Piezoelectricity, the linear relationship between stress and induced electrical charge, has attracted recent interest due to its manifestation in biological molecules such as synthetic polypeptides or amino acid crystals, including gamma (γ) glycine. It has also been demonstrated in bone, collagen, elastin and the synthetic bone mineral hydroxyapatite. Piezoelectric coefficients exhibited by these biological materials are generally low, typically in the range of 0.1-10 pm V, limiting technological applications. Guided by quantum mechanical calculations we have measured a high shear piezoelectricity (178 pm V) in the amino acid crystal beta (β) glycine, which is of similar magnitude to barium titanate or lead zirconate titanate. Our calculations show that the high piezoelectric coefficients originate from an efficient packing of the molecules along certain crystallographic planes and directions. The highest predicted piezoelectric voltage constant for β-glycine crystals is 8 V mN, which is an order of magnitude larger than the voltage generated by any currently used ceramic or polymer.

Research on the piezoelectric response of biomolecules has intensified following demonstration of open circuit voltages of over 20 V in biopiezoelectric generators. Organic piezoelectric nanotubes, fibers, and micro-islands have been grown and studied; however, the lack of fundamental understanding of the piezoelectric effect in nature hinders the rational design of biomaterials to provide a tailor-made piezoelectric response. Advances in high performance computing have facilitated the use of quantum mechanical calculations to predict the full piezoelectric tensor of biomolecular crystals, including amino acids and small peptides. By identifying directions of high piezoelectric response, the simulations can guide experimental crystal growth, device fabrication and electrical testing, which have led to the demonstration of unprecedented piezoelectric responses in organic crystals on the order of 200 pC/N. These large responses arise from strong supramolecular dipoles, which can be tuned by molecular chemistry and packing, opening new opportunities for the realization of technologically useful piezoelectric devices from renewable materials. The amino acids predicted to exhibit the highest piezoelectric response, such as glycine, hydroxyproline and lysine, are anticipated to be used to engineer highly piezoelectric peptides in the future. With improved scaling of advanced computational methods, such as density functional perturbation theory, the research community can begin to efficiently screen peptide structures for enhanced electromechanical properties. This capability will accelerate the experimental development of devices and provide much-needed insight into the evolution of a hierarchical relation in biological materials starting from strongly piezoelectric building blocks.

Molecular stacking modes, generally classified as H-, J-, and X-aggregation, play a key role in determining the optoelectronic properties of organic crystals. However, the control of stacking transformation of a specific molecule is an unmet challenge, and a priori prediction of the performance in different stacking modes is extraordinarily difficult to achieve. In particular, the existence of hybrid stacking modes and their combined effect on physicochemical properties of molecular crystals are not fully understood. Herein, unexpected stacking transformation from H- to J- and X-aggregation is observed in the crystal structure of a small heterocyclic molecule, 4,4′-bipyridine (4,4′-Bpy), upon coassembly with N -acetyl- l -alanine (AcA), a nonaromatic amino acid derivative. This structural transformation into hybrid stacking mode improves physicochemical properties of the cocrystals, including a large red-shifted emission, enhanced supramolecular chirality, improved thermal stability, and higher mechanical properties. While a single crystal of 4,4′-Bpy shows good optical waveguiding and piezoelectric properties due to the uniform elongated needles and low symmetry of crystal packing, the significantly lower band gap and resistance of the cocrystal indicate improved conductivity. This study not only demonstrates cocrystallization-induced packing transformation between H-, J-, and X-aggregations in the solid state, leading to tunable mechanical and optoelectronic properties, but also will inspire future molecular design of organic functional materials by the coassembly strategy.

Realization of a self-assembled, nontoxic and eco-friendly piezoelectric device with high-performance, sensitivity and reliability is highly desirable to complement conventional inorganic and polymer based materials. Hierarchically organized natural materials such as collagen have long been posited to exhibit electromechanical properties that could potentially be amplified via molecular engineering to produce technologically relevant piezoelectricity. Here, by using a simple, minimalistic, building block of collagen, we fabricate a peptide-based piezoelectric generator utilising a radically different helical arrangement of Phe-Phe-derived peptide, Pro-Phe-Phe and Hyp-Phe-Phe, based only on proteinogenic amino acids. The simple addition of a hydroxyl group increases the expected piezoelectric response by an order of magnitude (d35 = 27 pm V−1). The value is highest predicted to date in short natural peptides. We demonstrate tripeptide-based power generator that produces stable max current >50 nA and potential >1.2 V. Our results provide a promising device demonstration of computationally-guided molecular engineering of piezoelectricity in peptide nanotechnology.

Single crystal L-amino acids can exhibit technologically useful piezoelectric and nonlinear optical properties. Here we predict, using density functional theory, the piezoelectric charge and strain and voltage tensors of the racemic amino acid DL alanine, and use the modeling data to guide the first macroscopic and nanoscopic piezoelectric measurements on DL-alanine single crystals and polycrystalline aggregates. We demonstrate voltage generation of up to 0.8 V from DL-alanine crystal films under simple manual compression, twice as high as other amino acid crystals. Our results suggest that net molecular chirality is not a prerequisite for piezoelectric behavior in organic crystals. The transducer presented herein demonstrates that DL-alanine crystals can be used in applications such as temperature and force measurement in biosensors, data storage in flexible electronic devices, and mechanical actuation in energy harvesters.