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In recent years, titanium(iv) dioxide nanoparticles (TiO2NPs) have shown promising potential in various biological applications such as antimicrobials, drug delivery, photodynamic therapy, biosensors, and tissue engineering.

Low-energy electrons (Auger electrons) can be produced via the interaction of photons with gold atoms in gold nanorods (AuNRs). These electrons are similar to those emitted during the decay of technetium-99m (99mTc), a radioactive nuclide widely used for diagnostics in nuclear medicine. Auger and internal conversion (IC) electron emitters appropriately targeted to the DNA of tumors cells may, therefore, represent a new radiotherapeutic approach. 99mTc radiopharmaceuticals, which are used for diagnosis, could indeed be used in theragnostic fields when loaded on AuNRs and delivered to a tumor site. This work aims to provide a proof of concept (i) to evaluate AuNRs as carriers of 99mTc-based radiopharmaceuticals, and (ii) to evaluate the efficacy of Auger electrons emitted by photon-irradiated AuNRs in inducing radio-induced damage in T98G cells, thus mimicking the effect of Auger electrons emitted during the decay of 99mTc used in clinical settings. Data are presented on AuNRs’ chemical characterization (with an aspect ratio of 3.2 and Surface Plasmon Resonance bands at 520 and 680 nm) and the loading of pharmaceuticals (after 99mTc decay) on their surface. Spectroscopic characterizations, such as UV-Vis and synchrotron radiation-induced X-ray photoelectron (SR-XPS) spectroscopies, were performed to investigate the drug–AuNR interaction. Finally, preliminary radiobiological data on cell killing with AuNRs are presented.

od-like organometallic dithiol containing square-planar Pt(II) centers, i. e., trans,trans- [(H3COCS)Pt(PBu3)2(C�C C6H4 C6H4 C�C)(PBu3)2Pt(SCOCH3)] was used as bifunctional stabilizing agent for the synthesis of Pd-, Au-, and AgNPs (MNPs). All the MNPs showed diameters of about 4 nm, which can be controlled by carefully modulating the synthesis parameters. Covalent MNPs stabilization occurred through a single S bridge between Pt(II) and the noble metal nanocluster surfaces, leading to a network of regularly spaced NPs with the formation of dyads, as supported by SR-XPS data and by TEM imaging analysis. The chemical nature of NPs systems was also confirmed by EDS and NMR. Comparison between SR-XPS data of MNPs and self-assembled monolayers and multilayers of pristine rod-like dithiols deposited onto polycrystalline gold surfaces revealed an electronic interaction between Pt(II) centers and biphenyl moieties of adjacent ligands, stabilizing the organic structure of the network. The possibility to obtain networks of regularly spaced MNPs opens outstanding perspectives in optoelectronics.

Background:: Nimotuzumab is a humanized anti-epidermal growth factor receptor (EGFR) monoclonal antibody, nowadays used for tumour immunochemotherapy. This study aimed to label the conjugate DOTA-nimotuzumab with yttrium-90, in order to provide a β- emitting radioimmunoconjugate (90Y-DOTA-nimotuzumab) potentially useful to assess the feasibility of a new radio-guided surgery approach. Methods:: The synthesis of 90Y-DOTA-nimotuzumab was performed in two days. Nimotuzumab was conjugated with a 50 fold excess of DOTA and then labelled with 90Y3+. The 90Y-DOTA-nimotuzumab preparation was optimized considering several parameters such as pH, temperature and reaction volume. Moreover, the 90Y-DOTA-nimotuzumab stability was evaluated in human plasma. Results:: The radioimmunoconjugate 90Y-DOTA-nimotuzumab was obtained with a radiochemical purity greater than 96%, and showed a good stability at 20°C as well as at 37°C in human plasma. Conclusions:: The optimized conditions for a mild and easy preparation of 90Y-DOTA-nimotuzumab joined to a promising stability under physiological conditions suggest to propose this radioimmunoconjugate as a potential diagnostic radiopharmaceutical for β- radio-guided surgery.

The recognized antibacterial properties of silver nanoparticles (AgNPs) characterize them as attractive nanomaterials for developing new bioactive materials less prone to the development of antibiotic resistance. In this work, we developed new composites based on self-assembling Fmoc-Phe3 peptide hydrogels impregnated with in situ prepared AgNPs. Different methodologies, from traditional to innovative and eco-sustainable, were compared. The obtained composites were characterized from a hydrodynamic, structural, and morphological point of view, using different techniques such as DLS, SEM, and rheological measurements to evaluate how the choice of the reducing agent determines the characteristics of AgNPs and how their presence within the hydrogel affects their structure and properties. Moreover, the antibacterial properties of these composites were tested against S. aureus, a major human pathogen responsible for a wide range of clinical infections. Results demonstrated that the hydrogel composites containing AgNPs (hgel@AgNPs) could represent promising biomaterials for treating S. aureus-related infections.

The preparation of three different functionalized PdNPs systems for room temperature BTX sensing detection and their morphostructural characterization is described. PdNPs are prepared through two-phase water/toluene wet chemical reduction method in the presence of bifunctional organic thiols as stabilizing agents suitable for the formation of covalently linked PdNPs networks: p-terphenyl-4,4”-dithiol (PdNPs-TR), biphenyl-4,4’-dithiol (PdNPs-BP), or with 9,9-didodecyl-2,7-bis(acetylthio)fluorene (PdNPs-FL). Comparing the hydrodynamic diameter values, TR and BP ligands allow to obtain networks consisting of spherical NPs of about 2 nm, in which each bifunctional ligand act as a bridge between PdNPs. In contrast, PdNPs-FL show a population centered at = 45 ± 5 nm. To perform preliminary gas sensing measurements, PdNPs networks are cast deposited on interdigitated electrodes to study their resistive response towards volatile organic compounds (VOCs) such as benzene (0-5%), toluene (0-1.7%), and p-xylene (0-0.4%) (BTX) and common interfering gases (H2S, NH3, SO2, and relative humidity, RH). PdNPs-FL show enhanced response to BTX with an appreciable response also toward H2S and RH. PdNPs-TR exhibit better ability to discriminate benzene gas with negligible response after H2S exposure. Moreover, all the PdNPs systems show little to no response to NH3 and SO2 gases, offering an interesting perspective in practical sensing applications.

Peptide-based hydrogels have attracted increasing attention for biological applications and diagnostic research due to their impressive features including biocompatibility and biodegradability, injectability, mechanical stability, high water absorption capacity, and tissue-like elasticity. The aim of this review will be to present an updated report on the advancement of peptide-based hydrogels research activity in recent years in the field of anticancer drug delivery, antimicrobial and wound healing materials, 3D bioprinting and tissue engineering, and vaccines. Additionally, the biosensing applications of this key group of hydrogels will be discussed mainly focusing the attention on cancer detection.

Gold nanoparticles (AuNPs) modified with four organoselenium compounds, i.e., 4-selenocyanatoaniline (compound 1), 4,4'-diselanediyldianiline (compound 2), N-(4-selenocyanatophenyl)cinnamamide (compound 3), and N-(3-selenocyanatopropyl)cinnamamide (compound 4), were synthesized following two different approaches: direct conjugation and non-covalent immobilization onto hydrophilic and non-cytotoxic AuNPs functionalized with 3-mercapto-1-propanesulfonate (3MPS). Both free compounds and AuNPs-based systems were characterized via UV-Vis, FTIR NMR, mass spectrometry, and SR-XPS to assess their optical and structural properties. Size and colloidal stability were evaluated by DLS and ζ-potential measurements, whereas morphology at solid-state was evaluated by atomic force (AFM) and scanning electron (FESEM) microscopies. AuNPs synthesized through chemical reduction method in presence of Se-based compounds as functionalizing agents allowed the formation of aggregated NPs with little to no solubility in aqueous media. To improve their hydrophilicity and stability mixed AuNPs-3MPS-1 were synthesized. Besides, Se-loaded AuNPs-3MPS revealed to be the most suitable systems for biological studies in terms of size and colloidal stability. Selenium derivatives and AuNPs were tested in vitro via MTT assay against PC-3 (prostatic adenocarcinoma) and HCT-116 (colorectal carcinoma) cell lines. Compared to free compounds, direct functionalization onto AuNPs with formation of Au-Se covalent bond led to non-cytotoxic systems in the concentration range explored (0-100 μg/mL), whereas immobilization on AuNPs-3MPS improved the cytotoxicity of compounds 1, 3, and 4. Selective anticancer response against HCT-116 cells was obtained by AuNPs-3MPS-1. These results demonstrated that AuNPs can be used as a platform to tune the in vitro biological activity of organoselenium compounds.

In this work, the electronic and molecular structure, as well as the morphology, of innovative nanostructured materials whose optical properties respond to the presence of heavy metals in water samples was investigated. In particular, the here discussed silver nanoparticles (NPs) stabilized by a hydrophilic ligand (sodium 3-mercapto-1-propanesulfonate, 3MPS) are able to reveal the presence of mercury ions at ppm levels. The sensitivity of the proposed nanosensor to Hg(II) in 1-5 ppm range was ascertained by optical tests; then, the local chemistry and electronic structure of the nanostructured coordination compounds made of functionalized silver nanoparticles (NPs) and metal ions, and their correlation with the resulting nanoaggregates' shape and morphology, were investigated by state-of-the-art synchrotron radiation (SR)-induced spectroscopies and transmission electron microscopy (TEM). In particular, SR-induced X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements allowed us to gather complementary information about the silver-mercury interaction, which is only partially mediated by the negatively charged 3MPS ligand, different from what was observed for analogous nanosensors applied to other bivalent heavy metal ions, for example, Co(II) and Ni(II). TEM morphological analysis sheds light on the structure of the AgNP-3MPS/Hg aggregates, revealing the formation of Ag/Hg alloy nanoparticles.

Phase-transition materials provide exciting opportunities for controlling optical properties of photonic devices dynamically. Here, we systematically investigate the infrared emission from a thin film of vanadium dioxide (VO2). We experimentally demonstrate that such thin films are promising candidates to tune and control the thermal radiation of an underlying hot body with different emissivity features. In particular, we studied two different heat sources with completely different emissivity features, i.e. a black body-like and a mirror-like heated body. The infrared emission characteristics were investigated in the 3.5–5.1 μm spectral range using the infrared thermography technique which included heating the sample, and then cooling back. Experimental results were theoretically analyzed by modelling the VO2 film as a metamaterial for a temperature range close to its critical temperature. Our systematic study reveals that VO2 thin films with just one layer 80 nm thick has the potential to develop completely different dynamic tuning of infrared radiation, enabling both black-body emission suppression and as well as mirror emissivity boosting, in the same single layer device. Understanding the dynamics and effects of thermal tuning on infrared emission will benefit wide range of infrared technologies including thermal emitters, sensors, active IR filters and detectors.

Made available in DSpace on 2020-12-12T01:27:22Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-08-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) A switching memory device based on functionalized gold nanoparticles (AuNPs) and hexagonal copper sulfide nanocrystals (CuS), finely blended in polymethylmethacrylate matrix (PMMA), is herein presented. A two-electrode sandwich architecture has been implemented using aluminum top and bottom electrodes and a polymeric insulating layer based on PMMA/AuNPs/CuS. The device showed memory storage capabilities suitable for (Read Only Memory) ROM applications and behaves as a typical Write-Once, Read-Many-times (WORM) device. The results obtained with the blend containing AuNPs and/or CuS were compared with pure PMMA. By a voltage ramp in the range ± 9 V, it was possible to permanently change the electrical resistance between the electrodes yielding an ON/OFF current ratio above 105 with long-term stability over the whole experiment duration (30 days). Department of Chemistry University of Rome Sapienza, P.le A. Moro 5 POSMAT – Post-Graduate Program in Materials Science and Technology School of Sciences UNESP – São Paulo State University Department of Physics School of Sciences UNESP – São Paulo State University POSMAT – Post-Graduate Program in Materials Science and Technology School of Sciences UNESP – São Paulo State University Department of Physics School of Sciences UNESP – São Paulo State University CAPES: 024/2012 FAPESP: 2013/07396-7 FAPESP: 2016/17302-8 FAPESP: 2017/20809-0

The possibility to use β− decaying isotopes for radioguided surgery (RGS) has been recently proposed, and first promising tests on ex-vivo samples of Meningioma and intestinal Neuroendocrine Tumor (NET) have been published. This paper reports a study of the uptake of 68Ga-DOTATOC in pancreatic NETs (pNETs) in order to assess the feasibility of a new RGS approach using 90Y-DOTATOC. Tumor and healthy pancreas uptakes were estimated from 68Ga-DOTATOC PET/CT scans of 30 patients with pNETs. From the obtained SUVs (Standardised Uptake Value) and TNRs (Tumor Non tumor Ratio), an analysis algorithm relying on a Monte Carlo simulation of the detector has been applied to evaluate the performances of the proposed technique. Almost all considered patients resulted to be compatible with the application of β−-RGS assuming to administer 1.5 MBq/kg of activity of 90Y-DOTATOC 24 h before surgery, and a sampling time of few seconds. In just 2 cases the technique would have required a mildly increased amount of activity or of sampling time. Despite a high physiological uptake of 68Ga-DOTATOC in the healthy pancreas, the proposed RGS technique promises to be effective. This approach allows RGS to find application also in pancreatic diseases, where traditional techniques are not viable.

Gold nanoparticles functionalized with 3-mercapto-1-propansulfonate (AuNPs-3MPS) have been prepared and loaded with Methotrexate (MTX), an immunosuppressive agent used in the systemic treatment of moderate-severe inflammatory diseases. The effects of the AuNPs-3MPS@MTX topically administered in vitro on skin model and in vivo on imiquimod-induced psoriasis-like mice model, have been studied. Clinical response, epidermal thickness, cell proliferation rate and inflammation were tested. AuNPs-3MPS@MTX treated mice showed a decreasing of scaling and erythema score, reduction of epidermal thickness, parakeratosis and hyperkeratosis, compared to AuNPs-3MPS treated mice. Immunohistochemistry analysis staining displayed that Ki67, K6 CD3 and CD8 stainings were reduced in AuNPs-3MPS@MTX treated mice. Blood evaluation showed no differences in blood count and in ALT and AST levels before and after AuNPs-3MPS or AuNPs-3MPS@MTX treatment. Topical AuNPs-3MPS@MTX treatment is able to induce a reduction of keratinocytes hyperproliferation, epidermal thickness and also inflammatory infiltrate in vivo on imiquimod-induced psoriasis like mice model.

Photoacoustic signal detection has been used to build a new strategy to determine the mesoscale self-assembly of metal nanoparticles in terms of size distribution and aggregate packing density (metal nanoparticle filling factor). A synergistic approach integrating photoacoustic signal and theoretical studies, validated by conventional light scattering and electron microscopy techniques, allows us to obtain a well-defined morphological interpretation of nanoparticle-based super-aggregates. By pumping light in a complex system, the acousto-thermal effect was listened to, providing information on the aggregation phenomena. Super-aggregates of covalently interconnected silver nanoparticles (AgNPs) functionalized with an organometallic dithiol are identified in solution, as a proof of concept for the versatility of the photoacoustic approach. According to our results, tiny AgNPs (size less than 10 nm) assembled into a 3D-network of super-aggregates (SA-AgNPs) with sizes in the range 100–200 nm and a filling factor in the range of 30–50%. Low-cost, rapid, and easy photoacoustic measurement in the low frequency range (less than 100 Hz) was revealed to be an innovative method to characterize the fundamental structure/property correlation of metal nanoparticle super-aggregates. This morpho-optical approach, which uses the absorption and scattering properties of nanoparticles in the liquid phase, opens new perspectives for advanced biomedical and structural applications.

This paper presents the synthesis of silver nanoparticles (AgNPs) functionalized with fluorescent molecules, in particular with xanthene-based dyes, i.e., fluorescein isothiocyanate (FITC, λmax = 485 nm) and rhodamine B isothiocyanate (RITC, λmax = 555 nm). An in-depth characterization of the particle–dye systems, i.e., AgNPs–RITC and AgNPs–FITC, is presented to evaluate their chemical structure and optical properties due to the interaction between their plasmonic and absorption properties. UV–Vis spectroscopy and the dynamic light scattering (DLS) measurements confirmed the nanosize of the AgNPs–RITC and AgNPs–FITC. Synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS) was used to study the chemical surface functionalization by structural characterization, confirming/examining the isothiocyanate–metal interaction. For AgNPs–RITC, in which the plasmonic and fluorescence peak are not superimposed, the transient dynamics of the dye fluorescence were also studied. Transient absorption measurements showed that by exciting the AgNPs–RITC sample at a wavelength corresponding to the AgNP plasmon resonance, it was possible to preferentially excite the RITC dye molecules attached to the surface of the NPs with respect to the free dye molecules in the solution. These results demonstrate how, by combining plasmonics and fluorescence, these AgNPs can be used as promising systems in biosensing and imaging applications.

Starting from the 2000s, the use of magnetic nanoparticles (MNPs) has begun to find a place in the studies of analyte extraction. Within this framework, the synergic collaboration in analytical chemistry and material sciences has developed several methods for the efficient and rapid extraction of analytes, especially in complex matrices. The main application of MNPs in the extraction step is in the environmental field for example in river water, lake water or industrial discharge samples. Other applications have been found in food and biological analysis, such as for urine or blood samples. In this chapter the use of metal nanoparticles for analyte extraction, and the areas of application, i.e., food, environment, and health, are explored. Moreover, the limits of these new methodologies, the new opportunities that are offered and the challenges of these techniques are highlighted.

Nanomaterials such as gold nanoparticles employed as solid-state sensors have attracted attention in recent years due to their ability to detect poisonous elements in the indoor/outdoor environment. Herein, chemoresistive sensors based on gold nanoparticles (AuNPs) functionalized with mixed thiol ligands were tested as sensing materials. Specifically, the electrical response of gold nanoparticles-based sensors was tested against Hg0vap, H2S, SO2, NH3, and relative humidity (RH) at room temperature. Gold nanoparticles samples were synthesized by the wet reduction method and then deposited as thin films on suitable interdigitated transducers. Electrical conductivity measurements allowed evaluating a semiconducting behavior of the colloids. A selective and reproducible sensing behavior toward Hg0vap was observed in the range 0.1-1.0 ng/mL, allowing simple and reliable resistive devices to be obtained. An irreversible interaction mechanism, based on formation of an Au-Hg direct bond, was observed in the case of isolated AuNPs samples. Interconnected AuNPs exhibited a reversible behavior as assessed by Micro Raman, XRD, XPS, AFM, SEM, and UV-vis and FTIR spectroscopies together with DLS measurements. Broadening of the plasmonic band and an increase in the mean particle size upon contact with Hg0vap was observed. Morphological characterization revealed the formation of aggregates after interaction between Hg0vap and AuNPs. XRD and Micro Raman measurements collected on the nonexposed and Hg-exposed nanoparticles suggest their structural rearrangement at the surface and formation of an Au-Hg alloy with Hg mechanically trapped within the bulk material. The simple and cost-effective fabrication of these sensors has prospect in the future as nanodevices for real-time outdoor air quality monitoring.

In the last years, intense efforts have been made in order to obtain colloidal-based systems capable of pointing out the presence of melamine in food samples. In this work, we reported about the recognition of melamine in aqueous solution, using gold nanoparticles stabilized with 3-mercapto-1-propanesulfonate (AuNPs-3MPS), with the aim of deepening how the recognition process works. AuNPs were synthesized using a wet chemical reduction method. The synthesized AuNPs-3MPS probe was fully characterized, before and after the recognition process, by both physicochemical (UV–vis, FT-IR, 1H-NMR, DLS and ζ-potential) and morphostructural techniques (AFM, HR-TEM). The chemical and electronic structure was also investigated by SR-XPS. The sensing method is based on the melamine-induced aggregation of AuNPs; the presence of melamine was successfully detected in the range of 2.5−500 ppm. The results achieved also demonstrate that negatively charged AuNPs-3MPS are potentially useful for determining melamine contents in aqueous solution. SR-XPS measurements allowed to understand interaction mechanism between the probe and the analyte. The presence of sulfonate groups allows a mutual interaction mediated by electrostatic bonds between nanoparticles surface thiols and positively charged amino groups of melamine molecules.

Introduction The pathogenic mechanism underlying capsular contracture is still unknown. It is certainly a multifactorial process, resulting from human body reaction, biofilm activation, bacteremic seeding, or silicone exposure. The scope of the present article is to investigate the effect of hypofractionated radiotherapy protocol (2.66 Gy × 16 sessions) both on silicone and polyurethane breast implants. Methods Silicone implants and polyurethane underwent irradiation according to a hypofractionated radiotherapy protocol for the treatment of breast cancer. After irradiation implant shells underwent mechanical, chemical, and microstructural evaluation by means of tensile testing, infrared spectra in attenuated total reflectance mode, nuclear magnetic resonance, and field emission scanning electron microscopy. Results At superficial analysis, irradiated silicone samples show several visible secondary and tertiary blebs. Polyurethane implants showed an open cell structure, which closely resembles a sponge. Morphological observation of struts from treated polyurethane sample shows a more compact structure, with significantly shorter and thicker struts compared with untreated sample. The infrared spectra in attenuated total reflectance mode spectra of irradiated and control samples were compared either for silicon and polyurethane samples. In the case of silicone-based membranes, treated and control specimens showed similar bands, with little differences in the treated one. Nuclear magnetic resonance spectra on the fraction soluble in CDCl3 support these observations. Tensile tests on silicone samples showed a softer behavior of the treated ones. Tensile tests on Polyurethane samples showed no significant differences. Conclusions Polyurethane implants seem to be more resistant to radiotherapy damage, whereas silicone prosthesis showed more structural, mechanical, and chemical modifications.

Strongly hydrophilic gold nanoparticles (AuNPs), functionalized with citrate and L-cysteine, were synthetized and used as Resveratrol (RSV) vehicle to improve its bioavailability. Two different conjugation procedures were investigated: the first by adding RSV during AuNPs synthesis (1) and the second by adding RSV after AuNPs synthesis (2). The two different conjugated systems, namely AuNPs@RSV1 and AuNPs@RSV2 respectively, showed good loading efficiency (&eta, %): &eta, 1 = 80 &plusmn, 5% for AuNPs@RSV1 and &eta, 2 = 20 &plusmn, 3% for AuNPs@RSV2. Both conjugated systems were investigated by means of Dynamic Light Scattering (DLS), confirming hydrophilic behavior and nanodimension (&lt, 2RH&gt, 1 = 45 &plusmn, 12 nm and &lt, 2 = 170 &plusmn, 30 nm). Fourier Transform Infrared Spectroscopy (FT-IR), Synchrotron Radiation induced X-Ray Photoelectron Spectroscopy (SR-XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) techniques were applied to deeply understand the hooking mode of RSV on AuNPs surface in the two differently conjugated systems. Moreover, the biocompatibility of AuNPs and AuNPs@RSV1 was evaluated in the concentration range 1.0&ndash, 45.5 &micro, g/mL by assessing their effect on breast cancer cell vitality. The obtained data confirmed that, at the concentration used, AuNPs do not induce cell death, whereas AuNPs@RSV1 maintains the same anticancer effects as the unconjugated RSV.

Gold nanoparticles (AuNPs) are promising carriers in the field of nanomedicine and represent a very intriguing approach in drug delivery applications, due to their small size and enhanced properties. This work aims to highlight the interaction between functionalized AuNPs and the immune-system suppressant drug Methotrexate (MTX) at molecular level. Small and monodisperse ( 5 ± 1 nm) gold nanoparticles were prepared by a simple chemical route using hydrophilic thiol 3-mercapto-1-propanesulfonate (3MPS) as a functionalizing/capping agent and act as a platform for post-synthesis conjugation of MTX via non-covalent interaction. The AuNPs-3MPS@MTX bioconjugate and the AuNPs alone were characterized to investigate their optical, chemical, and morphological properties. Moreover, NMR, AFM, SAXS, HR-TEM and SR-XPS data confirmed the spherical shape of AuNPs and allowed to determine the mechanisms behind such drug-nanoparticle physicochemical interactions. These analyses define the overall structure of drug-loaded AuNPs-3MPS and drug location on the colloidal nanoparticles surface. Based on the experimental data, it is notable to assert that MTX was successfully loaded on the negatively charged nanoparticles surface via electrostatic interactions. The physicochemical behavior leads to the formation of large clusters with close packed arrangement of AuNPs-3MPS@MTX. This self-assembling property is of importance for delivery purpose affecting the drug-loaded nanoparticle size, functionality, and morphology. Knowledge of how these systems behave will aid in increasing drug efficacy and in understanding the pharmacodynamics and pharmacokinetic properties, opening to new physicochemical insight for therapy and drug delivery systems.

Olive Mill WasteWater (OMWW) is an important by-product of the Olive Oil production. Its high concentration in Phenolic Compounds (PC) gives OMWW antimicrobial and phytotoxic properties. The aim of this work is to develop a rapid, simple and sustainable method based on the use of gold nanoparticles (AuNPs) chosen to extract PC from OMWW. AuNPs can be used taking advantage of their unique surface properties and high surface/volume ratio. They also offer high stability, easy chemical synthesis and use of water or eco-friendly solvents for their synthesis procedures. Two different stabilizing layers were used on the AuNPs surface: Cysteamine hydrochloride (Cys), and 4,4’’- dithiolterphenyl (TR) obtaining AuNPs-Cys and AuNPs-TR, respectively. The extraction with AuNPs-Cys achieved 70% of the PC present in OMWW, allowing to make the by-product available for land fertilization and giving the possibility to use PC for other aims, as nutraceutical, active packaging, cosmetic or pharmaceutical.

The bifunctional hybrid thioester ligands containing square planar Pt(II) centers 2,7-bis[2-(trans-acetylthio-bis-(tributylphosphine)platinumII)ethynyl]-9,9-didodecyl-9H-fluorene (1) and trans-4,4′-bis[2-(trans-acetylthio-bis-(tributylphosphine)platinumII)ethynyl]stilbene (2) have been prepared in a four-step procedure and used as stabilizing and interconnecting ligands for gold and silver nanoparticles (MNPs), formed in-situ upon deacylation of the MeCOS-Pt(II)-terminal groups. The metallic surface is linked to the Pt(II) centers of the ligands via M-S-Pt(II) bridges. The size of the AuNPs and AgNPs which aggregate into a bi-dimensional network through hybrid metal-organic bridges was controlled by careful choice of synthetic parameters. The morpho-structural features of the nanoparticles, investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and synchrotron radiation induced X-ray photoelectron spectroscopy (SR-XPS), highlighted the linkage between the nanoparticles, featuring diameters below 10 nm.

In this study, two new hexyl bis(pyrazol-1-yl)acetate ligands and related copper(ii) complexes were prepared and fully characterized in the solid state and in solution. Their electronic and molecular structures were investigated by X-ray photoelectron spectroscopy and near edge X-ray absorption; their ligand molecular structural stability upon coordination to copper was also investigated. The Cu(ii) complexes were studied as new catalysts in copper-catalyzed C-H oxidation for allylic functionalization (the Kharasch-Sosnovsky reaction) avoiding the use of any external reducing agents. Using 5 mol% of these catalysts and tert-butylperoxybenzoate as the oxidant, allylic benzoates were obtained in up to 90% yield: the general reaction time was decreased to 6 h and a 5 to 1 ratio of the alkene and tert-butylperoxybenzoate was used to overcome the two most important limitations on their use in chemistry.

Enzyme immobilization on nanocarriers is nowadays considered a useful tool for improving activity and maintaining biocatalysts stability while facilitating their recovery and reuse. In this work we prepared Au and Ag based nanoparticles (AuNPs or AgNPs) stabilized with two different ligands, the organometallic dinuclear complex trans,trans-[dithiodibis(tributylphosphine)diplatinum(II)-4,4′-diethynylbiphenyl] (Pt-DEBP) and the organic dithiol 4,4′-dithiol-biphenyl (BI), able to link the NPs in 3D networks. We investigated the ability of these nanocarriers to interact with a model lipolytic enzyme from Pseudomonas fluorescens and maintain its activity, both in aqueous as well as in organic media. In particular, our results highlighted that the nature of the metal plays a role in enzyme adsorption, while enzyme activity is mostly influenced by the chemistry of the organic spacer. The obtained bioconjugate, between lipase and the most promising carrier, AgNPs-Pt-DEBP, was stable in a wide temperature range (25–55 °C) and it showed good activity retention both in aqueous (50%) as well as in organic media (75%), compared to the lipase used in soluble form.

Adsorption and detection of environmental total gaseous mercury (TGM) was studied by using gold nanoparticles (AuNPs) on purpose functionalized with dithiol ligands, i.e. Biphenyl-4,4′-dithiol (BI) or p-Terphenyl-4,4′′-dithiol (TR), suitable for nanoparticles based network formation. AuNPs-BI and AuNPs-TR with size 6–8 nm were deposited onto quartz fibres and used as adsorbent materials for the detection of TGM, both indoor for adsorption studies, at defined concentrations (∼4.5 ng m−3 Hg), and outdoor, at the vapour mercury concentration of the environmental countryside (∼1.5 ng m−3 Hg). The role of relative humidity (RH) in the absorption process has been observed. A high Hg adsorption capability, also when exposed to sub ppb concentration, has been observed. A cold vapour atomic fluorescence spectroscopy (CVAFS) detector was used to determine gaseous mercury concentrations lower than 2 ng m−3, with a robust and reproducible procedure. Moreover, the use of quartz fibres substrate covered with AuNPs-BI or AuNPs-TR, and used for more than thirty times during the experiments, makes them competitive in the use in large-scale measurement campaigns.

In this work commercially available bifunctional organic dithiols, 4,4′-dithiol-biphenyl (BI), 4,4′-dithiolterphenyl (TR) and the on purpose prepared precursor of 4,4′-dithiol- trans -stilbene (ST), have been used for the stabilization of gold and silver nanoparticles (AuNPs and AgNPs). The bifunctional thiols have been chosen with different conjugation length, to prepare interconnected system of nanoparticles in order to achieve a tuning of their optical properties. The obtained AuNPs and AgNPs have been characterized by means of UV–vis spectroscopy to investigate the presence and shift of the Surface Plasmon Resonance (SPR); Field Effect Scanning Electron Microscopy (FESEM) allowed to achieve information on the NP’s morphology and size. Furthermore, the X-ray Photoelectron spectroscopy (XPS) measurements have been carried out to obtain structural information. AuNPs and AgNPs with mean size in the range 5–20 nm appeared at regular distances in FESEM images and XPS analysis revealed the presence of physisorbed and chemisorbed thiols. In particular AgNPs showed a lower quantity of physisorbed thiol and an higher tendency to form interconnected networks, also suggested by UV–vis data, with a strong red shift of the SPR band up to 550 nm. ST dithiol showed high tendency in the formation either of AuNPs and AgNPs networks as highlight by the pronounced redshift of the Surface Plasmon Resonance absorption wavelength as revealed by XPS characterization, where no physisorbed thiol was observed, indicating that all the sulphur atoms are involved in the functionalization of the nanoparticles metal surface.

Functionalized gold and silver nanoparticles have been prepared and characterized by means of spectroscopic and morphological techniques together focused on electrical measurements on cast deposited films. The Au and Ag nanoparticles have been functionalized with a on purpose prepared conjugated dithiol, 9,9-didodecyl-2,7-bis-thiofluorene (FL), giving rise to organic solvents soluble AuNPs-FL and AgNPs-FL samples, respectively. In the case of AuNPs-FL, well separated nanoparticles, with an average size of about 4 nm, assembled into bidimensionally monolayer network and with regular spatial distributions have been observed by TEM. Synchrotron radiation-XPS data support the observed network formation, showing that all bifunctional ligands end-groups are covalently bonded to metal noble atoms at the nanoparticles surfaces. In order to investigate their interesting conduction properties, electrical measurements evidenced a non-ohmic behavior in the case of the AuNPs-FL thin film, with a conduction mechanism that strongly depends on polarons and bipolarons along the carbon active chain belonging to the fluorene bridge. By increasing the stacked layers of the AuNPs-FL thin film, the conductivity behavior changed following approximately the ohmic law. On the contrary, AgNPs-FL shows higher conductivity, and upon an aging process, a diode behavior was observed that opens perspectives as flexible optoelectronics devices.