Programming the Optoelectronic Properties of Atomically Precise Gold Nanoclusters Using the Conformational Landscape of Intrinsically Disordered Proteins

Identificador:  imarina:9499588

Handle: https://hdl.handle.net/20.500.11797/imarina9499588

Autors:  Rodriguez S; Kumanski S; Ayed Z; Fournet A; Bouanchaud C; Sagar A; Allemand F; Baulin VA; Resch-Genger U; Cortés J; Sibille N; Chirot F; Wegner KD; Antoine R; Le Guével X; Bernadó P

Resum:
The rational design of hybrid nanomaterials with precisely controlled properties remains a central challenge in materials science. While atomically precise gold nanoclusters (Au-NCs) offer molecule-like control over a metallic core, tuning their optoelectronic behavior via surface engineering is often empirically driven. Here, we establish a design principle by demonstrating that the conformational landscape of intrinsically disordered proteins (IDP) can be used as a programmable scaffold to rationally modulate the photophysical properties of a covalently bound Au-NC. We synthesized a series of bioconjugates between Au25 nanoclusters and bioengineered IDPs containing a variable number of cysteine anchoring points. A combination of mass spectrometry, small-angle X-ray scattering, and modeling on the conjugates indicates that increasing the number of covalent anchors systematically restricts the conformational ensemble, inducing a progressively more compact protein shell around nanoclusters. This structural rigidification at the interface directly translates into a 15-fold enhancement of the Au-NC near-infrared photoluminescence and a six-fold increase in its average lifetime. Our findings demonstrate that the conformational plasticity of IDPs and the capacity to engineer them can be harnessed as a molecular tuning knob, moving to a new regime of programmable soft-matter control over the properties of quantum-confined nanomaterials for tailored biotechnological applications.