Multifunctional Gadolinium‐Doped Mesoporous TiO2 Nanobeads: Photoluminescence,Enhanced Spin Relaxation,and Reactive Oxygen Species Photogeneration,Beneficial for Cancer Diagnosis and Treatment

Materials with controllable multifunctional abilities for optical imaging (OI) and magnetic resonant imaging (MRI) that also can be used in photodynamic therapy are very interesting for future applications. Mesoporous TiO₂ sub‐micrometer particles are doped with gadolinium to improve photoluminescence functionality and spin relaxation for MRI, with the added benefit of enhanced generation of reactive oxygen species (ROS). The Gd‐doped TiO₂ exhibits red emission at 637 nm that is beneficial for OI and significantly improves MRI relaxation times, with a beneficial decrease in spin–lattice and spin–spin relaxation times. Density functional theory calculations show that Gd³⁺ ions introduce impurity energy levels inside the bandgap of anatase TiO₂, and also create dipoles that are beneficial for charge separation and decreased electron–hole recombination in the doped lattice. The Gd‐doped TiO₂ nanobeads (NBs) show enhanced ability for ROS monitored via ^?OH radical photogeneration, in comparison with undoped TiO₂ nanobeads and TiO₂ P25, for Gd‐doping up to 10%. Cellular internalization and biocompatibility of TiO₂@x Gd NBs are tested in vitro on MG‐63 human osteosarcoma cells, showing full biocompatibility. After photoactivation of the particles, anticancer trace by means of ROS photogeneration is observed just after 3 min irradiation.     

CeO<Subscript>2</Subscript> and Co<Subscript>3</Subscript>O<Subscript>4</Subscript>–CeO<Subscript>2</Subscript> nanoparticles: effect of the synthesis method on the structure and catalytic properties in COPrOx and methanation reactions

CeO₂ and Co₃O₄–CeO₂ nanoparticles were synthesized, thoroughly characterized, and evaluated in the COPrOx reaction. The CeO₂ nanoparticles were synthesized by the diffusion-controlled precipitation method with ethylene glycol. A notably higher yield was obtained when H₂O₂ was used in the synthesis procedure. For comparison, two commercial samples of CeO₂ nanoparticles (Nyacol^®)—one calcined and the other sintered—were also studied. Catalytic results of bare CeO₂ calcined at 500 °C showed a strong influence of the method of synthesis. Despite having similar BET area values, the CeO₂ synthesized without H₂O₂ was the most active sample. Co₃O₄–CeO₂ catalysts with three different Co/(Co + Ce) atomic ratios, 0.1, 0.3, and 0.5, were prepared by the wet impregnation of the CeO₂ nanoparticles. TEM and STEM observations showed that impregnation produced mixed oxides composed of small CeO₂ nanoparticles located both over the surface and inside the Co₃O₄ crystals. The mixed oxide catalysts prepared with a cobalt atomic ratio of 0.5 showed methane formation, which started at 200 °C due to the reaction between CO₂ and H₂. However, above 250 °C, the reaction between CO and H₂ became important, thus contributing to CO elimination with a small H₂ loss. As a result, CO could be totally eliminated in a wide temperature range, from 200 to 400 °C. The methanation reaction was favored by the reduction of the cobalt oxide, as suggested by the TPR experiments. This result is probably originated in Ce–Co interactions, related to the method of synthesis and the surface area of the mixed oxides obtained.     

Cohesive surface model for fracture based on a two-scale formulation: computational implementation aspects

The paper describes the computational aspects and numerical implementation of a two-scale cohesive surface methodology developed for analyzing fracture in heterogeneous materials with complex micro-structures. This approach can be categorized as a semi-concurrent model using the representative volume element concept. A variational multi-scale formulation of the methodology has been previously presented by the authors. Subsequently, the formulation has been generalized and improved in two aspects: (i) cohesive surfaces have been introduced at both scales of analysis, they are modeled with a strong discontinuity kinematics (new equations describing the insertion of the macro-scale strains, into the micro-scale and the posterior homogenization procedure have been considered); (ii) the computational procedure and numerical implementation have been adapted for this formulation. The first point has been presented elsewhere, and it is summarized here. Instead, the main objective of this paper is to address a rather detailed presentation of the second point. Finite element techniques for modeling cohesive surfaces at both scales of analysis (FE\(^2\) approach) are described: (i) finite elements with embedded strong discontinuities are used for the macro-scale simulation, and (ii) continuum-type finite elements with high aspect ratios, mimicking cohesive surfaces, are adopted for simulating the failure mechanisms at the micro-scale. The methodology is validated through numerical simulation of a quasi-brittle concrete fracture problem. The proposed multi-scale model is capable of unveiling the mechanisms that lead from the material degradation phenomenon at the meso-structural level to the activation and propagation of cohesive surfaces at the structural scale.     

An adaptive method based on the improved LPA-ICI algorithm for MRI enhancement

Various diseases are diagnosed using medical imaging used for analysing internal anatomical structures. However, medical images are susceptible to noise introduced in both acquisition and transmission processes. We propose an adaptive data-driven image denoising algorithm based on an improvement of the intersection of confidence intervals (ICI), called relative ICI (RICI) algorithm. The 2D mask of the adaptive size and shape is calculated for each image pixel independently, and utilized in the design of the 2D local polynomial approximation (LPA) filters. Denoising performances, in terms of the PSNR, are compared to the original ICI-based method, as well as to the fixed sized filtering. The proposed adaptive RICI-based denoising outperformed the original ICI-based method by up to 1.32 dB, and the fixed size filtering by up to 6.48 dB. Furthermore, since the denoising of each image pixel is done locally and independently, the method is easy to parallelize.     

Study of DNA Origami Dimerization and Dimer Dissociation Dynamics and of the Factors that Limit Dimerization

Organizing DNA origami building blocks into higher order structures is essential for fabrication of large structurally and functionally diverse devices and molecular machines. Unfortunately, the yields of origami building block attachment reactions are typically not sufficient to allow programed assembly of DNA devices made from more than a few origami building blocks. To investigate possible reasons for these low yields, a detailed single‐molecule fluorescence study of the dynamics of rectangular origami dimerization and origami dimer dissociation reactions is conducted. Reactions kinetics and yields are investigated at different origami and ion concentrations, for different ion types, for different lengths of bridging strands, and for the “sticky end” and “weaving welding” attachment techniques. Dimerization yields are never higher than 86%, which is typical for such systems. Analysis of the dynamic data shows that the low yield cannot be explained by thermodynamic instability or structural imperfections of the origami constructs. Atomic force microscopy and gel electrophoresis evidence reveal self‐dimerization of the origami monomers, likely via blunt‐end interactions made possible by the presence of bridging strands. It is suggested that this mechanism is the major factor that inhibits correct dimerization and means to overcome it are discussed.     

A SLIT THROUGH PHOTOGRAPHY

Post-war experimental and conceptual photography in former Yugoslavia has only rarely been the subject of detailed study and interpretation. In considering this period, it is necessary to take into account several factors, including the absence of permanent exhibition spaces for photography, the lack of magazines in which photographic themes were presented and discussed, the impossibility of studying the field of photography and, finally, the inadequate knowledge and application of contemporary criticism and theories of photography. Nevertheless, from the mid-1950s onwards it is possible to note a variety of innovations in the field, in terms of both form and subject-matter. This article considers rare instances of institutional support for progressive photography-related events and unique, intellectual-poetic works. After the break-up of Yugoslavia, there is a dominant tendency to nationalize art created in the former state, thus ignoring the specific Yugoslav cultural field as well as the European context. Based on a methodology which surpasses the national (but still acknowledges it) and searches for meaning within the broader socio-political space to which art is referring, the research aims to change the paradigm of the peripheral position and general ignorance of the circumstances under which this innovative practice emerges.