Confocal ultrafast pump-probe spectroscopy: a new technique to explore nanoscale composites

This article is devoted to the exploration of the benefits of a new ultrafast confocal pump-probe technique, able to study the photophysics of different structured materials with nanoscale resolution. This tool offers many advantages over standard stationary microscopy techniques because it directly interrogates excited state dynamics in molecules, providing access to both radiative and non-radiative deactivation processes at a local scale. In this paper we present a few different examples of its application to organic semiconductor systems. The first two are focussed on the study of the photophysics of phase-separated polymer blends: (i) a blue-emitting polyfluorene (PFO) in an inert matrix of PMMA and (ii) an electron donor polythiophene (P3HT) mixed with an electron acceptor fullerene derivative (PCBM). The experimental results on these samples demonstrate the capability of the technique to unveil peculiar interfacial dynamics at the border region between phase-segregated domains, which would be otherwise averaged out using conventional pump-probe spectroscopy. The third example is the study of the photophysics of isolated mesoscopic crystals of the PCBM molecule. Our ultrafast microscope could evidence the presence of two distinctive regions within the crystals. In particular, we could pinpoint for the first time areas within the crystals showing photobleaching/stimulated emission signals from a charge-transfer state.     

Fluoro-functionalized PLA polymers as potential water-repellent coating materials for protection of stone

A series of sixteen fluoro-functionalized poly(lactic acid)s were synthesised using two commercial fluorinated alcohols [3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol and 4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)benzyl alcohol] as co-initiators in the ring-opening polymerization of L-lactide and rac-lactide (the racemic mixture of L- and D-lactide) catalyzed by Tin(II) 2-ethylhexanoate. The polymers were characterized by NMR, IR, GPC, DSC and tested as potential protective coating for stone. The performances were comparatively evaluated in terms of water protection efficacy and colour changes of the treated stone. Furthermore, the photo-stability of nine selected polymers under Solar Box condition was also investigated. It has been shown that the presence of fluorine makes the stone more water-repellent. The polymers showed also interesting photo-stability and some of them provided a behavior close to PLA-FLK-PLA block copolymers recently reported in the literature, in spite of their lower fluorine content © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Boosting Infrared Light Harvesting by Molecular Functionalization of Metal Oxide/Polymer Interfaces in Efficient Hybrid Solar Cells

Hybrid solar cells based on light absorbing semiconducting polymers infiltrated in nanocrystalline TiO₂ electrodes, have emerged as an attractive concept, combining benefits of both low material and processing costs with well controlled nano‐scale morphology. However, after over ten years of research effort, power conversion efficiencies remain around 0.5%. Here, a spectroscopic and device based investigation is presented, which leads to a new optimization route where by functionalization of the TiO₂ surface with a molecular electron acceptor promotes photoinduced electron transfer from a low‐band gap polymer(poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b0]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadia‐zole)] (PCPDTBT) to the metal oxide. This boosts the infrared response and the power conversion efficiency to over 1%. As a further step, by “co‐functionalizing” the TiO₂ surface with the electron acceptor and an organic dye‐sensitizer, panchromatic spectral photoresponse is achieved in the visible to near‐IR region. This novel architecture at the heterojunction opens new material design possibilities and represents an exciting route forward for hybrid photovoltaics.     

Thermoelastic finite element model updating with application to monumental buildings

A reliable and predictive model of an existing structure entails the use of model updating techniques, which are usually performed on the basis of operational modal analysis campaigns. In this paper, a new model calibration strategy is proposed that adopts a multiphysics approach to exploit data collected by both static and dynamic monitoring systems. More specifically, mechanical and temperature data are assimilated into the model through a thermoelastic updating. The proposed scheme is validated with numerical simulations and applied on the Sanctuary of Vicoforte, a complex historical building that is subjected to both static and dynamic monitoring.     

Morphology and temperature dependence of the thermal conductivity of nanoporous SiGe

Using molecular dynamics simulations, we show that the thermal conductivity (κ) of Si(0.5)Ge(0.5) can be reduced by more than one order of magnitude by etching nanometer-sized holes in the material, and it becomes almost constant as a function of temperature between 300 and 1100 K for samples with 1 nm wide pores. In nanoporous SiGe, thermal conduction is largely determined by mass disorder and boundary scattering, and thus the dependence of κ on pore distance and on structural, atomistic disorder is much weaker than in the case of nanoporous Si. This indicates that one may minimize κ of the alloy with less stringent morphological constraints than for pure Si.     

A multiscale model of atherosclerotic plaque formation at its early stage

A multiscale model of atherosclerotic plaque formation at its early stage has been developed in order to integrate the various phenomena leading to fatty streak formation. The different scales considered in this model are in both the spatial domain (from cellular to organism level) and the time domain (from seconds to months). The cellular level was considered by modeling the transport and chemical interactions of low-density lipoproteins (LDL) and other agents in a stenosed artery. This was linked to arterial thickening (organ level). Mean blood LDL level (organism level) was selected as one of the critical factors for atherosclerotic formation along with wall shear stress (WSS) exerted on the endothelium (the inner portion of the artery). It was observed that plaque location was dependent on WSS and that plaque size, number, and growth was dependent on mean blood LDL levels as well.     

Prevalence of Anisakis spp. and Hysterothylacium spp. larvae in teleosts and cephalopods sampled from waters off Sardinia

A study was carried out on the presence of Anisakis and Hysterothylacium larvae in fish and cephalopods caught in Sardinian waters. A total of 369 specimens of 24 different species of teleosts and 5 species of cephalopods were collected from different fishing areas of Sardinia. Larvae were detected and isolated by both visual inspection and enzymatic digestion. These methods allowed Anisakis type I and type II third-stage larvae and Hysterothylacium third- and fourth-stage larvae to be detected. The prevalence, mean intensity, and mean abundance were calculated. The results obtained showed the highest prevalence of Anisakidae in Zeus faber (100%) and of Anisakis in Micromesistius poutassou (87.5%). The highest prevalence of Anisakis type I larvae was in M. poutassou (81.2%), and that of Anisakis type II larvae was in Todarodes sagittatus (20%). The highest values for prevalence, mean intensity, and mean abundance for Hysterothylacium were found in Z. faber. These prevalences and the mean intensity and abundance were higher than those reported by different authors in other Mediterranean areas. This may be because the enzymatic digestive method used in this research resulted in higher recovery levels. The data suggest that Sardinia may be a high-risk area for zoonotic diseases and that measures such as information campaigns, aimed at both sanitary service personnel and consumers, should be employed to limit the spread of such zoonosis.     

Saliva Proteomics as Fluid Signature of Inflammatory and Immune-Mediated Skin Diseases

Saliva is easy to access, non-invasive and a useful source of information useful for the diagnosis of serval inflammatory and immune-mediated diseases. Following the advent of genomic technologies and -omic research, studies based on saliva testing have rapidly increased and human salivary proteome has been partially characterized. As a proteomic protocol to analyze the whole saliva proteome is not currently available, the most common aim of the proteomic analysis is to discriminate between physiological and pathological conditions. The salivary proteome has been initially investigated in several diseases: oral squamous cell carcinoma and oral leukoplakia, chronic graft-versus-host disease, and Sjögren’s syndrome. Otherwise, salivary proteomics studies in the dermatological field are still in the initial phase, thus the aim of this review is to collect the best research evidence on the role of saliva proteomics analysis in immune-mediated skin diseases to understand the direction of research in this field. The results of PRISMA analysis reported herein suggest that human saliva analysis could provide significant data for the diagnosis and prognosis of several immune-mediated and inflammatory skin diseases in the next future.     

Cyanine Dyes for Photo-Thermal Therapy: A Comparison of Synthetic Liposomes and Natural Erythrocyte-Based Carriers

Cyanine fluorescent dyes are attractive diagnostic or therapeutic agents due to their excellent optical properties. However, in free form, their use in biological applications is limited due to the short circulation time, instability, and toxicity. Therefore, their encapsulation into nano-carriers might help overcome the above-mentioned issues. In addition to indocyanine green (ICG), which is clinically approved and therefore the most widely used fluorescent dye, we tested the structurally similar and cheaper alternative called IR-820. Both dyes were encapsulated into liposomes. However, due to the synthetic origin of liposomes, they can induce an immunogenic response. To address this challenge, we proposed to use erythrocyte membrane vesicles (EMVs) as “new era” nano-carriers for cyanine dyes. The optical properties of both dyes were investigated in different biological relevant media. Then, the temperature stability and photo-stability of dyes in free form and encapsulated into liposomes and EMVs were evaluated. Nano-carriers efficiently protected dyes from thermal degradation, as well as from photo-induced degradation. Finally, a hemotoxicity study revealed that EMVs seem less hemotoxic dye carriers than clinically approved liposomes. Herein, we showed that EMVs exhibit great potential as nano-carriers for dyes with improved stability and hemocompatibility without losing excellent optical properties.