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The biological mediation of mineral formation (biomineralization) is realized through diverse organic macromolecules that guide this process in a spatial and temporal manner. Although the role of these molecules in biomineralization is being gradually revealed, the molecular basis of their regulatory function is still poorly understood. In this study, the incorporation and distribution of the model intrinsically disordered starmaker-like (Stm-l) protein, which is active in fish otoliths biomineralization, within calcium carbonate crystals, is revealed. Stm-l promotes crystal nucleation and anisotropic tailoring of crystal morphology. Intracrystalline incorporation of Stm-l protein unexpectedly results in shrinkage (and not expansion, as commonly described in biomineral and bioinspired crystals) of the crystal lattice volume, which is described herein, for the first time, for bioinspired mineralization. A ring pattern was observed in crystals grown for 48 h; this was composed of a protein-enriched region flanked by protein-depleted regions. It can be explained as a result of the Ostwald-like ripening process and intrinsic properties of Stm-l, and bears some analogy to the daily growth layers of the otolith., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Multilayer nanocarriers loaded with optically activated payloads are gaining increasing attention due to their anticipated crucial role for providing new mechanisms of energy transfers in the health-oriented applications, as well as for energy storage and environmental protection. The combination of careful selection of optical components for efficient Förster resonance energy transfer, and surface engineering of the nanocarriers, allowed us to synthesize and characterize novel theranostic nanosystems for diagnosis and therapy of deep-seated tumors. The cargo, constrained within the oil core of the nanocapsules, composed of NaYF 4 :Tm +3 , Yb +3 up-converting nanoparticles together with a second-generation porphyrin-based photosensitizing agent-Verteporfin, assured requisite diagnostic and therapeutic functions under near-IR laser excitation. The outer polyaminoacid shell of the nanocapsules was functionalized with a ligand-poly(l-glutamic acid) functionalized by PEG-ylated folic acid-to ensure both a "stealth" effect and active targeting towards human breast cancer cells. The preparation criteria of all nanocarrier building blocks meet the requirements for sustainable and green chemistry practices. The multifunctionality of the proposed nanocarriers is a consequence of both the surface-functionalized organic exterior part, which was accessible for selective accumulation in cancer cells, and the hydrophobic optically active interior, which shows phototoxicity upon irradiation within the first biological window., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

At the core of luminescence color and lifetime tuning of rare earth doped upconverting nanoparticles (UCNPs), is the understanding of the impact of the particle architecture for commonly used sensitizer (S) and activator (A) ions. In this respect, a series of core@shell NaYF 4 UCNPs doped with Yb 3+ and Ho 3+ ions are presented here, where the same dopant concentrations are distributed in different particle architectures following the scheme: YbHo core and YbHo@…, …@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core-shell NPs. As revealed by quantitative steady-state and time-resolved luminescence studies, the relative spatial distribution of the A and S ions in the UCNPs and their protection from surface quenching has a critical impact on their luminescence characteristics. Although the increased amount of Yb 3+ ions boosts UCNP performance by amplifying the absorption, the Yb 3+ ions can also efficiently dissipate the energy stored in the material through energy migration to the surface, thereby reducing the overall energy transfer efficiency to the activator ions. The results provide yet another proof that UC phosphor chemistry combined with materials engineering through intentional core@shell structures may help to fine-tune the luminescence features of UCNPs for their specific future applications in biosensing, bioimaging, photovoltaics, and display technologies., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Multi-photon absorption (MPA) is among the most prominent nonlinear optical (NLO) effects and has applications, for example in telecommunications, defense, photonics, and bio-medicines. Established MPA materials include dyes, quantum dots, organometallics and conjugated polymers, most often dispersed in solution. We demonstrate how metal-organic frameworks (MOFs), a novel NLO solid-state materials class, can be designed for exceptionally strong MPA behavior. MOFs consisting of zirconium- and hafnium-oxo-clusters and featuring a chromophore linker based on the tetraphenylethene (TPE) molecule exhibit record high two-photon absorption (2PA) cross-section values, up to 3600 GM. The unique modular building-block principle of MOFs allows enhancing and optimizing their MPA properties in a theory-guided approach by combining tailored charge polarization, conformational strain, three-dimensional arrangement, and alignment of the chromophore linkers in the crystal., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)