Firing-Induced Microstructural Properties of Quasi-Diamagnetic Carbonate-Based Porous Ceramics: a <Superscript>1</Superscript>H NMR Relaxation Correlation Study

This study deals with the application of two-dimensional proton nuclear magnetic resonance relaxometry (2D ¹H NMR-R) to the characterization of porous ceramics nearly free of magnetic compounds. Different microstructural properties were obtained by firing a diamagnetic mixture of kaolin, calcium, and magnesium carbonate over a wide range of maximum temperatures (600–1100 °C) and firing times at the maximum temperature (soaking times) (0–10 h). The 2D ¹H NMR-R method relies on the correlated measurement of ¹H longitudinal (T ₁) and transverse (T ₂) relaxation times of pore-filling water by which the properties of the interconnected pore space may be investigated. In the absence of significant magnetic susceptibility effect due to para- and ferro-magnetic compounds, the 2D ¹H NMR-R maps allow studying the conjoint effects on pore size distribution and inter-pore coupling due to the variations in both time and temperature of firing. The NMR experiments were performed with a low-field ¹H NMR sensor, which allows non-destructive and in situ analysis. For ceramic specimens fired at 600 and 700 °C, the fraction of smallest pores increases with firing time at the expenses of those with intermediate size. The pore shrinkage occurring at this stage, and likely associated with the transformation of kaolinite in metakaolinite, is affected in a similar way by soaking time and firing temperature, in line with the concept of equivalent firing temperature. At temperatures from 800 to 1100 °C, the structural modifications involving interconnectivity and average pore size are driven primarily by firing temperature and, secondarily, by soaking time. The 2D ¹H NMR-R results are confirmed by more traditional, but destructive, mineralogical, and structural analyses like X-ray powder diffraction, helium pycnometry, mercury intrusion porosimetry, and nitrogen adsorption/desorption method.     

Vector-valued perturbed equilibrium problems

The goal of this paper is to prove some general vector-valued perturbed equilibrium principles and some existence results of vector equilibrium points for bifunctions satisfying a new natural notion of lower semi-continuity. We obtain these results by going through a new concept of approximative equilibrium point.     

Multifunctional nanostructures based on inorganic nanoparticles and oligothiophenes and their exploitation for cellular studies

The combination of materials that possess different properties (such as, for instance, fluorescence and magnetism) into one single object of nanoscale size represents an attractive challenge for biotechnology, especially for their potential relevance in biomedical applications. We report here the preparation of novel bifunctional conjugates based on the linkage of inorganic nanoparticles to organic oligothiophene fluorophores (OTFs). In comparison to the organic dyes commonly used in bioimaging and more similarly to colloidal quantum dots, OTFs have broad optical absorption spectra, and therefore OTF fluorophores emitting at different colors can be excited with a single excitation source, allowing for easier multiplexing analysis. In this work we show the preparation of OTF-nanoparticle conjugates based on gold and iron oxide nanoparticles and their characterization using different techniques such as gel electrophoresis, photoluminescence spectroscopy, dynamic light scattering, and so on. In addition, by performing an in vitro study on human tumor cells we show that OTF-nanoparticle conjugates emitting at different colors can be used for multiplexing detection. Also, in the case of iron oxide-OTF conjugates, once uptaken by the cells, we show that they preserve both their fluorescent and their magnetic properties.     

Algebras in sets of queer functions

We show that the set of continuous nowhere differentiable functions, the set of Dirichlet series which are bounded in the right half-plane and diverge everywhere on the imaginary axis, and the set of continuous interpolating functions contain big algebras. Partially supported by a grant from the “Banque Nationale de Belgique”.     

High-resolution radiocarbon dating of prehistoric sites in southern Italy

A new facility for accelerator mass spectrometry radiocarbon dating has been put in operation at the University of Lecce in southern Italy. The general features of the facility are described, showing how by the use of electrostatic and magnetic analyzers the radiocarbon content in several kinds of sample materials can be measured. The performances of the system are also given in terms of precision, accuracy and background. The results of the radiocarbon dating of two prehistoric sites are also reported. PACS 93.85.+q     

Magnetic properties of novel superparamagnetic MRI contrast agents based on colloidal nanocrystals

Novel systems based on colloidal magnetic nanocrystals (NCs), potentially useful as superparamagnetic (SP) contrast agents for magnetic resonance imaging (MRI) have been investigated. The NCs we have studied comprise organic-capped single-crystalline maghemite (γ-Fe₂O₃) cores possessing controlled sizes and shapes. We have comparatively examined spherical and tetrapod-like NCs, the latter being branched particles possessing four arms which depart out at tetrahedral angles from a central point. The as-synthesized NCs are passivated by hydrophobic surfactant molecules and thus are fully dispersible in nonpolar media only. The NCs have been made soluble in aqueous solution by applying a procedure based on the surface intercalation and coating with an amphiphilic polymer shell. NMR relaxivities R₁ and R₂ were compared with ENDOREM^®, one of the standard commercial SP-MRI contrast agent. We found that the spherical NCs exhibit R₁ and R₂ relaxivities slightly lower than those of ENDOREM^®, over the whole frequency range; on the contrary, tetrapods show relaxivities about one order of magnitude lower. The physical origin of such difference in relaxivities between tetrapod- and spheres-based nanostructures is under investigation and it is possibly related to different sources of the magnetic anisotropy.     

Precious coral non‐destructive characterization by Raman and XRF spectroscopy

Precious corals are some of the most valuable living marine resources, growing and commercially exploited only in limited areas of the world, namely the Mediterranean Sea and the Northern Pacific Ocean. Their skeleton is formed by calcium carbonate crystallized in the form of calcite whereas their color is because of the presence of partially demethylated polyene pigments. Recently, Pacific corals have been included in the appendix II of CITES list, while Mediterranean corals are still excluded. Different Corallium species of Corallidae family (e.g. Corallium rubrum, Corallium elatius and Corallium secundum) collected from different locations of the Mediterranean Sea and the Pacific Ocean were analyzed by Raman spectroscopy for the characterization of the reddish pigment and by X‐ray fluorescence (XRF) for the determination of the chemical composition of their skeletons, in order to obtain molecular and elemental data with two relatively easy and non‐destructive techniques, which can be used quite steadily for authentication purposes. Raman analysis demonstrated the presence of specific vibrational bands useful to identify the colored pigments as a mixture involving methylated and demethylated polyenes such as carotenoids and parrodienes, characterized by the presence of ―CH₃ groups along the polyene chain. The ratio between the Raman signal and fluorescence background was found to vary as a function of the macroscopic color of the coral, but Raman analyses resulted inadequate for distinguishing between corals having similar color but different origins. On the other side, XRF data provided reliable information for an appropriate separation between Pacific and Mediterranean corals at the elemental level. The results of this study will be of great relevance for the authentication and identification of the origin of corals in trade market by means of completely non‐destructive techniques. Copyright © 2016 John Wiley & Sons, Ltd.     

An integrated accelerator mass spectrometry radiocarbon dating and ion beam analysis approach for the study of archaeological contexts

The integration in the accelerator-based facility at CEDAD (Centro di Datazione e Diagnostica), University of Lecce, of a state-of-the art AMS (accelerator mass spectrometry) ¹⁴C dating system, and three different beam lines for IBA (ion beam analysis) compositional investigations, has given the possibility of developing an integrated IBA-AMS approach to the study of a wide range of archaeological problems. Here we present three cases where in air IBA methods were involved for the elemental characterisation of objects found in archaeological contexts, chronologically defined on the basis of high resolution AMS¹⁴C measurements.In particular we report on the identification of cinnabar (HgS) on Neolithic bones, the compositional analysis of a set of golden artefacts dated at the final Bronze age, and the analysis of red decorations on Neolithic pottery. PACS 32.30.Rj; 34.50.Dy; 82.80.Ms     

A cast-mold approach to iron oxide and Pt/iron oxide nanocontainers and nanoparticles with a reactive concave surface

We report the synthesis of various iron oxide nanocontainers and Pt-iron oxide nanoparticles based on a cast-mold approach, starting from nanoparticles having a metal core (either Au or AuPt) and an iron oxide shell. Upon annealing, the particles evolve to asymmetric core-shells and then to heterodimers. If iodine is used to leach Au out of these structures, asymmetric core-shells evolve into "nanocontainers", that is, iron oxide nanoparticles enclosing a cavity accessible through nanometer-sized pores, while heterodimers evolve into particles with a concave region. When starting from a metal domain made of AuPt, selective leaching of the Au atoms yields the same iron oxide nanoparticle morphologies but now encasing Pt domains (in their concave region or in their cavity). We found that the concave nanoparticles are capable of destabilizing Au nanocrystals of sizes matching that of the concave region. In addition, for the nanocontainers, we propose two different applications: (i) we demonstrate loading of the cavity region of the nanocontainers with the antitumoral drug cis-platin; and (ii) we show that nanocontainers encasing Pt domains can act as recoverable photocatalysts for the reduction of a model dye.