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Luigia Sabbatini
Ruolo
Professore Ordinario
Organizzazione
Università degli Studi di Bari Aldo Moro
Dipartimento
DIPARTIMENTO DI CHIMICA
Area Scientifica
AREA 03 - Scienze chimiche
Settore Scientifico Disciplinare
CHIM/01 - Chimica Analitica
Settore ERC 1° livello
Non Disponibile
Settore ERC 2° livello
Non Disponibile
Settore ERC 3° livello
Non Disponibile
Increased need for non-destructive investigation methods in archaeology has become a major issue since sampling is in most cases restricted in view of the importance or uniqueness of the objects. For this reason, preliminary investigation using non-destructive techniques was performed on five samples of amber beads obtained from different excavation and archaeological sites. The use of FTIR and micro-Raman analysis revealed the presence of carboxyl, peroxide, hydroxyl, and complex ester functional groups as well as single and double bonds in the structure of the studied resin varieties. Further analysis of the amber samples from both archaeological and geological types by XPS, XRF, and SEM showed the presence of sulfur and a wide range of trace elements on the surface of the analysed samples. Our results proved that the combination of structural-molecular and surface elemental techniques for amber characterisation provides a very useful and simple methodology for the description of geological and archaeological amber samples from different regions of Europe.
The investigation was aimed at defining the compositional and structural characteristics of a group of monochrome blue faiences recovered in Pompeii to assess provenance on the basis of their technological features. Different complementary analytical techniques were used: Scanning Electron Microscopy (SEM) to investigate the morphological aspects of the samples and in particular of the interfaces, micro-Raman Spectroscopy and XRPD to identify crystalline phases and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) to assess the elemental composition due to its sensitivity to a wide range of elements and the adequate lateral resolution. Statistical data treatment of the elemental concentrations of both the ceramic bodies and the glazes allowed us to classify the objects into compositional groups and to verify the previously established archaeological hypothesis suggesting an Egyptian provenance for faience of Pompeii.
Bio-plastics are starting to graduate from the 'emerging technology' stage to market acceptance as everyday materials. In the present study, nanocomposite coatings embedding copper nanoparticles (CuNPs) were developed as new active packaging for fresh dairy products. In order to combine the bioactivity of CuNPs with a biodegradable polymer matrix, copper nanoparticles were satisfactorily incorporated into polylactic acid (PLA). Two different routes were carried out to prepare active films by picosecond-pulsed laser ablation. The nano-materials were characterized by UV-Vis spectroscopy and X-ray Photoelectron spectroscopy. Copper release was also measured through atomic absorption analyses. To assess the antimicrobial effects of nanocomposite systems, both in vitro and in vivo tests were carried out. The active polylactic acid films showed good antibacterial activity. In fiordilatte samples stored at 4 C during 9 days, proliferation of main spoilage microorganisms was delayed with a consequent preservation of sensory attributes. These results represent a step forward in the possible application of copper in the food packaging industry. Industrial relevance Bio-plastics with active properties represent the most emerging technology in food packaging field. Results from the current paper demonstrate that antimicrobial films of PLA embedding copper nanoparticles could be developed and applied to fresh dairy products as fiordilatte. In fact, the in vivo test confirmed the antimicrobial effects on fiordilatte spoilage, without compromising sensory attributes. Results could gain great importance from the industrial dairy sector.
Head space(HS)solid-phasemicro extraction(SPME)combinedwith gaschromatography–mass spectrometry (GC–MS) was used to analyze the volatile fraction of ambers of different geological origin. In particular, Romanian (romanite)and Baltic (succinite)amber samples were studied.Both types of amber have nearly similar bulk chemical compositions and could probably reflect only some differences of paleo biological and/or diagenetic origin. The present study shows that amber headspace fingerprint, obtained bySPME/GC–MS, can provide a simple and quasi non-destructive method capable of romanite/succinite differentiation. Among the numerous compounds present in the headspace,a number of few informative variables could be selected that were able to differentiate the ambers as demonstrated by Principal Component and Cluster Analysis.
A simple protocol, based on Bligh–Dyer (BD) extraction followed by MALDI-TOF-MS analysis, for fast identification of paint binders in single microsamples is proposed. For the first time it is demonstrated that the BD method is effective for the simultaneous extraction of lipids and proteins from complex, and atypical matrices, such as pigmented paint layers. The protocol makes use of an alternative denaturing anionic detergent (RapiGestTM) in order to improve efficiency of protein digestion and purification step. Detection of various lipid classes, such as triacylglycerols (TAGs) and phospholipids (PLs), and their oxidation by-products was accomplished, whereas proteins could be identified by peptide mass fingerprinting. The effect of pigments on ageing of lipids and proteins was also investigated. Finally, the proposed protocol was successfully applied to the study of a late-15th century Italian panel painting allowing the identification of various proteinaceous and lipid sections in organic binders, such as egg yolk, egg white, animal glue, casein, and drying oil. ©
Fibulae from the archaeological site of Egnatia were examined with the aim of identifying types of alloys, the processes employed for their manufacturing, and outlining the corrosion products. The results obtained, by identifying the raw materials and the technological solutions used allowed us to provide convincing answers to most of the archaeological questions and confirmed the integration of Egnatia in a complex commercial network. In addition, investigations focused on the study of corrosion products, with a view to the planning of more suitable restoration and preservation strategies.
Microbial colonization and biofilm formation on implanted devices represent an important complication in orthopaedic and dental surgery and may result in implant failure. Controlled release of antibacterial agents directly at the implant site may represent an effective approach to treat these chronic complications. Resistance to conventional antibiotics by pathogenic bacteria has emerged in recent years as a major problem of public health. In order to overcome this problem, non-conventional antimicrobial agents have been under investigation. In this study, polyacrylate-based hydrogel thin coatings have been electrosynthesised on titanium substrates starting from poly(ethylene glycol diacrylate)–co– acrylic acid. Silver nanoparticles (AgNPs) with a narrow size distribution have been synthesized using a “green” procedure and immobilized on Ti implant surfaces exploiting hydrogel coatings’ swelling capabilities. The coatings have been characterized by XPS and SEM/EDX, while their silver release performances have been monitored by ICP–MS. The antibacterial activity of these AgNP-modified hydrogel coatings was tested evaluating in vitro inhibition growth of Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli, among the most common pathogens in orthopaedic infections. Moreover, a preliminary investigation of the biocompatibility of silver-loaded coatings versus MG63 human osteoblast-like cells has been performed. An important point of strength of this paper, in fact, is the concern about the effect of silver species on the surrounding cell system in implanted medical devices. Silver ion release has been properly tuned in order to assure antibacterial activity while preserving osteoblasts’ response
Painted Canosa ceramicswere examined to identify the nature of the pigments employed and theirmanufacturing technology. A multi-technique approach was used, comprising Raman microspectroscopy and laser ablation hyphenated to inductively coupled plasma-mass spectrometry (LA-ICP-MS). The analysed samples were mainly produced for burial in tombs and were not intended for everyday use. They belong to the period between the end of themid-7th century andthe first half of the 4th century BC, and were excavated from the Toppicelli archaeological district near the suburbs of Canosa (Puglia, Italy). Forty-eight pottery fragments were available for this study. No handling of the samples was required for the Raman study, and it was possible to excise the pigmented layer in such a way that the lacunae were not distinguishable to the naked eye due to the micrometric size of the laser spot as far as LA-ICP-MS is concerned. Their combination turned out to be quite useful for the investigation of these archaeological materials: the chemical nature of the white, red, brown and black pigments employed in the pottery manufacture was investigated. Iron and manganese compounds were identified as the red and brown/black main colouring substances, respectively; on the other hand, whites and engobes (whitish slips) were based on kaolinite. This set of colouring substances is of importance, as it enabled the artisan to obtain in one oxidising firing cycle brown, black and red paints. Finally, the finding of manganese black in these Canosa potsherds confirms that Canosa was an important centre connecting the near East to central Italy and Europe since the pre-Roman age.
A new type of nanomaterial has been developed as antibacterial additive for food packaging applications. This nanocomposite is composed of copper nanoparticles embedded in polylactic acid, combining the antibacterial properties of copper nanoparticles with the biodegradability of the polymer matrix. Metal nanoparticles have been synthesised by means of laser ablation, a rising and easy route to prepare nanostructures without any capping agent in a liquid environment. As prepared, nanoparticle suspensions have been easily mixed to a polymer solution. The resulting hybrid solutions have been deposited by drop casting, thus obtaining self-standing antibacterial packages. All samples have been characterized by UV-Vis spectroscopy, X-ray photoelectron spectroscopy and electro-thermal atomic absorption spectroscopy. Ion release data have been matched with bioactivity tests performed by Japanese Industrial Standard (JIS) method (JIS Z 2801:2000) against Pseudomonas spp., a very common Gram-negative microbial group able to proliferate in processed food.
Bio-sensing represents one of the most attractive applications of carbon material based electronic devices; nevertheless, the complete integration of bioactive transducing elements still represents a major challenge, particularly in terms of preserving biological function and specificity while maintaining the sensor’s electronic performance. This review highlights recent advances in the realization of field-effect transistor (FET) based sensors that comprise a bio-receptor within the FET channel. A birds-eye view will be provided of the most promising classes of active layers as well as different device architectures and methods of fabrication. Finally, strategies for interfacing bio-components with organic or carbon nanostructured electronic active layers are reported.
Pyrolysis gas chromatography–mass spectrometry (PyGC-MS) was used as a rapid method for the characterization of permanent marker ink. Twenty-four samples of various colours purchased from different manufacturers were characterised. Four main typologies of polymer-binding medium could be distinguished on the basis of the pyrolysis products, and differentiation between permanent markers of different manufacturers could be accomplished. For some permanent marker samples, PyGC-MS analysis allowed pigment identification as well.
In this study, a preventive method for fighting bio-deterioration of stone substrates is proposed. This is based on the use of bioactive zinc oxide nanoparticles (ZnO-NPs), which are able to exert a marked biological activity over a long period of time due to their peculiar structure. ZnO-NPs are synthesised by a simple and reproducible electrochemical procedure. The nanomaterials are embedded in consolidant/ water-repellent matrices to obtain nanostructured coatings. Commonly used products based on tetraethoxysilane and/or polysiloxanes were tested. The resulting nanomaterials were fully characterised by X-ray photoelectron spectroscopy (XPS) to investigate the amount and composition of the NPs and the behaviour of the nanocomposites. Inductively coupled plasma mass spectrometry (ICP-MS) was used for the study of the release of metal from the composites when put in contact with artificial rainwater. The nanocomposites were applied to specimens composed of three different types of stone and chromatic changes upon curing were measured by spectrophotocolorimetry. Finally, morphological characterization by scanning electron microscopy (SEM) was performed. The bioactivity of ZnO-NPs nanocomposites was also assessed in preliminary tests against Aspergillus niger fungus
Synthesis and fabrication and assembly of functional particles and capsules Material Research Society, San Francisco (USA), April 2012
New promising and versatile materials for the development of in situ sustained release systems consisting of thin films of either poly(2-hydroxyethyl methacrylate) or a copolymer based on poly(ethylene-glycol diacrylate) and acrylic acid were investigated. These polymers were electrosynthesized directly on titanium substrates and loaded with ciprofloxacin (CIP) either during or after the synthesis step. X-ray photoelectron spectroscopy was used to check the CIP entrapment efficiency as well as its surface availability in the hydrogel films, while high-performance liquid chromatography was employed to assess the release property of the films and to quantify the amount of CIP released by the coatings. These systems were then tested to evaluate the in vitro inhibition of methicillin-resistant Staphylococcus aureus (MRSA) growth. Moreover, a model equation is proposed which can easily correlate the diameter of the inhibition haloes with the amount of antibiotic released. Finally, MG63 human osteoblast-like cells were employed to assess the biocompatibility of CIP-modified hydrogel coatings.
The present work is aimed at developing gold nanostructures functionalized with antenna systems to exploit the synergistic nanostructure/antenna desorption-ionization efficiency. A potential Matrix- Assisted Laser Desorption Ionisation (MALDI) organic matrix has been modified introducing specific functional groups or molecular linker and used as a capping agent for gold nanostructures. In particular, conjugated naphthyl-thio-derivative, i.e. 4-mercaptonaphthalene-1,8-dicarboxylic acid, was synthesized and characterized by means of nuclear magnetic resonance, UVevisible and X-ray photoelectron spectroscopies. Afterwards, the thio-derivative was used as covalent surface modifier for flat gold surfaces and nanostructured gold films. These surfaces were thoroughly characterized by means of parallel angle-resolved X-ray photoelectron spectroscopy to obtain quantitative information about elemental composition, chemical speciation, and in-depth distribution of the target chemical functional groups. Finally the compound was preliminarily tested as a non-conventional matrix in Laser Desorption Ionisation Mass Spectrometry (LDI-MS) analysis of low molecular weight biomolecules in order to assess its capability of acting as the antenna system and proton donor after covalent bonding to gold nanomaterials.
Osteointegration of titanium implants could be significantly improved by coatings capable of promoting both mineralization and angiogenesis. In the present study, a copolymeric hydrogel coating, poly-2-hydroxyethyl methacrylate-2-methacryloyloxyethyl phosphate (P(HEMA-MOEP)), devised to enhance calcification in body fluids and to entrap and release growth factors, was electrosynthesized for the first time on titanium substrates and compared to poly-2-hydroxyethyl methacrylate (PHEMA), used as a blank reference. Polymers exhibiting negatively charged groups, such as P(HEMA-MOEP), help to enhance implant calcification. The electrosynthesized coatings were characterized by X-ray photoelectron spectroscopy and atomic force microscopy. MG-63 human osteoblast-like cell behaviour on the coated specimens was investigated by scanning electron microscopy, MTT viability test and osteocalcin mRNA detection. The ability of negatively charged phosphate groups to promote hydroxyapatite-like calcium phosphate deposition on the implants was explored by immersing them in simulated body fluid. Similar biological responses were observed in both coated specimens, while calcium-phosphorus globules were detected only on P(HEMA-MOEP) surfaces pretreated with alkaline solution. Testing of the ability of P(HEMA-MOEP) hydrogels to entrap and release human recombinant vascular endothelial growth factor, to tackle the problem of insufficient oxygen and nutrient delivery, suggested that P(HEMA-MOEP)-coated titanium prostheses could represent a multifunctional material suitable for bone restoration applications.
The formulation and characterization of dopamine (DA)-loaded chitosan nanoparticles (CSNPs) are described as preliminary steps for the development of potential DA carrier systems intended for Parkinson's disease treatment. For this purpose, CSNPs were firstly produced and, afterwards, they were incubated in a DA aqueous solution to promote neurotransmitter loading. The characterization of the resulting nanoparticles started with Fourier transform infrared spectroscopy analysis to ascertain the presence of DA in the nanocarrier, whereas X-ray photoelectron spectroscopy analysis provided evidence of the localization of DA on the nanoparticle surface. A quartz crystal microbalance with dissipation monitoring (QCM-D) was then exploited to investigate both swelling of CSNPs and interaction of DA with CSNPs. In particular, the QCM-D revealed that this interaction is fast and so this allows a stable nanostructured system to be obtained.
In the present study, gold/surfactant core/shell colloidal nanoparticles with a controlled morphology and chemical composition have been obtained via the so-called sacrificial anode technique, carried out in galvanostatic mode. As synthesized Au-NPs had an average core diameter comprised between 4 and 8 nm, as a function of the electrochemical process experimental conditions. The UV–Vis characterization of gold nanocolloids showed clear spectroscopic size effects, affecting both the position and width of the nanoparticle surface plasmon resonance peak. The nanomaterial surface spectroscopic characterization showed the presence of two chemical states, namely nanostructured Au(0) (its abundance being higher than 90%) and Au(I). Au-NPs were then deposited on the top of a capacitive field effect sensor and subjected to a mild thermal annealing aiming at removing the excess of stabilizing surfactant molecules. Au-NP sensors were tested towards some gases found in automotive gas exhausts. The sensing device showed the largest response towards NOx, and much smaller – if any – responses towards interferent species such as NH3, H2, CO, and hydrocarbons.
A matrix-assisted laser desorption ionization time-of-flight mass spectrometry-based approach was applied for the detection of various lipid classes, such as triacylglycerols (TAGs) and phospholipids (PLs), and their oxidation by-products in extracts of small (50–100 μg) samples obtained from painted artworks. Ageing of test specimens under various conditions, including the presence of different pigments, was preliminarily investigated. During ageing, the TAGs and PLs content decreased, whereas the amount of diglycerides, short-chain oxidative products arising from TAGs and PLs, and oxidized TAGs and PLs components increased. The examination of a series of model paint samples gave a clear indication that specific ions produced by oxidative cleavage of PLs and/or TAGs may be used as markers for egg and drying oil-based binders. Their elemental composition and hypothetical structure are also tentatively proposed. Moreover, the simultaneous presence of egg and oil binders can be easily and unambiguously ascertained through the simultaneous occurrence of the relevant specific markers. The potential of the proposed approach was demonstrated for the first time by the analysis of real samples from a polyptych of Bartolomeo Vivarini (fifteenth century) and a “French school” canvas painting (seventeenth century).
Graphene/ionic liquids nanocomposite gels were synthesized by an electrochemical etching approach and fully characterized under a morphological and structural point of view. For this purpose, several analytical techniques were applied, as HR-TEM/EDX (High Resolution-Transmission Electron Microscopy/Energy Dispersive X-Ray Analysis); FE-SEM/EDX (Field Emission-Scanning Electron Microscopy/Energy Dispersive X-Ray Analysis); XPS (X-Ray Photoelectron Spectroscopy); FT-IR (Fourier Transform-Infrared Spectroscopy) and electrochemical techniques. After the characterization study, nanocomposite-gel paste electrodes were assembled, exhibiting a selective and specific detection toward the caffeic acid oxidation. Better performances in terms of linear range of concentration (from 0.025 to 2.00 M), reproducibility (intra-; 1.40% and inter-electrode reproducibility-3.20%), sensitivity (3389/μA mM-1 cm-2), fast response time (2 s) and detection limit (0.005 mM) were obtained, in comparison with other chemically modified electrodes, described in literature for the caffeic acid detection. This nanocoposite-gel could represent a new prototype of miniaturized nanostructured sensors useful for the "in situ" quantification of an important molecule, having pharmacological properties, anti-inflammatory, antibacterial, antiviral, immunomodulatory and antioxidant effects.
Oxidized Single-Wall Carbon Nanohorns (o-SWCNHs) were used, for the first time, to assemble chemically modified Screen Printed Electrodes (SPEs) selective towards the electrochemical detection of Epinephrine (Ep), in the presence of Serotonine-5-HT (S-5HT), Dopamine (DA), Nor-Epineprhine (Nor- Ep), Ascorbic Acid (AA), Acetaminophen (Ac) and Uric Acid (UA). The Ep neurotransmitter was detected by using Differential Pulse Voltammetry (DPV), in a wide linear range of concentration (2–2500 μM) with high sensitivity (55.77 A M1 cm2), very good reproducibility (RSD% ranging from 2 to 10 for different SPEs), short response time for each measurement (only 2 s) and low detection of limit (LOD¼0.1 μM). o-SWCNHs resulted in higher analytical performances when compared with other nanomaterials used in literature for electrochemical sensors assembly.
L’esame del dipinto su tela “San Rocco e gli appestati” di Jacopo Tintoretto ha avuto inizio in occasione del recente restauro, descritto dettagliatamente in questo volume. Scopo delle indagini scientifiche era ottenere informazioni sui materiali e sulle tecniche usate al fine di ampliare le conoscenze sul modus operandi del Tintoretto, confrontando i risultati ottenuti con i dati di letteratura, nonché fornire un supporto di conoscenza alla programmazione degli interventi di restauro. Negli anni passati numerosi dipinti di Jacopo Tintoretto sono stati sottoposti ad un’indagine scientifica. I primi studi, risalenti agli anni 1970-1980, trattano, in particolare, alcuni dipinti della National Gallery di Londra, “San Giorgio e il Drago”, “Cristo lava i piedi ai suoi Discepoli”, L’origine della Via Lattea”, “Ritratto di Vincenzo Morosini” , ed altri quattro attribuiti o associati al Tintoretto nonché vari capolavori conservati a Venezia, in particolare nella Chiesa della Madonna dell’Orto , nella Scuola di San Rocco , nella Chiesa di San Simeone Grande e nella Galleria dell’Accademia . Studi più recenti sono dedicati rispettivamente ai pigmenti del ciclo Gonzaga ed al “Dreams of men” del Detroit Institute of Arts . Dell’impiego di materiali vetrosi nei dipinti veneziani del Rinascimento tratta, invece, Barbara Berrie, includendo il “Cristo sul mare di Galilea” della collezione Samuel H. Kress di Washington. Tintoretto non costituisce un oggetto di studio facile in quanto poche sue opere sono firmate o datate, e poche sono databili con certezza. Dei dipinti studiati sono stati esaminati gli strati di preparazione, i pigmenti ed i leganti pittorici. Le indagini condotte, mediante tecniche analitiche di livello più o meno avanzato, hanno fornito una banca dati significativa sulla tecnica pittorica del Tintoretto. Il presente lavoro costituisce un piccolo contributo nell’ambito di una ricerca più ampia e sistematica sulla tecnica pittorica del pittore veneto. Per lo studio dei materiali e della tecnica pittorica del “San Rocco e gli Appestati” ci si è avvalsi di tecniche analitiche non distruttive e microdistruttive in quanto applicabili a quantitativi di materiale inferiori al milligrammo, prelevati in punti diversi del dipinto. In vari punti del dipinto sono state effettuate delle misure colorimetriche al fine di descrivere le qualità dei colori e di monitorare eventuali variazioni prima e dopo l’intervento di restauro e nel tempo. Gli spettri ottenuti permettono, a volte, anche l’identificazione dei pigmenti. Nel corso del restauro, dal dipinto in questione sono stati prelevati campioni da zone diverse. Dapprima tutti i campioni sono stati sottoposti ad un attento esame allo stereomicroscopio. Tre frammenti di campioni provenienti da punti diversi sono stati inglobati in resina epossidica per ricavarne delle sezioni trasversali che poi sono state osservate al microscopio ottico (MO) in luce visibile riflessa ed al microscopio elettronico a scansione (SEM) ed analizzate mediante spettroscopia micro-Raman. Sulle sezioni trasversali è stata condotta un’analisi chimica elementare con l’ausilio del SEM dotato di un dispositivo per la spettroscopia a dispersione di energia (EDS). In effetti, la tecnologia ESEM è frequentemente impiegata nel campo dei beni culturali, in particolare per lo studio di sezioni stratigrafiche di dipinti. Al fine di stabilire la composizione chimica delle diverse vernici presenti sul dipinto, sono stati effettuati dei campionamenti tramite batuffoli imbevuti di alcuni solventi. L’intento è stato quello di fornire indicazioni utili al restauratore per proseguire correttamente le operazioni di pulitura previste. Per il riconoscimento delle sostanze organiche presenti nelle vernici campionate è stata impiegata la gas cromatografia accoppiata alla spettrometria di massa (GC-MS).
Biosystems integration into an organic field-effect transistor (OFET) structure is achieved by spin coating phospholipid or protein layers between the gate dielectric and the organic semiconductor. An architecture directly interfacing supported biological layers to the OFET channel is proposed and, strikingly, both the electronic properties and the biointerlayer functionality are fully retained. The platform bench tests involved OFETs integrating phospholipids and bacteriorhodopsin exposed to 1–5% anesthetic doses that reveal drug-induced changes in the lipid membrane. This result challenges the current anesthetic action model relying on the so far provided evidence that doses much higher than clinically relevant ones (2.4%) do not alter lipid bilayers’ structure significantly. Furthermore, a streptavidin embedding OFET shows label-free biotin electronic detection at 10 parts-per-trillion concentration level, reaching state-of-the-art fluorescent assay performances. These examples show how the proposed bioelectronic platform, besides resulting in extremely performing biosensors, can open insights into biologically relevant phenomena involving membrane weak interfacial modifications.
A new class of nano-antimicrobials was developed by Ion Beam co-Sputtering of ZnO and polytetrafluoro_ ethylene targets. The resulting nanostructured coatings combine the antimicrobial properties of ZnO nanoparticles with the water repellence and anti-stain characters of the dispersing fluoropolymer (CFx). ZnO-CFx nanocomposites were prepared varying ZnO volume fraction (φ) in the CFx matrix by tuning the sputter- ing deposition parameters. Morphological analysis confirmed the presence of homogenously distributed ZnO nanoclusters in the polymer. ZnO loadings ranging in the 0.05-0.15 interval were explored and the nano-composites were characterized by X-ray Photoelectron Spectroscopy (XPS) to investigate their surface chemical composition. XPS spectra evidenced a high degree of polymer defluorina-tion along with the formation of ZnF2 at increasing φ valu-es. Zn speciation was performed on Zn L3M45M45 Auger signal. Coatings bioactivity was assessed against Escheri-chia coli, Staphylococcus aureus, and Kluyveromyces marxianus. At φ ≥ 0.10, ZnO-CFx composites exhibited appreciable antibacterial activity, irrespective of the target organism.
Clay minerals have revealed highly potential in soil remediation due to their low cost, availability, and low toxicity. Mechanochemical processes allow to activate chemical reactions by inducing different kinds of mechanical stress and without any other energy supply. This study investigated the effect of dry milling on the ability of dioctahedral and trioctahedral smectites to immobilize heavy metals cations. To this purpose a dioctahedral smectite “bentolite L” and a trioctahedral one “laponite RD” were ground with different amount of copper(II) chloride in dry conditions into a zirconia planetary ball mill (mechanochemical treatment). Increasing milling time and Cu/clay minerals mass ratio were selected for experimental tests. From the ground mixtures two different kinds of samples were extracted using the following procedures: 1) with deionised water; 2) with 1 M MgCl2 solution. Copper immobilization degree was evaluated by ICP/OES analysis of exstracts as difference between the amount of Cu(II) spiked in the mixture and the amount of Cu(II) ions present in the extracted fraction. The analyses showed an increased Cu retention as time increases for both bentolite L and laponite RD. Mechanochemical treatments, depending on time and different mass ratio, induced the increase of retention efficiency. The solid phases were also characterized by means of solid-state NMR and spectroscopic techniques such as FTIR and XPS, to investigate the mechanisms of the “mechanochemical retention” of copper by both the clay minerals
Gilded and enamelled glasses of Islamic style, coming from a 13th century landfill in Melfi castle, a Swabian emperor Frederick II fortress, were subjected to a multi-techniques approach in order to explore the complex and very fascinating ancient production technology of gilding and enamelling on glass. Non-destructive μ-Raman spectroscopy was employed on the most important and well-preserved objects, optical (OM) and electron (SEM) microscopies were used to investigate the sections stratigraphy of tiny fragments sampled from the borders of the already damaged objects. In order to provide the chemical analyses of the bodies and the enamels, energy dispersive X-rays spectroscopy (EDS) and X-rays photoelectron spectroscopy (XPS) were also employed. The body of the objects proved to be made of silica-soda-lime glass, while the enamels of lead-rich glass (“soft enamels”) and coloured by lapis lazuli and cobalt for blue, hematite and minium for red, lead-tin yellow for green and calcium phosphate for white. The gilding was found to be applied on a red enamel basis. The presence of carbon inside the gildings and the detection of two different gold signals by XPS suggested the hypothesis of the use of the so-called “liquid gold”. This study gave thus an important contribution to the understanding of the production of this class of rare and precious objects, also confirming that the materials and technological procedures are consistent with the Islamic tradition, probably due to the presence of Islamic artisans at the court of Frederick II.
Mastic incrustation sculptureswere used to decorate different types of objects by filling themarble incisionswith an impasto containing materials such as crushed pottery, glass or rock fragments, possibly in combination with organic substances, and was employed both in Byzantine and Occidental areas. From the 11th century onwards these sculptures are applied in important churches such as San Marco in Venice (Italy), but, despite their widespread use and conservation problems, the composition of these amalgams has never been thoroughly studied. Here we present the results of the examination of the mastic encrustations present on the medieval marble panels and precious cathedra in the San Nicola church of Bari (Italy). The matrixwas analysedwith Fourier transform infrared spectroscopy and pyrolysis gas chromatography-mass spectrometry. Organic binders were found and, in particular, the occurrence of heated Pinaceae resin, as well as of beeswaxwas assessed. The inclusions, including different types of rock, carbon black and opaque glass fragments,were characterised with opticalmicroscopy, scanning electronmicroscopy, and powderX-ray diffraction.Micro-Raman spectroscopywas carried out on both inclusions and matrix.
The Crucifix panel painting in the Santa Maria a Mare church on the Isle of St. Nicholas (Isole Tremiti, Italy), painted on both sides, was executed between the late 12th century and the early 13th century and several times restored in the following centuries. The precious artefact was studied by various complementary analytical techniques in order to characterize the original medieval painting technique and the subsequently applied restoration materials. Optical microscopy (OM), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), micro-Raman spectroscopy, pyrolysis-gas chromatography/mass spectrometry (Py-GC/ MS), and Matrix Assisted Laser Desorption Ionisation–Time of Flight–Mass Spectrometry (MALDI-TOF-MS) were applied on various samples taken from significant parts of the painting. The compositional data were used for a correct planning of the recent restoration treatments and as a support for the historical-artistic study of the painting. The results obtained confirm that both paintings—recto and verso—were realized by following the 13th century Italian painting tradition. Egg-based paint layerswere applied on a gypsum/animal glue ground. Various pigments could be identified amongwhich the precious lapis lazuli. Interestingly, thewater-gilding of the recto was performed without the use of a bole layer. Pinaceae resin as well as acrylic resins were found.
In the present contribution Angle Resolved X-ray Photoelectron Spectroscopy (AR-XPS) was proposed as useful tool to address the challenge of probing the near-surface region of bio-active sensors surface. A model bio-functionalized surface was characterized by Parallel AR-XPS and commercially available Thermo Avantage-ARProcess software was used to generate non-destructive concentration depth profiles of protein functionalized silicon oxide substrates. At each step of the functionalization procedure, the surface composition, the overlayer thickness, the in-depth organization and the in-plane homogeneity were evaluated. The critical discussion of the generated profiles highlighted the relevance of the information provided by PAR-XPS technique.
Label-free biosensors are of considerable interest for various clinical and biological applications. In these systems, achieving an optimized receptor immobilization strategy critically influence the sensing performance in terms of specificity, sensitivity, response kinetics and detection limits. However, monitoring the receptor spatial organization and the interfaces composition on a nanometer or sub-nanometer scale is a very hard challenge. In the present contribution Parallel Angle Resolved X-ray Photoelectron Spectroscopy (PAR-XPS) was proposed as useful tool to address the challenge of probing the near-surface region of bio-active sensors surface (1). A model receptor was chosen and a well-established functionalization procedure (2) was systematically characterized by PAR-XPS. Commercially available Thermo Avantage-ARProcess software was used to generate non-destructive concentration depth profiles of protein functionalized silicon oxide substrates. At each step of the functionalization procedure, the surface composition, the over layer thickness, the in-depth organization and the in-plane homogeneity were evaluated. Compared to multi-techniques characterization approaches previously proposed in the literature, the present analytical approach boasted the peculiar advantage of providing, simultaneously, morphological and compositional information from the same data set. The critical discussion of the generated profiles highlighted the relevance of the information provided by PAR-XPS technique.
One- and two-dimensional carbon nanostructures, i.e. carbon nanotubes (CNTs) and graphene possess exceptional physical properties owing to their distinctive structure and atomic arrangement. High electrical conductivity, highly exposed surface area and stability of these carbon nanostructures institute them as the leading choice of nanomaterials for a number of electrical and industrial applications. Besides these carbon nanostructures are extremely sensitive towards minute changes in the surrounding gas atmosphere, i.e. their conductance (or resistance) varies greatly with the adsorption-desorption of gas molecules such as nitrogen oxides (NOx). This article critically reviews the most recent advances in NOx sensors based on one- and two-dimensional carbon nanostructures and nanohybrids as gas sensitive materials. The advantages and limitations of CNT- and graphene-based devices are briefly discussed in the light of recent literature. The potential and future perspectives of these devices are also outlined in this study.
21st century has already seen huge progress in science and technology of small, highly sensitive gas sensors, which can selectively detect environmental toxins like NOx – the oxides of nitrogen – a byproduct of fossil fuel combustion. Into this bargain, public became more health-aware and environmental bodies grew stricter, stimulating analytical and material scientists to find new strategies from material synthesis to fabrication of NOx sensors in order to produce fast and reliable gas detectors. To the scientists, semiconducting metal oxides, owing to their low cost, easy processing, high gas response, good electrical properties and above all tunable structure at the nanoscale, always presented a first-hand choice for sensor fabrication. This article presents an overview of the most recent developments in semiconducting NOx gas sensors based on these metal oxide nanostructures and their applications in vehicle exhaust and environmental monitoring. A strong emphasis is presented on chemiresistor and field effect transistor devices using semiconducting metal oxides as active layers. The performance levels of these NOx sensors are compared to those of other devices as well as other semiconductor materials. Furthermore, keeping in mind the ultimate user demands, limitations of the current sensor technologies and future strategies are discussed
The kinetics of electrochemical deposition of copper particles from Cu2+ solution on platinum and poly-3- methylthiophene modified platinum electrode was studied in potentiostatic conditions in presence of Cl− anions. The complex behavior of current transients suggests that the deposition process involves several stages with different kinetics. Results obtained on platinum show that after an initial adsorption process, the copper deposition is accomplished through two different models: a three-dimensional nucleation and growth under diffusive control (3DPD model) and a progressive nucleation and two-dimensional growth (2DP model). The analysis of current transients recorded on platinum poly-3-methylthiophene modified electrode (Pt/PMT) shows a very different behavior. On Pt modified electrode a process of growth related to a semi-infinite diffusion to a planar surface was accompanied by two different mechanisms of nucleation and growth: a three-dimensional nucleation and growth with no diffusive control (3DP model) and an instantaneous nucleation with two-dimensional growth (2DP model).
In this study, the simultaneous identification of lipids and proteins is achieved by matrix assisted laser desorption ionization - mass spectrometry (MALDI-MS) analysis after direct on-plate processing of micro-samples supported on graphite. Taking advantages of large surface area and thermal conductivity, graphite provided an ideal substrate for on-plate proteolysis and lipid extraction without interfering with MALDI analysis. The new protocol was first developed on simple standards as bovine serum albumin to set up the best experimental conditions for proteolysis. Then, its feasibility and performance were demonstrated by processing more complex samples as milk and egg powder for simultaneous lipid/protein analysis. By such a protocol, proteins could be efficiently digested on-plate within 15 minutes, with sequence coverages comparable to those obtained by conventional overnight in-solution digestion. As an additional feature, detection of hydrophilic phosphorylated peptides could be achieved without any further enrichment procedure. Furthermore, lipids could be identified in the same analysis without any additional treatment/processing step. The present strategy is simple and efficient, of large applicability, offering great promise for high-throughput proteo-lipidomics in very small samples since no conventional solvent extraction is required reducing sample loss.
A Functional Bio-Interlayer Organic Field-Effect Transistor (FBI-OFET) sensor, embedding a streptavidin protein capturing layer, capable to perform label-free specific electronic detection of biotin at 3 part-per-trillion (mass fraction) or 15 pM, is here proposed. The response shows a logarithmic dependence on the analyte concentration along with a dynamic range spanning over five orders of magnitude. The optimization of the FBI analytical performances is achieved by depositing the capturing layer through a controllable Layer-by-Layer (LbL) assembly, while an easy processable spin-coating deposition is proposed for potential low-cost production of equally highly performing sensors. A Langmuirian adsorption based model allows to rationalize the analyte binding to the capturing layer whose analytical performances are discussed accordingly. The FBI-OFET device is shown to operate also with an antibody interlayer as well as with an ad hoc designed micro-fluidic system. These occurrences, along with the proven extremely high sensitivity and selectivity, open to FBI-OFETs appraisal as a suitable platform for disposable electronic strip-tests for assays in biological fluids requiring very low detection limits.
We report on the use of a polyanionic proton conductor, poly(acrylic acid), to gate a poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene]-based organic field-effect transistor (OFET). A planar configuration of the OFET is evaluated, and the electrical performance and implementation on a flexible substrate are discussed.
The present work investigated the possibility of preparing nanoparticles based on methacryloylglycylglycine (MAGG) and chitosan (CS) by in situ polymerization. The study revealed that nanoparticle formation was strictly dependent on ionic interactions between NH3 ? groups from CS and COO- groups arising from the anionic monomer MAGG. The subsequent in situ polymerizations of MAGG in the presence of CS led to the formation of nanoparticles with homogeneous morphology, a uniform particle size distribution, and a good spherical shape as confirmed by laser diffraction granulometry and scanning electron microscopy analyses. Nanoparticle formulations with different amounts of CS and MAGG were prepared, and their chemical compositions were investigated by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The obtained results showed that the polymerization of MAGG in the presence of CS appears to be a very promising approach in the preparation of nanoparticles for drug delivery applications.
Single-Wall Carbon Nanohorns (SWNHs) were discovered by Iijima (1) and represent a new carbon material having a horn-shaped sheath of single-wall graphitic sheets. They associate each other to form a ‘Dahlia- flower’-like aggregate. In this study, SWNHs were characterized by using HR-TEM (High-Resolution Transmission Electron Microscopy), FE-SEM/EDX (Field Emission-Scanning Electron Microscopy), Raman spectroscopy, FT-IR (Fourier Transform-Infrared) spectroscopy, XPS (X-ray Photoelectron Spectroscopy), XRD (X-ray Diffraction) and TG/DTA (Differential Thermogravimetric analysis). Then, a stable and homogeneous SWNHs colloid phase, realized in ethanolic medium, was subsequently used to chemically modify SPEs surfaces (2). The modified electrochemical devices were applied for the detection of H2O2, β-NADH, several neurotransmitters, ascorbic, uric and caffeic acids, guanine and tyrosine, very important targets for interesting bio-medical applications (3).
The on–board quantification of exhaust emission from the internal combustion engines is of global concern in order to monitor and control release of toxic gaseous pollutants such as the oxides of nitrogen (NOx). This scenario calls for highly performing, cost–effective and long lasting gas sensors. In this regard, semiconducting metal oxides present the foremost choice of active materials for real–time detection of exhaust gases due to their low cost, good electrical properties, high sensitivity and stability at temperatures as high as >500°C [1]. In this work, we report on the synthesis, analytical characterization, and surface modification of metal oxide nanoparticles (ZnO–, ZrOx, InOx- NPs) for their potential application as semiconductor gas sensors. ZnO is a promising material and one of the earliest oxides studied for gas adsorption [2]. However, owing to its high working temperature and limited selectivity, ZnO did not achieve commercial success. ZrOx and InOx nanomaterials are well known active components of NOx sensors, which have shown some performance limitations –either in selectivity or in response intensity and kinetics-. To overcome these limitations, in recent years semiconductor metal oxides (MO) are being frequently modified by selected inclusions of transition metal nanoparticles, bringing their own surface reactivity characteristics to the hybrid catalyst-MO system [3]. In the present study, MO–NPs are prepared via simple and economical sol–gel methods. The surface of MO–NPs is subsequently modified by electro–chemical decoration of nanoscale gold (nano–Au), performed under surfactant stabilization conditions. Since Au nanoparticles exhibit pronounced selectivity toward NOx gases [4], the nano–Au/MO–NPs hybrids are believed to enhance the sensing properties of MO–NPs such as the selectivity and long–term stability of the nanomaterial. Both the pristine MO–NPs and the composite nano–Au/MO–NPs are calcined at temperatures >500°C to induce stability at the usual operating temperature of gas-sensing experiments and the effect of calcination on nanostructure and morphology is systematically studied. The as–prepared and the calcined nanomaterials are characterized by transmission electron microscopy, scanning electron microscopy, X–ray photoelectron spectroscopy, and X–ray diffraction techniques. The results demonstrate that these nanomaterials are highly stable and even ultrafine gold nanophases retain their morphology and surface chemical speciation upon annealing. The experimental evidences support further application of these composite nano–Au/MO–NPs as active elements in semiconductor NOx gas sensors.
Low density lipoprotein self-assembled layers on gold support, proposed as model for oxidation studies, were subjected to oxidation processes using different oxidative agents: 2,20-Azobis(2methylpropionamidine)dihydrochloride, atmospheric oxygen, and metal-induced oxidation. The freshly prepared and the oxidized layers were characterized by X ray photoelectron spectroscopy (XPS), Fourier-Transformed infrared spectroscopy, and Matrix-Assisted Laser Desorption/Ionization-Time of Flight (MALDI-ToF) mass spectrometry to discriminate the effects of oxidative reagents. Data obtained from FTIR and MALDI spectra proved the lipoperoxide formation subsequent to reactive oxygen species attack and the opportunity to use the model to discriminate between oxidation toxicity.
The presence of heavy metals in the environment is a potential risk for the ecosystem due to their toxicity to plant, animals and human life. Lots of technologies and treatments have been developed to remove them from aqueous solutions, employing natural or synthetic sorbents. Among them, clay minerals have revealed interesting properties in soil remediation due to their natural occurrence, low toxicity, and low cost. Moreover, mechanochemical processes allow to activate chemical reactions by inducing different kinds of mechanical stress and without any other energy supply. In this study the effect of mechanochemical treatments on the ability of dioctahedral and trioctahedral smectites to “entrap” heavy metals is investigated. To this purpose a dioctahedral smectite “bentolite L” and a trioctahedral one “laponite RD” were ground with different distinct amounts of copper and cadmium chloride in dry conditions by means of zirconia planetary ball mill. Experimental tests were performed modifying the milling time and metal/clay minerals mass ratio, whereas grinding energy and ball to powder ratio were kept constant. The efficiency of the mechanochemical process to promote the interaction between smectites and heavy metals was evaluated by means of different analytical techniques: the immobilization degree was evaluated by ICP/OES analyses and expressed by the leachable fraction of metal ions. While the investigation on the main adsorption sites of the heavy metals on the ground surfaces was tested by means of solid-state measurements through the combined use of X-ray Fluorescence Spectroscopy, Fourier Transform Infrared Spectroscopy, X-ray Diffraction, Nuclear Magnetic Resonance and X-ray Photoelectron Spectroscopy.
Nowadays we have no doubt that surfaces exist, we recognize that their physicochemical properties are different from those of the bulk, we exploit this fact for a variety of fundamental studies and applications, and surface science is a mature and distinct discipline. It was not so in the past, when surfaces were a matter of lively debate among ancient philosophers. The thoughts of Plato, Aristotle, and Posidonius in favour or against the existence and definition of surfaces, and the historical excursus of the surface concept during the centuries has been well reviewed (Paparazzo E. (2003) Surfaces—lost and found, Nature 3:351–353). The claim of Wolfgang Pauli that the bulk of a bodywas created byGod while the devil invented the surface is further proof of the concern that scientists had and still have about surfaces. Perversely, the mixture of attraction and distrust surfaces exerted on researchers stimulated the development of instruments and strategies able to guarantee scientists full control of them. Once scientists became confident of dominating surface chemistry and physics, they went as far as issuing the challenge of fabricating and manipulating nano-sized materials, for which the surface effects are enormously amplified. Nowadays functionalization of nano-patterned or nanostructured surfaces and surface engineering approaches are mature technology and are formidable tools in a plethora of applications in different fields. In analytical chemistry, surface architecture is designed and developed mainly for use in applications in which selectivity is needed, e.g. separation science, recognition assays, capture/release of drugs, sensors. Several approaches are available for building a suitable molecular recognition interface, the choice being related to the principles of transduction, and the nature of the receptor and the analyte. Generally speaking, a crucial point is immobilization of the receptor, which can be accomplished by adsorption, physical entrapment, covalent binding, or use of a chemical and/or biochemical “capture system”. These approaches may take advantage of a variety of surfaceengineering techniques, for example self-assembly of monolayers (SAM), Langmuir–Blodgett (LB), Langmuir–Schafer (LS), layer by layer assembly (LBL), surface functionalization, molecular imprinting in polymers (MIP), nanoscale patterning, and chemical or physical vapour deposition. This issue covers a broad range of examples of surface architecture designed and realized mainly for fabrication of highly selective and highly sensitive sensing devices able to meet today’s challenges in analyte detection and discrimination. A series of reviews present the state of the art spanning from functionalization of nano-structured materials for DNA detection to construction of protein layered architecture for recognition of biomolecules; from viable cell immobilization to molecular template integration for detection of analytes of medical, toxicological, and environmental interest; from interlocked surface-attached architecture for ion recognition to the many configurations of active components in organic field-effect transistors for detection of organic and/or inorganic species of biological interest. Reviews critically discuss crucial issues which affect more or less all classes of sensors and in some cases still limit their performances and/or prevent their use in real life; important aspects of these are immobilization of the recognition element, which should preserve its chemical and/or biological functionality, and the integration between recognition element and transducer. Moreover, insights are provided on problems related to miniaturization, stability, reliability, and lowcost production, and future perspectives for each class of sensing device are emphasized. We thank the authors for their valuable and timely contribution
The ability to predict the in vivo performance of multiblock-copolymer-based biomaterials is crucial for their applicability in the biomedical field. In this work, XPS analysis of PCL-PEG copolymers was carried out, as well as morphological and wettability evaluations by SEM and CA measurements, respectively. XPS analysis on films equilibrated in PBS demonstrated a further enrichment in the PEG component on the surface. Copolymer films obtained by casting using different solvents showed a dependence in segregation according to the solvent employed. Cell adhesion tests demonstrated the importance of copolymer segregation and rearrangement in a wet environment, with a dependence of these phenomena on the copolymer molecular weight.
Biological agents play an important role in the deterioration of cultural heritage causing aesthetic, biogeophysical and biogeochemical damages. Conservation is based on the use of preventive and remedial methods. The former aims at inhibiting biological attack, and the latter aims at eradicating the biological agents responsible for biodeterioration. Here, we propose the preparation and the analytical characterisation of copper-based nanocoating, capable of acting both as a remedy and to prevent microbial proliferation. Core–shell CuNPs are mixed with a siliconbased product, commonly used as a water-repellent/consolidant, to obtain a combined bioactive system to be applied on stone substrates. The resulting coatings exert a marked biological activity over a long period of time due to the continuous and controlled release of copper ions acting as biocides. To the best of our knowledge, this is the first time that a multifunctional material is proposed, combining the antimicrobial properties of nanostructured coatings with those of the formulations applied to the restoration of stone artworks. A complete characterisation based on a multitechnique analytical approach is presented.
In this study, two different strategies for the synthesis of graphene are reported. In the first case, Oxidized Graphene Nanoribbons (GO) are obtained by the oxidative unzipping of Single-Wall Carbon Nanotubes (SWCNTs), as described in our previous work (1). Then, GO was dispersed in several different ILs and the resulting nano-dispersion were fully characterized, under a morphological and structural point of view (2). In particular, several studies performed by HR-TEM (High Resolution- Transmission Electron Microscopy), FT-IR (Fourier Transform-Infrared spectroscopy) and XPS (X-ray Photoelectron Spectroscopy), demonstrated that ILs were physically adsorbed on the GO surfaces, their edges and walls. The second approach concerns the electrochemical synthesis of graphene gels, covalently functionalized with ILs (3), by the etching of a graphite anode. Also in this case, HR-TEM, FT-IR and XPS analyses revealed interesting information on the interaction between ILs and GO. In particular, nitrogen XP spectra of functionalized GO presented a component ascribable to the coordination of N with electron-rich functionalities. This experimental evidence was observed in all the materials investigated, no matter the IL.
In this study for the first time the bulk chemical composition of Sicilian amber (simetite) was determined using pyrolysis-gas chromatography-mass spectrometry with thermally assisted hydrolysis and methylation (Py(THM)-GC-MS). The results evidenced that the polymer fraction of Sicilian amber is based on a polylabdanoid structure with an enantio configuration, mainly including ozic acid and biformene. In addition, numerous monocyclic and bicyclic terpene degradation products could be detected. At higher retention times several characteristic compounds were found. Very low amounts of succinic acid could be revealed. The chemical data allowed to classify simetite as a Class 1c resinite and to suggest a botanical origin from Fabaceae.
The detailed action mechanism of volatile general anesthetics is still unknown despite their effect has been clinically exploited for more than a century. Long ago it was also assessed that the potency of an anesthetic molecule well correlates with its lipophilicity and phospholipids were eventually identified as mediators. As yet,the direct effect of volatile anesthetics at physiological relevant concentrations on membranes is still under scrutiny. Organic field-effect transistors(OFETs)integrating a phospholipid (PL) functional biointer-layer(FBI)are here proposed for the electronic detection of archetypal volatile anesthetic molecules such as diethylether and halothane. This technology allows to directly interface a PL layer to an electronic transistor channel,and directly probe subtle changes occurring in the bio-layer. Repeatable responses of PLFBI-OFET to anesthetics are produced in a concentration range that reaches few percent,namely the clinically relevant regime. The PLFBI-OFET is also shown to deliver a comparably weaker response to a non-anesthetic volatile molecule such as acetone
Chitosan- and glycol-chitosan thiol conjugates have been developed, in order to realize nanocarriers which can be useful in the transmucosal drug delivery. The aim of the study is to compare the mucoadhesive properties of the two classes of conjugates. Indeed, the presence of thiol groups on the polymer surface is expected both to increase the interaction with the mucin and to promote the absorption of the delivered drugs. Glutathione and N-acetylcysteine have been chosen to synthesize new thiol-derivatives of glycol chitosan to be compared to the analogous chitosan derivatives (1) in terms of mucoadhesion properties. All the conjugates have been formulated as promising nanoparticles (NPs) for drug delivery. In the present contribution, x-ray photoelectron spectroscopy has been performed to analyze the surface chemical composition of both the synthesized polymers and the resulting NPs. The preliminary investigations showed the presence of sulphur on the NPs outer shell thus encouraging the eventual surface mucoadhesive properties of the nanocarriers. Further work is in progress to localize the in-depth distribution (2), once the nanocarriers have been loaded with a model drug.
Il progetto di ricerca propone il rafforzamento della conoscenza del patrimonio artistico finalizzato alla conservazione, valorizzazione e fruizione (turistica), azioni che richiedono lo sviluppo di materiali e metodi ad alto contenuto tecnologico e con caratteristiche di sostenibilità ed eco-compatibilità.Il risultato atteso è una significativa implementazione della conoscenza dei meccanismi di degrado dei sistemi pittorici di manufatti policromi, che permetterà di delineare modelli predittivi per la valutazione della stabilità chimico-fisica nel tempo. I risultati saranno propedeutici alla pianificazione di interventi efficaci, tempestivi e, nello stesso tempo, eco-sostenibili e compatibili. Difatti, lo sviluppo di metodi di conservazione innovativi (nanotecnologie, laser, ...) e basati sulla green chemistry (enzimi, sistemi acquosi, ...) non può prescindere da queste conoscenze. Inoltre, la comprensione dell'influenza dei parametri ambientali e delle condizioni museali sulle trasformazioni chimiche che causano il degrado degli oggetti artistici costituisce un prezioso contributo alla possibilità di rallentare questi processi mediante il controllo delle condizioni ambientali e di conservazione. I risultati della ricerca saranno quindi sfruttabili ai fini di orientare sempre di più le strategie conservative verso una filosofia di conservazione preventiva, più sostenibile dal punto di vista dei costi e dei rischi rispetto a interventi di restauro spesso invasivi e costosi.
Transistore comprendente almeno uno strato conduttivo (4), almeno uno strato dielettrico di gate (3) e almeno un film semiconduttore (1) depositato su uno strato di molecola recettore (2) precedentemente depositato o collegato in modo covalente alla superficie del gate dielettrico (3). Detto strato di materiale biologico è costituito da strati singoli o doppi di fosfolipidi, strati costituiti da proteine quali recettori, anticorpi, canali ionici ed enzimi, singoli o doppi strati di fosfolipidi con inclusione o ancoraggio di proteine quali: recettori, anticorpi, ionici canali ed enzimi, strati fatti di sonde oligonucleotidiche (DNA, RNA, PNA), strati fatti di cellule o virus, strati fatti di recettori sintetici per esempio molecole o macromolecole simili ai recettori biologici per proprietà, reattività o aspetti sterici.
Nanoparticles having a core formed of a metal selected from Ag, Cu, Sn and Zn and a shell formed of a plurality of molecules of quaternary ammonium compounds NR 1 R 2 R 3 R 4 + X - , where X is selected from Cl, Br and I and where NR 1 R 2 R 3 R 4 + is a quaternary ammonium compound wherein at least one R is different from the others and is an alkyl chain, linear or functionalised or provided with branches or aromatic lateral groups with length preferably between 8 and 18 atoms of carbon.
In nanoparticles having formula (Me)(NR 4 + X - ) n wherein Me is the metal core selected from Ag, Cu, Sn and Zn; (NR 4 + X - ) is the shell, where X is selected from Cl, Br and I, and R is an alkyl chain C 4 -C 12 , the length of the alkyl chain is chosen to control the release speed of metal ions from the core; several types of nanoparticles all with equal chains in the same particle can form a composition for antimicrobial applications to fabrics and the like.
Transistor comprising at least one conductive layer (4), at least one gate dielectric layer (3) and at least one semiconducting film (1) deposited on top of a receptor molecule layer (2) previously deposited or covalently linked to the surface of the gate dielectric (3). Said layer of biological material is constituted by single or double layers of phospholipids, layers made of proteins such as receptors, antibodies, ionic channels and enzymes, single or double layers of phospholipids with inclusion or anchoring of proteins such as: receptors, antibodies, ionic channels and enzymes, layers made of oligonucleotide (DNA, RNA, PNA) probes, layers made of cells or viruses, layers made of synthetic receptors for example molecules or macromolecules similar to biological receptors for properties, reactivity or steric aspects.
Transistor comprising at least one conductive layer, at least one dielectric layer and at least one thin organic semiconductor film and characterized by at least one layer of biological material deposited directly on the surface of the dielectric. Said layer of biological material is constituted by single or double layers of phospholipids, layers made of proteins such as receptors, antibodies, ionic channels and enzymes, single or double layers of phospholipids with inclusion or anchoring of proteins such as: receptors, antibodies, ionic channels and enzymes, layers made of oligonucleotide (DNA, RNA, PNA) probes, layers made of cells or viruses, layers made of synthetic receptors for example molecules or macromolecules similar to biological receptors for properties, reactivity or steric aspects.
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