Organización bio-inspirada y jerarquizada de arquitecturas supramoleculares electroactivas basadas en nanoestructuras de carbono

Tesis inédita de la Universidad Complutense de Madrid, Facultad de Ciencias Químicas, Departamento de Química Orgánica I, leída el 04-12-2015La nanotecnología, referida a la manipulación de la materia a nivel molecular y supramolecular, es un área emergente con prometedores beneficios para la humanidad.1 En particular, las nanoestructuras de carbono han captado gran atención debido a sus atractivas propiedades electrónicas y mecánicas. Imitar la naturaleza mediante el desarrollo de procedimientos bioinspirados puede ser una interesante estrategia para organizar nanomateriales ricos en carbono con el fin de maximizar sus propiedades optoelectrónicas...Nanotechnology, referring as the manipulation of matter at the molecular and supramolecular scale, is an emerging area with promising benefits for humanity.1 In particular, carbon nanostructures have received a great attention due to their exciting electronic and mechanical properties. Mimicking nature, that is, developing bioinspired procedures, could be one of the most intelligent strategies to organize matter, in particular carbon-rich nanostructures, with the aim of maximizing their fabulous optoelectronic properties...Depto. de Química OrgánicaFac. de Ciencias QuímicasTRUEunpu

Auto-ensamblaje de estructuras supramoleculares electroactivas: estrategias bio-inspiradas

Tesis inédita de la Universidad Complutense de Madrid, Facultad de Ciencias Químicas, Departamento de Química Orgánica, leída el 25/10/2019Accomplishing the great level of complexity and sophistication of natural systems is presented as a major challenge to scientists. A multidisciplinary approach is intended to design and create the next generation of advanced materials and, in this regard, supramolecular chemistry can play a key role. In particular, the combination of organic molecules and biomolecules has appeared as a fascinating approach to take advantage of the self-assembling properties and great specificity of the biological systems to obtain materials with enhanced photophysical features. Peptides and proteins are crucial components in living beings and have demonstrated their versatility to construct artificial systems. Although great progress has been made in terms of control and diversity of structure, translating structure into functionality still remains as a major challenge...Conseguir el gran nivel de complejidad y sofisticación que presentan los sistemas naturales constituye un gran reto científico. Para el diseño y desarrollo de una nueva generación de materiales avanzados es necesario un enfoque multidisciplinar, donde la química supramolecular puede jugar un papel clave. En concreto, la combinación de moléculas orgánicas y biomoléculas se figura como una estrategia fascinante con la que beneficiarse de la capacidad de auto-ensamblaje y la gran especificidad de los sistemas biológicos y, así, obtener materiales con mejores propiedades fotofísicas. Los péptidos y las proteínas son componentes esenciales en los seres vivos y han demostrado su gran versatilidad a la hora de crear sistemas artificiales. Sin embargo, pese al gran progreso conseguido en términos de control y diversidad estructural, su aplicación práctica continúa presentándose como un gran reto...Depto. de Química OrgánicaFac. de Ciencias QuímicasTRUEunpu

Protein-directed crystalline 2D fullerene assemblies

Water soluble 2D crystalline monolayers of fullerenes grow on planar assemblies of engineered consensus tetratricopeptide repeat proteins. Designed fullerene-coordinating tyrosine clamps on the protein introduce specific fullerene binding sites, which facilitate fullerene nucleation. Through reciprocal interactions between the components, the hybrid material assembles into two-dimensional 2 nm thick structures with crystalline order, that conduct photo-generated charges. Thus, the protein-fullerene hybrid material is a demonstration of the developments toward functional materials with protein-based precision control of functional elements

Repeat protein scaffolds: ordering photo- and electroactive molecules in solution and solid state

The precise control over the organization of photoactive components at the nanoscale is one of the main challenges for the generation of new and sophisticated macroscopically ordered materials with enhanced properties. In this work we present a novel bioinspired approach using protein-based building blocks for the arrangement of photo and electroactive porphyrin derivatives. We used a designed repeat protein scaffold with demonstrated unique features that allow for the control of their structure, functionality, and assembly. Our designed domains act as exact biomolecular templates to organize porphyrin molecules at the required distance. The hybrid conjugates retain the structure and assembly properties of the protein scaffold and display the spectroscopic features of orderly aggregated porphyrins along the protein structure. Finally,we achieved a solid ordered bio-organic hybrid thin film with anisotropic photoconductivity

HaloFlippers: A General Tool for the Fluorescence Imaging of Precisely Localized Membrane Tension Changes in Living Cells.

Tools to image membrane tension in response to mechanical stimuli are badly needed in mechanobiology. We have recently introduced mechanosensitive flipper probes to report quantitatively global membrane tension changes in fluorescence lifetime imaging microscopy (FLIM) images of living cells. However, to address specific questions on physical forces in biology, the probes need to be localized precisely in the membrane of interest (MOI). Herein we present a general strategy to image the tension of the MOI by tagging our newly introduced HaloFlippers to self-labeling HaloTags fused to proteins in this membrane. The critical challenge in the construction of operational HaloFlippers is the tether linking the flipper and the HaloTag: It must be neither too taut nor too loose, be hydrophilic but lipophilic enough to passively diffuse across membranes to reach the HaloTags, and allow partitioning of flippers into the MOI after the reaction. HaloFlippers with the best tether show localized and selective fluorescence after reacting with HaloTags that are close enough to the MOI but remain nonemissive if the MOI cannot be reached. Their fluorescence lifetime in FLIM images varies depending on the nature of the MOI and responds to myriocin-mediated sphingomyelin depletion as well as to osmotic stress. The response to changes in such precisely localized membrane tension follows the validated principles, thus confirming intact mechanosensitivity. Examples covered include HaloTags in the Golgi apparatus, peroxisomes, endolysosomes, and the ER, all thus becoming accessible to the selective fluorescence imaging of membrane tension

Repeat protein scaffolds: Ordering photo- and electroactive molecules in solution and solid state

The precise control over the organization of photoactive components at the nanoscale is one of the main challenges for the generation of new and sophisticated macroscopically ordered materials with enhanced properties. In this work we present a novel bioinspired approach using protein-based building blocks for the arrangement of photo- and electroactive porphyrin derivatives. We used a designed repeat protein scaffold with demonstrated unique features that allow for the control of their structure, functionality, and assembly. Our designed domains act as exact biomolecular templates to organize porphyrin molecules at the required distance. The hybrid conjugates retain the structure and assembly properties of the protein scaffold and display the spectroscopic features of orderly aggregated porphyrins along the protein structure. Finally, we achieved a solid ordered bio-organic hybrid thin film with anisotropic photoconductivity. ¸ 2016 The Royal Society of Chemistry.This work has been supported by the European Commission IRG-246688 Bionanotools (ALC), the Spanish Ministry of Economy and Competitiveness (MINECO) BIO2012-34835 (ALC) and CTQ2014-520456-R (NM) and the European Research Council ERC-320441-Chirallcarbon (NM), and ERC-2014-CoG-648071 (ProNANO) (ALC). C. A. thanks to the Ramón y Cajal granted and J. L.-A. thanks to Spanish Ministry of Education for FPU granted. SHM thanks the Basque Government for financial support through a PhD fellowship. KPE gives thanks for financial support from the MIT–Spain internship program