Electrospray Methodologies for Characterization and Deposition of Nanoparticles

Electrospray is an aerosolization method that generates highly charged droplets from solutions or suspensions and, after a series of solvent evaporation - droplet fission cycles, it results in particles carrying multiple charges. Highly charged particles are used in a variety of applications, including particle characterization, thin film deposition, nanopatterning, and inhalation studies among several others. In this work, a soft X-ray photoionization was coupled with an electrospray to obtain monodisperse, singly charged nanoparticles for applications in online size characterization with electrical mobility analysis. Photoionization with the soft X-ray charger enhanced the diffusion neutralization rate of the highly charged bacteriophages, proteins, and solid particles. The effect of nanoparticle surface charge and nanoparticle agglomeration in liquids on the electrospray process was studied experimentally and a modified expression to calculate the effective electrical conductivity of nanosuspensions was proposed. The effective electrical conductivity of TiO2 nanoparticle suspensions is strongly dependent on the electrical double layer and the agglomeration dynamics of the particles; and such dependence is more remarkable in liquids with low ionic strength. TiO2 nanoparticle agglomerates with nearly monodisperse sizes in the nanometer and submicrometer ranges were generated, by electrospraying suspensions with tuned effective electrical conductivity, and used to deposit photocatalytic films for water-splitting. Nanostructured films of iron oxide with uniform distribution of particles over the entire deposition area were formed with an electrospray system. The micro-Raman spectra of the iron oxide films showed that transverse and longitudinal optical modes are highly sensitive to the crystallize size of the electrospray-deposited films. The fabrication of films of natural light-harvesting complexes, with the aim of designing biohybrid photovoltaic devices, was explored with an electrospray. The ability to charge chlorosomes with large number of charges allowed their ballistic deposition onto TiO2 nanostructured columnar films simultaneously maintaining their light-harvesting properties. Single units of natural light-harvesting complexes were isolated in charged electrospray droplets for subsequent size characterization. The charge distribution of natural light-harvesting complexes, aerosolized with a collision nebulizer, was determined with tandem differential mobility analysis. It was found that nebulized light-harvesting complexes were multiply charged; hence they have potential applications in the deposition of functional films using electric fields. The studies conducted as part of this dissertation addressed fundamental issues in the characterization and deposition of nanoparticle suspensions and elucidated applications of the electrospray technique, particularly for solar energy utilization

Fabrication and Actuation of Magnetic Shape-Memory Materials

Soft actuators are deformable materials that change their dimensions and/or shape in response to external stimuli. Among the various stimuli, remote magnetic fields are one of the most attractive forms of actuation, due to their ease of use, fast response and safety in biological systems. Composites of magnetic particles with polymer matrices are the most common material for magnetic soft actuators. In this paper, we demonstrate the fabrication and actuation of magnetic shape-memory materials based on hydrogels containing field-structured magnetic particles. These actuators are formed by placing the pregel dispersion into a mold of the desired on-field shape and exposing this to a homogeneous magnetic field until the gel point is reached. At this point the material may be removed from the mold and fully gelled in the desired off-field shape. The resultant magnetic shape-memory material then transitions between these two shapes when subjected to successive cycles of a homogeneous magnetic field, acting as a large deformation actuator. For actuators that are planar in the off-field state, this can result in significant bending to return to the on-field state. In addition, it is possible to make shape-memory materials that twist under the application of a magnetic field. For these torsional actuators, both experimental and theoretical results are given.Departamento de Física AplicadaGrupo FQM144Ministerio de Ciencia, Innovación y UniversidadesAgencia Estatal de InvestigaciónDeutsche Forschungsgemeinschaft (DFG

Injectable Magnetic-Responsive Short-Peptide Supramolecular Hydrogels: Ex Vivo and In Vivo Evaluation

This study was supported by project FIS2017-85954-R funded by MCIN/AEI/10.13039/501100011033/FEDER "Una manera de hacer Europa", Spain, grants FIS PI20/0317 and ICI19/00024 (BIOCLEFT) (MINECO, Instituto de Salud Carlos III, Spain, cofinanced by FEDER funds, European Union), grant PE-0395-2019 (Consejeri ' a de Salud y Familias, Junta de Andalucia ', Spain), and project PPJIB2020.07 (Universidad de Granada, Spain). M.C.M.-T. acknowledges grant PRE2018-083773 funded by MCIN/AEI/10.13039/501100011033 and FSE "El FSE invierte en tu futuro", Spain. C.G.-V. acknowledges grant FPU17/00491 funded by MCIN/AEI/10.13039/501100011033 and FSE "El FSE invierte en tu futuro", Spain. P.K., D.M., and J.-C.S. acknowledge the French Agence Nationale de la Recherche, Project Future Investments UCA JEDI no. ANR-15-IDEX-01 (project RheoGels) for financial support. Funding for open access charge: Universidad de Granada/CBUA.The inclusion of magnetic nanoparticles (MNP) in a hydrogel matrix to produce magnetic hydrogels has broadened the scope of these materials in biomedical research. Embedded MNP offer the possibility to modulate the physical properties of the hydrogel remotely and on demand by applying an external magnetic field. Moreover, they enable permanent changes in the mechanical properties of the hydrogel, as well as alterations in the micro- and macroporosity of its threedimensional (3D) structure, with the associated potential to induce anisotropy. In this work, the behavior of biocompatible and biodegradable hydrogels made with Fmoc-diphenylalanine (Fmoc-FF) (Fmoc = fluorenylmethoxycarbonyl) and Fmoc−arginine−glycine− aspartic acid (Fmoc-RGD) short peptides to which MNP were incorporated was studied in detail with physicochemical, mechanical, and biological methods. The resulting hybrid hydrogels showed enhance mechanical properties and withstood injection without phase disruption. In mice, the hydrogels showed faster and improved self-healing properties compared to their nonmagnetic counterparts. Thanks to these superior physical properties and stability during culture, they can be used as 3D scaffolds for cell growth. Additionally, magnetic short-peptide hydrogels showed good biocompatibility and the absence of toxicity, which together with their enhanced mechanical stability and excellent injectability make them ideal biomaterials for in vivo biomedical applications with minimally invasive surgery. This study presents a new approach to improving the physical and mechanical properties of supramolecular hydrogels by incorporating MNP, which confer structural reinforcement and stability, remote actuation by magnetic fields, and better injectability. Our approach is a potential catalyst for expanding the biomedical applications of supramolecular short-peptide hydrogels.Instituto de Salud Carlos III FIS PI20/0317 ICI19/00024European CommissionFSE "El FSE invierte en tu futuro", SpainFrench National Research Agency (ANR) ANR-15-IDEX-01Universidad de Granada/CBUAFIS2017-85954-R MCIN/AEI/10.13039/501100011033/FEDER PE-0395-2019 PPJIB2020.07 PRE2018-083773 MCIN/AEI/10.13039/501100011033 FPU17/0049

Short-Peptide Supramolecular Hydrogels for In Situ Growth of Metal–Organic Framework-Peptide Biocomposites

The development of bio-MOFs or MOF biocomposites through the combination of MOFs with biopolymers offers the possibility of expanding the potential applications of MOFs, making use of more environmentally benign processes and reagents and giving rise to a new generation of greener and more bio-oriented composite materials. Now, with the increasing use of MOFs for biotechnological applications, the development of new protocols and materials to obtain novel bio-MOFs compatible with biomedical or biotechnological uses is needed. Herein, and as a proof of concept, we have explored the possibility of using short-peptide supramolecular hydrogels as media to promote the growth of MOF particles, giving rise to a new family of bio-MOFs. Short-peptide supramolecular hydrogels are very versatile materials that have shown excellent in vitro and in vivo biomedical applications such as tissue engineering and drug delivery vehicles, among others. These peptides self-assemble by noncovalent interactions, and, as such, these hydrogels are easily reversible, being more biocompatible and biodegradable. These peptides can self-assemble by a multitude of stimuli, such as changes in pH, temperature, solvent, adding salts, enzymatic activity, and so forth. In this work, we have taken advantage of this ability to promote peptide self-assembly with some of the components required to form MOF particles, giving rise to more homogeneous and well-integrated composite materials. Hydrogel formation has been triggered using Zn2+ salts, required to form ZIF-8, and formic acid, required to form MOF-808. Two different protocols for the in situ MOF growth have been developed. Finally, the MOF-808 composite hydrogel has been tested for the decontamination of water polluted with phosphate ions as well as for the catalytic degradation of toxic organophosphate methyl paraoxon in an unbuffered solution.Grants PID2020-118498GB-I00PID2020-113608RB-I00MCIN/AEI/10.13039/ 501100011033,Projects P18-FR-3533 and A-FQM-340-UGR20 by FEDER/Junta de Andaluci ́ a-Consejería de Transformación Económica, Industria, Conocimiento y Universidades (Spain)PPJIA2021.20 by Universidad de GranadaMarie Skłodowska-Curie Individual Fellowship (H2020-MSCA-IF-2019-EF-ST-888972-PSustMOF)European Union H2020 programme and EU FEDERGrant PRE2018-083773MCIN/ AEI/10.13039/501100011033ESF Investing in your future”, Spain

The Helicobacter pylori Genome Project : insights into H. pylori population structure from analysis of a worldwide collection of complete genomes

Helicobacter pylori, a dominant member of the gastric microbiota, shares co-evolutionary history with humans. This has led to the development of genetically distinct H. pylori subpopulations associated with the geographic origin of the host and with differential gastric disease risk. Here, we provide insights into H. pylori population structure as a part of the Helicobacter pylori Genome Project (HpGP), a multi-disciplinary initiative aimed at elucidating H. pylori pathogenesis and identifying new therapeutic targets. We collected 1011 well-characterized clinical strains from 50 countries and generated high-quality genome sequences. We analysed core genome diversity and population structure of the HpGP dataset and 255 worldwide reference genomes to outline the ancestral contribution to Eurasian, African, and American populations. We found evidence of substantial contribution of population hpNorthAsia and subpopulation hspUral in Northern European H. pylori. The genomes of H. pylori isolated from northern and southern Indigenous Americans differed in that bacteria isolated in northern Indigenous communities were more similar to North Asian H. pylori while the southern had higher relatedness to hpEastAsia. Notably, we also found a highly clonal yet geographically dispersed North American subpopulation, which is negative for the cag pathogenicity island, and present in 7% of sequenced US genomes. We expect the HpGP dataset and the corresponding strains to become a major asset for H. pylori genomics

Size distribution and morphology of liposome aerosols generated by two methodologies

Pulmonary delivery of sustained release formulations needs drug encapsulation in a suitable matrix, as well as the generation of aerosols with high lung penetration and suitable release characteristics. Nanometer sized liposomes offer the potential for biocompatibility, controlled release and easy internalization in the lung. For uniform dose delivery and drug release kinetics, it is of interest to understand generation techniques to obtain aerosols containing nearly monodispered nanometer sized dry particles. Two aerosolization techniques, air-jet atomization and Electrohydrodynamic Atomization (EHDA) were studied to identify conditions under which the inclusion of one-liposome-per-drop could be achieved. In air-jet atomization, low lipid concentrations resulted in a unimodal aerosol with a median mobility diameter of 94 (± 3.5) nm, while higher concentrations led to larger median diameters, implying possible inclusion of multiple liposomes per drop. In EHDA, tuning drop sizes in the range of 130 to 200 nm, as well as the use of high lipid concentrations, resulted in a bimodal aerosol distribution, with peaks at 35 and 100 nm mobility diameters. TEM images of the liposome aerosol from EDHA showed fused liposomes, resulting in cylindrical structures with different physical diameters. It was hypothesized that deformation of liposomes to cylindrical structures in the micro-capillary liquid tip of the electrospray and interactions along the axial or cross sectional surfaces led to dry particles with different mobility sizes

Alginate Hydrogels Reinforced by Dehydration under Stress—Application to a Soft Magnetic Actuator

We investigated the effect of partial dehydration under mechanical stress in the properties of alginate hydrogels. For this aim, we characterized the mechanical properties of the hydrogels under tensile and shear stress, as well as their swelling behavior, macroscopic appearance, and microscopic structure. We found that the processes of dehydration under a mechanical stress were irreversible with fully rehydration being impossible. What is more, these processes gave rise to an enhancement of the mechanical robustness of the hydrogels beyond the effect due to the increase in polymer concentration caused by dehydration. Finally, we analyzed the applicability of these results to alginate-based magnetic hydrogel grippers that bended in response to an applied magnetic field. Remarkably, our study demonstrated that the dehydration of the magnetic hydrogels under compression facilitated their bending response