Benzo(a)pyrene air concentrations and emission inventory in Lombardy region, Italy

Three years of particle phase B(a)P air concentration measurements in 13 sites in Lombardy (Italy) and a detailed emission inventory at the municipal scale for the whole region were used to infer the contribution of different sources to B(a)P atmospheric levels. The analyses of the weekly and monthly profiles of B(a)P concentrations, the cluster analysis and the comparison between the B(a)P/PM10 ratios in ambient air and in the emissions allowed identifying wood burning in small residential appliances as the key source for all the sites, except for those located in Milan. The highest values of the average B(a)P concentrations were not found in the wider urban areas, where in general the highest PM10 levels were registered. Regarding the seasonal variability, a marked reduction of both B(a)P concentrations and B(a)P/PM10 ratios was observed in the summer season. The cluster analysis of PM10 and B(a)P concentrations showed that the two pollutants tend to have a separate pattern; moreover the cluster analysis of B(a)P/PM10 ratios showed that the trend of this ratio split the stations depending on their location: plain area, piedmont and valley zones, and mountain sites. The dominance of the wood combustion highlighted by the emission inventory, originating from the residential sector and from pizzerias in the city of Milan, is consistent with the findings of other studies based on a source apportionment approach or air quality modeling, although some patterns of ambient B(a)P concentrations in one site were not adequately explained by the emission sources included in the emission inventory

Assessing the Economic Value of a Regional Air Quality Plan

When developing an air quality plan, environmental authorities usually devise a number of individual actions, constituted by the application of both technical (end-of-pipe) and energy efficiency measures. They may range from the incentives to buy less polluting vehicles, to the enforcement of stricter rules on domestic heating. The assessment of the economic effectiveness for the society as a whole of the individual measures and of the overall plan requires a flexible support system able to quickly perform air quality impact evaluations on the specific area. One such system is RIAT+, a software package developed and tested during a series of European research projects, which has been used to evaluate costs and benefits of the Lombardy Region Air Quality Plan (PRIA), constituted by about 90 different actions to be implemented within 2020. The adoption of each measure means a certain change in the emission, which is distributed over the regional territory in different way, depending on the type of measure. A shift of the car fleet to a different EURO class, for instance, means an emission reduction only on the road network, while a reduced use of electricity may imply a lower emission of power plants at specific sites. To evaluate the effects of these emission changes, RIAT+ adopts a surrogate model approach, namely using a neural network calibrated on few results of a full chemical transport model. It is thus possible to rapidly evaluate the improvements in the population exposure and health and the consequent reduction of external costs. The final economic assessment is obtained by comparing the sum of energy savings and external cost reductions with the implementation costs of the corresponding measures

Correction: Near-infrared emitting single squaraine dye aggregates with large Stokes shifts

Correction for 'Near-infrared emitting single squaraine dye aggregates with large Stokes shifts' by G. M. Paternò et al., J. Mater. Chem. C, 2017, 5, 7732–7738

Membrane Environment Enables Ultrafast Isomerization of Amphiphilic Azobenzene

G.M.P. and E.C. contributed equally to this work. G.M.P. acknowledges the financial support from Fondazione Cariplo, grant no. 2018-0979. The authors thank the financial support from the EU Horizon 2020 Research and Innovation Programme under Grant Agreement No. 643238 (SYNCHRONICS). The authors also thank Dr. Daniele Viola for helping with the analysis of the TA data.The non‐covalent affinity of photoresponsive molecules to biotargets represents an attractive tool for achieving effective cell photo‐stimulation. Here, an amphiphilic azobenzene that preferentially dwells within the plasma membrane is studied. In particular, its isomerization dynamics in different media is investigated. It is found that in molecular aggregates formed in water, the isomerization reaction is hindered, while radiative deactivation is favored. However, once protected by a lipid shell, the photochromic molecule reacquires its ultrafast photoisomerization capacity. This behavior is explained considering collective excited states that may form in aggregates, locking the conformational dynamics and redistributing the oscillator strength. By applying the pump probe technique in different media, an isomerization time in the order of 10 ps is identified and the deactivation in the aggregate in water is also characterized. Finally, it is demonstrated that the reversible modulation of membrane potential of HEK293 cells via illumination with visible light can be indeed related to the recovered trans→cis photoreaction in lipid membrane. These data fully account for the recently reported experiments in neurons, showing that the amphiphilic azobenzenes, once partitioned in the cell membrane, are effective light actuators for the modification of the electrical state of the membrane.Fondazione Cariplo. Grant Number: 2018‐0979EU Horizon 2020 Research and Innovation Programme. Grant Number: 64323

The Impact of Bacteria Exposure on the Plasmonic Response of Silver Nanostructured Surfaces

Silver, especially in the form of nanostructures, is widely employed as an antimicrobial agent in a large range of commercial products. The origin of the biocidal mechanism has been elucidated in the last decades, and most likely originates from silver cation release due to oxidative dissolution followed by cellular uptake of silver ions, a process that causes a severe disruption of bacterial metabolism and eventually leads to eradication. Despite the large number of works dealing with the effects of nanosilver shape/size on the antibacterial mechanism and on the (bio)physical chemistry pathways that drive bacterial eradication, little effort has been devoted to the investigation of the silver NPs plasmon response upon interaction with bacteria. Here we present a detailed investigation of the bacteria-induced changes of the plasmon spectral and dynamical features after exposure to one of the most studied bacterial models, Escherichia Coli. Ultrafast pump-probe measurements indicate that the dramatic changes on particle size/shape and crystallinity, which stem from a bacteria-induced oxidative dissolution process, translate into a clear modification of the plasmon spectral and dynamical features. This study may open innovative new avenues in the field of biophysics of bio-responsive materials, with the aim of providing new and reliable biophysical signatures of the interaction of these materials with complex biological environments

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

Published versio

Evaluating the risk of ovarian cancer before surgery using the ADNEX model to differentiate between benign, borderline, early and advanced stage invasive, and secondary metastatic tumours: prospective multicentre diagnostic study

Objectives To develop a risk prediction model to preoperatively discriminate between benign, borderline, stage I invasive, stage II-IV invasive, and secondary metastatic ovarian tumours. Design Observational diagnostic study using prospectively collected clinical and ultrasound data. Setting 24 ultrasound centres in 10 countries. Participants Women with an ovarian (including para-ovarian and tubal) mass and who underwent a standardised ultrasound examination before surgery. The model was developed on 3506 patients recruited between 1999 and 2007, temporally validated on 2403 patients recruited between 2009 and 2012, and then updated on all 5909 patients. Main outcome measures Histological classification and surgical staging of the mass. Results The Assessment of Different NEoplasias in the adneXa (ADNEX) model contains three clinical and six ultrasound predictors: age, serum CA-125 level, type of centre (oncology centres v other hospitals), maximum diameter of lesion, proportion of solid tissue, more than 10 cyst locules, number of papillary projections, acoustic shadows, and ascites. The area under the receiver operating characteristic curve (AUC) for the classic discrimination between benign and malignant tumours was 0.94 (0.93 to 0.95) on temporal validation. The AUC was 0.85 for benign versus borderline, 0.92 for benign versus stage I cancer, 0.99 for benign versus stage II-IV cancer, and 0.95 for benign versus secondary metastatic. AUCs between malignant subtypes varied between 0.71 and 0.95, with an AUC of 0.75 for borderline versus stage I cancer and 0.82 for stage II-IV versus secondary metastatic. Calibration curves showed that the estimated risks were accurate. Conclusions The ADNEX model discriminates well between benign and malignant tumours and offers fair to excellent discrimination between four types of ovarian malignancy. The use of ADNEX has the potential to improve triage and management decisions and so reduce morbidity and mortality associated with adnexal pathology

The nature of singlet exciton fission in carotenoid aggregates.

Singlet exciton fission allows the fast and efficient generation of two spin triplet states from one photoexcited singlet. It has the potential to improve organic photovoltaics, enabling efficient coupling to the blue to ultraviolet region of the solar spectrum to capture the energy generally lost as waste heat. However, many questions remain about the underlying fission mechanism. The relation between intermolecular geometry and singlet fission rate and yield is poorly understood and remains one of the most significant barriers to the design of new singlet fission sensitizers. Here we explore the structure-property relationship and examine the mechanism of singlet fission in aggregates of astaxanthin, a small polyene. We isolate five distinct supramolecular structures of astaxanthin generated through self-assembly in solution. Each is capable of undergoing intermolecular singlet fission, with rates of triplet generation and annihilation that can be correlated with intermolecular coupling strength. In contrast with the conventional model of singlet fission in linear molecules, we demonstrate that no intermediate states are involved in the triplet formation: instead, singlet fission occurs directly from the initial 1B(u) photoexcited state on ultrafast time scales. This result demands a re-evaluation of current theories of polyene photophysics and highlights the robustness of carotenoid singlet fission.This work was supported by the EPSRC (UK) (EP/G060738/ 1), the European Community (LASERLAB-EUROPE, grant agreement no. 284464, EC’s Seventh Framework Programme; and Marie-Curie ITN-SUPERIOR, PITN-GA-2009-238177), and the Winton Programme for the Physics of Sustainability. G.C. acknowledges support by the European Research Council Advanced Grant STRATUS (ERC-2011-AdG No. 291198). J.C. acknowledges support by the Royal Society Dorothy Hodgkin Fellowship and The University of Sheffield’s Vice- Chancellor’s Fellowship scheme.This is the final published version. It was first made available by ACS at http://pubs.acs.org/doi/abs/10.1021/jacs.5b01130