Laboratory tests addressed to realize customized restoration procedures of underwater archaeological ceramic finds

The present contribution is part of a biennial research project funded by the Italian Ministry of Education, Universities and Research (MIUR). This study, currently in progress, deals with innovative experimental approaches applied to the chemical, mineralogical and physical transformations occurring during the prolonged permanence of archaeological ceramic finds in seawater environments as well as to restoration and conservation issues of the same underwater artifacts. The experimental approach used in this research consisted in the manufacture of ceramic test-pieces (briquettes) and their successive placing in underwater environment. This work aims at assessing how textural and compositional parameters along with firing temperatures of a ceramic paste could affect total porosity, pore size distribution and kinetics of capillary water absorption. A further purpose is concerned with the study of the potential modification of porosity and pore size distribution in the same ceramic bodies after immersion in seawater (3 and 6 months). The study was carried out using a multi-technique approach including investigations through polarized light microscopy (PLM), capillary water absorption test, mercury intrusion porosimetry (MIP) analyses and theoretical calculation of salt crystallization pressures. The obtained results show a different behavior of the six experimental pastes as a function of their compositional and textural features as well as pore size distribution and firing temperatures. These parameters, in various extents, have been found significantly influencing the kinetics of water absorption and the susceptibility of ceramic artifacts to salt crystallization processes, with important implications on conservation procedures needed before the musealization.     

Heterogeneous nucleation mechanisms and formation of metastable phase assemblages induced by different crystalline seeds in a rapidly cooled andesitic melt

Pt-capsules loaded with a Pt-coil and two crystalline seeds immersed into an andesitic melt were rapidly cooled from 1300 to 1100 °C with a rate of 3 °C/min at atmospheric pressure and air oxygen fugacity. Results show that the Pt-coil does not induce any heterogeneous crystallization process as well as iron diffusion process from the melt into the platinum substrate. In contrast, the presence of crystalline seeds in a solidifying andesitic melt significantly alters the phase assemblage, composition and texture of the new-forming crystals in response to a heterogeneous nucleation mechanism and the formation of metastable phases.     

Fluorinated PLGA Nanoparticles for Enhanced Drug Encapsulation and 19F NMR Detection

In the continuous search for multimodal systems with combined diagnostic and therapeutic functions, several efforts have been made to develop multifunctional drug delivery systems. In this work, through a covalent approach, a new class of fluorinated poly(lactic-co-glycolic acid) co-polymers (F-PLGA) were designed that contain an increasing number of magnetically equivalent fluorine atoms. In particular, two novel compounds, F₃-PLGA and F₉-PLGA, were synthesized and their chemical structure and thermal stability were analyzed by solution NMR, DSC, and TGA. The obtained F-PLGA compounds were proven to form in aqueous solution colloidal stable nanoparticles (NPs) displaying a strong ¹⁹F NMR signal. The fluorinated NPs also showed an enhanced ability to load hydrophobic drugs containing fluorine atoms compared to analogous pristine PLGA NPs. Preliminary in vitro studies showed high cell viability and the NP ability to intracellularly deliver and release a functioning drug.     

Spectroscopic characterization of a functionalized NAD+ analogue and its polyethyleneimine-bound derivative

The ¹H and ¹³C NMR spectra of deuterium oxide solutions of two NAD⁺ derivatives, i.e. nicotinamide-6-(2-hydroxy-3-carboxypropylamino)purine dinucleotide and 4(NAD⁺-N⁶)-3-hydroxybutyryl-polyethylememine, have been examined over a range of pH, as well as the fluorescence spectra of their reduced forms. The results have been compared with those obtained with NAD⁺. Small shifts have been observed in both the proton and carbon magnetic resonance spectra in passing from low to high pH. This behavior, as well as the fluorescence studies, indicate that, analogously to NAD⁺, the two NAD⁺ derivatives exist in solution as a pH dependent equilibrium of folded and unfolded forms, with the folded form prevailing at basic pH. As consequence of the folding, an intramolecular interaction takes place between the adenine and nicotinamide rings. The variation of proton and carbon resonances with pH changes has been utilized to evaluate the strength of this intramolecular interaction.     

New heterocyclic structures. [1,2,5]Thiadiazolo[3′,4′:4,5]pyrimido-[2,1-b][1,3]thiazine and thiazolo[3,2a][1,2,5]thiadiazolo[3,4-d]pyrimidine

Derivatives of two new molecular structures, namely, 7,8-dihydro-6H,10H-[1,2,5]thiadiazolo[3′,4′:4,5]pyrimido[2,1-b][1,3]thiazin-10-one and 6,7-dihydro-9H-thiazolo[3,2-a][1,2,5]thiadiazolo[3,4-d][pyrimidin-9-one, and derivatives of N-substituted sulfamic acid, namely, (8-amino-3,4-dihydro-2H,6H-pyrimido[2,1-b][1,3]thiazin-6-on-7-yl)sulfamic acid and (7-amino-2,3-dihydro-5H-thiazolo[3,2-a]pyrimidin-5-on-6-yl)sulfamic acid, were separated out as by-products in the reduction reaction of 8-amino-3,4-dihydro-7-nitroso-2H,6H-pyrimido[2,1- b][1,3]thiazin-6-one and 7-amino-2,3-dihydro-6-nitroso-5H-thiazolo[3,2-a]pyrimidin-5-one derivatives, respectively, with sodium hydrosulfite. A mechanism of reaction, which hypothesizes the action of sodium hydrosulfite in an asymmetic form, is proposed. The results of single-crystal X-ray investigation on 7,8-dihydro-6H,10H-[1,2,5]thiadiazolo[3′,4′:4,5]pyrimido[2,1-b][1,3]thiazin-10-one (R = 0.032 for 863 reflections) and (8-amino-3,4-dihydro-2H,6H-pyrimido[2,1-b]- [1,3]thiazin-6-on-7-yl)sulfamic acid, sodium salt (R = 0.028 for 3507 reflections) are reported.     

Improved procedure for the preparation of DNA restriction fragments suitable for sequencing

A rapid and integrated procedure was developed for the preparation of small DNA restriction fragments ( ≤ 1000 bp) starting from a large cosmid (35,000 bp) containing exogenous DNA. The process is based on restriction enzymatic digestion followed by HPLC separation and fractions collection. All DNA fragments are separated in a single run, detected “on-line” by UV absorption, and straightforward collected with very high recovery. Small fragments can be directly subjected to the sequence procedure, whereas those larger than 1000 bp are redigested with a second enzyme, the fractionated subfragments are separated, ligated to plas-mid vector, and sequenced. A human genomic cosmid of 35,000 bp (26H7) has been chosen as a model.     

Efficacy of nanolime in restoration procedures of salt weathered limestone rock

Salt crystallisation process is one of the most powerful weathering agents in stone materials, especially in the coastal areas, where sea-spray transports large amount of salts on the stone surface. The consolidation of such degraded stone material represents a critical issue in the field of restoration of cultural heritage. In this paper, the nanolime consolidation behaviour in limestone degraded by salt crystallization has been assessed. For this purpose, a stone material taken from a Sicilian historical quarry and widely used in the eastern Sicilian Baroque architecture has been artificially degraded by the salt crystallization test. Then degraded samples have been treated with NanoRestore^®, a suspension of nanolime in isopropyl alcohol. To evaluate the consolidating effectiveness, the peeling test and point load test were performed. Moreover, mercury intrusion porosimetry has been executed to evaluate the variations induced by treatment, while colorimetric measurements have been aimed to assess aesthetical issues.     

Back-to-back comparison of impedance measurement techniques applied to the characterization of aero-engine nacelle acoustic liners

The aim of this paper is to assess three different measurement techniques applied to the characterization of the acoustic impedance of a Single-Degree-of-Freedom (SDOF) liner installed in nacelle ducts of turbofan engines. The “two-microphones” method, the “in-situ” impedance measurement technique and the “impedance eduction” approach are respectively compared in representative flight environment, characterized by normal and grazing incidence sound, with and without grazing flow. Goal of the study is to collect evidences of the unique and complementary features offered by these techniques, providing deeper insight into their strengths and limitations.