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Hierarchically-Structured Metalloprotein Composite

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Hierarchically-Structured Metalloprotein Composite ARTICLE There are amendments to this paper https://doi.org/10.1038/s41467-020-14709-y OPEN Hierarchically-structured metalloprotein composite coatings biofabricated from co-existing condensed liquid phases ✉ Franziska Jehle 1, Elena Macías-Sánchez1, Sanja Sviben1, Peter Fratzl1, Luca Bertinetti 1 & ✉ Matthew J. Harrington 1,2 1234567890():,; Complex hierarchical structure governs emergent properties in biopolymeric materials; yet, the material processing involved remains poorly understood. Here, we investigated the multi- scale structure and composition of the mussel byssus cuticle before, during and after for- mation to gain insight into the processing of this hard, yet extensible metal cross-linked protein composite. Our findings reveal that the granular substructure crucial to the cuticle’s function as a wear-resistant coating of an extensible polymer fiber is pre-organized in con- densed liquid phase secretory vesicles. These are phase-separated into DOPA-rich proto- granules enveloped in a sulfur-rich proto-matrix which fuses during secretion, forming the sub-structure of the cuticle. Metal ions are added subsequently in a site-specific way, with iron contained in the sulfur-rich matrix and vanadium coordinated by DOPA-catechol in the granule. We posit that this hierarchical structure self-organizes via phase separation of specific amphiphilic proteins within secretory vesicles, resulting in a meso-scale structuring that governs cuticle function. 1 Department of Biomaterials, Max Planck Institute of Colloids and Interfaces, 14424 Potsdam, Germany. 2 Department of Chemistry, McGill University, 801 ✉ Sherbrooke Street West, Montréal, QC H3A 0B8, Canada. email: [email protected]; [email protected] NATURE COMMUNICATIONS | (2020) 11:862 | https://doi.org/10.1038/s41467-020-14709-y | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-14709-y he ability to endow polymeric materials with nano-scale microscopy (TEM) and scanning transmission electron micro- Tand meso-scale structural hierarchy via self-assembly is an scopy with energy dispersive X-ray spectroscopy (STEM-EDS). important materials design challenge with implications for By examining the different stages of assembly, we gain important tissue engineering, drug delivery and smart polymer engineer- new insights into the formation process and function of this ing1–4. Polymer scientists aim to achieve control of multiscale complex biological material, with bearing on the design of tech- organization through precisely defined chemical structure and nically and biomedically relevant composite materials. engineered supramolecular interactions2,5,6, which can be employed for example, as scaffolds for guiding polymerization of Results fi 7–9 materials with de ned hierarchy (e.g., mesoporous silica) . Nanostructural investigation of cuticle secretory vesicles. Pre- Similarly, proteins also possess an inherent capacity for supra- vious investigations have identified that the precursor proteins molecular self-organization—determined by amino acid sequence — forming the cuticle are stored in secretory vesicles in the mussel that has been harnessed through evolution for fabricating bulk foot within a region known as the enzyme or cuticle gland materials/tissues with enhanced function, controlled through 13,26 10–15 (Fig. 1d) . Transmission electron microscopy (TEM) imaging multiscale hierarchical structure . Therefore, elucidating the of post-stained thin sections of the cuticle gland of Mytilus edulis physical and chemical underpinnings of biological material revealed that each micron-sized secretory vesicle possesses at least assembly provides a rich source of inspiration for designing two distinctive regions—a darker outer phase (more heavily bottom-up processes to fabricate hierarchically structured, func- stained with Os) and a lighter, less-stained inner phase (Fig. 2a). tional polymeric materials. The distinctive biphasic brain-like texture of the inner phase The mussel byssus is a hierarchically structured protein-based consisting of lighter stained connected layers was previously material that has emerged as an exciting model system for observed in cuticle secretory vesicles of another species, Mytilus understanding supramolecular assembly of complex material 26 11,13 galloprovincialis , and is highly reminiscent of native thread structures under sustainable processing conditions (Fig. 1) . cuticle granule structure (Fig. 1h)—leading us to name this the Mussels fabricate a byssus as an attachment holdfast for proto-granule and the outer phase, the proto-matrix. A third, very anchoring on rocky surfaces in seashore habitats (Fig. 1a), where 16 lightly stained crescent-shaped phase is also observed at the outer they face forces from crashing waves . Each byssal thread is periphery of most cuticle secretory vesicles. FIB-SEM of chemi- covered by a thin protective cuticle at its distal end (i.e., away cally fixed foot tissue samples enabled 3D rendering of secretory from the mussel) (Fig. 1), which is highly extensible, yet stiff and vesicles in a small region of the cuticle gland close to the secretion hard17–21. These typically opposing properties likely function to fi point, revealing a tightly packed arrangement of nearly spherical protect the stretchy brous core within and originate from the vesicles (Fig. 2b, c). Consistent with TEM, there are at least three composite-like structure of micron-sized inclusions known as discernible phases in these vesicles that stain differently, corre- 18 – granules embedded in a continuous matrix (Fig. 1f h). While it sponding to the proto-granule, proto-matrix and crescent phase was originally proposed that the granules are hard inclusions in a – 17,18 (Fig. 2b d). Volumetric analysis of the 3D data of 28 individual softer matrix , more recent results suggest that granules cuticle secretory vesicles indicates similar distribution of volume function to retain water at low hydration, behaving softer than 21 fractions of the three phases in all vesicles suggesting a highly the matrix under dry conditions . Regardless, nanoindentation regulated formation process (Supplementary Fig. 1). experiments indicate that the cuticle acquires nearly 85% of its stiffness/hardness from metal coordination cross-links between metal ions (such as Fe and V) and 3,4-dihydroxyphenylalanine Compositional investigation of cuticle secretory vesicles. (DOPA), a post-translational modification of Tyrosine elevated in Compositional analysis of cuticle secretory vesicles was per- the cuticle protein, mussel foot protein 1 (mfp-1) (Fig. 1i)20. formed with STEM-EDS, revealing an elevated and uniform Notably, the DOPA-metal interactions are more concentrated in nitrogen content in cuticle secretory vesicles compared with the the granules than the matrix17.(n.b. species specific forms of surrounding intracellular material (Fig. 2e). In contrast, there is mfp-1 are named according to the species; e.g., mefp-1 for an approximately two to three-fold higher sulfur content in the proto-matrix relative to the proto-granules (Fig. 2e, f). Notably, Mytilus edulis) fi Numerous reviews highlight recent efforts to mimic the DOPA- recent transcriptomic studies have identi ed a family of putative cysteine-rich proteins (mfp-16–mfp-19) within the cuticle gland metal cross-link strategy with mussel-inspired catechol-functio- 28 nalized polymers22–25; yet, none of these materials reproduces the of a related species Mytilus californianus . This is consistent with complex hierarchical structure of the cuticle or its properties. previous cytochemical studies predicting the presence of cysteine- rich proteins within the cuticle secretory vesicles of Mytilus gal- Indeed, little is understood about how the nanostructure of the 26 cuticle and granules is achieved. It is known that the proteins that loprovinicialis . The fact that the proto-granule contains a lower comprise the cuticle are stored within secretory vesicles in the sulfur signal substantiates the previous supposition that the — granules mainly contain mefp-1, which completely lacks mussel foot the organ responsible for synthesizing and stock- 17 13,26,27 cysteine . Furthermore, cysteine is a strong target of OsO4 piling the proteins that make the byssus (Fig. 1b, c) . Self- 29,30 assembly of the cuticle occurs within minutes via release of vesicle staining , which helps explain the contrast observed in TEM contents into a groove running along the foot, during which they and FIB-SEM. Notably, within the sensitivity limit, we did not coalesce and spread over the already formed collagenous core of detect peaks indicative of transition metal ions (e.g., Fe and V) in the byssus fiber (Fig. 1b–e)13. However, many questions remain the EDS spectra from unstained cuticle secretory vesicles (Sup- plementary Fig. 2), even though these metals were previously concerning how the intricate cuticle substructure emerges via self- 17,19,20 assembly and how metal ions are infiltrated to cure the formed detected in the mature cuticle . This result is consistent with recent findings suggesting that metal ions are added into the cuticle. 13 Here, we report an in-depth compositional and ultrastructural cuticle in a post-secretion curing step . investigation of the structure and self-assembly of the mussel byssus cuticle. Specifically, we investigate the 3D nanostructure Structural investigation of cuticle formation. To investigate the and elemental composition of the secretory vesicles and
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