Recent advances in smart biotechnology: Hydrogels and nanocarriers for tailored bioactive molecules depot

Over the past ten years, the global biopharmaceutical market has remarkably grown, with ten over the top twenty worldwide high performance medical treatment sales being biologics. Thus, biotech R&D (research and development) sector is becoming a key leading branch, with expanding revenues. Biotechnology offers considerable advantages compared to traditional therapeutic approaches, such as reducing side effects, specific treatments, higher patient compliance and therefore more effective treatments leading to lower healthcare costs. Within this sector, smart nanotechnology and colloidal self-assembling systems represent pivotal tools able to modulate the delivery of therapeutics. A comprehensive understanding of the processes involved in the self assembly of the colloidal structures discussed therein is essential for the development of relevant biomedical applications. In this review we report the most promising and best performing platforms for specific classes of bioactive molecules and related target, spanning from siRNAs, gene/plasmids, proteins/growth factors, small synthetic therapeutics and bioimaging probes.Istituto Italiano di Tecnologia (IIT)COST Action [CA 15107]People Program (Marie Curie Actions) of the European Union's Seventh Framework Program under REA [606713 BIBAFOODS]Portuguese Foundation for Science and Technology (FCT) [PTDC/AGR-TEC/4814/2014, IF/01005/2014]Fundacao para a Ciencia e Tecnologia [SFRH/BPD/99982/2014]Danish National Research Foundation [DNRF 122]Villum Foundation [9301]Italian Ministry of Instruction, University and Research (MIUR), PRIN [20109PLMH2]"Fondazione Beneficentia Stiftung" VaduzFondo di Ateneo FRAFRAinfo:eu-repo/semantics/publishedVersio

Phase Coexistence and Structural Dynamics of Redox Metal Catalysts Revealed by Operando TEM

Metal catalysts play an important role in industrial redox reactions. Although extensively studied, the state of these catalysts under operating conditions is largely unknown, and assignments of active sites remain speculative. Herein, an operando transmission electron microscopy study is presented, which interrelates the structural dynamics of redox metal catalysts to their activity. Using hydrogen oxidation on copper as an elementary redox reaction, it is revealed how the interaction between metal and the surrounding gas phase induces complex structural transformations and drives the system from a thermodynamic equilibrium toward a state controlled by the chemical dynamics. Direct imaging combined with the simultaneous detection of catalytic activity provides unparalleled structure–activity insights that identify distinct mechanisms for water formation and reveal the means by which the system self-adjusts to changes of the gas-phase chemical potential. Density functional theory calculations show that surface phase transitions are driven by chemical dynamics even when the system is far from a thermodynamic phase boundary. In a bottom-up approach, the dynamic behavior observed here for an elementary reaction is finally extended to more relevant redox reactions and other metal catalysts, which underlines the importance of chemical dynamics for the formation and constant re-generation of transient active sites during catalysis

Vibrotactile-based rehabilitation on balance and gait in patients with neurological diseases: A systematic review and metanalysis

Postural instability and fear of falling represent two major causes of decreased mobility and quality of life in cerebrovascular and neurologic diseases. In recent years, rehabilitation strategies were carried out considering a combined sensorimotor intervention and an active involvement of the patients during the rehabilitation sessions. Accordingly, new technological devices and paradigms have been developed to increase the effectiveness of rehabilitation by integrating multisensory information and augmented feedback promoting the involvement of the cognitive paradigm in neurorehabilitation. In this context, the vibrotactile feedback (VF) could represent a peripheral therapeutic input, in order to provide spatial proprioceptive information to guide the patient during task-oriented exercises. The present systematic review and metanalysis aimed to explore the effectiveness of the VF on balance and gait rehabilitation in patients with neurological and cerebrovascular diseases. A total of 18 studies met the inclusion criteria and were included. Due to the lack of high-quality studies and heterogeneity of treatments protocols, clinical practice recommendations on the efficacy of VF cannot be made. Results show that VF-based intervention could be a safe complementary sensory-motor approach for balance and gait rehabilitation in patients with neurological and cerebrovascular diseases. More high-quality randomized controlled trials are needed

Supported CeO₂ catalysts in technical form for sustainable chlorine production

Bulk CeO2 has been recently reported as a promising catalyst for the oxidation of HCl to Cl2. In order to undertake the scale up of this system, various oxides (TiO2, Al2O3 , and low- and high-surface area ZrO2) have been evaluated as carriers. Supported CeO2 catalysts (3–20 wt.% Ce) prepared by dry impregnation were isothermally tested at the lab scale. Their performance was ranked as: CeO2/ZrO2 ≫ CeO2/Al2O3 ≥ CeO2/TiO2. Kinetic data revealed a lower activation energy and a similar activity dependence on the partial pressure of O2 for CeO2/ZrO2 compared to bulk CeO2. Pilot-scale testing over 3-mm pellets of this catalyst evidenced outstanding stability for 700 h on stream. In-depth characterization of the carriers and fresh catalysts by N2 sorption, Hg porosimetry, X-ray diffraction, temperature-programmed reduction with H2, Raman spectroscopy, electron microscopy, and in situ prompt gamma activation analysis, enabled to rationalize the different catalytic behavior of the materials. ZrO2 stabilizes nanostructures of CeO2 and a Ce–Zr mixed oxide phase, which offer high dispersion and improved oxidation properties. The catalyst also shows reduced chlorine uptake, and overall stands as a better Deacon material compared to bulk CeO2 and other supported systems. CeO2 is present on Al2O3 predominantly as well-distributed nanoparticles. Still, alumina does not induce any electronic effect, thus the supported phase behaves similarly to bulk ceria. TiO2, likely due to the structural collapse and dramatic sintering suffered during calcination, leads to the formation of very large ceria particles. Based on our results, CeO2/ZrO2 appears as a robust and cost-effective alternative to the current RuO2-based catalysts for large-scale chlorine recovery

A nanoporous surface is essential for glomerular podocyte differentiation in three-dimensional culture.

Although it is well recognized that cell-matrix interactions are based on both molecular and geometrical characteristics, the relationship between specific cell types and the three-dimensional morphology of the surface to which they are attached is poorly understood. This is particularly true for glomerular podocytes - the gatekeepers of glomerular filtration - which completely enwrap the glomerular basement membrane with their primary and secondary ramifications. Nanotechnologies produce biocompatible materials which offer the possibility to build substrates which differ only by topology in order to mimic the spatial organization of diverse basement membranes. With this in mind, we produced and utilized rough and porous surfaces obtained from silicon to analyze the behavior of two diverse ramified cells: glomerular podocytes and a neuronal cell line used as a control. Proper differentiation and development of ramifications of both cell types was largely influenced by topographical characteristics. Confirming previous data, the neuronal cell line acquired features of maturation on rough nanosurfaces. In contrast, podocytes developed and matured preferentially on nanoporous surfaces provided with grooves, as shown by the organization of the actin cytoskeleton stress fibers and the proper development of vinculin-positive focal adhesions. On the basis of these findings, we suggest that in vitro studies regarding podocyte attachment to the glomerular basement membrane should take into account the geometrical properties of the surface on which the tests are conducted because physiological cellular activity depends on the three-dimensional microenvironment

Do observations on surface coverage-reactivity correlations always describe the true catalytic process? A case study on ceria

In situ (operando) investigations aim at establishing structure-function and/or coverage-reactivity correlations. Herein, we investigated the gas-phase HCl oxidation (4HCl + O2 → 2Cl2 + 2H2O) over ceria. Despite its remarkable performance, under low oxygen over-stoichiometry, this oxide is prone to a certain extent to subsurface/bulk chlorination, which leads to deactivation. In situ Prompt Gamma Activation Analysis (PGAA) studies evidenced that the chlorination rate is independent of the pre-chlorination degree but increases at lower oxygen over-stoichiometry, while dechlorination is effective in oxygen-rich feeds, and its rate is higher for a more extensively pre-chlorinated ceria. Even bulk CeCl3 could be transformed into CeO2 under oxygen excess. Electron Paramagnetic Resonance experiments strongly suggested that oxygen activation is inhibited by a high surface chlorination degree. The coverages of most abundant surface intermediates, OH and Cl, were monitored by in situ infrared spectroscopy and PGAA under various conditions. Higher temperature and p(O2) led to enhanced OH coverage, reduced Cl coverage, and increased reactivity. Variation of p(HCl) gave rise to opposite correlations, while raising p(Cl2) did not induce any measurable increase in the Cl coverage, despite the strong inhibition of the reaction rate. The results indicate that only a small fraction of surface sites is actively involved in the reaction, and most of the surface species probed in the in situ observation are spectators. Therefore, when performing in situ steady-state experiments, a large set of variables should be considered to obtain accurate conclusions

International overview of somatic dysfunction assessment and treatment in osteopathic research: A scoping review

Background: Osteopathic manipulative treatment (OMT) is a patient-centred, whole-body intervention aimed at enhance the person’s self-regulation. OMT interventions are focused on somatic dysfunctions (SD) that can be defined as an altered regulative function associated with inflammatory signs palpable in the body framework in different body regions. The conceptual model that sustains SD, as well as its usefulness for the osteopathic profession, is still being discussed by the osteopathic community. Understanding the role and the application of SD is the aim of this scoping review. Methods: A literature search was carried out through the main biomedical databases: Pubmed (Medline), Cochrane, Central (Cochrane), Embase, PEDro and Scopus. Grey literature was considered via Google Scholar and the Osteopathic Research Web. The review was prepared by referring to the “Preferred Reporting Items for Systematic reviews and Meta-Analysis extension for Scoping Reviews” (PRISMA-ScR). Results: A total of 37,279 records were identified through database searching and other sources. After the duplicates were removed, 27,023 titles and abstracts were screened. A total of 1495 full-text articles were assessed for eligibility. The qualitative synthesis included 280 studies. Conclusions: Treating SD is an important part of osteopathic practice that varies from country to country. SD should be considered as a clinical value that assists in the clinical assessment and guides the decision-making process of osteopathic practitioners. Further studies should be designed to better understand why and how to choose the different assessment and intervention modalities to approach SD and to evaluate new osteopathic models

Performance, structure, and mechanism of CeO₂ in HCl oxidation to Cl₂

Experimental and theoretical studies reveal performance descriptors and provide molecular-level understanding of HCl oxidation over CeO2. Steady-state kinetics and characterization indicate that CeO2 attains a significant activity level, which is associated with the presence of oxygen vacancies. Calcination of CeO2 at 1173 K prior to reaction maximizes both the number of vacancies and the structural stability of the catalyst. X-ray diffraction and electron microscopy of samples exposed to reaction feeds with different O2/HCl ratios provide evidence that CeO2 does not suffer from bulk chlorination in O2-rich feeds (O2/HCl ≥ 0.75), while it does form chlorinated phases in stoichiometric or sub-stoichiometric feeds (O2/HCl ≤ 0.25). Quantitative analysis of the chlorine uptake by thermogravimetry and X-ray photoelectron spectroscopy indicates that chlorination under O2-rich conditions is limited to few surface and sub-surface layers of CeO2 particles, in line with the high energy computed for the transfer of Cl from surface to sub-surface positions. Exposure of chlorinated samples to a Deacon mixture with excess oxygen rapidly restores the original activity levels, highlighting the dynamic response of CeO2 outermost layers to feeds of different composition. Density functional theory simulations reveal that Cl activation from vacancy positions to surface Ce atoms is the most energy-demanding step, although chorine-oxygen competition for the available active sites may render re-oxidation as the rate-determining step. The substantial and remarkably stable Cl2 production and the lower of CeO2 make it an attractive alternative to RuO2 for catalytic chlorine recycling in industry

Constraints on the interpretation of S-to-P receiver functions

We present results from forward modelling to study the feasibility of using S-to-P converted phases to image the seismic discontinuity structure of the crust and upper mantle. We show that a significant level of P-wave energy arriving before the direct S-wave arrival can interfere with the S-to-P converted phases of interest and may result in Sp receiver function phases that do not represent true earth structure. The source of this P-wave energy is attributable to a number of phases, including those that have undergone multiple reflections off the Earth's surface. For deep focus earthquakes (300–600 km deep), a significant amount of P-wave energy is observed from pPPP, pPPPP and sPPPP phases, and arrives within the same time window as predicted for S-to-P converted phases from the direct S phase arrival. Furthermore, for earthquakes at all depths, interfering P-wave energy arrives within the same time window as predicted for S-to-P converted phases from the SKS phase arrival, limiting the usefulness of SKSp receiver functions for upper mantle imaging. To isolate true Sp receiver function phases from contamination due to other P-wave phases, we find it necessary to stack receiver functions from a range of epicentral distances and depths in order to aid the suppression of noise and other unwanted phases. We provide constraints on the noise levels to be expected as a function of epicentral distance and earthquake depth. We find that the lowest noise levels are achievable by restricting epicentral distance to less than 75 degrees and the depth of earthquakes used to less than 300 km