Evolutionary selection of enzymatically synthesized semiconductors from biomimetic mineralization vesicles

Bawazer, Lukmaan A.; Izumi, Michi; Kolodin, Dmitriy; Neilson, James R.; Schwenzer, Birgit; Morse, Daniel E.

doi:10.1073/pnas.1116958109

Cited by 44 publications

(43 citation statements)

References 51 publications

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“…Native silicatein harvested from sea sponge or engineered forms produced recombinantly are active for biomineralization of silica and titania into structures that are amorphous or crystalline (7,18,19). In particular, biomineralization confined within an inverse micelle using an engineered silicatein has been demonstrated to form crystalline nanomaterials (20).With regard to semiconducting metal sulfides, the majority of prior reports have used biological components to template structure during synthesis from reactive sulfur precursors, typically Na 2 S (21-23). For example, peptides displayed on the surface of bacteriophage have been used to produce intricately ordered CdS and ZnS nanowires (24), whereas engineered viral particles (25, 26) along with recombinant, self-assembled cage-like proteins (27) have served as nucleation cavities for CdS nanocrystals.…”

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Single-enzyme biomineralization of cadmium sulfide nanocrystals with controlled optical properties

Dunleavy

Kiely

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

115

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Nature has evolved several unique biomineralization strategies to direct the synthesis and growth of inorganic materials. These natural systems are complex, involving the interaction of multiple biomolecules to catalyze biomineralization and template growth. Herein we describe the first report to our knowledge of a single enzyme capable of both catalyzing mineralization in otherwise unreactive solution and of templating nanocrystal growth. A recombinant putative cystathionine γ-lyase (smCSE) mineralizes CdS from an aqueous cadmium acetate solution via reactive H 2 S generation from L-cysteine and controls nanocrystal growth within the quantum confined size range. The role of enzymatic nanocrystal templating is demonstrated by substituting reactive Na 2 S as the sulfur source. Whereas bulk CdS is formed in the absence of the enzyme or other capping agents, nanocrystal formation is observed when smCSE is present to control the growth. This dualfunction, single-enzyme, aerobic, and aqueous route to functional material synthesis demonstrates the powerful potential of engineered functional material biomineralization.cadmium sulfide | quantum dot | biomineralization | enzyme | nanoparticle B iological systems have evolved a diverse array of mechanisms to synthesize inorganic materials from aqueous solutions under ambient conditions. This inherent control over material properties has created interest in using these biological routes to synthesize materials (1-3) such as biosilica from sponges and diatoms (4-8), biogenic CaCO 3 from mollusks (9-12), and magnetic particles from magnetotactic bacteria (13-15). Designing a biomineralization strategy requires control of both the material composition and structure; in nature, this control is typically achieved through the assembly of a multiprotein complex, including both structuredirecting proteins and proteins responsible for mineralization of a specific composition. In the current work, we demonstrate the reduction of this complexity to its simplest form: a single enzyme capable of both catalyzing CdS mineralization and controlling particle size within the quantum confined size range to form functional biomineralized CdS quantum dots.Two of the most studied biomineralization proteins are perlucin and silicatein. Perlucin (16) has been shown to mineralize crystalline forms of CaCO 3 , a common structural material that constitutes the shell of many marine organisms, in the form of organic-inorganic composites. The role of the nacre protein perlucin in crystallite templating has been elucidated through experiments demonstrating crystallite formation in the presence of purified perlucin, and perlucin selectively being removed from solution during crystallite formation in the presence of a mixture of water-soluble, nacre-associated proteins (17). Native silicatein harvested from sea sponge or engineered forms produced recombinantly are active for biomineralization of silica and titania into structures that are amorphous or crystalline (7,18,19). In particular, biomineralizatio...

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confidence: 99%

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confidence: 99%

Single-enzyme biomineralization of cadmium sulfide nanocrystals with controlled optical properties

Dunleavy

Kiely

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

115

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“…Experimental strategies are therefore required which enable rapid screening of a potentially vast reaction space. As an elegant approach, DNA-based technologies have been used to evolve libraries of nucleic acids, [ 14 ] short polypeptides [ 15 ] and enzymes [ 16 ] which, when combined with appropriate screening technologies, can be used to identify active biopolymer sequences. However, plate-reader (Figure 1 B).…”

Section: Doi: 101002/adma201403185mentioning

confidence: 99%

Genetic Algorithm‐Guided Discovery of Additive Combinations That Direct Quantum Dot Assembly

et al. 2014

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these techniques are limited by the requirement for complex enzymatic reactions. As an alternative strategy that bypasses the need for genetic engineering, combinatorial methods can be employed. These can be used to explore tens to hundreds of reaction conditions, where the most promising or "lead" conditions may be selected based on the structures or properties of the resultant material. [ 17,18 ] Lead conditions can then be used to narrow the reaction landscape in successive screening rounds. Surprisingly, although combinatorial methods are often used in solid-state chemistry to explore, for example, different reagent compositions, [ 18 ] we are not aware of their use in identifying soluble additives capable of directing mineralization.In this article we demonstrate how combinatorial methods can be used in conjunction with effi cient screening processes to rapidly identify combinations of small organic molecules that are capable of directing the formation of photoluminescent quantum dot minerals in aqueous solution and at room temperature. Indeed, a key feature of biomineralization processes is that control over mineral formation is achieved using many soluble additives that operate in concert. That this feature has seldom been addressed in bioinspired methods is almost certainly due to the vast number of potential variables, which renders a full, systematic exploration intractable. As a solution to this challenge, we here utilize a genetic algorithm as a bioinspired heuristic that mimics natural evolution. Genetic algorithms use selection, recombination, and mutation strategies to rapidly identify and optimize the combination of conditions (here, soluble additives), which gives rise to materials with target properties. [ 19 ] Using a pipetting robot to prepare reaction sets and a UV-light table to rapidly assess the reactions for the formation of photoluminescent minerals, we are able to rapidly identify the key additives that promote the formation of quantum dot superstructures from one-pot aqueous reactions.Our initial library of organic mediators included 23 components, of which 17 were amino acids and 6 were surfactants. Stock solutions of the amino acids were prepared to initial concentrations of 100 × 10 −3 M , and explored at concentrations ranging from 0.01 to 50 × 10 −3 M , while surfactants were prepared to near their solubility limits in water. Surfactants were included as potential structure-directing agents to drive hierarchical assembly in aqueous solution. The overall screening approach used to identify the key additive set is summarized in Figure 1 . First, library amino acids and surfactants were randomly mixed in 48 wells of a multi-well plate, such that each well contained between 1-6 amino acids and 1-3 surfactants (Figure 1 A). Cadmium chloride and thioacetic acid (as a sulfur source) [ 20 ] were then added to a concentration of 1 × 10 −3 M in all wells, as precursors for CdS. After 3 d the plate was viewed under UV illumination (Figure 1 A) and with a fl uorimetric Biomineralization, whi...

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“…Artificial protocells are increasingly being made, not according to biological principles of construction but by self-assembly without a biological membrane ( figure 6c,d) [83]. Artificial cells can include primitive gels and can be used as containers for biochemical reactions and gene expression [82] ( figure 6c,d). There has been a need for facile gene expression systems without the disadvantages of interference from cellular protein secretions.…”

Section: Extraordinary Biomineralization Systemsmentioning

confidence: 99%

“…Fascinating examples of this approach can be seen in investigations of the proto-biological world. Artificial protocells are simplified replicates of cells made with natural (proteins) and un-natural materials [82]. Artificial protocells are increasingly being made, not according to biological principles of construction but by self-assembly without a biological membrane ( figure 6c,d) [83].…”

Section: Extraordinary Biomineralization Systemsmentioning

confidence: 99%

Calcifying tissue regeneration via biomimetic materials chemistry

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Kim

et al. 2014

J. R. Soc. Interface.

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Materials chemistry is making a fundamental impact in regenerative sciences providing many platforms for tissue development. However, there is a surprising paucity of replacements that accurately mimic the structure and function of the structural fabric of tissues or promote faithful tissue reconstruction. Methodologies in biomimetic materials chemistry have shown promise in replicating morphologies, architectures and functional building blocks of acellular mineralized tissues dentine, enamel and bone or that can be used to fully regenerate them with integrated cell populations. Biomimetic materials chemistry encompasses the two processes of crystal formation and mineralization of crystals into inorganic formations on organic templates. This review will revisit the successes of biomimetics materials chemistry in regenerative medicine, including coccolithophore simulants able to promote in vivo bone formation. In-depth knowledge of biomineralization throughout evolution informs the biomimetic materials chemist of the most effective techniques for regenerative framework construction exemplified via exploitation of liquid crystals (LCs) and complex self-organizing media. Therefore, a new innovative direction would be to create chemical environments that perform reaction–diffusion exchanges as the basis for building complex biomimetic inorganic structures. This has evolved widely in biology, as have LCs, serving as self-organizing templates in pattern formation of structural biomaterials. For instance, a study is highlighted in which artificially fabricated chiral LCs, made from bacteriophages are transformed into a faithful copy of enamel. While chemical-based strategies are highly promising at creating new biomimetic structures there are limits to the degree of complexity that can be generated. Thus, there may be good reason to implement living or artificial cells in ‘morphosynthesis’ of complex inorganic constructs. In the future, cellular construction is probably key to instruct building of ultimate biomimetic hierarchies with a totality of functions.

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Evolutionary selection of enzymatically synthesized semiconductors from biomimetic mineralization vesicles

Cited by 44 publications

References 51 publications

Single-enzyme biomineralization of cadmium sulfide nanocrystals with controlled optical properties

Single-enzyme biomineralization of cadmium sulfide nanocrystals with controlled optical properties

Genetic Algorithm‐Guided Discovery of Additive Combinations That Direct Quantum Dot Assembly

Calcifying tissue regeneration via biomimetic materials chemistry

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