisms underlying flipping in EmrE and derive bioinspired design rules, we employ atomistic molecular dynamics simulations and enhanced sampling techniques to systematically investigate the flipping of truncated segments of EmrE. Our results demonstrate that a membrane-exposed charged glutamate residue at the center of the N-terminal helix lowers the energetic barrier for flipping (from ~12.1 kcal mol-1 to ~5.4 kcal mol-1) by stabilizing water defects and minimizing membrane perturbation. Comparative analysis reveals that the marginal hydrophobicity of this helix, rather than the marginal hydrophilicity of its loop, is the key determinant of flipping propensity. Our results further indicate that interhelical hydrogen bonding upon dimerization inhibits flipping. These findings establish several bioinspired design principles to govern flipping in related materials: (1) marginally hydrophobic helices with membrane-exposed charged groups promote flipping, (2) modulating protonation states of membrane-exposed groups tunes flipping efficiency, and (3) interhelical hydrogen bonding can be leveraged to arrest flipping. These insights provide a foundation for engineering synthetic peptides, engineered proteins, and biomimetic nanomaterials with controlled flipping or translocation behavior for applications in intracellular drug delivery and membrane protein design. 

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