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Carmen Bartic

Publications and source records attributed to Carmen Bartic.

2 recordsLinked to original sources

Shear stress during self-assembly encodes stiffness of network-based materials

The mechanical properties of network-based materials have been extensively studied under qui- escent conditions, yet their self-assembly in nature occurs mainly in a mechanically stressed envi- ronment. Here, we show that the stiffness of collagen networks, one of the main building blocks of the mammalian extracellular matrix, can be tuned by applying shear stress during gelation, which first strains and aligns the material, then triggers a dramatic irreversible increase in the elastic modulus. This stiffening is anchored by maintaining the stress until the gel is fully matured. Using particle-based simulations, we show that the underlying microscopic mechanism is likely generic to a broad class of network-based systems and arises from two synergetic effects: changes in the network orientation and topology through the formation of permanent contacts that stabilize the system. Our findings are rationalized using a rigidity percolation framework and offer a general principle for encoding elasticity in biological and synthetic networks.

cond-mat.soft↗

Amorphous to Crystalline Transformation: How Cluster Aggregation Drives the Multistep Nucleation of ZIF-8

Nucleation, the pivotal first step of crystallization, governs essential characteristics of crystallization products, including size distribution, morphology, and polymorphism. While understanding this process is paramount to the design of chemical, pharmaceutical and industrial production processes, major knowledge gaps remain, especially with respect to the crystallization of porous solids. Also for nanocrystalline ZIF-8, one of the most widely studied metal-organic frameworks, questions regarding the species involved in the nucleation pathway and their structural and chemical transformations remain unanswered. By combining harmonic light scattering, inherently sensitive to structural changes, with NMR spectroscopy, which reveals molecular exchanges between particles and solution, we were able to capture the crystallization mechanism of ZIF-8 in unprecedented detail. This dual approach provides concurrent structural and chemical insights, revealing key processes not previously observed in ZIF crystallization. Upon mixing small charged prenucleation clusters (PNCs) are formed, exhibiting an excess of ligands and net positive charge. We show that nucleation is initiated by aggregation of PNCs, through the release of ligands and associated protons to the liquid. This leads to the formation of charge neutral amorphous precursor particles (APPs) which incorporate neutral monomers from solution, and crystallize ZIF-8. Our work highlights chemical dynamics as a vital, yet often overlooked, dimension in the multi-stage structural evolution of MOFs. By establishing the critical role of PNCs in the nucleation of ZIF-8, new pathways open up for controlling crystallization of metal-organic frameworks through targeted chemical interactions with these species.

cond-mat.mtrl-sci↗