Identification Techniques I

Infrared (IR) and Raman spectroscopy have a high potential for characterisation of material. Extensive series of wet chemical analysis may be substituted by a single spectroscopic measurement followed by detailed chemometric data evaluation. Topics of this chapter are: (i) basics of IR and Raman spectroscopy, (ii) the registration of “correct” spectra, and (iii) spectra evaluation. Dedicated applications in the area of conservation science are collected in separate chapters. The infrared (IR) spectrum is often called the fingerprint of a substance. An IR spectrum identifies a substance like a human fingerprint. Due to their origin the features of an IR spectrum are bands, not peaks. They in…

Low-Q peak in X-ray patterns of choline-phenylalanine and homophenylalanine: a combined effect of chain and stacking

Abstract In this contribution we report for the first time the X-ray patterns of choline-phenylalanine and choline-homophenylalanine ionic liquids. The presence of a low Q peak in both systems is another evidence that a long alkyl chain is not always needed to establish a nanodomain segregation in the liquid sufficient to be revealed by the diffraction experiment. These new data are compared with the diffraction patterns and the theoretical calculations of other choline-aminoacid ionic liquids recently reported. A significant role might be played by the stacking interactions between aromatic rings.

Effect of the cerium loading on the HMS structure. Preparation, characterization and catalytic properties

Abstract Ce–HMS mesoporous materials were prepared by incipient wetness method starting from HMS synthesized in acid condition. The effect of cerium quantity, in the range of Ce/Si atomic ratio 0.02–0.3, on its structure and properties was investigated. Results showed that the HMS hexagonal structure was maintained after the cerium adding. Furthermore, the surface area and the pore volume were reduced. The presence of the cerianite nanoparticles located within the HMS channels up to 0.05, thus covering the HMS surface at higher Ce/Si atomic ratio, was observed. The catalytic performances of the materials were tested in ethanol partial oxidation reaction.

Microwave Assisted Synthesis of dry CdS Nanoparticles in Water in Oil Microemulsion

Micro-X-Ray Fluorescence and the Old Masters Non-destructive in situ characterisation of the varnish of historical Low Countries stringed musical instruments

Applied Physics A, 107

Newly discovered orichalcum ingots from Mediterranean sea: Further investigation

Abstract In February 2016, 47 ingots were found in the seabed of Contrada Bulala (Gela, CL, Italy) near the site where 40 ingots had previously been recovered. The ingots composition was determined to be a Cu - Zn alloy, dated by the archaeologist to the VI century B.C. This specific alloy was then known as Orichalcum. From an archaeological point of view, the first question raised about the new discovery was whether the ingots of the first and the second excavations belonged to the same shipwreck. Following the previous study, an elemental analysis was performed on the ingots from the second finding by using ICP-OS and ICP-MS techniques. The chemometric treatment of the analytical results …

Sintesi e caratterizzazione di compositi polimetilmetacrilato e nano-SiO2, -TiO2 o -ZrO2

Improved Photocatalytic Activity of Polysiloxane TiO2 Composites by Thermally Induced Nanoparticle Bulk Clustering and Dye Adsorption

Fine control of nanoparticle clustering within polymeric matrices can be tuned to enhance the physicochemical properties of the resulting composites, which are governed by the interplay of nanoparticle surface segregation and bulk clustering. To this aim, out-of-equilibrium strategies can be leveraged to program the multiscale organization of such systems. Here, we present experimental results indicating that bulk assembly of highly photoactive clusters of titanium dioxide nanoparticles within an in situ synthesized polysiloxane matrix can be thermally tuned. Remarkably, the controlled nanoparticle clustering results in improved degradation photocatalytic performances of the material under …

Loading and release of the complex [Pt(DTBTA)(DMSO)Cl]Cl·CHCl3 with the 2,2′-dithiobis(benzothiazole) ligand into mesoporous silica and studies of antiproliferative activity on MCF-7 cells

Abstract Synthetic delivery systems have great potential for overcoming problems associated with systemic toxicity that accompanies chemotherapy with the use of cisplatin and family of platinum anticancer drugs. Mesoporous silicates have been studied in context of drug delivery and drug targeting. In this paper we report the studies of loading and release of a platinum complex, [Pt(DTBTA)(DMSO)Cl]Cl∙CHCl3 (1) where DTBTA = 2,2′-dithiobis(benzothiazole), that was recently synthesized and structurally characterized. Evaluation in vitro of antitumor activity against a human breast cancer cell line (MCF-7) showed a very potent activity of complex(1). Therefore, we thought to incorporate this co…

1H NMR-Based Metabolomics to Assess the Impact of Soil Type on the Chemical Composition of Nero d’Avola Red Wines

: In this study, the soil effect on the micro-component composition of Nero d'Avola wines obtained from different locations was investigated through 1H NMR-based metabolomics. Two different approaches were applied: the targeted (TA) and the non-targeted one (NTA). The former differentiated the wines by profiling (i.e., by identifying and quantifying) a number of different metabolites. The latter provided wine fingerprinting by processing the entire spectra with multivariate statistical analysis. NTA also allowed investigation of the hydrogen bond network inside wines via the analysis of 1H NMR chemical shift dispersions. Results showed that the differences among wines were due not only to t…

Polyaminocyclodextrin nanosponges: synthesis, characterization and pH-responsive sequestration abilities

New pH-responsive nanosponges were obtained by reacting four different polyaminocyclodextrins with heptakis-(6-bromo)-(6-deoxy)-β-cyclodextrin. The materials obtained were characterized by various techniques (FT-IR, potentiometric titration, differential scanning calorimetry (DSC), porosimetry (BET), 13C{1H} CP-MAS NMR). Their adsorption abilities at different pH values were verified towards a suitable set of model guests, and seem mainly controlled by electrostatic interactions, as a function of the protonation/charge status of the polymer matrix. By contrast, data positively point out a lesser importance assumed by the induced-fit effect, important in affecting the formation of host–guest…

Recent Developments in Understanding Biochar’s Physical–Chemistry

Biochar is a porous material obtained by biomass thermal degradation in oxygen-starved conditions. It is nowadays applied in many fields. For instance, it is used to synthesize new materials for environmental remediation, catalysis, animal feeding, adsorbent for smells, etc. In the last decades, biochar has been applied also to soils due to its beneficial effects on soil structure, pH, soil organic carbon content, and stability, and, therefore, soil fertility. In addition, this carbonaceous material shows high chemical stability. Once applied to soil it maintains its nature for centuries. Consequently, it can be considered a sink to store atmospheric carbon dioxide in soils, thereby mitigat…

Pre- and post-modification of mixed cyclodextrin-calixarene co-polymers: A route towards tunability

Various pre-modified and post-modified cyclodextrin-calixarene hyper-reticulated co-polymers were synthesized, fully characterized by different techniques (FT-IR, 13C{1H} CP-MAS and LGFS solid-state NMR, thermogravimetry, porosimetry), and tested to assess their absorption abilities as nanosponges. The construction of the polymer network was accomplished exploiting the well-known CuAAC reaction between two different heptakis-6-azido-β-cyclodextrins and two different propargyloxy-calix[4]arenes. Post-modification was aimed to achieve the presence of ionizable (acidic or basic) groups on the polymer framework. Sequestration tests towards two model pollutant molecules surprisingly showed that …

Microwave-assisted synthesis of anhydrous CdS nanoparticles in a water-oil microemulsion.

Abstract Microwave irradiation at a frequency of 2.45 GHz and a power ranging between 22 and 30 W was used, in a water–oil microemulsion at 35 ± 2 ° C , to obtain stable, small, crystalline, anhydrous CdS nanoparticles exhibiting enhanced luminescence properties. The process of nanoparticles growth at different irradiation times was followed by UV–vis spectroscopy. It was observed that irradiated nanoparticles grew faster and their size reached a constant value. The final mean nanoparticle diameter was 2.7 nm, smaller than that observed in a non-irradiated sample, in which particle dimensions slowly increased even after 10 h. This finding was confirmed by high resolution transmission electr…

Preparation of Nd:YAG Nanopowder in a Confined Environment

Nanopowder of yttrium aluminum garnet (YAG, Y3Al5O12) doped with neodymium ions (Nd:YAG) was prepared in the water/cetyltrimethylammonium bromide/1-butanol/n-heptane system. Aluminum, yttrium, and neodymium nitrates were used as starting materials, and ammonia was used as a precipitating agent. Coprecipitate hydroxide precursors where thermally treated at 900 degrees C to achieve the garnet phase. The starting system with and without reactants was characterized by means of the small-angle neutron scattering technique. The system, without reactants, is constituted by a bicontinuous structure laying near the borderline with the lamellar phase region. The introduction of nitrates stabilizes th…

Effect of halloysite nanotubes filler on polydopamine properties

Abstract Hypothesis Polydopamine (PDA) is widely used as hydrophilic coating for several applications. However, most of the methods studied to improve or manipulate PDA properties are multistep and time-consuming, and there is a need for versatile strategies aimed at controlling and modifying the properties of PDA. Experiments PDA-halloysite nanocomposites were produced under different oxidation conditions in alkaline and acidic media and were characterized by UV–visible and attenuated total refraction- Fourier Transform Infrared spectroscopies, thermogravimetric analysis, porosimetry, scanning electron microscopy, X-ray diffraction and contact angle measurements against the reference PDA p…

Synthesis of Nd:YAG nanopowder by microemulsion method

Differentiation among dairy products by combination of fast field cycling NMR relaxometry data and chemometrics

A set of commercial milk and Sicilian cheeses was analysed by a combination of fast field cycling (FFC) nuclear magnetic resonance (NMR) relaxometry and chemometrics. The NMR dispersion (NMRD) curves were successfully analysed with a mathematical model applied on Parmigiano-Reggiano (PR) cheese. Regression parameters were led back to the molecular components of cheeses (water trapped in casein micelles, proteins and fats) and milk samples (water belonging to hydration shells around dispersed colloidal particles of different sizes and bulk water). The application of chemometric analysis on relaxometric data enabled differentiating milk from cheeses and revealing differences within the two sa…

SPAIS. Quali conoscenze per comprendere l'innovazione?

Effect of the dopant selection (Er, Eu, Nd or Ce) and its quantity on the formation of yttrium aluminum garnet nanopowders

Abstract Hydroxide precursors, synthesized using the co-precipitation method, were calcined for 1 h at the temperatures of 900, 1000 and 1100 °C, respectively, and heated directly to 1500 °C to produce various Y 3 Al 5 O 12 (YAG) nanopowders with different doping quantities of erbium, europium, neodymium and cerium. All samples were investigated using thermo-gravimetry (TG) and differential thermal analysis (DTA), field emission gun-scanning electron microscopy (FEG-SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). TG and DTA experiments were performed from room temperature up to 1500 °C; the weight loss curves combined with the presence of exo- and endo-thermal even…

FDA dimension reduction techniques and components separation in Fourier-transform infrared spectroscopy

FTIR spectroscopy is a measurement technique used to obtain an infrared spectrum of absorption of a solid (or a liquid or a gas), for the characterization of specific chemical components of materials. When repeated measures are taken on samples of materials, the result is a collection of spectra representing a set of samples from continous functions (signals) defined in the domain of the frequencies. An unifying approach to the study of a collection of FTIR spectra is proposed to deal with the presence of random shifts in the peaks, the identification of representative spectra and finally the characterization of the observed differences: in the functional data framework, the performance of …

Micelles formed from photochemically active amphiphiles: structural characterization by small-angle neutron scattering

Abstract A novel class of photochemically active amphiphiles has been synthesized containing a ketone moiety as a biradical or radical pair precursor on the hydrophobic tail of sodium sulfate surfactants. Alteration of the molecular structure of each ketone-containing surfactant allows for the systematic and predictable manipulation of the micellar size and shape, both of which are important in determining the coupling between the unpaired electrons confined within the micelle and the intraradical dynamics. The structure of the resulting aggregates has been analyzed by small-angle neutron scattering (SANS). The results show that the amphiphiles form ellipsoidal micelles with aggregation num…

Archaeometric study of execution techniques of white Attic vases: the case of the Perseus crater in Agrigento

The white ground crater by the Phiale Painter (450–440 BC) exhibited in the “Pietro Griffo” Archaeological Museum in Agrigento (Italy) depicts two scenes from Perseus myth. The vase is of utmost importance to archaeologists because the figures are drawn on a white background with remarkable daintiness and attention to detail. Notwithstanding the white ground ceramics being well documented from an archaeological and historical point of view, doubts concerning the compositions of pigments and binders and the production technique are still unsolved. This kind of vase is a valuable rarity, the use of which is documented in elitist funeral rituals. The study aims to investigate the constituent m…

ART AND TECHNIQUE: ARTISTIC REPRODUCTION OF THE ANCIENT BRONZE IL GUERRIERO DA PETRALIA SOTTANA

The reproduction of artistic objects is useful for museological, teaching, and commercial purposes. In some cases, the reproduction is carried out to replace the originals located in outdoor environments and to prevent the deterioration due to weathering or pollution. This article describes the different phases that led to the reproduction of the Il Guerriero da Petralia Sottana. The observation of stylistic characteristics and the physical-chemical investigation were carried out in order to obtain information about the composition of the alloy and the technological properties of the artifact by using Optical Microscopy and X- ray Fluorescence. The reproduction in wax was performed by using…

Disidratazione di nanoparticelle sintetizzate in microemulsione w/o

Green Synthesis, Molecular Characterization and Associative Behavior of Some Gemini Surfactants without a Spacer Group.

A series of new gemini surfactants without a spacer group, disodium 2,3-dialkyl-1,2,3,4-butanetetracarboxylates, were synthesized in a green chemistry context minimizing the use of organic solvents and applying microwaves (MW) when activation energy was required. Once the desired architecture was confirmed by means of the nuclear magnetic resonance technique (1H-NMR, 1H-1H COSY) for all the studied surfactants, the critical micellization concentration was determined by conductance measurements. The diffusion coefficient of micelles formed by the four compounds was characterized using pulsed field gradient (PFG)-NMR. Diffusion coefficients were found to be dependent on the concentration and …

Chromium liquid waste inertization in an inorganic alkali activated matrix: Leaching and NMR multinuclear approach

A class of inorganic binders, also known as geopolymers, can be obtained by alkali activation of aluminosilicate powders at room temperature. The process is affected by many parameters (curing time, curing temperature, relative humidity etc.) and leads to a resistant matrix usable for inertization of hazardous waste. In this study an industrial liquid waste containing a high amount of chromium (≈ 2.3 wt%) in the form of metalorganic salts is inertized into a metakaolin based geopolymer matrix. One of the innovative aspects is the exploitation of the water contained in the waste for the geopolymerization process. This avoided any drying treatment, a common step in the management of liquid ha…

Production of Antibacterial Compounds from Actinomycetes

Actinomycetes are soil-dwelling Gram-positive bacteria, industrially relevant as producers of a wide range of bioactive secondary metabolites, including many antibiotics of clinical and commercial importance.The understanding of actinomycete biology has been based on extensive studies on the model organism Streptomyces coelicolor over many years and on the availability of its complete genome sequence. This bacterium has an unusual complex developmental cycle that includes programmed cell death phenomena that make this bacterium a multicellular prokaryotic model.Morphological differentiation in S. coelicolor is strictly related to physiological differentiation: indeed the onset of morphologi…

A multi-analytical non-invasive and micro-invasive approach to canvas oil paintings. General considerations from a specific case

Abstract The investigation of artwork to understand story, state of conservation and to know about the composing materials is an issue that is getting growing attention in specialized literature. From a methodological point of view the scientific community is trying to reach a common proposal that could contribute to define a Standard Operating Procedure (SOP) for the application of portable non-invasive and microinvasive techniques for in-situ analyses. In this paper the oil painting on canvas “St. Girolamo nello studio” by Nicolo Buttafoco was investigated to known the materials and techniques used by the artist as well as to evaluate its preservation status. The survey has been conducted…

Solid state NMR investigation of the roman Acqualadroni rostrum: tenth year assessment of the consolidation treatment of the wooden part

Abstract: This work follows a previous one dealing with the state of conservation study of the wooden part of the roman Acqualadroni rostrum soon after its finding in the seabed of Acqualadroni (Messina, Italy). The archaeological survey and recovery were particularly relevant since this artefact is one of the two rostrums, nowadays known,found together with its wooden part. Following the recovery, it was consolidated by immersion in a melamine-formaldehyde resin (Kauramin) aqueous solution for eight months at the “Centro di Restauro del Legno Bagnato” (Pisa, Italy). The present investigation is aimed to determine at microscopic scale the wood state of conservation and to highlight interact…

A combined physical-chemical and microbiological approach to unveil the fabrication, provenance, and state of conservation of the Kinkarakawa-gami art.

AbstractKinkarakawa-gami wallpapers are unique works of art produced in Japan between 1870 and 1905 and exported in European countries, although only few examples are nowadays present in Europe. So far, neither the wallpapers nor the composing materials have been characterised, limiting the effective conservation–restoration of these artefacts accounting also for the potential deteriogen effects of microorganisms populating them. In the present study, four Kinkarakawa-gami wallpapers were analysed combining physical–chemical and microbiological approaches to obtain information regarding the artefacts’ manufacture, composition, dating, and their microbial community. The validity of these met…

Synthesis of Nd:YAG nanopowder using the citrate method with microwave irradiation

Abstract Nd:YAG nanopowders were prepared using the Pechini process with microwave irradiation ( MWs ). A reference sample was also prepared using conventional heating. XRD pattern analysis showed that nanopowder obtained by means of conventional heating and calcination for 1 h at 900 °C has a structure made up of the garnet phase together with the hexagonal phase that disappeared after two additional hours of thermal treatment. The MWs powder calcined for 1 h consists of the single garnet phase. SAXS data analysis indicated that nanoparticles are characterized by a sharp interface. TEM investigation showed crystalline particles with remarkable agglomeration in both samples, although a more…

Preparation and characterisation of Ce:YAG -polycarbonate composites for white LED

Ce:YAG-polycarbonate composites were prepared with several amounts of Ce:YAG in the range 0.1-5 wt.% by using melt compounding. The structure and morphology of the composites were investigated by means of X-ray diffractometry and transmission electron microscopy. The optical properties of the composites were studied by using photoluminescence spectroscopy. The intermolecular interaction between the polymer and the filler surface was investigated using 13C cross-polarization magic-angle spinning NMR spectroscopy (13C {1H} CP-MAS NMR). The results showed that the dispersion of the particles in the polymer, and the optical properties, depend on the Ce:YAG amount. The composites were combined w…

Structural and spectroscopic characterization of a hierarchical material made of MCM41 and CdS nanoparticles

Nonprecious Copper‐Based Transparent Top Electrode via Seed Layer–Assisted Thermal Evaporation for High‐Performance Semitransparent n‐i‐p Perovskite Solar Cells

Semitransparent perovskite solar cells (ST‐PSCs) are highly attractive for applications in building‐integrated photovoltaics as well as in multijunction tandem devices. To fabricate high‐performance ST‐PSCs, suitable transparent top electrodes are strongly needed. Dielectric/metal/dielectric (DMD) multilayer structures have been shown to be promising candidates, though generally based on high‐value metals such as gold or silver, the latter causing also stability issues by reacting with perovskite. Here, a novel DMD transparent electrode based on nonprecious, less‐reactive copper is developed via thermal evaporation and used as a top anode in the fabrication of high‐performance semitranspare…

Polyaminoazide mixtures for the synthesis of pH-responsive calixarene nanosponges

Two mixtures of polyaminoazides were synthesized by a nucleophilic displacement strategy providing no separation of the components. The mixtures were adequately characterized by means of combined HR-ESIMS, FTIR and NMR techniques and, despite their complexity, they were successfully used to accomplish the subsequent preparation of pH-sensitive calixarene hyper-reticulated nanosponge materials. The desired responsivity to pH variations of the nanosponges obtained was verified by means of absorption tests on a set of organic pollutant model molecules.

Indagini diagnostiche sui “Vasi di Centuripe” del Museo Archeologico Regionale “A. Salinas” di Palermo

In questa saggio si intende presentare i risultati delle indagini diagnostiche eseguite in situ sui vasi centuripini conservati presso il Museo Archeologico Regionale “A. Salinas” di Palermo. Le indagini, condotte nell’ottica della multidisciplinarità insieme ad archeologi e restauratori, sono state applicate per step via via più approfonditi a partire dalle tecniche globali di immaging con luce visibile ed UV per lo studio della superfice, proseguendo con quelle puntuali di spettroscopia XRF ed FT-IR per lo studio dei pigmenti, del legante e dello strato di preparazione. In this essay we intend to present the results of the diagnostic investigations carried out in situ on the centuripine v…

Formulation of Mesoporous Silica Nanoparticles for Controlled Release of Antimicrobials for Stone Preventive Conservation

The biotic deterioration of artifacts of archaeological and artistic interest mostly relies on the action of microorganisms capable of thriving under the most disparate environmental conditions. Thus, to attenuate biodeterioration phenomena, biocides can be used by the restorers to prevent or slow down the microbial growth. However, several factors such as biocide half-life, its wash-out because of environmental conditions, and its limited time of action make necessary its application repeatedly, leading to negative economic implications. Sound and successful treatments are represented by controlled release systems (CRSs) based on porous materials. Here, we report on the design and developm…

As the filler influences morphology, mechanical properties and thermal degradation of a polymer

Photosynthesized silver-polyaminocyclodextrin nanocomposites as promising antibacterial agents with improved activity

Ag nanocomposites were prepared by photoreduction of ammoniacal silver acetate in the presence of poly-{6-[3-(2-(3-aminopropylamino)ethylamino)propylamino]}-(6-deoxy)-β-CD (amCD). The obtained systems were characterized by means of various complementary techniques (UV-vis, FT-IR, TEM, SAED). In particular, FT-IR spectroscopy evidenced a partial oxidative degradation of the polyamine branches of the capping auxiliary, due to the fact that these groups function as a sacrificial reducing agent in the photoinduced formation of the Ag metal core. TEM and SAED micrographs showed that the Ag cores possess a relatively low polydispersity and a significantly crystalline character. The Ag–amCD system…

Polyamide-Based Fibers Containing Microwave-Exfoliated Graphite Nanoplatelets

Exfoliated Graphite NanoPlatelets (GNP) have been obtained from Graphite Intercalation Compounds (GIC) subjected to thermal and microwave treatments. Accurate morphological and structural characterization of obtained GNP, performed to compare the degree of exfoliation, show that microwave-treated GNP, exhibit well-exfoliated structure, without any reduction in dimensions compared with the native GIC, differently to the thermal-treated ones. Microwave-treated GNP have been introduced in polyamide (PA) through melt-mixing to obtain nanocomposite that has been subjected to elongational flow, with the aim to improve the nanofiller dispersion and induce GNP orientation along the fiber direction.…

Nanolimes-based ternary formulations for paper reduction, deacidification and consolidation

Investigation on four centuripe vases (late 3rd-2nd cent. B.C.) by portable X-ray fluorescence and total reflectance-FTIR

Abstract Four Centuripe vases dated back to the late 3rd-2nd centuries B.C. were analysed using imaging under visible and ultra-violet illumination as well as complementary non-invasive and non-destructive portable X-Ray Fluorescence (XRF) and Total Reflectance – Fourier Transform InfraRed (TR-FTIR) spectroscopies. The vases are of great importance since they represent a rare expression of the Hellenistic vase painting. Four specimens, a “pyxis”, a “lebes gamikos” and two “lekanides” decorated with figures of different type, are exhibited in the Antonino Salinas Archaeological Museum in Palermo-Italy. The investigation was aimed to identify the used pigments and the painting technique, to r…

Synthesis and characterization of Ln3+ (Ln3+=Nd3+, Eu3+, Ce3+) doped YAG nanocrystalline

Development of controlled release systems of biocides for the conservation of cultural heritage

Abstract The presence of microorganisms is one of the main causes of monument deterioration. Biocides are usually applied after or before restoration in order to prevent or slow down microbial growth. Frequent applications are necessary leading to increased costs and high risks to humans and the environment. The aim of this study is the design of novel controlled release systems comprising a biocide loaded into a mesoporous silica. Pristine MCM41 as well as MCM41 functionalised with carboxy- (MCM41-COOH) and amino-groups (MCM41-NH2) were used. Biotin T and New Des 50, two commercial formulations, were chosen as biocides. The biocide encapsulation was performed adding the mesoporous silica t…

Simultaneous structural and elemental analysis by Energy Dispersive X-ray Diffraction: its potentiality in the field of Cultural Heritage

Water Dynamics at the Solid-Liquid Interface to Unveil the Textural Features of Synthetic Nanosponges.

A Fast-Field-Cycling NMR investigation was carried out on a set of polyurethane cyclodextrin nanosponges, in order to gain information on their textural properties, which have been proven to be quite difficult to assess by means of ordinary porosimetric techniques. Experiments were performed on both dry and wet samples, in order to evaluate the behavior of the “non-exchangeable” C-bound 1H nuclei, as well as the one of the mobile protons belonging to the skeletal hydroxyl groups and the water molecules. The results acquired for the wet samples accounted for the molecular mobility of water molecules within the channels of the nanosponge network, leading back to the possible pore size distrib…

Influence of Temperature on Calcium Hydroxyapatite Nanopowders

The aim of this work is to investigate the effects of thermal treatment, in the range of temperature between 80°C - 900°C, on crystallinity, morphology and particles size of calcium hydroxylapatite nanopowders (HAp). A complete study was carried out applying 31P Magic Angle Spinning NMR, X-ray diffraction, nitrogen porosimetry and Transmis- sion Electron Microscopy techniques. HAp specimens were prepared by chemical precipitation in an aqueous solution of calcium nitrate and ammonium hydrogen phosphate. The thermal treatment performed, showed the formation of crystals whose appearance has three main morphologies and different particles size. HAp treated up to 500°C showed a set of needle-li…

Synthesis of yttrium aluminum garnet nanoparticles in confined environment, and their characterization

Abstract Nanopowders of yttrium aluminum garnet (YAG, Y3Al5O12) have been prepared by thermal treatment of hydroxides obtained by synthesis in a confined environment constituted by water/Cetyltrimethylammonium bromide (CTAB)/1-butanol/n-heptane. The phase behavior of the above system has been investigated on varying the water/CTAB molar ratio (R) at constant 1-butanol/CTAB and heptane/CTAB molar ratio. The dispersed aqueous phases were constituted by solutions of ammonia and of yttrium and aluminum nitrates, respectively. Measures of Kinematic Viscosity, Electrical Conductivity and Small Angle X-ray Scattering have been carried out. It was found that, on increasing the ammonia solution cont…

Ce:YAG nanoparticles embedded in a PMMA matrix: preparation and characterization

A Ce:YAG-poly(methyl methacrylate) composite was prepared using in situ polymerization by embedding the Ce:YAG nanopowder in a blend of methyl methacrylate (MMA) and 2-methacrylic acid (MAA) monomers and activating the photopolymerization using a radical initiator. The obtained nanocomposite was yellow and transparent. Its characterization was performed using transmission electron microscopy, small angle X-ray scattering, (13)C cross-polarization magic-angle spinning nuclear magnetic resonance, and photoluminescence spectroscopy. Results showed that Ce:YAG nanoparticles are well dispersed in the polymeric matrix whose structure is organized in a lamellar shape. The luminescence properties o…

Self-cleaning ZnO/ITO/PET Bending Sensors

The design of multifunctional materials is of pivotal importance for developing wearable biosensors. In particular, the advancement in self-cleaning materials suitable for bending sensors, i.e. devices able to track human body movements for healthcare monitoring [1], has raised much interest in recent pandemic times. Such technology can be facilitated by leveraging piezo-photocatalytic cleaning effects under visible light [2]. Herein, we show a new class of ZnO-based nanosheets (NSs) synthesized in aqueous solution (85 °C, 24 hours) onto seeded or seedless ITO/PET surfaces that couple sensing to photocatalysis. UV-vis and FT-IR spectroscopies show the typical absorption peaks of ZnO. A nano…

Silver nanoparticles stabilized by a polyaminocyclodextrin as catalysts for the reduction of nitroaromatic compounds

Abstract Silver nanoparticles stabilized by means of poly -(6- N , N -dimethyl-propylenediamino)-(6-deoxy)-β-cyclodextrin were synthesized, characterized by different techniques (UV–vis spectroscopy, Dynamic Light Scattering, High Resolution Transmission Electron Microscopy, Fourier-transform IR Spectroscopy) and used as catalysts for the reduction of various nitrobenzene derivatives with sodium borohydride. The nanocomposites obtained appear to have an organized structure, with a metal core surrounded by a layer-structured coating shell. Kinetic data, rationalized in terms of a modified Langmuir–Hinshelwood model, evidenced a non-linear dependence of the reaction rate on the concentration …

A New Water-Soluble Bactericidal Agent for the Treatment of Infections Caused by Gram-Positive and Gram-Negative Bacterial Strains

Grapefruit and lemon pectin obtained from the respective waste citrus peels via hydrodynamic cavitation in water only are powerful, broad-scope antimicrobials against Gram-negative and -positive bacteria. Dubbed IntegroPectin, these pectic polymers functionalized with citrus flavonoids and terpenes show superior antimicrobial activity when compared to commercial citrus pectin. Similar to commercial pectin, lemon IntegroPectin determined ca. 3-log reduction in Staphylococcus aureus cells, while an enhanced activity of commercial citrus pectin was detected in the case of Pseudomonas aeruginosa cells with a minimal bactericidal concentration (MBC) of 15 mg mL&minus

An insight into the interaction between functionalized thermoplastic elastomer and layered double hydroxides through rheological investigations

Abstract Nanocomposites based on maleated poly(styrene-(ethylene-co-butylene)-styrene) copolymer (SEBSgMA) and organo-modified layered double hydroxide (OLDH) have been formulated with the aim to investigate the effects of interfacial interactions between the grafted maleic anhydride groups of the copolymer and the OLDH nanolayers on the rheological properties of nanocomposites. The spectroscopic analysis indicates the establishment of specific polymer/nanofiller interactions, whose extent has been highlighted through morphological and rheological investigations. Specifically, oscillatory melt rheology and shear relaxation tests have been considered in order to deeply investigate the interf…

Self-Cleaning Bending Sensors Based on Semitransparent ZnO Nanostructured Films

The design of multifunctional nanostructured materials is the key to the development of smart wearable devices. For instance, nanostructures endowed with both piezoelectric and photocatalytic activities could well be the workhorse for solar-light-driven self-cleaning wearable sensors. In this work, a simple strategy for the assembly of a flexible, semitransparent piezophotocatalytic system is demonstrated by leveraging rational wet chemistry synthesis of ZnO-based nanosheets/nanoflowers (NSs/NFs) under basic pH conditions onto flexible ITO/PET supports. A KMnO4 pretreatment before the ZnO synthesis (seeded ZnO) allows for the control of the density, size, and orientation of the NSs/NFs syst…

Influence of the Ce: YAG amount on structure and optical properties of Ce:YAG-PMMA composites for white LED

Ce:YAG-poly(methyl methacrylate) (PMMA) composites were prepared by using a melt compounding method, adding several amounts of Ce:YAG in the range 0.1–5wt.%. The optical properties of the obtained composites and of the composites combined with a blue LED were measured to investigate the effect of the amount of Ce:YAG on the resulting emitted light in view of possible application in white LED manufacture. An increase in Ce:YAG amount caused an increase in the emission and a shift of 15 nm, influencing the white LED performance. The structure and morphology of the composites were studied. The results show that the interaction between the two components, observed by using solid state NMR exper…

Volatile Compounds of Lemon and Grapefruit IntegroPectin

An HS-SPME GC-MS analysis of the volatile compounds adsorbed at the outer surface of lemon and grapefruit pectins obtained via the hydrodynamic cavitation of industrial waste streams of lemon and grapefruit peels in water suggests important new findings en route to understanding the powerful and broad biological activity of these new pectic materials. In agreement with the ultralow degree of esterification of these pectins, the high amount of highly bioactive &alpha

Miniatures of Iranian booklet: in situ examination with Micro-Raman Spectroscopy and Energy Dispersive X-Ray Diffractometry

Consolidation and protection by nanolime: recent advances for the conservation of the graffiti, Carceri dello Steri Palermo and of the 18th century lunettes, SS. Giuda e Simone Cloister, Corniola (Empoli)

Abstract Nanolime dispersed in 2-propanol was extensively used for the consolidation of wall paintings. The knowledge of the advances of this methodology dealing with all the possible effects associated with the nanolime new material in conservation is fundamental to assess and improve the technique. In this paper, four different dispersions of Ca(OH) 2 nanoparticles were characterised by Small Angle X-rays Scattering technique (SAXS) and Transmission Electron Microscopy (TEM) in order to achieve information on size, shape, polydispersity, agglomeration, and crystal structure (by SAED patterns) of the particles. Once characterised, the dispersions were tested in two different case studies, …

Heuristic Algorithm for the Analysis of Fast Field Cycling (FFC) NMR Dispersion Curves

Evaluation of nuclear magnetic relaxation dispersion (NMRD) curves obtained by the fast field cycling nuclear magnetic resonance (FFC-NMR) relaxometry technique is a valuable tool for analyzing the microscopic dynamics of condensed matter systems. However, quantitative data analysis involves several conceptual and practical issues. Moving forward from previous literature approaches, we propose a new analysis method, relying on the elaboration of the inverse integral transform of the NMRD curve. Our approach results in a true heuristic method, able to unambiguously individuate the dynamic domains in the system, thereby avoiding the possible introduction of any element of discretion. The anal…

More insight into characterization of the waterlogged wooden part of Acqualadroni Roman Rostrum by solid-state NMR

Abstract Solid-state NMR spectroscopy was applied to characterize the wooden part of a roman Rostrum recovered in the Tyrrhenian Sea in the Acqualadroni area (Messina, Italy). The Acqualadroni Rostrum has been, in the recent past, investigated to establish its provenance and conservation. In this paper, solid-state NMR was used to obtain information on the conservation state of the wood as a preliminary step for the conservation process. A wooden sample of this artifact, collected by coring, was divided in four parts in order to correlate the conservation state to the depth. Results were compared with those obtained for a modern wood of the same species. A structural study was performed by …

Micro-analytical identification of the components of varnishes from South Italian historical musical instruments by PLM, ESEM-EDX, microFTIR, GC-MS, and Py-GC-MS

Abstract A multi-analytical investigation was carried out to study varnish micro-samples from historical stringed musical instruments from the collection of the “Vincenzo Bellini” Conservatory in Palermo (Italy). This paper reports on the results of the application of five micro-destructive techniques: optical microscopy analysis of cross-sections, micro-Fourier transform infrared spectroscopy, gas chromatography coupled with mass spectrometry, pyrolysis gas chromatography coupled with mass spectrometry with thermochemolysis, and environmental scanning electron microscopy with X-ray microanalysis. The study provides microchemical information about the composition of the varnishes of the ins…

New hydroxyapatite- and selenium-based nanoformulations as potential antimicrobial tools for orthopedic implants

Morphology, mechanical properties and thermal degradation kinetics of PMMA-zirconia nanocomposites prepared by melt compounding

Zirconia nanoparticles were synthesized by means of a sol-gel method and embedded in poly(methyl methacrylate) (PMMA) by melt compounding. The zirconia was well dispersed in the PMMA matrix, with only a few clusters, especially for the highest investigated zirconia content. NMR results showed heteronuclear dipolar interactions involving the carbons and the surrounding hydrogen nuclei. The effect of the amount of zirconia, in the range of 1–5!wt%, on the thermomechanical properties and thermal degradation kinetics of PMMA was also investigated by means of dynamic mechanical analysis (DMA), thermogravimetric analyses (TGA), and Fourier-transform infrared spectroscopy (FTIR). The presenc…

Synthesis of nanosized powders Nd-doped YAG by coprecipitation and microemulsion methods

Photochemical preparation of polyaminocyclodextrin-capped silver nanocomposites: mechanistic insights

Photoreduction of silver salts in the presence of three polyaminocyclodextrin derivatives (AmCD, Figure 1) constitutes a simple and straightforward route to obtain stable Ag nanoparticles. These systems have been suitably characterized (UV-vis, FT-IR, TEM, Figure 2) and tested for their antimicrobial activity.1 We observed that Ag photoreduction is effectively induced by irradiation with green light (513 nm); however, best performances are achieved with the use of a light source having at the same time a significant emission in the near-infrared (NIR) region. On the grounds of analytical and kinetic evidences, we hypothesized a multi-step mechanism for nanoparticle formation. In particular,…

Identification of microplastics using 4‐dimethylamino‐4′‐nitrostilbene solvatochromic fluorescence

In this work, we introduce the use of 4-dimethylamino-4'-nitrostilbene (DANS) fluorescent dye for applications in the detection and analysis of microplastics, an impendent source of pollution made of synthetic organic polymers with a size varying from less than 5 mm to nanometer scale. The use of this dye revealed itself as a versatile, fast and sensitive tool for readily discriminate microplastics in water environment. The experimental evidences herein presented demonstrate that DANS efficiently absorbs into a variety of polymers constituting microplastics, and its solvatochromic properties lead to a positive shift of the fluorescence emission spectrum according to the polarity of the poly…

Changes in Physicochemical Properties of Biochar after Addition to Soil

It is recognized that biochar undergoes changes when it is applied to soils. However, the mechanisms of biochar alterations are not fully understood yet. To this purpose, the present study is designed to investigate the transformations in the soil of two different biochars obtained from pyrolysis of fir-wood pellets. The production of the biochars differed for the dry and wet quenching procedures used to terminate the pyrolysis. Both biochars were applied to clay soil (26% sand, 6% silt, and 68% clay) placed into lysimeters. After water saturation and 15 days of equilibration, seeds of watercress (Lepidium sativum) were cultivated. After a further 7 weeks, the biochars were manually separat…

The Small Angle Scattering technique: an effective tool in the structural investigation of archaeologically relevant specimens

An overview of application of Small Angle X-ray Scattering (SAXS) techniques to topics of interest in the field of Cultural Heritage is presented. The basic concepts of the technique, a description of sources and laboratory instrumentation and some models and methods for data analysis are discussed. Applications of SAXS to various kinds of materials are reported to obtain information on the structure useful to shed light in some subjects such as preparation, physical treatment, traceability and degradation of materials.

Hyper-reticulated calixarene polymers: a new example of entirely synthetic nanosponge materials

New calixarene-based nanosponges (CaNSs), i.e., hyper-reticulated polymers constituted by calixarene monomer units joined by means of bis(1,2,3-trialzolyl)alkyl linkers, were synthesized, characterized and subjected to preliminary tests to assess their supramolecular absorption abilities towards a set of suitable organic guests, selected as pollutant models. The synthesis was accomplished by means of a CuAAC reaction between a tetrakis(propargyloxy)calix[4]arene and an alkyl diazide. The formation of the polymeric network was assessed by means of FTIR and 13C{1H} CP-MAS solid-state NMR techniques, whereas morphological characterization was provided by SEM microghaphy. The materials were pro…

Synthesis and characterization of neodimium doped yttrium aluminum garnet (Nd-YAG) nanoparticles.

Ce:Y3Al5O12−Poly(methyl methacrylate) Composite for White-Light-Emitting Diodes

A Ce:YAG-poly(methyl methacrylate) (PMMA) composite was prepared by using the melt compounding method. The structure and morphology were investigated by X-ray diffractometry, transmission electron microscopy, and small-angle X-ray scattering. The optical properties (emission, excitation, and fluorescence decay rate) of the composite were studied by using photoluminescence spectroscopy. The polymer–filler interactions were studied using 13C cross-polarization magic-angle spinning NMR spectroscopy (13C{1H} CP-MAS NMR). The results indicated that Ce:YAG particles are well-dispersed in the PMMA matrix without loss of their luminescence properties or significant spectral shift, thus suggesting t…

A multivariate approach to the study of orichalcum ingots from the underwater Gela's archaeological site

Abstract In this work a careful ICP-OES and ICP-MS investigation of 38 ancient ingots has been performed to determine both major components and trace elements content to find a correlation between the observed different features and the composition. The ingots, recovered in an underwater archaeological site of various finds near Gela (CL, Italy), were previously investigated by X-Ray Fluorescence (XRF) spectroscopy to know the composition of the alloy and it was found that the major elements were copper and zinc, in a ratio compatible with the famous orichalcum similar to the contemporary brass that was considered a precious metal in ancient times. The discovery of huge amount this alloy is…

Biogenic Selenium Nanoparticles: A Fine Characterization to Unveil Their Thermodynamic Stability

Among the plethora of available metal(loid) nanomaterials (NMs), those containing selenium are interesting from an applicative perspective, due to their high biocompatibility. Microorganisms capable of coping with toxic Se-oxyanions generate mostly Se nanoparticles (SeNPs), representing an ideal and green alternative over the chemogenic synthesis to obtain thermodynamically stable NMs. However, their structural characterization, in terms of biomolecules and interactions stabilizing the biogenic colloidal solution, is still a black hole that impairs the exploitation of biogenic SeNP full potential. Here, spherical and thermodynamically stable SeNPs were produced by a metal(loid) tolerant Mic…

Metodi non distruttivi per la diagnosi dei Beni Culturali

La conoscenza dei materiali, in termini di composizione, di morfologia e di struttura, costituenti manufatti di varia natura è, oggi, di grande importanza in vari settori scientifici e tecnologici. La comprensione dei processi che possiamo, genericamente, raggruppare secondo la definizione “interazione radiazione-materia” ha portato allo sviluppo di una serie di tecniche di caratterizzazione spettroscopica e strutturale della materia che trovano applicazione nello studio di materiali dai più nuovi e innovativi a quelli archeologici. Negli ultimi decenni, l’approfondimento delle problematiche legate alla comprensione dei processi di sviluppo delle conoscenze ha promosso un connubio sempre pi…

Nanometric semiconductor particles in mesoporous silica: synthesis and characterization

Study on the stability of dispertions of zirconia nanoparticles

Convenient Photochemical Synthesis of Silver-Polyaminocyclodextrin Nanocomposites: The Role of the Light Source from a Mechanistic Viewpoint

An investigation on the light-driven reduction of the [Ag(NH3)2]+complex in the presence of polyaminocyclodextrins was carried out, in order to clarify the mechanism of the process. The role of the organic auxiliary as both the sacrificial reductant and the capping agent was positively assessed. Moreover, particular attention was paid to the role of the irradiation source. Experimental results indicate that a complex mechanism is involved in the formation of the nanocomposite, with a primary photoinduced single-electron-transfer process promoted by irradiation with green light, followed by a secondary chemical reduction process activated by NIR. Representative composites were characterized …

Synthesis of yttrium aluminum garnet nanoparticles in confined environment II: Role of the thermal treatment on the composition and microstructural evolution

Abstract Nanoparticles of yttrium aluminum garnet (YAG, Y 3 Al 5 O 12 ) have been obtained by thermal treatments, at several temperature in the range 400–950 °C, of the precursors synthetized via co-precipitation in water in oil microemulsion. The obtained nanoparticles have been characterized by means of X-ray Diffraction and Transmission Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (EDS) and Select Area Electron Diffraction (SAED). Results show the phase evolution occurring to obtain not aggregated nanoparticles of YAG phase. A possible growth mechanism of YAG nanoparticles is discussed on the basis of observed particle microstructure and morphology. The results i…

Determination of selected polyaromatic hydrocarbons by gas chromatography–mass spectrometry for the analysis of wood to establish the cause of sinking of an old vessel (Scauri wreck) by fire

Abstract The aim of this paper was to establish the cause of sinking of an old wooden vessel by polycyclic aromatic hydrocarbon (PAH) analyses because wood combustion is a source of PAHs. In particular, the molecular PAH patterns generated by each source are like fingerprints and it is possible to determine the processes that generate PAHs by studying their distribution in wood samples. The relative abundance of high molecular weight PAHs, together with the PAH compound ratios and with total index (proposed by us) has demonstrated that samples owe their PAHs in wood archaeological material to a predominant single mode of origin, i.e. combustion processes, therefore we can say that the sinki…

Structure of a quaternary microemulsion by changing its composition

ENERGY DISPERSIVE X-RAY DIFFRACTION IN CULTURAL HERITAGE SCIENCE: THE WINNING DUO OF STRUCTURAL AND ELEMENTAL ANALYSIS

The capabilities of Energy-Dispersive X-ray Diffraction (EDXD) in the field of Cultural Heritage are disccussed. EDXD diffractometer, equipped with a white source, is particularly suited for the structural and elemental analysis of items having different nature. Given its compact and versatile design, the instrument allows to collect data from samples without tearing down of any portion and with no specific preparation. In the wide energy range sampled during the measurements, both X-ray fluorescence and diffraction features appear. In all cases, data are acquired in air and in a non-destructive way, and their collection is fast.

Chemogenic versus biogenic synthesis of Selenium nanoparticles: a structural characterization

Among the plethora of available metal- and metalloid-based nanomaterials (NMs), selenium nanostructures (SeNSs) are one of the most interesting from an applicative perspective due to their intermediate properties between metals and non-metals, as well as their high biocompatibility. In this regard, the capability of microorganisms to biotransform toxic Se-oxyanions – i.e., selenite (SeO32-) and selenate (SeO42-) – into their less bioavailable elemental forms [Se(0)], mostly generating Se nanoparticles (SeNPs), represents as a useful and green alternative over chemogenic synthesis allowing to obtain highly thermodynamically stable NMs. However, their structural characterization, in terms of …

Boosting the Performance of One-Step Solution-Processed Perovskite Solar Cells Using a Natural Monoterpene Alcohol as a Green Solvent Additive

The perovskite film is the core of a perovskite solar cell (PSC), and its quality is crucial for the performance of such devices. The morphology, crystallinity, and surface coverage of the perovskite layer greatly affect the power conversion efficiency (PCE), hysteresis, and long-term stability of PSCs. The incorporation of appropriate solvent additives in the perovskite precursor solution is an effective strategy to control the film morphology and reduce the defects and grain boundaries. However, the commonly used solvent additives are environmentally harmful and highly toxic. In this work, α-terpineol (a nontoxic, eco-friendly, and low-cost monoterpene alcohol) is employed for the first t…

Alcoholic nanolime dispersion obtained by the insolubilisation-precipitation method and its application for the deacidification of ancient paper

Abstract Nanolime dispersions for the deacidification of ancient paper constitute a valid alternative to the lime traditional ones. Their efficacy depends on particles size, polydispersity and agglomeration that can be controlled depending on the preparation method. In this work, nanolime preparation by insolubilisation-precipitation method is reported. Nanoparticles dispersed in a water-isopropanol mixture were obtained without any manipulation of the dispersion. The stability of the dispersion together with particle size and morphology were found to be dependent on water to isopropanol molar ratio and on the synthesis temperature. One of the dispersion was applied on a manuscript to asses…

Energy dispersive X-ray diffraction potentiality in the field of cultural heritage: simultaneous structural and elemental analysis of various artefacts.

The applicability of an Energy Dispersive X-ray Diffractometer to some technical questions in the field of Cultural Heritage is presented. This diffractometer, equipped with a white source, has been utilized for the structural and elemental analysis of some items having different nature. Given its design, the instrument allows to collect data from samples as big as a book or a little more. Samples, without collection of any portion and without any preliminary preparation, have been placed in the instrument and spectra have been collected in a wide energy range that contains X-ray fluorescence and diffraction features. In all cases, data acquired in air and in a non destructive way were reli…