A lack of focus on data sharing, stakeholders, and economic benefits in current global green infrastructure planning.

Green infrastructure (GI) is increasingly popular in solving urban environmental challenges and enhancing ecosystem services. Yet the research status and challenges of GI planning have not been comprehensively benchmarked to date. We explored the GI types, actions, goals, and spatiotemporal characteristics of GI planning cases worldwide based on the available literature. The challenges of GI planning were also investigated by the cases included in this manuscript. Additionally, the urban governance solutions to address these challenges were proposed. We found that multi-type GI planning is the most popular. Data sharing, stakeholder participation, economic benefits and research funding for GI planning research were generally inadequate, although they have improved trend over time. Multiple-goal GI planning frequently has higher levels of data sharing, stakeholder participation and economic benefits than GI planning that just takes into account one purpose. We conclude that the future transformation of GI planning requires efficient data sharing mechanisms, effective co-design among stakeholders, systematic business models, and available research funding.

Lutein/ß-carotene ratio in extra virgin olive oil: An easy and rapid quantification method by Raman spectroscopy.

Carotenoids play an important role in the stability, freshness, and nutritional value of extra-virgin olive oil (EVOO). However, the carotenoid content in EVOO changes over time as a function of olive ripening and degrading events. A reliable quality marker is the ratio between the two most abundant carotenoids, namely lutein and ß-carotene, since the second degrades more rapidly. Thus, to obtain a fast quantification of the lutein/ß-carotene ratio in olive oil could deserve a certain interest. Resonant Raman spectroscopy is a rapid and non-destructive technique, widely applied for food chemical characterization. In this work, using high-performance liquid chromatography and UV-vis absorption spectroscopy as calibration techniques, we present a reliable method to assess the lutein/ß-carotene ratio in EVOO using a single Raman spectrum. The novel approach deserves several methodological and applicative interests, since it would allow rapid, on-site screening of EVOO quality and authenticity, especially if implemented as a portable system.

Revealing Soil and Tree Leaves Deposited Particulate Matter PTE Relationship and Potential Sources in Urban Environment.

Trees play a pivotal role in improving urban environmental quality and provide several ecosystem services including the removal of pollutants from the air, such as particular matter (PM) and potentially toxic elements (PTE). Therefore, understanding the tree PM and PTE capturing potential, also in connection with plant species, is of great concern, especially in urban areas. This study aims to reveal the link between the elemental composition of PM deposited on tree leaves and soils PTE contents, as well as to rank the PM capturing efficiency of 10 different tree species growing under the impact of urban environments. This also allowed us to test the efficiency of PM deposited on tree leaves as a PTE biomonitoring and pollution source identification tool, in the two biggest urban areas of Armenia. Indeed, high contents of PTE are detected in both soil- and leaf-deposited PM from sites characterized by the presence of localized and active pollution sources (i.e., industrial unites, high traffic, etc.), which are identified by specific tracers (such as Mo, Cu, Zn, Pb, and Cd). Among the studied tree species, the highest PM amount per unit leaf area is observed for Platanus orientalis, but elm species are also identified as promising canditates to be considered for their PM removing potential, and need to be included in future more details studies.

Comparing i-Tree Eco Estimates of Particulate Matter Deposition with Leaf and Canopy Measurements in an Urban Mediterranean Holm Oak Forest.

Trees and urban forests remove particulate matter (PM) from the air through the deposition of particles on the leaf surface, thus helping to improve air quality and reduce respiratory problems in urban areas. Leaf deposited PM, in turn, is either resuspended back into the atmosphere, washed off during rain events or transported to the ground with litterfall. The net amount of PM removed depends on crown and leaf characteristics, air pollution concentration, and weather conditions, such as wind speed and precipitation. Many existing deposition models, such as i-Tree Eco, calculate PM2.5 removal using a uniform deposition velocity function and resuspension rate for all tree species, which vary based on leaf area and wind speed. However, model results are seldom validated with experimental data. In this study, we compared i-Tree Eco calculations of PM2.5 deposition with fluxes determined by eddy covariance assessments (canopy scale) and particulate matter accumulated on leaves derived from measurements of vacuum/filtration technique as well as scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (leaf scale). These investigations were carried out at the Capodimonte Royal Forest in Naples. Modeled and measured fluxes showed good overall agreement, demonstrating that net deposition mostly happened in the first part of the day when atmospheric PM concentration is higher, followed by high resuspension rates in the second part of the day, corresponding with increased wind speeds. The sensitivity analysis of the model parameters showed that a better representation of PM deposition fluxes could be achieved with adjusted deposition velocities. It is also likely that the standard assumption of a complete removal of particulate matter, after precipitation events that exceed the water storage capacity of the canopy (Ps), should be reconsidered to better account for specific leaf traits. These results represent the first validation of i-Tree Eco PM removal with experimental data and are a starting point for improving the model parametrization and the estimate of particulate matter removed by urban trees.

A Reliable BioFET Immunosensor for Detection of p53 Tumour Suppressor in Physiological-Like Environment.

The concentration of wild-type tumour suppressor p53wt in cells and blood has a clinical significance for early diagnosis of some types of cancer. We developed a disposable, label-free, field-effect transistor-based immunosensor (BioFET), able to detect p53wt in physiological buffer solutions, over a wide concentration range. Microfabricated, high-purity gold electrodes were used as single-use extended gates (EG), which avoid direct interaction between the transistor gate and the biological solution. Debye screening, which normally hampers target charge effect on the FET gate potential and, consequently, on the registered FET drain-source current, at physiological ionic strength, was overcome by incorporating a biomolecule-permeable polymer layer on the EG electrode surface. Determination of an unknown p53wt concentration was obtained by calibrating the variation of the FET threshold voltage versus the target molecule concentration in buffer solution, with a sensitivity of 1.5 ± 0.2 mV/decade. The BioFET specificity was assessed by control experiments with proteins that may unspecifically bind at the EG surface, while 100pM p53wt concentration was established as limit of detection. This work paves the way for fast and highly sensitive tools for p53wt detection in physiological fluids, which deserve much interest in early cancer diagnosis and prognosis.

Innovative Characterization of Particulate Matter Deposited on Urban Vegetation Leaves through the Application of a Chemical Fractionation Procedure.

In this study, we have evaluated the efficiency of a chemical fractionation procedure for the characterization of both the water-soluble and the insoluble fraction of the main elemental components of particulate matter (PM) deposited on urban leaves. The proposed analytical approach is based on the chemical analysis of leaf washing solutions and membrane filters used for their filtration. The ionic concentration of leaf washing solutions was compared with their electrical conductivity, making it a valuable proxy for the quantification of the water-soluble and ionic fraction of leaf deposited PM. The chemical composition of both the water-soluble and the insoluble fraction of PM, resulting from this fractionation procedure, was compared with results obtained by scanning electron microscopy coupled with energy-dispersed X-Rays spectroscopy (SEM/EDX) and processed through chemometrics. Results obtained proved that the proposed approach is able to provide an estimation of total leaf deposited PM and it is highly reliable for the evaluation of the emission impact of different PM sources, being able to increase the selectivity of PM elemental components as specific source tracers; consequently providing useful information also for the assessment of human health risks.

An ultra-spatially resolved method to quali-quantitative monitor particulate matter in urban environment.

Monitoring the amount and composition of airborne particulate matter (PM) in the urban environment is a crucial aspect to guarantee citizen health. To focus the action of stakeholders in limiting air pollution, fast and highly spatially resolved methods for monitoring PM are required. Recently, the trees' capability in capturing PM inspired the development of several methods intended to use trees as biomonitors; this results in the potential of having an ultra-spatially resolved network of low-cost PM monitoring stations throughout cities, without the needing of on-site stations. Within this context, we propose a fast and reliable method to qualitatively and quantitatively characterize the PM present in urban air based on the analysis of tree leaves by scanning electron microscopy combined with X-ray spectroscopy (SEM/EDX). We have tested our method in the Real Bosco di Capodimonte urban park (Naples, Italy), by collecting leaves from Quercus ilex trees along transects parallel to the main wind directions. The coarse (PM10-2.5) and fine (PM2.5) amounts obtained per unit leaf area have been validated by weighting the PM washed from leaves belonging to the same sample sets. PM size distribution and elemental composition match appropriately with the known pollution sources in the sample sites (i.e., traffic and marine aerosol). The proposed methodology will then allow the use of the urban forest as an ultra-spatially resolved PM monitoring network, also supporting the work of urban green planners and stakeholders.

Vibrational Changes Induced by Electron Transfer in Surface Bound Azurin Metalloprotein Studied by Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy.

The copper protein azurin, due to the peculiar coupling of its optical and vibronic properties with electron transfer (ET) and its biorecognition capabilities, is a very promising candidate for bioelectronic, bio-optoelectronic and biosensor applications. However, a complete understanding of the fundamental processes relating azurin ET and its optical and vibronic characteristics with the charge transport mechanisms occurring in proteins bound to a conductive surface, the typical scenario for a biosensor or bioelectronic component, is still lacking. We studied azurin proteins bound to a gold electrode surface by scanning tunneling microscopy combined with tip-enhanced Raman spectroscopy (STM-TERS). Robust TER spectra were obtained, and the protein's vibronic response under optical excitation in resonance with its ligand-to-metal charge transfer band was found to be affected by the tunneling parameters, indicating a direct involvement of the active site vibrations in the electron transport process.

Structure, Dynamics, and Electron Transfer of Azurin Bound to a Gold Electrode.

Blue copper redox protein azurin (AZ) constitutes an ideal active element for building bionano-optoelectronic devices based on the intriguing interplay among its electron transfer (ET), vibrational, and optical properties. A full comprehension of its dynamical and functional behavior is required for efficient applications. Here, AZ bound to gold electrode via its disulfide bridge was investigated by a molecular dynamics simulation approach taking into account for gold electron polarization which provides a more realistic description of the protein-gold interaction. Upon binding to gold, AZ undergoes slight changes in its secondary structure with the preservation of the copper-containing active site structure. Binding of AZ to gold promotes new collective motions, with respect to free AZ, as evidenced by essential dynamics. Analysis of the ET from the AZ copper ion to the gold substrate, performed by the Pathways model, put into evidence the main residues and structural motifs of AZ involved in the ET paths. During the dynamical evolution of the bionanosystem, transient contacts between some lateral protein atoms and the gold substrate occurred; concomitantly, the opening of additional ET channels with much higher rates was registered. These results provide new and detailed insights on the dynamics and ET properties of the AZ-gold system, by also helping to rationalize some imaging and conductive experimental evidences and also to design new bionanodevices with tailored features.

How Does the Amount and Composition of PM Deposited on Platanus acerifolia Leaves Change Across Different Cities in Europe?

Particulate matter (PM) deposited on Platanus acerifolia tree leaves has been sampled in the urban areas of 28 European cities, over 20 countries, with the aim of testing leaf deposited particles as indicator of atmospheric PM concentration and composition. Leaves have been collected close to streets characterized by heavy traffic and within urban parks. Leaf surface density, dimensions, and elemental composition of leaf deposited particles have been compared with leaf magnetic content, and discussed in connection with air quality data. The PM quantity and size were mainly dependent on the regional background concentration of particles, while the percentage of iron-based particles emerged as a clear marker of traffic-related pollution in most of the sites. This indicates that Platanus acerifolia is highly suitable to be used in atmospheric PM monitoring studies and that morphological and elemental characteristics of leaf deposited particles, joined with the leaf magnetic content, may successfully allow urban PM source apportionment.

Lying-down metallic single-walled carbon nanotubes as efficient linkers for metalloprotein-based nanodevices.

Metalloproteins recently emerged as good candidates for signal transduction in bionanodevices, but the feasibility of such novel devices is strongly connected to the achievement of an efficient charge transport between single metalloproteins and metal electrodes. In this work, we propose the use of metallic single-walled carbon nanotubes as efficient linkers between metalloproteins and metal surfaces. By means of a conductive atomic force microscopy investigation, we compare the conduction across single yeast cytochrome c molecules covalently bound both to bare gold and to functionalized metallic single-walled carbon nanotubes lying on gold. At comparable forces applied by the microscope tip (i.e., comparable physical contact), the measured current is higher when a metallic single-walled carbon nanotubes is in between the metalloprotein and the gold surface. The analysis of the single molecule current responses by means of a non-resonant tunneling transport model suggests that the increasing in the conduction is due both to the strong electronic conjugation existing at the nanotubes/gold interface and to the participation of the nanotube electronic bands to the charge transport.

Mixing of electronic states in pentacene adsorption on copper.

By combining experimental and theoretical approaches, we study the adsorption of pentacene on copper as a model for the coupling between aromatic molecules and metal surfaces. Our results for the interface electronic structure are not compatible with a purely physisorption picture, which is conventionally employed for such systems. Nay, we demonstrate electronic mixing between molecular orbitals and metal electronic states.

Adsorption of pentacene on filled d-band metal surfaces: long-range ordering and adsorption energy.

The growth of pentacene on suitable metallic templates is studied by means of low-energy electron diffraction and ultraviolet photoelectron spectroscopy. Highly ordered pentacene single layers can be prepared by deposition on filled d-band metal templates kept at 370 K. The presence of the steps for the Cu(119) vicinal surface and of the Au troughs for the Au(110)-(1 x 2) surface allows the formation of commensurate long-range ordered structures with (3 x 7) and (3 x 6) periodicities, respectively. A detailed analysis of the molecular induced electronic states evolution is performed for different growth morphologies. The adsorption energy of the ordered molecular single layers on the Au(110) surface is lower (1.90 eV) than on the Cu vicinal surface (2.36 eV), where the steps enhance the molecule adsorption energy.

Core-shell photoabsorption and photoelectron spectra of gas-phase pentacene: experiment and theory.

The C K-edge photoabsorption and 1s core-level photoemission of pentacene (C22H14) free molecules are experimentally measured, and calculated by self-consistent-field and static-exchange approximation ab initio methods. Six nonequivalent C atoms present in the molecule contribute to the C 1s photoemission spectrum. The complex near-edge structures of the carbon K-edge absorption spectrum present two main groups of discrete transitions between 283 and 288 eV photon energy, due to absorption to pi* virtual orbitals, and broader structures at higher energy, involving sigma* virtual orbitals. The sharp absorption structures to the pi* empty orbitals lay well below the thresholds for the C 1s ionizations, caused by strong excitonic and localization effects. We can definitely explain the C K-edge absorption spectrum as due to both final (virtual) and initial (core) orbital effects, mainly involving excitations to the two lowest-unoccupied molecular orbitals of pi* symmetry, from the six chemically shifted C 1s core orbitals.