Sintesi di materiali silicei mesoporosi per catalisi eterogenea

A step forward in disclosing the secret of stradivari's varnish by NMR spectroscopy

It is commonly thought that the varnishes used by the great violin-maker Antonio Stradivari may have a role in determining not only the esthetical features but also the acoustic properties of his instruments, and the idea of a “lost secret” is still widespread among musicians and violin-makers. Previous scientific researches on varnish samples of Stradivari's instruments revealed that they were generally made by a mix of linseed oil with and colophony or metal rosinates in different ratios ranging between 75/25 (oil/resin) and 60/40 (oil/rosinate). However, it is still not clear whether the mixture composition can be related to any structural and/or functional feature of the resulting varni…

The effect of silica nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of PMMA

Abstract Silica–PMMA nanocomposites with different silica quantities were prepared by a melt compounding method. The effect of silica amount, in the range 1–5 wt.%, on the morphology, mechanical properties and thermal degradation kinetics of PMMA was investigated by means of transmission electron microscopy (TEM), X-ray diffractometry (XRD), dynamic mechanical analysis (DMA), thermogravimetric analyses (TGA), Fourier-transform infrared spectroscopy (FTIR), 13 C cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy ( 13 C{ 1 H} CP-MAS NMR) and measures of proton spin-lattice relaxation time in the rotating frame ( T 1 ρ ( H )), in the laboratory frame ( T 1 ( H )) a…

Examination of Dyeing Properties on Silk of Some Flavonoids by Spectroscopic Techniques

In this study, the silk fabrics mordanted at the rates of 1%, 2%, 3%, 4%, 6%, 9%, 12%, 14%, 18%, 21%, 24%, 27%, 30%, 33% and 36% of alum (KAl(SO4)2.12H2O) were separately dyed with chrysin, quercet...

Interaction of Gold with Co-Condensed and Grafted HMS-SH Silica: A 29Si {1H} CP-MAS NMR Spectroscopy, XRD, XPS and Au LIII EXAFS Study

Hexagonal mesoporous silica (HMS) is functionalised with mercaptopropyl groups by adopting two different procedures ; co-condensation and grafting. In both cases tetraethylorthosilicate (TEOS) and 3-mercaptopropyltriethoxysilane (3-MPTES) are used as the silicon and sulfur precursors, respectively. The obtained materials are analysed by several techniques such as N 2 sorption, TG-DTA, XRD, SAXS and-solid state 29 Si { 1 H} CP-MAS NMR spectroscopy. By taking advantage of the chemical interaction between gold and the -SH groups, the effect of the thiol addition procedure on the supporting capability of the functionalised silica is evaluated by depositing gold through the incipient wet impregn…

Applying the Techniques on Materials I

The knowledge of the composition of the natural dye mixtures gives hints on appropriate procedures for restoration strategies. Identification of the dyes used, the establishment of their biological source, how they have been prepared, how these historical textiles were made, can provide important information. The dyestuffs used up to nineteenth century were either of plant (weld, madder, indigo, etc.) or animal origin (cochineal, shellfish, etc.) and belonged to various chemical types, such as flavonoids (yellow), anthraquinones (red) and indigoids (blue and violet). In this study microsamples (19) were examined from 11 Mevlana’s kaftans, dervishs’ dresses and dated from the thirteenth cent…

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…

Copolymerization of Vinylidene Fluoride and Acrylic Acid in Supercritical Carbon Dioxide

The free-radical copolymerization of vinylidene fluoride (VDF) and acrylic acid (AA) was carried out in supercritical carbon dioxide using both precipitation and dispersion techniques in the presence of an ammonium carboxylate perfluoropolyether compound. Formation of a copolymer was confirmed by variable contact time CP MAS NMR spectroscopy. Macromolecular matrices were significantly enriched in AA with respect to the initial feed composition and we found that the nonfluorinated monomer has a much higher reactivity ratio with respect to VDF. The cumulative concentration, crystallinity, and water affinity of the synthesized copolymers could be modified changing the initial feed composition,…

Structural characterization of triorganotin(IV) complexes with sodium fusidate and DFT calculations

Abstract Three new complexes of the steroid sodium fusidate (sodium 2-[(1 S ,2 S ,5 R ,6 S ,7 S ,10 S ,11 S ,13 S , 14 Z ,15 R ,17 R )-13-(acetyloxy)-5,17-dihydroxy-2,6,10,11-tetramethyl tetracyclo[8.7.0.0 2,7 .0 11,15 ] heptadecan-14-ylidene]-6-methylhept-5-enoate = (NaFusidate, Na FA )]), with triorganotin(IV) moieties have been prepared and investigated by conventional techniques as FTIR, Mossbauer, ESI-MS and NMR spectroscopy. The isolated compounds showed stoichiometries organotin(IV)/fusidate 1/1, R 3 Sn(IV) FA (R = Me, FA1 ; Bu, FA2 ; Ph, FA3 ). The ligand coordination sites were determined by FTIR spectroscopic measurements. In the complexes, the carboxylate group of the fusidate li…

Lithium ion conducting PVdF-HFP composite gel electrolytes based on N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide ionic liquid

Blends of PVDF-HFP and ionic liquids (ILs) are interesting for application as electrolytes in plastic Li batteries. They combine the advantages of the gel polymer electrolytes (GPEs) swollen by conventional organic liquid electrolytes with the nonflammability, and high thermal and electrochemical stability of ILs. In this work we prepare and characterize PVDF-HFP composite membranes swollen with a solution of LiTFSI in ether-functionalized pyrrolidinium-imide (PYRA12O1). The membranes are filled in with two different types of silica: i) mesoporous SiO2 (SBA-15) and a commercial nano-size one (HiSilTM T700). The ionic conductivity and the electrochemical properties of the gel electrolytes ar…

Cross-Linked Polyamine from Imidazolium-Based Materials: A Simple Route to Useful Catalytic Materials

Cross-linked polyamine-based materials were easily prepared by reduction of the corresponding cross-linked imidazolium-based materials with sodium borohydride in hot ethanol. Overall, the synthetic procedure is based on the polymerization of a suitable bis-vinylimidazolium salt with or without a suitable support, such as silica or silica-coated magnetic nanoparticles (γ-Fe2O3@SiO2), followed by reduction. This simple approach allows the synthesis of materials based on a network of secondary and tertiary amines. Materials were characterized by13C cross-polarization magic angle spinning NMR (13C CPMAS NMR), proton spin-lattice relaxation times in the rotating frame (T1ρH) and thermogravimet…

Solid state 13C-NMR methodology for the cellulose composition studies of the shells of Prunus dulcis and their derived cellulosic materials.

Lignocellulosic fibers and microcellulose have been obtained by simple alkaline treatment from softwood al- mond shells. In particular, the Prunus dulcis Miller (D.A.) Webb. was considered as a agro industrial waste largely available in southern Italy. The materials before and after purification have been characterized by 13C CPMAS NMR spectroscopy methodology. A proper data analysis provided the relative composition of lignin and holo- cellulose at each purification step and the results were compared with thermogravimetric analysis and FT-IR. To value the possibility of using this material in a circular economy framework, the fibrous cellulosic material was used to manufacture a handmade c…

PMMA-titania nanocomposites: Properties and thermal degradation behavior

Titania nanoparticles were prepared using a solegel method and calcination at 200 and 600 � C in order to obtain anatase and rutile phases, respectively. The obtained powders were used to prepare PMMAe titania nanocomposites by a melt compounding method. The effect of the crystalline phase and the amount of titania, in the range 1e5 wt.%, on the morphology, mechanical properties and thermal degradation kinetics of PMMA was investigated by means of X-ray diffractometry (XRD), transmission electron microscopy (TEM), 13 C cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy ( 13 C{ 1 H}CP-MAS NMR), including the measurement of proton spinelattice relaxation time in t…

Synthesis of functionalized mesoporous silica assisted by microwave irradiation

Phytochemical investigation of the needles of Aabies nebrodensis (Lojac.) Mattei

Abies nebrodensis (Lojac.) Mattei (Pinaceae) is a species living in a very small population only in a confined area of Sicily. In this study, the dichloromethane extract of the leaves was analyzed. Apart from three already known metabolites namely dehydroabietic acid; maltol; and rheosmin, previously detected in other species of Abies, a lanostane derivative was isolated. Its chemical structure was elucidated by means of extensive spectroscopic methods.

Materiali catalitici a base di nanoparticelle di palladio immobilizzate su nanoforme di carbonio

Microwave Dehydration Of Water In Oil Microemulsion Containing Nanoparticles Synthesized In Situ

Disidratazione di nanoparticelle sintetizzate in microemulsione w/o

PHYSICO-CHEMICAL CHARACTERIZATION OF THE ACQUALADRONE ROSTRUM

The archaeological discovery of the Acqualadrone rostrum (an offensive naval weapon mounted on the prow at the waterline), off the Italian coast near Messina in 2008, has led to the need for scientific research in order to plan the conservation treatment of this artefact. The discovery is exceptional because of the presence of a wooden section from the original ship. This paper describes the physico-chemical characterization of a metallic and two wooden samples by inductively coupled plasma – optical emission spectroscopy, inductively coupled plasma – mass spectrometry, Fourier transform infrared spectroscopy, 13 C{ 1 H} cross-polarization magic angle spinning NMR spectroscopy, energy-dispe…

Organic-inorganic materials through first simultaneous frontal polymerization and frontal geopolymerization

Abstract The first frontal geopolymerization (FGP) took place in the same reaction medium in which the frontal polymerization (FP) of 1,6-hexanediol diacrylate (HDDA) was occurring, thus giving rise to an organic-inorganic hybrid in one step in just a few minutes. Because of their exothermicity, the two reactions support each other and sustain propagating fronts. By contrast, using the classical techniques (prolonged heating) instead of FP, due to large gas formation, the reaction is explosive or, if carried out at room temperature, phase separation occurred.

Free radical copolymerization of vinylidene fluoride and acrylic acid in supercritical carbon dioxide

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 …

Identifying the Unknown Content of an Ancient Egyptian Sealed Alabaster Vase from Kha and Merit’s Tomb Using Multiple Techniques and Multicomponent Sample Analysis in an Interdisciplinary Applied Chemistry Course

This article highlights the multianalytical study of exuded liquid from an ancient Egyptian sealed alabaster vase by Master's students in an applied chemistry for cultural heritage course. Master students are introduced to the field of Archaeometry that see the collaboration of experts in different areas of research such as conservators, curators of museums, physicists, chemists, etc. The sample is a residue exuded on the linen strip sealing an ancient Egyptian alabaster vase (inventory number S.8448) from the collection of the Museo Egizio in Turin (Italy). The students start to plan the noninvasive investigation by X-ray fluorescence (XRF), transmission electron microscopy (TEM), and ener…

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…

Study of the curing of a DGEBA based system through structural investigation

Improvement of interaction in and properties of PMMA-MWNT nanocomposites through microwave assisted acid treatment of MWNT

Soluble derivatives of multi-walled carbon nanotubes (MWNT) embedded in a poly(methylmethacrylate) (PMMA) matrix forming thick, homogeneous and transparent nanocomposites, were prepared and characterized. A new photo-assisted method using microwaves, to purify the MWNTs from amorphous carbon and synthesis catalyst clusters, was tested in a sulphonitric mix. This method shortened the processing time compared to other methods. Pristine and functionalized MWNTs were introduced into the MMA, then in situ photo-polymerized. Transmission electron microscopy (TEM) and X-ray diffractometry (XRD), as well as Fourier-transform infrared (FTIR), Raman and nuclear magnetic resonance (NMR) spectroscopy w…

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…

Synergistic Activity of Silver Nanoparticles and Polyaminocyclodextrins in Nanosponge Architectures

Four new composite materials, formed by silver nanoparticles embedded in polyamino-cyclodextrin nanosponge architectures, were designed exploiting the affinity of polyamino-cyclodextrins towards Ag+ ions. These materials were characterized by means of different techniques (thermogravimetry, FT-IR, solid state NMR, SEM, HR-TEM), and tested as catalysts for the reduction of nitroarenes and the oxidative coupling of anilines. The results obtained showed synergistic activity between the supramolecular binding abilities of the nanosponge matrix and the catalytic properties of the metal nanoparticle, and open the way towards the design of new composite smart nanomaterials with improved catalytic …

Conservation state of two paintings in the Santa Margherita cliff cave: role of the environment and of the microbial community

Abstract The conservation of ancient paintings sited in humid environments is an actual challenge for restorers, because it needs the knowledge of the materials the paintings are made up and of their interaction with a peculiar surrounding environment; thus, tailored procedures and strategies aimed at restoring and preserving paintings are necessary. The Santa Margherita’s cave in Castellammare del Golfo (Trapani, Italy) is a natural cave, containing the remains of paintings, in a poor state of conservation, belonging to an ancient church dated back to the Middle Age. The present manuscript reports the monitoring of environmental conditions (i.e., temperature and humidity) in a full year as…

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.

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…

Templating effect of carbon nanoforms on highly cross-linked imidazolium network: Catalytic activity of the resulting hybrids with Pd nanoparticles

Two different carbon nanoforms (CNFs), namely multi-walled carbon nanotubes (MWCNTs) and carbon nanohorns (CNHs), have been chosen as support for the direct polymerization of a bis-vinylimidazolium salt. Transmission electron microscopy analyses revealed a templating effect of the CNFs on the growth of the polymeric network, which perfectly covers their whole surfaces creating a cylindrical or spherical coating for MWCNTs and CNHs, respectively. Subsequently, the CNFs-polyimidazolium have been used as stabilizers for Pd nanoparticles (Pd NPs), and the obtained materials have been characterized by means of analytical and spectroscopic techniques and then employed as easily recoverable and re…

Characterization of Nd-MCM41 obtained by impregnation

Synthesis and Characterisation of Functionalized borosilicate nanoparticles for boron neutron capture therapy applications

Boron Neutron Capture Therapy (BNCT) is a promising therapy for the cure of diffuse tumors. The successful clinical application of BNCT requires finding new boron-based compounds suitable for an efficient 10B delivery to the cancerous tissues. The purpose of this work is to synthesize borosilicate nanoparticles by a sol–gel recipe, and to functionalize them with folic acid in order to promote their capture by the tumor cells. Whereas sol–gel is a promising technique for the synthesis of nanoparticles, in case of borosilicate systems this approach is affected by significant boron loss during preparation. Here we show that functionalization of borosilicate nanoparticles with folic acid can re…

Copolymerization of vinylidene fluoride and acrylic acid in supercritical carbon dioxide

The free-radical copolymerization of vinylidene fluoride (VDF) and acrylic acid (AA) was carried out in supercritical carbon dioxide using both precipitation and dispersion techniques in the presence of an ammonium carboxylate perfluoropolyether compound. Formation of a copolymer was confirmed by variable contact time CP MAS NMR spectroscopy. Macromolecular matrices were significantly enriched in AA with respect to the initial feed composition and we found that the nonfluorinated monomer has a much higher reactivity ratio with respect to VDF. The cumulative concentration, crystallinity, and water affinity of the synthesized copolymers could be modified changing the initial feed composition,…

Phytochemical investigation of the needles of Abies nebrodensis (Lojac.) Mattei

Abies nebrodensis (Lojac.) Mattei (Pinaceae) is a species living in a very small population only in a confined area of Sicily. In this study, the dichloromethane extract of the leaves was analyzed. Apart from three already known metabolites namely dehydroabietic acid; maltol; and rheosmin, previously detected in other species of Abies, a lanostane derivative was isolated. Its chemical structure was elucidated by means of extensive spectroscopic methods.

Synthesis and characterization of mesoporous Mn-MCM-41 materials

Si { 1 H} CP-MAS NMR X-ray photo-emission spectroscopy a b s t r a c t MCM-41 has been synthesized at two different pH using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 ◦ C for 4 h. Mn-MCM-41 powders with different Mn/Si molar ratios were prepared using the incipient wetness method, followed by calcination at 550 ◦C for 5 h. At the end of the impregnation process the powders colour changed from white to brown whose intensity depends on manganese quantity. The materials characterization was performed by X-ray diffraction, N2 adsorption, 29 Si Cross Polarization–Mag…

Structural, Spectroscopic and Electrical Features of Undoped and Mn Doped LiTi2(PO4)3

The study of the ionic conducting material LiTi2(PO 4)3 and of its Mn-substituted derivate reveals that the Mn distribution is strictly related to the synthetic method. The results of the structural refinement of X-ray and neutron (ToF) powder diffraction data and of XPS analysis demonstrate that Mn2+ ions are located on the lithium octahedral site, while Mn3+ and Mn4+ ions occupy the titanium ones. The Mn2+ amount on the lithium site seems to be the main factor responsible for the conductivity decrease observed in doped samples. The EPR spectra evidence clustering effects of Mn on both Li and Ti sites and the presence of more insulated Mn2+ ions. The effect of the major Mn amount on Ti sit…

Effect of methaacrylic acid on the structure of Eu:YAG-PMMA composites

Polymeric composites of lanthanide-doped materials were recently considered as potential candidates for the development of light emitting diodes, lasers and luminescent concentrators for solar cells. In particular, nanoparticles of yttrium aluminum garnet (YAG) doped with cerium ions embedded in polymetylmetacrylate (PMMA) have been valuable for white LED devices [1,2]. Different structures and micromechanical properties have been observed when the methacrylic acid (MAA) is present in the composite. With the aim to understand the effect of MAA on the composite structure, a series of Eu:YAG composites prepared by in situ polymerization starting from mixtures of MAA and methylmetacrylate (MMA…

Macro-micro relationship in nanostructured functional composites

This paper examines the results of the characterization of two functional composites: Poly(methyl methacrylate) (PMMA)-Ce:YAG (yttrium aluminium garnet doped with cerium) and PMMA-cobalt hexacyanoferrate (CoHCF). The composites were prepared as possible emitters in the fields of lighting thermal sensors. The prepared composites were char- acterized using transmission electron microscopy (TEM), nuclear magnetic resonance (NMR) spectroscopy, thermogravi- metric analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) analyses to study the correlation between micro and macro characteristics. We found that the molecular interactions of the two different fill…

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…

Physico-chemical characterization of the Acqualadrone rostrum

The archaeological discovery of the Acqualadrone rostrum (an offensive naval weapon mounted on the prow at the waterline), off the Italian coast near Messina in 2008, has led to the need for scientific research in order to plan the conservation treatment of this artefact. The discovery is exceptional because of the presence of a wooden section from the original ship. This paper describes the physico-chemical characterization of a metallic and two wooden samples by inductively coupled plasma – optical emission spectroscopy, inductively coupled plasma – mass spectrometry, Fourier transform infrared spectroscopy, 13C {1H} crosspolarization magic angle spinning NMR spectroscopy, energy-dispersi…

Cross-Linked Polyamine from Imidazolium-Based Materials: A Simple Route to Useful Catalytic Materials

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…

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 …

Characterization of Nd-MCM41 obtained by impregnation

Abstract Silica mesoporous molecular sieves (MCM-41), prepared by using micelles as template, were functionalized by means of incipient wetness method. Evidence for the neodymium presence in the silica matrix was obtained by means of EDX. SEM micrographs showed that impregnation does not change significantly MCM-41 morphology. The maintenance of the hexagonal structure was confirmed by XRD pattern analysis. However, the observed loss of long-range ordering, the cell parameter increase and the surface area decrease, observed by gas adsorption technique, were attributed to the introduction of neodymium oxide inside the MCM-41 mesochannels. By FT-IR and Raman spectra it was found that the main…

Study of the Curing Process of DGEBA Epoxy Resin Through Structural Investigation

In this work, a multi-scale approach with different analytical methods is applied to study the curing process and the structural properties of a diglycidyl ether of bisphenol A (DGEBA) epoxy resin. This monomer, thermally cured using 4,4′-diaminodiphenilsulfone (DDS) as hardener, is analyzed after 10, 45, 90, and 120 min of reaction time at 180 °C to obtain information on samples with different cross-linking densities. Samples are also characterized after extraction in acetone in order to obtain structural information on the insoluble parts. For this purpose, differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), solid-state nuclear magnetic resonance (ss-NMR),…

First Evidence of Tris(catecholato)silicate Formation from Hydrolysis of an Alkyl Bis(catecholato)silicate

The hydrolysis of 3-ammoniumpropylbis(catecholato)silicate 1, giving two different silica-based materials containing different amounts of tris(catecholato)silicate, is reported. The latter species can be formed through an attack of catechol to the silicon atom in the pentacoordinate complex, in which the silicon-carbon bond is further activated toward electrophilic proton cleavage. The Knoevenagel reaction was used as a probe in order to test the availability of functional groups on the surface of such materials.

Corrigendum to “The effect of silica nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of PMMA [Pol. Degrad. Stab. 97 (2012) 452-459]. Polymer Degradation and Stability 97 (2012) 2477

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…

High Resolution-magic Angle Spinning NMR Study of Olive Leaves

In recent years HR-MAS 1H NMR spectroscopy has proven to be a useful tool for the rapid determination of the metabolic profile of several solid and semisolid foods, such as fruits and vegetables, cheese and meat. Olive leaves are today recognized as direct sources of bioactive compounds and natural antioxidants (flavonoids, secoiridoids) suitable as food additives, and their extracts form the basis of beauty care products and pharmaceutical supplements. Thus, olive leaves are emerging as a new and potentially important product for olive tree growing regions. In this report we present the application of 1H and 13C HR-MAS 1D and 2D NMR spectroscopy for the characterization and analysis of tri…

Corrigendum to “The effect of silica nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of PMMA” [Polym Degrad Stab 97 (2012) 452–459]

Structure of e-beam sculptured poly(N-vinylpyrrolidone) networks across different length-scales, from macro to nano

Abstract Study of macromolecular structure and dynamics of networks formed by pulsed electron-beam irradiation of poly(N-vinyl pyrrolidone) (PVP) aqueous solutions, at relatively low energy per pulse and across different concentration regimes, provides the basis for the understanding of a new generation of functional nanostructures. Networks are the result of the follow–up reactions initiated by a continuous series of electron pulse-generated hydroxyl radicals, which may have a different fate at the variance of polymer concentration. Different spectroscopic techniques, FT-IR, 13 C { 1 H} CP-MAS NMR and Raman, applied to characterize the formed networks, describe a profound modification of t…

Average versus local structure in K2NiF4-type LaSrAlO4: direct experimental evidence of local cationic ordering

The long-range ordering of a crystalline material can be accurately determined by analyzing the Bragg intensities and positions. In contrast, direct observation of short-range ordering in crystalline materials, which is increasingly considered of fundamental importance to unravel the structure-property relationships that underpin their technological applications, is a challenging task. In this study we have investigated the structure of LaSrAlO4, a representative example of compounds with the K2NiF4-type structure. By the combined use of synchrotron and neutron diffraction, pair distribution function analysis, Al-27 MQMAS NMR and atomistic simulations we have highlighted differences between…

Solid State NMR Spectroscopy Investigation of the Molecular Structure of Epoxy Based Materials Cured in Different Conditions

In this work two epoxy resin model systems, whose monomers are typically used in structural composites, were thermally cured in different cure conditions in order to obtain different cross-linking densities. Their molecular structures were investigated through solid state NMR spectroscopy in order to correlate them to the cure process conditions used and the results were discussed in the light of the dynamical mechanical thermal analysis (DMTA) performed.

Solid state NMR applications in the field of cultural heritage

Solid State NMR characterization of the waterlogged wooden part of Acqualadrone roman rostrum

Resine epossidiche: studio delle proprietà microscopiche mediante NMR in stato solido

A New Methodological Approach to Correlate Protective and Microscopic Properties by Soft X-ray Microscopy and Solid State NMR Spectroscopy: The Case of Cusa’s Stone

Hydrophobic treatment is one of the most important interventions usually carried out for the conservation of stone artefacts and monuments. The study here reported aims to answer a general question about how two polymers confer different protective performance. Two fluorinated-based polymer formulates applied on samples of Cusa’s stone confer a different level of water repellence and water vapour permeability. The observed protection action is here explained on the basis of chemico-physical interactions. The distribution of the polymer in the pore network was investigated using scanning electron microscopy and X-ray microscopy. The interactions between the stone substrate and the protective…

Structural investigation of e-beam cured epoxy resins through solid state NMR

Abstract In this paper the network structure of e-beam cured DGEBF based epoxy resins is investigated. Two epoxy systems, having different reactivity and cured in different process conditions, were analyzed through solid state NMR spectroscopy. The analysis shows that the more reactive system has higher cross-linking density and higher uniformity of network distribution. Similar information were obtained, in a previous work, on the same systems through dynamic mechanical thermal analysis. It is worth noting that unlike DMTA tests, which interfere with the molecular structure of the analyzed material, due to the heating during the analysis itself, more reliable information, without any artef…

Synthesis, In Vitro and In Silico Analysis of New Oleanolic Acid and Lupeol Derivatives against Leukemia Cell Lines: Involvement of the NF-κB Pathway

Oleanolic acid (OA) and Lupeol (LU) belong to the class of natural triterpenes and are endowed with a wide range of biological activities, including cytotoxicity toward several cancer cell lines. In this context, we investigated a set of compounds obtained from the two natural precursors for the cytotoxicity against leukemia HL60 cells and the multidrug-resistant (MDR) variant HL60R. Six new semi-synthetic triterpenes have been synthetized, fully characterized, and were investigated together with other triterpenes compounds for their pharmacological mechanism of action. The interaction of the more cytotoxic compounds with the nuclear factor kappa B (NF-κB) pathway has been also evalua…

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 …

The Acqualadrone Rostrum: a physical-chemical investigation to understand the Material History

The aim of this work is to define the conservation state and to ascertain the provenance of raw materials used in the construction of the Acqualadrone Rostrum. In 2008 the rostrum (an offensive naval weapon mounted on the prow at the waterline), from an ancient warship was recovered from the Mediterranean near Acqualadrone, Messina, Sicily. The archaeological discovery has led to the need for scientific research in order to plan the conservation treatment of this artefact. The discovery is exceptional because of the presence of a wooden section from the original ship. The physical-chemical investigation, by using some complementary spectroscopic techniques, was focused on the characterizati…

Organic-inorganic nanocomposites prepared by reactive suspension method: investigation on filler/matrix interactions and their effect on the nanoparticles dispersion

Epoxy resin/TiO2 nanocomposites prepared by both reactive suspension method, based on in situ synthesis, and conventional mechanical mixing are analysed by solid-state nuclear magnetic resonance and transmission electron microscopy in order to have a deeper insight into the nature of interactions at the polymer/particle interface and their effect on the nanoparticles dispersion. Specifically, solid-state nuclear magnetic resonance experiments showed that the nanoparticles, synthesized by reactive suspension method, can efficiently link the matrix by hydrogen bonds forming a hybrid organic-inorganic 3D network. Such evidences strongly supports our previously reported theory, in which the nan…

Cytotoxicity of oleanolic and ursolic acid derivatives toward hepatocellular carcinoma and evaluation of NF-κB involvement.

Oleanolic and ursolic acids are two ubiquitous isomeric triterpene phytochemicals known for their anticancer activity. A set of derivatives of the two compounds with a modified oxidation state and lipophylicity at C-3 and C-28 positions, were prepared and tested as anticancer agents versus the lines HepG2, Hep3B and HA22T/VGH of hepatocarcinoma, a strongly aggressive tumor that is not responsive toward the standard therapies. New derivatives containing a three carbons side chain on the C-3 position were synthetized in both stereoisomeric forms by the Barbier-Grignard procedure and three of them were found to be active toward all of the three targets. The implication of the transcriptional n…

Synthesis, Characterization and Catalytic Activity of mesoporous Mn-MCM-41 materials

MCM-41 has been synthesized at two different pH using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 ◦C for 4 h. Mn-MCM-41 powders with different Mn/Si molar ratios were prepared using the incipient wetness method, followed by calcination at 550 ◦C for 5 h. At the end of the impregnation process the powders colour changed from white to brown whose intensity depends on manganese quantity. The materials characterization was performed by X-ray diffraction, N2 adsorption, 29Si Cross Polarization–Magic Angle Spinning NMR, and X-ray Photoelectron Spectroscopy. The effects …

H3PW12O40 supported on mesoporous MCM-41 and Al-MCM-41 materials: preparation and characterisation

MCM-41 and Al–MCM-41 has been synthesized using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 °C for 4 h. HPW heteropolyacid supported on the mesoporous were prepared using the incipient wetness method. The characterization of materials was performed by X-ray diffraction, Transmission Electron Microscopy, N2 adsorption, 29Si Cross Polarization–Magic Angle Spinning and 27Al MAS NMR. Results showed that the hexagonal structure is obtained in both cases. The Aluminium species are located inside an extra-framework. The impregnation reduces the surface area of the mesopo…