Photochemical synthesis, characterization, and electrochemical sensing properties of CD-AuNP nanohybrids.

Among the existing nanosystems used in electrochemical sensing, gold nanoparticles (AuNPs) have attracted considerable attention owing to their intriguing chemical and physical properties such as good electrical conductivity, high electrocatalytic activity, and high surface-to-volume ratio. However, despite these useful characteristics, there are some issues due to their instability in solution that can give rise to aggregation phenomena and the use of hazardous chemicals in the most common synthetic procedures. With an aim to find a solution to these issues, recently, we prepared and characterized carbon dots (CDs), from olive solid wastes, and employed them as reducing and capping agents in photo-activated AuNP synthesis, thus creating CD-Au nanohybrids. These nanomaterials appear extremely stable in aqueous solutions at room temperature, are contemporary, and have been obtained using CDs, which are exclusively based on non-toxic elements, with an additional advantage of being generated from an otherwise waste material. In this paper, the synthesis and characterization of CD-Au nanohybrids are described, and the electrochemical experiments for hydroquinone detection are discussed. The results indicate that CD-Au acts as an efficient material for sensing hydroquinone, matching a wide range of interests in science from industrial processes to environmental pollution.

Self-assembled BiFeO3@MIL-101 nanocomposite for antimicrobial applications under natural sunlight.

In this paper, we report on the synthesis of a new hybrid photocatalytic material activated by natural sunlight irradiation. The material consists of multiferroic nanoparticles of bismuth ferrite (BFO) modified through the growth of the Fe-based MIL-101 framework. Material characterization, conducted using various techniques (X-ray diffraction, transmission electron microscopy, FTIR, and X-ray photoelectron spectroscopies), confirmed the growth of the MIL-101 metal-organic framework on the BFO surface. The obtained system possesses the intrinsic photo-degradative properties of BFO nanoparticles significantly enhanced by the presence of MIL-101. The photocatalytic activity of this material was tested in antibacterial experiments conducted under natural sunlight exposure within the nanocomposite concentration range of 100-0.20 µg/ml. The MIL-modified BFO showed a significant decrease in both Minimum Inhibiting Concentration and Minimum Bactericide Concentration values compared to bare nanoparticles. This confirms the photo-activating effect of the MIL-101 modification. In particular, they show an increased antimicrobial activity against the tested Gram-positive species and the ability to begin to inhibit the growth of the four Escherichia coli strains, although at the maximum concentration tested. These results suggest that the new nanocomposite BiFeO3@MOF has been successfully developed and has proven to be an effective antibacterial agent against a wide range of microorganisms and a potential candidate in disinfection processes.

Physicochemical Characterization and Antibacterial Properties of Carbon Dots from Two Mediterranean Olive Solid Waste Cultivars.

Carbon nanomaterials have shown great potential in several fields, including biosensing, bioimaging, drug delivery, energy, catalysis, diagnostics, and nanomedicine. Recently, a new class of carbon nanomaterials, carbon dots (CDs), have attracted much attention due to their easy and inexpensive synthesis from a wide range of precursors and fascinating physical, chemical, and biological properties. In this work we have developed CDs derived from olive solid wastes of two Mediterranean regions, Puglia (CDs_P) and Calabria (CDs_C) and evaluated them in terms of their physicochemical properties and antibacterial activity against Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa). Results show the nanosystems have a quasi-spherical shape of 12-18 nm in size for CDs_P and 15-20 nm in size for CDs_C. UV-Vis characterization indicates a broad absorption band with two main peaks at about 270 nm and 300 nm, respectively, attributed to the π-π* and n-π* transitions of the CDs, respectively. Both samples show photoluminescence (PL) spectra excitation-dependent with a maximum at λem = 420 nm (λexc = 300 nm) for CDs_P and a red-shifted at λem = 445 nm (λexc = 300 nm) for CDs_C. Band gaps values of ≈ 1.48 eV for CDs_P and ≈ 1.53 eV for CDs_C are in agreement with semiconductor behaviour. ζ potential measures show very negative values for CDs_C compared to CDs_P (three times higher, -38 mV vs. -18 mV at pH = 7). The evaluation of the antibacterial properties highlights that both CDs have higher antibacterial activity towards Gram-positive than to Gram-negative bacteria. In addition, CDs_C exhibit bactericidal behaviour at concentrations of 360, 240, and 120 µg/mL, while lesser activity was found for CDs_P (bacterial cell reduction of only 30% at the highest concentration of 360 µg/mL). This finding was correlated to the higher surface charge of CDs_C compared to CDs_P. Further investigations are in progress to confirm this hypothesis and to gain insight on the antibacterial mechanism of both cultivars.

Synthesis of MIL-Modified Fe3O4 Magnetic Nanoparticles for Enhancing Uptake and Efficiency of Temozolomide in Glioblastoma Treatment.

A nanometric hybrid system consisting of a Fe3O4 magnetic nanoparticles modified through the growth of Fe-based Metal-organic frameworks of the MIL (Materials Institute Lavoiser) was developed. The obtained system retains both the nanometer dimensions and the magnetic properties of the Fe3O4 nanoparticles and possesses increased the loading capability due to the highly porous Fe-MIL. It was tested to load, carry and release temozolomide (TMZ) for the treatment of glioblastoma multiforme one of the most aggressive and deadly human cancers. The chemical characterization of the hybrid system was performed through various complementary techniques: X-ray-diffraction, thermogravimetric analysis, FT-IR and X-ray photoelectron spectroscopies. The nanomaterial showed low toxicity and an increased adsorption capacity compared to bare Fe3O4 magnetic nanoparticles (MNPs). It can load about 12 mg/g of TMZ and carry the drug into A172 cells without degradation. Our experimental data confirm that, after 48 h of treatment, the TMZ-loaded hybrid nanoparticles (15 and 20 µg/mL) suppressed human glioblastoma cell viability much more effectively than the free drug. Finally, we found that the internalization of the MIL-modified system is more evident than bare MNPs at all the used concentrations both in the cytoplasm and in the nucleus suggesting that it can be capable of overcoming the blood-brain barrier and targeting brain tumors. In conclusion, these results indicate that this combined nanoparticle represents a highly promising drug delivery system for TMZ targeting into cancer cells.

The Interplay between Fe3O4 Superparamagnetic Nanoparticles, Sodium Butyrate, and Folic Acid for Intracellular Transport.

Combined treatments which use nanoparticles and drugs could be a synergistic strategy for the treatment of a variety of cancers to overcome drug resistance, low efficacy, and high-dose-induced systemic toxicity. In this study, the effects on human colon adenocarcinoma cells of surface modified Fe3O4 magnetic nanoparticles (MNPs) in combination with sodium butyrate (NaBu), added as a free formulation, were examined demonstrating that the co-delivery produced a cytotoxic effect on malignant cells. Two different MNP coatings were investigated: a simple polyethylene glycol (PEG) layer and a mixed folic acid (FA) and PEG layer. Our results demonstrated that MNPs with FA (FA-PEG@MNPs) have a better cellular uptake than the ones without FA (PEG@MNPs), probably due to the presence of folate that acts as an activator of folate receptors (FRs) expression. However, in the presence of NaBu, the difference between the two types of MNPs was reduced. These similar behaviors for both MNPs likely occurred because of the differentiation induced by butyrate that increases the uptake of ferromagnetic nanoparticles. Moreover, we observed a strong decrease of cell viability in a NaBu dose-dependent manner. Taking into account these results, the cooperation of multifunctional MNPs with NaBu, taking into consideration the particular cancer-cell properties, can be a valuable tool for future cancer treatment.

Bistatic radar configuration for soil moisture retrieval: analysis of the spatial coverage.

Some outcomes of a feasibility analysis of a spaceborne bistatic radar mission for soil moisture retrieval are presented in this paper. The study starts from the orbital design of the configuration suitable for soil moisture estimation identified in a previous study. This configuration is refined according to the results of an analysis of the spatial resolution. The paper focuses on the assessment of the spatial coverage i.e., on the verification that an adequate overlap between the footprints of the antennas is ensured and on the duty cycle, that is the fraction of orbital period during which the bistatic data are acquired. A non-cooperating system is considered, in which the transmitter is the C-band Advanced Synthetic Aperture Radar aboard Envisat. The best performances in terms of duty cycle are achieved if the transmitter operates in Wide Swath Mode. The higher resolution Image Swath Modes that comply with the selected configuration have a duty cycle that is never less than 12% and can exceed 21%. When Envisat operates in Wide Swath Mode, the bistatic system covers a wide latitude range across the equator, while in some of the Image Swath Modes, the bistatic measurements, collected from the same orbit, cover mid-latitude areas. In the latter case, it might be possible to achieve full coverage in an Envisat orbit repeat cycle, while, for a very large latitude range such as that covered in Wide Swath Mode, bistatic acquisitions could be obtained over about 65% of the area.

Neural network emulation of the integral equation model with multiple scattering.

The Integral Equation Model with multiple scattering (IEMM) represents a well-established method that provides a theoretical framework for the scattering of electromagnetic waves from rough surfaces. A critical aspect is the long computational time required to run such a complex model. To deal with this problem, a neural network technique is proposed in this work. In particular, we have adopted neural networks to reproduce the backscattering coefficients predicted by IEMM at L- and C-bands, thus making reference to presently operative satellite radar sensors, i.e., that aboard ERS-2, ASAR on board ENVISAT (C-band), and PALSAR aboard ALOS (L-band). The neural network-based model has been designed for radar observations of both flat and tilted surfaces, in order to make it applicable for hilly terrains too. The assessment of the proposed approach has been carried out by comparing neural network-derived backscattering coefficients with IEMM-derived ones. Different databases with respect to those employed to train the networks have been used for this purpose. The outcomes seem to prove the feasibility of relying on a neural network approach to efficiently and reliably approximate an electromagnetic model of surface scattering.

Coupling a Neural Network-Based forward Model and a Bayesian Inversion Approach to Retrieve Wind Field from Spaceborne Polarimetric Radiometers.

A simulation study to assess the potentiality of sea surface wind vector estimation based on the approximation of the forward model through Neural Networks and on the Bayesian theory of parameter estimation is presented. A polarimetric microwave radiometer has been considered and its observations have been simulated by means of the two scale model. To perform the simulations, the atmospheric and surface parameters have been derived from ECMWF analysis fields. To retrieve wind speed, Minimum Variance (MV) and Maximum Posterior Probability (MAP) criteria have been used while, for wind direction, a Maximum Likelihood (ML) criterion has been exploited. To minimize the cost function of MAP and ML, conventional Gradient Descent method, as well as Simulated Annealing optimization technique, have been employed. Results have shown that the standard deviation of the wind speed retrieval error is approximately 1.1 m/s for the best estimator. As for the wind direction, the standard deviation of the estimation error is less than 13° for wind speeds larger than 6 m/s. For lower wind velocities, the wind direction signal is too weak to ensure reliable retrievals. A method to deal with the non-uniqueness of the wind direction solution has been also developed. A test on a case study has yielded encouraging results.

Inversion of Electromagnetic Models for Bare Soil Parameter Estimation from Multifrequency Polarimetric SAR Data.

The potentiality of polarimetric SAR data for the estimation of bare soil geophysical parameters (i.e., roughness and soil moisture) is investigated in this work. For this purpose, two forward models available in the literature, able to simulate the measurements of a multifrequency radar polarimeter, have been implemented for use within an inversion scheme. A multiplicative noise has been considered in the multidimensional space of the elements of the polarimetric Covariance Matrix, by adopting a complex Wishart distribution to account for speckle effects. An additive error has been also introduced on the simulated measurements to account for calibration and model errors. Maximum a Posteriori Probability and Minimum Variance criteria have been considered to perform the inversion. As for the algorithms to implement the criteria, simple optimization/integration procedures have been used. A Neural Network approach has been adopted as well. A correlation between the roughness parameters has been also supposed in the simulation as a priori information, to evaluate its effect on the estimation accuracy. The methods have been tested on simulated data to compare their performances as function of number of looks, incidence angles and frequency bands, thus identifying the best radar configuration in terms of estimation accuracy. Polarimetric measurements acquired during MAC Europe and SIR-C campaigns, over selected bare soil fields, have been also used as validation data.

Topographic Effects on the Surface Emissivity of a Mountainous Area Observed by a Spaceborne Microwave Radiometer.

A simulation study to understand the influence of topography on the surfaceemissivity observed by a satellite microwave radiometer is carried out. We analyze theeffects due to changes in observation angle, including the rotation of the polarization plane.A mountainous area in the Alps (Northern Italy) is considered and the information on therelief extracted from a digital elevation model is exploited. The numerical simulation refersto a radiometric image, acquired by a conically-scanning radiometer similar to AMSR-E,i.e., flying at 705 km of altitude with an observation angle of 55°. To single out the impacton surface emissivity, scattering of the radiation due to the atmosphere or neighboringelevated surfaces is not considered. C and X bands, for which atmospheric effects arenegligible, and Ka band are analyzed. The results indicate that the changes in the localobservation angle tend to lower the apparent emissivity of a radiometric pixel with respectto the corresponding flat surface characteristics. The effect of the rotation of thepolarization plane enlarges (vertical polarization), or attenuates (horizontal polarization)this decrease. By doing some simplifying assumptions for the radiometer antenna, theconclusion is that the microwave emissivity at vertical polarization is underestimated,whilst the opposite occurs for horizontal polarization, except for Ka band, for which bothunder- and overprediction may occur. A quantification of the differences with respect to aflat soil and an approximate evaluation of their impact on soil moisture retrieval areyielded.

Integrating Physical and Topographic Information Into a Fuzzy Scheme to Map Flooded Area by SAR.

A flood mapping procedure based on a fuzzy sets theory has been developed. The method is based on the integration of Synthetic Aperture Radar (SAR) measurements with additional data on the inundated area, such as a land cover map and a digital elevation model (DEM). The information on land cover has allowed us to account for both specular reflection, typical of open water, and double bounce backscattering, typical of forested and urban areas. DEM has been exploited to include simple hydraulic considerations on the dependence of inundation probability on surface characteristics. Contextual information has been taken into account too. The proposed algorithm has been tested on a flood occurred in Italy on November 1994. A pair of ERS-1 images, collected before and after (three days later) the flood, has been used. The results have been compared with the data provided by a ground survey carried out when the flood reached its maximum extension. Despite the temporal mismatch between the survey and the post-inundation SAR image, the comparison has yielded encouraging results, with the 87% of the pixels correctly classified as inundated.