Aerosol source apportionment uncertainty linked to the choice of input chemical components.

For a Positive Matrix Factorization (PMF) aerosol source apportionment (SA) studies there is no standard procedure to select the most appropriate chemical components to be included in the input dataset for a given site typology, nor specific recommendations in this direction. However, these choices are crucial for the final SA outputs not only in terms of number of sources identified but also, and consequently, in the source contributions estimates. In fact, PMF tends to reproduce most of PM mass measured independently and introduced as a total variable in the input data, regardless of the percentage of PM mass which has been chemically characterized, so that the lack of some specific source tracers (e.g. levoglucosan) can potentially affect the results of the whole source apportionment study. The present study elaborates further on the same concept, evaluating quantitatively the impact of lacking specific sources' tracers on the whole source apportionment, both in terms of identified sources and source contributions. This work aims to provide first recommendations on the most suitable and critical components to be included in PMF analyses in order to reduce PMF output uncertainty as much as possible, and better represent the most commons PM sources observed in many sites in Western countries. To this aim, we performed three sensitivity analyses on three different datasets across EU, including extended sets of organic tracers, in order to cover different types of urban conditions (Mediterranean, Continental, and Alpine), source types, and PM fractions. Our findings reveal that the vehicle exhaust source resulted to be less sensitive to the choice of analytes, although source contributions estimates can deviate significantly up to 44 %. On the other hand, for the detection of the non-exhaust one is clearly necessary to analyze specific inorganic elements. The choice of not analysing non-polar organics likely causes the loss of separation of exhaust and non-exhaust factors, thus obtaining a unique road traffic source, which provokes a significant bias of total contribution. Levoglucosan was, in most cases, crucial to identify biomass burning contributions in Milan and in Barcelona, in spite of the presence of PAHs in Barcelona, while for the case of Grenoble, even discarding levoglucosan, the presence of PAHs allowed identifying the BB factor. Modifying the rest of analytes provoke a systematic underestimation of biomass burning source contributions. SIA factors resulted to be generally overestimated with respect to the base case analysis, also in the case that ions were not included in the PMF analysis. Trace elements were crucial to identify shipping emissions (V and Ni) and industrial sources (Pb, Ni, Br, Zn, Mn, Cd and As). When changing the rest of input variables, the uncertainty was narrow for shipping but large for industrial processes. Major and trace elements were also crucial to identify the mineral/soil factor at all cities. Biogenic SOA and Anthropogenic SOA factors were sensitive to the presence of their molecular tracers, since the availability of OC alone is unable to separate a SOA factor. Arabitol and sorbitol were crucial to detecting fungal spores while odd number of higher alkanes (C27 to C31) for plant debris.

Light-triggered cardiac microphysiological model.

Light is recognized as an accurate and noninvasive tool for stimulating excitable cells. Here, we report on a non-genetic approach based on organic molecular phototransducers that allows wiring- and electrode-free tissue modulation. As a proof of concept, we show photostimulation of an in vitro cardiac microphysiological model mediated by an amphiphilic azobenzene compound that preferentially dwells in the cell membrane. Exploiting this optical based stimulation technology could be a disruptive approach for highly resolved cardiac tissue stimulation.

Light-induced charge generation in polymeric nanoparticles restores vision in advanced-stage retinitis pigmentosa rats.

Retinal dystrophies such as Retinitis pigmentosa are among the most prevalent causes of inherited legal blindness, for which treatments are in demand. Retinal prostheses have been developed to stimulate the inner retinal network that, initially spared by degeneration, deteriorates in the late stages of the disease. We recently reported that conjugated polymer nanoparticles persistently rescue visual activities after a single subretinal injection in the Royal College of Surgeons rat model of Retinitis pigmentosa. Here we demonstrate that conjugated polymer nanoparticles can reinstate physiological signals at the cortical level and visually driven activities when microinjected in 10-months-old Royal College of Surgeons rats bearing fully light-insensitive retinas. The extent of visual restoration positively correlates with the nanoparticle density and hybrid contacts with second-order retinal neurons. The results establish the functional role of organic photovoltaic nanoparticles in restoring visual activities in fully degenerate retinas with intense inner retina rewiring, a stage of the disease in which patients are subjected to prosthetic interventions.

Conjugated polymers mediate effective activation of the Mammalian Ion Channel Transient Receptor Potential Vanilloid 1.

Selective and rapid regulation of ionic channels is pivotal to the understanding of physiological processes and has a crucial impact in developing novel therapeutic strategies. Transient Receptor Potential (TRP) channels are emerging as essential cellular switches that allow animals to respond to their environment. In particular, the Vanilloid Receptor 1 (TRPV1), besides being involved in the body temperature regulation and in the response to pain, has important roles in several neuronal functions, as cytoskeleton dynamics, injured neurons regeneration, synaptic plasticity. Currently available tools to modulate TRPV1 activity suffer from limited spatial selectivity, do not allow for temporally precise control, and are usually not reversible, thus limiting their application potential. The use of optical excitation would allow for overcoming all these limitations. Here, we propose a novel strategy, based on the use of light-sensitive, conjugated polymers. We demonstrate that illumination of a polymer thin film leads to reliable, robust and temporally precise control of TRPV1 channels. Interestingly, the activation of the channel is due to the combination of two different, locally confined effects, namely the release of thermal energy from the polymer surface and the variation of the local ionic concentration at the cell/polymer interface, both mediated by the polymer photoexcitation.

Engineering thiophene-based nanoparticles to induce phototransduction in live cells under illumination.

We report that nanoparticles prepared from appropriately functionalized polythiophenes once administered to live cells can acquire phototransduction properties under illumination, becoming photoactive sites able to absorb visible light and convert it to an electrical signal through cell membrane polarization. Amine-reactive fluorescent nanoparticles with pendant N-succinimidyl-ester groups (NPs-NHS) are prepared from polythiophenes alternating unsubstituted and 3-(2,5-dioxopyrrolidin-1-yl-8-octanoate)-substituted thiophenes by a nanoprecipitation method. By 1H NMR of nanoparticles prepared using THF-d8/D2O (solvent/non-solvent) we demonstrate that the hydrolysis of the N-succinimidyl-ester group to free N-hydroxysuccinimide takes place slowly over several hours. NPs-NHS reactivity towards primary amine groups is tested towards the NH2 of d- and l-enantiomers of tryptophan. We show that the formation of a tryptophan-nanoparticle amidic bond creates a chiral shell displaying opposite CD signals for the nanoparticles bound to d or l enantiomers. The interaction of NPs-NHS with live HEK-293 cells is monitored via LSCM. We show that the NPs-NHS are not internalized but remain docked on the cell membrane. We assume that this is mainly the result of the reaction of the NHS groups in the external layer with NH2 groups present in cell membrane proteins, although the contribution of alternative mechanisms cannot be excluded. To support this assumption LSCM experiments show that nanoparticles of comparable size obtained from poly(3-hexylthiophene), NPs-P3HT, are rapidly internalized by live HEK-293 cells. Finally, using the whole-cell current clamp technique under light illumination we demonstrate that NPs-NHS can polarize the cell membrane upon light irradiation while NPs-P3HT cannot.

Thermoelectric characterization of flexible micro-thermoelectric generators.

A new experimental setup for the characterization of flexible micro-thermoelectric generators is reported. The system can measure the power generated and the thermoelectric conversion efficiency of devices under mechanical stresses and deformations, in atmospheric environment and under vacuum, in the temperature interval 293 K-423 K, as a function of the load resistance and of the mechanical pressure, with an uncertainty on the temperature difference of ±0.02 K. The system has been tested on commercial rigid devices and on a custom-made, flexible, proof-of-concept, organic-inorganic hybrid generator made of eight thermocouples. Repeatability on the power generated and conversion efficiency within 5% and 3%, respectively, was demonstrated, and accuracy of the measurement was granted by minimization of all the potential sources of heat flux losses.

Below-gap excitation of semiconducting single-wall carbon nanotubes.

We investigate the optoelectronic properties of the semiconducting (6,5) species of single-walled carbon nanotubes by measuring ultrafast transient transmission changes with 20 fs time resolution. We demonstrate that photons with energy below the lowest exciton resonance efficiently lead to linear excitation of electronic states. This finding challenges the established picture of a vanishing optical absorption below the fundamental excitonic resonance. Our result points towards below-gap electronic states as an intrinsic property of semiconducting nanotubes.

Reliable measurement of the Seebeck coefficient of organic and inorganic materials between 260 K and 460 K.

A new experimental setup for reliable measurement of the in-plane Seebeck coefficient of organic and inorganic thin films and bulk materials is reported. The system is based on the "Quasi-Static" approach and can measure the thermopower in the range of temperature between 260 K and 460 K. The system has been tested on a pure nickel bulk sample and on a thin film of commercially available PEDOT: PSS deposited by spin coating on glass. Repeatability within 1.5% for the nickel sample is demonstrated, while accuracy in the measurement of both organic and inorganic samples is guaranteed by time interpolation of data and by operating with a temperature difference over the sample of less than 1 K.

The study of polythiophene/water interfaces by sum-frequency generation spectroscopy and molecular dynamics simulations.

Semiconducting polymer/water interfaces are gaining increasing attention due to a variety of promising applications in the fields of biology and electrochemistry, such as electrochemically-gated transistors and photodetectors, which have been used for biosensing and neuroscience applications. However, a detailed characterization of the polymer surface in the presence of an aqueous environment is still lacking. In this work, we employed sum-frequency generation vibrational spectroscopy, a surface-specific technique compatible with electrochemical/biological conditions, to demonstrate that the surface of thin films of regio-regular poly-3-hexylthiophene (rr-P3HT) undergoes a molecular reorientation when exposed to aqueous electrolytes, with respect to their surface structure in air. Experimental results are corroborated by molecular dynamics simulations. Since surface molecular orientation is believed to play a fundamental role in electrochemical and environmental stability of conjugated polymers, the reported findings not only contribute to the fundamental understanding of conjugated polymer/water interfaces, but they may also have implications in the design of conjugated polymers for enhancing their performance in electrolytic environments.

The critical role of interfacial dynamics in the stability of organic photovoltaic devices.

Understanding the stability and degradation mechanisms of organic solar materials is required to achieve long device lifetimes. Here we study photodegradation mechanisms of the (poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)]):[6,6]-phenyl-C61-butyric acid methyl ester (PCPDTBT:PCBM) low band gap-based photovoltaic blend. We apply quasi steady state Photo-induced Absorption Optical Spectroscopy, time-resolved Electron Spin Resonance Spectroscopy and theoretical modeling to investigate the dynamics of long-lived photoexcited species. The role of the interfacial physics in the efficiency and robustness of the photovoltaic blend is clarified. We demonstrate that the polymer triplet state (T), populated through the interfacial charge transfer (CT) state recombination, coexists with charge carriers. However, in contrast to previous suggestions, it has no role in the degradation process caused by air exposure. Instead, the long-lived emissive interfacial CT state is responsible for the blend degradation in air. It mediates direct electron transfer to contaminants, leading to the formation of reactive and harmful species, such as the superoxide.

Effect of polymer morphology on P3HT-based solid-state dye sensitized solar cells: an ultrafast spectroscopic investigation.

Solid-state dye sensitized solar cell devices are fabricated with poly(3-hexylthiophene) (P3HT) as the hole transporting layer. Upon annealing treatment we obtained ≈ 70% increase in the device efficiency compared to un-annealed devices. Our investigation, by means of ultrafast transient absorption spectroscopic characterization, correlates the increased device performances to a more efficient hole-transfer at the dye/polymer interface in the thermally treated P3HT.

Organic semiconductors for artificial vision.

Organic semiconductors have emerged in the past two decades as promising materials for many technological applications. Thanks to their unique optoelectronic properties, they represent an ideal system to mimic natural photoreceptor functioning. This similarity has been exploited, on one hand, to realize organic-based devices for image detection, taking advantage of typical features of natural visual systems, such as trichromatic sensing; on the other hand, these materials can be interfaced with biological tissues for cell photo-stimulation, with the main goal of restoring light sensitivity in the case of retinas affected by photoreceptor degeneration.

Hot exciton dissociation in polymer solar cells.

The standard picture of photovoltaic conversion in all-organic bulk heterojunction solar cells predicts that the initial excitation dissociates at the donor/acceptor interface after thermalization. Accordingly, on above-gap excitation, the excess photon energy is quickly lost by internal dissipation. Here we directly target the interfacial physics of an efficient low-bandgap polymer/PC(60)BM system. Exciton splitting occurs within the first 50 fs, creating both interfacial charge transfer states (CTSs) and polaron species. On high-energy excitation, higher-lying singlet states convert into hot interfacial CTSs that effectively contribute to free-polaron generation. We rationalize these findings in terms of a higher degree of delocalization of the hot CTSs with respect to the relaxed ones, which enhances the probability of charge dissociation in the first 200 fs. Thus, the hot CTS dissociation produces an overall increase in the charge generation yield.

Radiofrequency ablation of hepatocellular carcinoma in patients with and without cirrhosis.

INTRODUCTION: Hepatocellular carcinoma (HCC) is a leading cause of death in patients with cirrhosis. Around 12% of all cases are associated with chronic liver disease without cirrhosis. The aim of our study was to compare primary tumor ablation rates, local tumor progression, safety, and long-term outcomes of radiofrequency ablation for single (less than 3.5 cm in diameter) or multiple HCC nodules (up to three nodules, each less than 3 cm) in both types of patients. METHODS: We treated 200 consecutive HCC patients recruited from a local sonographic screening program: 175 with cirrhosis and 25 with non-cirrhotic chronic liver disease. RESULTS: Complete ablation was achieved in 150 of the 175 patients (85.7%) (174 of the 206 nodules treated, 84.4%) in the cirrhotic group and in 24 of the 25 patients (96%) (27 of the 29 nodules treated; 93%) in the non-cirrhotic group. The two groups were not significantly different in terms of local tumor progression rates 1, 3, and 5 years after treatment (11%, 23%, and 24% among cirrhotics vs. 4%, 14%, and 14% among non-cirrhotic patients). Multifocal disease was more frequent among the cirrhotics. One-, three- and five-year survival rates were also similar in the cirrhotic (93%, 77%, and 61%) and non-cirrhotic groups (92%, 72%, and 64%). There were no treatment-related deaths. Severe complications occurred only in the cirrhotic group (2.2%). CONCLUSIONS: Radiofrequency ablation is safe and effective treatment for HCC in patients with or without cirrhosis. The latter group has a significantly lower rate of multifocal disease.

Stark spectroscopy of excited-state transitions in a conjugated polymer.

Stark spectroscopy, which is well established for probing transitions between the ground and excited states of many material classes, is extended to transitions between transient excited states. To this end, it is combined with femtosecond pump-probe spectroscopy on a conjugated polymer with appropriately introduced traps which harvest excitation energy and build up a sufficient excited state population. The results indicate a significant difference in the effective dipole moments between two short lived excited states.

Effects of exposure to air pollution on blood coagulation.

BACKGROUND: Consistent evidence has indicated that air pollution increases the risk of cardiovascular diseases. The underlying mechanisms linking air pollutants to increased cardiovascular risk are unclear. OBJECTIVES: We investigated the association between the pollution levels and changes in such global coagulation tests as the prothrombin time (PT) and the activated partial thromboplastin time (APTT) in 1218 normal subjects from the Lombardia Region, Italy. Plasma fibrinogen and naturally occurring anticoagulant proteins were also evaluated. METHODS: Hourly concentrations of particulate (PM10) and gaseous pollutants (CO, NO2, SO2, and O3) were obtained from 53 monitoring sites covering the study area. Generalized additive models were applied to compute standardized regression coefficients controlled for age, gender, body mass index, smoking, alcohol, hormone use, temperature, day of the year, and long-term trends. RESULTS: The PT became shorter with higher ambient air concentrations at the time of the study of PM10 (coefficient = -0.06; P < 0.05), CO (coefficient = -0.11; P < 0.001) and NO2 (coefficient =-0.06; P < 0.05). In the 30 days before blood sampling, the PT was also negatively associated with the average PM(10) (coefficient = -0.08; P < 0.05) and NO2 (coefficient = -0.08; P < 0.05). No association was found between the APTT and air pollutant levels. In addition, no consistent relations with air pollution were found for fibrinogen, antithrombin, protein C and protein S. CONCLUSIONS: This investigation shows that air pollution is associated with changes in the global coagulation function, suggesting a tendency towards hypercoagulability after short-term exposure to air pollution. Whether these changes contribute to trigger cardiovascular events remains to be established.

Photoinduced transient stark spectroscopy in organic semiconductors: a method for charge mobility determination in the picosecond regime.

Subpicosecond photoinduced Stark spectroscopy experiments are carried out for measuring charge carrier mobility in organic semiconductors. The technique is demonstrated in state-of-art devices based on methanofullerene. The transient mobility of photogenerated charge carriers is measured in the picosecond time domain. Electric field dependent mobility is observed from the earliest time scales. In addition, two distinct transport regimes are revealed: a short-lived state, approximately 10 ps, of high mobility and a transient towards the trap limited transport, associated with the mesoscopic structure of the medium.

Intersubband exciton relaxation dynamics in single-walled carbon nanotubes.

We study exciton (EX) dynamics in single-walled carbon nanotubes (SWNTs) included in polymethylmethacrylate by two-color pump-probe experiments with unprecedented temporal resolution. In the semiconducting SWNTs, we resolve the intersubband energy relaxation from the EX2 to the EX1 transition and find time constants of about 40 fs. The observation of a photoinduced absorption band strictly correlated to the photobleaching of the EX1 transition supports the excitonic model for primary excitations in SWNTs. We also detect in the time domain coherent oscillations due to the radial breathing modes at approximately 250 cm(-1).

Ultrafast intrachain photoexcitation of polymeric semiconductors.

We report on excited state dynamics in isolated poly(9,9-dioctylfluorene) chains obtained by embedding the polymer in an inert plastic matrix. Early events (<300 fs) of intrachain photophysics are detected by pump-probe spectroscopy using tunable UV 25-fs pump pulses and sub-10-fs visible probe pulses. We show that higher-lying optical states, reached by multiphoton transitions, give rise to on-chain charge separation on the ultrafast time scale. The intrachain charge pair decays geminately within 500 fs to the lowest singlet state. Characteristic time scales for internal conversion and intramolecular vibrational redistribution are also determined.