Hierarchically Structured Magnetic Nanoconstructs with Enhanced Relaxivity and Cooperative Tumor Accumulation

Iron oxide nanoparticles are formidable multifunctional systems capable of contrast enhancement in magnetic resonance imaging, guidance under remote fields, heat generation, and biodegradation. Yet, this potential is underutilized in that each function manifests at different nanoparticle sizes. Here, sub‐micrometer discoidal magnetic nanoconstructs are realized by confining 5 nm ultra‐small super‐paramagnetic iron oxide nanoparticles (USPIOs) within two different mesoporous structures, made out of silicon and polymers. These nanoconstructs exhibit transversal relaxivities up to ≈10 times (r ₂ ≈ 835 mm ^?1 s^?1) higher than conventional USPIOs and, under external magnetic fields, collectively cooperate to amplify tumor accumulation. The boost in r ₂ relaxivity arises from the formation of mesoscopic USPIO clusters within the porous matrix, inducing a local reduction in water molecule mobility as demonstrated via molecular dynamics simulations. The cooperative accumulation under static magnetic field derives from the large amount of iron that can be loaded per nanoconstuct (up to ≈65 fg) and the consequential generation of significant inter‐particle magnetic dipole interactions. In tumor bearing mice, the silicon‐based nanoconstructs provide MRI contrast enhancement at much smaller doses of iron (≈0.5 mg of Fe kg^?1 animal) as compared to current practice.     

Self‐Assembled Conjugated Thiophene‐Based Rotaxane Architectures: Structural,Computational, and Spectroscopic Insights into Molecular Aggregation

A comparative study of the self‐assembly at a variety of surfaces of a dithiophene rotaxane 1 ?β‐CD and its corresponding dumbbell, 1, by means of atomic force microscopy (AFM) imaging and scanning tunneling microscopy (STM) imaging on the micrometer and nanometer scale, respectively. The dumbbell is found to have a greater propensity to form ordered supramolecular assemblies, as a result of π–π interactions between dithiophenes belonging to adjacent molecules, which are hindered in the rotaxane. The fine molecular structure determined by STM was compared to that obtained by molecular modelling. The optical properties of both rotaxane and dumbbell in the solid state were investigated by steady‐state and time‐resolved photoluminescence (PL) experiments on spin‐cast films and diluted solutions. The comparison between the optical features of the threaded and unthreaded systems reveals an effective role of encapsulation in reducing aggregation and exciton migration for the rotaxanes with respect to the dumbbells, thus leading to higher PL quantum efficiency and preserved single‐molecule photophysics for longer times after excitation in the threaded oligomers.     

Advanced receiver design for satellite‐based automatic identification system signal detection

This paper describes an innovative receiver architecture for the satellite‐based automatic identification system. The receiver performance has been fully validated in the presence of the typical satellite channel characteristics. In particular, it is shown that the devised receiver provides an excellent performance against the noise, as well as a large resilience against message collisions, Doppler shift, and delay spread. Copyright © 2012 John Wiley & Sons, Ltd.     

Analysis of Optical Losses in a Photoelectrochemical Cell: A Tool for Precise Absorptance Estimation

Optical losses in a photoelectrochemical (PEC) cell account for a substantial part of solar‐to‐hydrogen conversion losses, but limited attention is paid to the detailed investigation of optical losses in PEC cells. In this work, an optical model of combined coherent and incoherent light propagation in all layers of the PEC cell based on spectroscopic measurements is presented. Specifically, photoelectrodes using transparent conductive substrates such as F:SnO₂ coated with thin absorber films are focused. The optical model is verified for hematite photoanodes fabricated by atomic layer deposition and successfully used to determine wavelength‐dependent reflection, transmission, layer absorptances, and charge generation rates. Furthermore, the calculated absorptances enable 20–30% more accurate calculations of the absorbed photon‐to‐current efficiency of PEC cells. Our optical model is a powerful tool for the optimization of the optical performance of PEC cells focusing on single absorber or tandem configurations and represents a cornerstone of a complete (optical and electrical) model for PEC water splitting cells.     

A Low Temperature Route toward Hierarchically Structured Titania Films for Thin Hybrid Solar Cells

The requirement of high‐temperature calcination for titanium dioxide in (solid‐state) dye‐sensitized solar cells (DSSCs) implies challenges with respect to reduced energy consumption and the potential for flexible photovoltaic devices. Moreover, the use of dye molecules increases production costs and leads to problems related with dye bleaching. Therefore, fabrication of dye‐free hybrid solar cells at low temperature is a promising alternative for current DSSC technology. In this work the authors fabricate hierarchically structured titania thin films by combining a polystyrene‐block‐polyethylene oxide template assisted sol–gel synthesis with nano‐imprint lithography at low temperatures. The achieved films are filled with poly(3‐hexylthiophene) to form the active layer of hybrid solar cells. The surface morphology is probed via scanning electron microscopy and atomic force microscopy, and the bulk film morphology is examined with grazing incidence X‐ray scattering. Good light absorption by the active layer is proven by UV–vis spectroscopy. An enhancement in light absorption is observed and ascribed to light scattering in mesoporous titania films with imprinted superstructures. Accordingly a better photovoltaic performance is found for nano‐imprinted solar cells at various angles of light incidence.     

Overview of the geometrical influence on the fatigue strength of steel butt welds by a nonlocal approach

The paper deals with the high‐cycle fatigue behaviour of steel butt‐welded joints in the as‐welded condition, under constant amplitude loading. It tackles the problem of strength assessment by changing the geometrical shape and features of the weldment. This investigation considers the recommendations available in design standards, particularly referring to the Eurocodes, and it re‐analyses experimental data where a clear profile of the actual weld shape is available. For the available weld profiles, numerical investigations are shown by applying the Implicit Gradient approach for the evaluation of the nonlocal effective stress in the fatigue strength assessment. The results are very promising since the nonlocal approach significantly agrees with design standard recommendations in conventional cases, but it is also able to provide specific indications on the influence of the geometrical features, as well as the tip radius and opening angles, specifying their influence when no explicitly detailed indications are available in the design standards.     

Design of novel 3D gene activated PEG scaffolds with ordered pore structure

The ability to genetically modify cells seeded inside synthetic hydrogel scaffolds offers a suitable approach to induce and control tissue repair and regeneration guiding cell fate. In fact the transfected cells can act as local in vivo bioreactor, secreting plasmid encoded proteins that augment tissue regeneration processes. We have realized a DNA bioactivated high porous poly(ethylene glycol) (PEG) matrix by polyethyleneimine (PEI)/DNA complexes adsorption. As the design of the microarchitectural features of a scaffold also contributes to promote and influence cell fate, we appropriately designed the inner structure of gene activated PEG hydrogels by gelatine microparticles templating. Microarchitectural properties of the scaffold were analysed by scanning electron microscopy. 3D cell migration and transfection were monitored through time-lapse videomicroscopy and confocal laser scanning microscopy.     

Supercritical carbon dioxide-treated blood orange juice as a new product in the fresh fruit juice market

The work described here deals with the effectiveness of using high-pressure carbon dioxide treatment (HPCD) to stabilise freshly squeezed blood orange juice. Technical planning of a continuous high-pressure supercritical carbon dioxide pilot system, suitable for development on an industrial scale, was carried out in our lab. To determine the optimal operating conditions (temperature, pressure, and CO₂/juice ratio), three different experimental trials were carried out. The first trial was conducted at 230 bar, 36 ± 1 °C, 5.08 L/h juice flow rate, and 3.91 L/h CO₂ flow rate, corresponding to a g_CO2/g_juice ratio of 0.770. The second trial utilised the same conditions except that the operative pressure was reduced (130 bar). The third trial was carried out at 130 bar, 36 ± 1 °C, 5.08 L/h juice flow rate, 1.96 L/h CO₂ flow rate, corresponding to a 0.385 g_CO2/g_juice ratio. The effects of processing were evaluated by determining physicochemical, antioxidant, and microbiological parameters of the treated juices. In addition, once the best operative parameters had been determined, physicochemical, antioxidant, microbiological and sensory evaluation of fresh blood orange juice stabilised by HPCD treatment was carried out during refrigerated storage of juices at 4 ± 1 °C for thirty days. The results showed that HPCD treatment cannot be considered as an alternative to traditional thermal methods but as a new mild technology for producing a stabilised blood orange juice with a shelf-life of 20 days.Industrial relevanceBlood oranges are the main cultivated varieties of Citrus sinensis (L.) Osbeck in Italy. Freshly squeezed blood orange juice exert a high antiradical and antioxidant activity, due to its rich phenolic profile, but its preservation is usually assured by thermal treatment which affects its nutritional and sensory value. In this study we proposed a “milder” continuous HPCD process suitable for implementation on an industrial scale. The HPCD stabilised juice retains its physicochemical, antioxidant, and sensory properties and could be placed within a new retail framework, namely, that of fresh juices with a shelf-life of 20 days.     

Temperature and storage effects on antioxidant activity of juice from red and white grapes

The effect of temperature and storage time on the phenolic composition and on the antioxidant activity of grape (Vitis vinifera L.) juices made using a red (Sangiovese, SG) and a white (Muscat of Alexandria, MA) variety was studied. Total phenolics, flavonoids, flavan‐3‐ols and hydroxycinnamoyl‐tartrates (HCT) were determined on grape extracts (GE) and juices. Total anthocyanins and anthocyanins composition were measured on GE. The antioxidant activity was assessed by means of two different in vitro tests: scavenging of the stable 2,2‐diphenyl‐1‐picrylhydrazyl radical and the inhibition of tyrosine nitration mediated by authentic peroxynitrite (ONOO^?). All the juices were analysed after 24 h and 2 weeks of storage by means of two‐way anova (factors being cultivar and temperature). Anthocyanins were not detected in MA extract, whereas in SG their content was 534 mg malvidin‐equivalent per 100 g of dry matter (d.m.) and malvidin derivatives (glycosylated and coumaroylated) were the most represented (respectively 169 and 41 malvidin‐equivalent per 100 g of d.m.). HCT content of the extracts was higher in SG (overall +33%). Also in grape juices, HCT were lower in MA and in this variety, the trans‐fertaric and cis‐coutaric acids were also undetectable. Cultivar effect proved to be highly significant, while no significant differences in the phenolic composition were observed for storage temperatures (4 and ?20 °C) and cultivar × temperature interaction. However, when statistical analysis was focused on each cultivar, MA was found to be more sensible to storage conditions and a significant reduction in total phenolics (?20%) and flavonoids (?53%) content and in the ONOO^? scavenging potential (?32%) was evident after 2 weeks at 4 °C (when compared with the same storage temperature after 24 h). On the contrary, SG juices did not show significant differences among the four storage treatments investigated. These results could be explained suggesting that anthocyanins presence in red grape plays a key role in juice stability.