Polishchuk, I. | bioRxiv Science

bioRxiv2020

Bio-Inspired Molecular Bridging in a Hybrid Perovskite Leads to Enhanced Stability and Tunable Properties

Hybrid organic-inorganic halide perovskites demonstrate high potential in several applications such as solar cells, field-effect transistors, light-emitting diodes and more. However, the main drawback which limits their use in such applications is their low stability in humid conditions. In this paper we implement one of Natures strategies found in bio-crystals in order to improve the stability of the hybrid perovskite methylammonium lead bromide (MAPbBr3) in water, as well as to tune its structure, optical and thermal properties. This was achieved, for the first time, by the incorporation of amino acids into the lattice of MAPbBr3. The amino acid lysine, which possesses two NH3+ groups, is incorporated into the hybrid unit cell, by substituting two methylammonium ions and serves as a "molecular bridge". This incorporation induces a decrease in the lattice parameter of the host, accompanied with an increase in the band gap and noticeable changes in its morphology. Furthermore, we observed an increase in thermal expansion coefficient and a shift of the phase transformation temperature of the hybrid crystal. The level of amino acid incorporation depends on the conditions of crystallization, which also influence the extent of MAPbBr3 band gap changes. Notably, lysine incorporation strongly increases the perovskite stability in water. This study demonstrates the unique and promising approach to tune the properties and stability of hybrid perovskites via this novel bio-inspired route.

bioengineering↗

bioRxiv2020

Acidic monosaccharides become incorporated into calcite single crystals

Carbohydrates, along with proteins and peptides, are known to represent a major class of biomacromolecules involved in calcium carbonate biomineralization. However, in spite of multiple physical or biochemical characterizations, the explicit role of saccharide macromolecules (long chains of carbohydrate molecules) is not yet understood in mineral deposition. In the present study we investigated the influence of two common acidic monosaccharides (MSs), which are the simplest form of carbohydrates and are represented here by glucuronic and galacturonic acids, on the formation of calcite crystals in vitro. We show that the size, morphology and microstructure of calcite crystals are altered when they are grown in the presence of these MSs. More importantly, MSs were found to become incorporated into the calcite crystalline lattice and induce anisotropic lattice distortions, a widely studied phenomenon in other biomolecules related to CaCO3 biomineralization but never before reported in the case of single MSs. Changes in the calcite lattice induced by MS incorporation were precisely determined by the technique of high-resolution synchrotron powder X-ray diffraction. We believe that the results of this research may deepen our understanding of the interaction of saccharide polymers with an inorganic host and shed light on the implications of carbohydrates for biomineralization processes.

bioengineering↗