Nature-based solutions for monitoring the impact of vehicular particulate matter and for the preventive conservation of the Palatine Hill archaeological site in Rome, Italy.

Magnetic and chemical biomonitoring methodologies were applied to the southern slopes of the Palatine Hill archaeological area in Rome, Italy. Plant leaves and lichen transplants were respectively sampled and exposed between July 2022 and June 2023 to assess the impact of vehicular particulate matter from Via dei Cerchi, a trafficked road coasting Circus Maximus, towards the archaeological area upon the Palatine Hill. The magnetic properties of leaves and lichens, inferred from magnetic susceptibility, hysteresis loops and first order reversal curves, were combined with the concentration of trace elements. It was demonstrated that the bioaccumulation of magnetite-like particles, associated with tracers of vehicular emissions, such as Ba and Sb, decreased with longitudinal distance from the road, without any important influence of elevation from the ground. Lichens demonstrated to be more efficient biomonitors of airborne PM than leaves, irrespective of the plant species. Conversely, leaves intercepted and accumulated all PM fractions, including road dusts and resuspended soil particles. Thus, plant leaves are suitable for providing preventive conservation services that limit the impact of particulate pollution on cultural heritage sites within busy metropolitan contexts.

Assessing the impact of vehicular particulate matter on cultural heritage by magnetic biomonitoring at Villa Farnesina in Rome, Italy.

Magnetic biomonitoring methodologies were applied at Villa Farnesina, Rome, a masterpiece of the Italian Renaissance, with loggias frescoed by renowned artists such as Raffaello Sanzio. Plant leaves were sampled in September and December 2020 and lichen transplants were exposed from October 2020 to early January 2021 at increasing distances from the main trafficked road, Lungotevere Farnesina, introducing an outdoor vs. indoor mixed sampling design aimed at assessing the impact of vehicular particulate matter (PM) on the Villa Loggias. The magnetic properties of leaves and lichens - inferred from magnetic susceptibility values, hysteresis loops and first order reversal curves - showed that the bioaccumulation of magnetite-like particles, associated with trace metals such as Cu, Ba and Sb, decreased exponentially with the distance from the road, and was mainly linked to metallic emission from vehicle brake abrasion. For the frescoed Halls, ca. 30 m from the road, the exposure to traffic-related emissions was very limited or negligible. Tree and shrub leaves of the Lungotevere and of the Villa's Gardens intercepted much traffic-derived PM, thus being able to protect the indoor cultural heritage and providing an essential conservation service. It is concluded that the joint use of magnetic and chemical analyses can profitably be used for evaluating the impact of particulate pollution on cultural heritage within complex metropolitan contexts as a preventive conservation measure.

Redox-switchable devices based on functionalized graphene nanoribbons.

The possibility of tuning the electronic properties of graphene by tailoring the morphology at the nanoscale or by chemical functionalization opens interesting perspectives towards the realization of devices for nanoelectronics. Indeed, the integration of the intrinsic high carrier mobilities of graphene with functionalities that are able to react to external stimuli allows in principle the realization of highly efficient nanostructured switches. In this paper, we report a novel approach to the design of reversible switches based on functionalized graphene nanoribbons, operating upon application of an external redox potential, which exhibit unprecedented ON/OFF ratios. The properties of the proposed systems are investigated by electronic structure and transport calculations based on density functional theory and rationalized in terms of valence-bond theory and Clar's sextet theory.

Towards nano-organic chemistry: perspectives for a bottom-up approach to the synthesis of low-dimensional carbon nanostructures.

Low-dimensional carbon nanostructures, such as nanotubes and graphenes, represent one of the most promising classes of materials, in view of their potential use in nanotechnology. However, their exploitation in applications is often hindered by difficulties in their synthesis and purification. Despite the huge efforts by the research community, the production of nanostructured carbon materials with controlled properties is still beyond reach. Nonetheless, this step is nowadays mandatory for significant progresses in the realization of advanced applications and devices based on low-dimensional carbon nanostructures. Although promising alternative routes for the fabrication of nanostructured carbon materials have recently been proposed, a comprehensive understanding of the key factors governing the bottom-up assembly of simple precursors to form complex systems with tailored properties is still at its early stages. In this paper, following a survey of recent experimental efforts in the bottom-up synthesis of carbon nanostructures, we attempt to clarify generalized criteria for the design of suitable precursors that can be used as building blocks in the production of complex systems based on sp(2) carbon atoms and discuss potential synthetic strategies. In particular, the approaches presented in this feature article are based on the application of concepts borrowed from traditional organic chemistry, such as valence-bond theory and Clar sextet theory, and on their extension to the case of complex carbon nanomaterials. We also present and discuss a validation of these approaches through first-principle calculations on prototypical systems. Detailed studies on the processes involved in the bottom-up fabrication of low-dimensional carbon nanostructures are expected to pave the way for the design and optimization of precursors and efficient synthetic routes, thus allowing the development of novel materials with controlled morphology and properties that can be used in technological applications.

Multivariate chemical mapping of pigments and binders in easel painting cross-sections by micro IR reflection spectroscopy.

Paintings are composed of superimposed layers of inorganic and organic materials (pigments and binders). Knowledge of the stratigraphic sequence of these heterogeneous layers is fundamental for understanding the artist's painting technique and for conservation issues. In this study, micro-IR mapping experiments in reflection mode have been carried out on cross-sections taken from simulations of ancient easel paintings. The objective was to locate both organic binders and inorganic pigments. Chemical maps have been re-constructed using the common approach based on the integration of specific infrared bands. However, owing to the complexity of painting materials, this approach is not always applicable when dealing with broad and superimposed spectral features and with reststrahlen or derivative-like bands resulting from acquisition in reflection mode. To overcome these limitations, principal-component analysis has been successfully used for the re-construction of the image, extracting the relevant information from the complex full spectral data sets and obtaining reliable chemical distributions of the stratigraphy materials. Different pigment-binder combinations have been evaluated in order to understand limitations and strengths of the approach. Finally, the method has been applied for stratigraphic characterization of a cross-section from a 17th century wooden sculpture identifying both the original paint layer and the several overpaintings constituting the complex stratigraphy.

On the use of overtone and combination bands for the analysis of the CaSO4-H2O system by mid-infrared reflection spectroscopy.

With the aim of characterizing ground preparations of paintings by infrared reflection spectroscopy, the CaSO(4)-H(2)O system (gypsum/bassanite/anhydrite) has been re-investigated, evaluating and assigning the SO(4)(2-) and OH overtone and combination bands, respectively, in the ranges 1900-2700 cm(-1) and 5000-6000 cm(-1) resulting from reflection and high concentration transmission spectra. The second-order modes have been proven to be highly specific, reliable, and less affected by overlap with bands of organic binders and can hence be exploited for the identification of the sulfate hydration phase using infrared (IR) reflection spectroscopy. Subsequently, the characterization and identification of hydration phases in unknown sulfate-based ground preparations on authentic artworks have been carried out noninvasively by fiber-optic reflection IR spectroscopy and on cross-sections by infrared reflection micro-spectroscopy. The spectroscopic data collected both on standards and artworks have been cross-validated by X-ray diffraction.

In situ noninvasive study of artworks: the MOLAB multitechnique approach.

Driven by the need to study precious and irreplaceable artworks without compromising their integrity, researchers have undertaken numerous efforts to develop noninvasive analytical tools and methodologies that can provide a chemical description of cultural heritage materials without any contact with the object. The challenge is that artworks are made of complex mixtures, often with heterogeneous and unknown layered materials. Their components must be identified over a range of size scales, from the molecular identification of constituent compounds to the mapping of alteration phases. In this Account, we review recent research in spectroscopic techniques accessible from the mobile laboratory (MOLAB). The lab is equipped with an array of state-of-the-art, portable, and noninvasive instruments specifically tailored to tackle the different issues confronted by archaeologists, curators, and conservators. The MOLAB approach is suitable for studying a variety of objects, from ceramics to manuscripts or from historical wall paintings to contemporary canvases. We begin by discussing issues related to the acquisition and interpretation of reflectance or backscattered spectra from the surface of heterogeneous materials. Then we show how the selectivity needed for the noninvasive identification of pigments in paintings, even in mixtures or in layered matrices, can be acquired by combining elemental information from X-ray fluorescence with molecular and structural insights from electronic and vibrational spectroscopies. Discriminating between original pigments and restoration retouches is possible, even when both comprise similar chromophores, as highlighted in the study of paintings by Jordaens and Raphael. The noninvasive approach permits the examination of a very large number of artworks with a virtually limitless number of measurements. Thus, unexpected and uncommon features may be uncovered, as in the case of a lead pyroantimonate yellow doped with zinc that was discovered by micro-Raman and X-ray fluorescence on an Italian Renaissance majolica. For characterizing binding media, we discuss the strengths and limitations of using mid- and near-FTIR (Fourier transform infrared) spectroscopies supported by a multivariate statistical analysis, detailing the study of organic materials in a wall painting by Perugino and a survey of the painting technique on 18 contemporary paintings by Burri. In Michelangelo's David, we show how the noninvasive mapping of contaminants and alteration phases might inform decisions on preventive conservation plans. The multitechnique MOLAB approach overcomes the intrinsic limitation of individual spectroscopic methods. Moreover, the ability to analyze artworks without the need to move them is an invaluable asset in the study and preservation of cultural heritage.

Computational chemistry meets cultural heritage: challenges and perspectives.

Chemistry is central to addressing topics of interest in the cultural heritage field, offering particular insight into the nature and composition of the original materials, the degradation processes that have occurred over the years, and the attendant physical and chemical changes. On the one hand, the chemical characterization of the constituting materials allows researchers to unravel the rich information enclosed in a work of art, providing insight into the manufacturing techniques and revealing aspects of artistic, chronological, historical, and sociocultural significance. On the other hand, despite the recognized contribution of computational chemistry in many branches of materials science, this tool has only recently been applied to cultural heritage, largely because of the inherent complexity of art materials. In this Account, we present a brief overview of the available computational methods, classified on the basis of accuracy level and dimension of the system to be simulated. Among the discussed methodologies, density functional theory (DFT) and time-dependent DFT represent a good compromise between accuracy and computational cost, allowing researchers to model the structural, electronic, and spectroscopic properties of complex extended systems in condensed phase. We then discuss the results of recent research devoted to the computer simulation of prototypical systems in cultural heritage, namely, indigo and Maya Blue, weld and weld lake, and the pigment minium (red lead). These studies provide insight into the basic interactions underlying the materials properties and, in some cases, permit the assignment of the material composition. We discuss properties of interest in the cultural heritage field, ranging from structural geometries and acid-base properties to IR-Raman vibrational spectra and UV-vis absorption-emission spectra (including excited-state deactivation pathways). We particularly highlight how computational chemistry applications in cultural heritage can complement experimental investigations by establishing or rationalizing structure-property relations of the fundamental artwork components. These insights allow researchers to understand the interdependence of such components and eventually the composition of the artwork materials. As a perspective, we aim to extend the simulations to systems of increasing complexity that are similar to the realistic materials encountered in works of art. A challenge is the computational investigation of materials degradation and their associated reactive pathways; here the possible initial components, intermediates, final materials, and various deterioration mechanisms must all be simulated.

Complexation of apigenin and luteolin in weld lake: a DFT/TDDFT investigation.

A DFT-TDDFT investigation on the aluminium complexation of apigenin and luteolin has been carried out. We have focused our attention on these hydroxyflavonoids, which are the main components of weld, one of the earliest natural dyestuff used in art. In particular, weld, upon complexation with Al(iii) forms a highly prized lake which has been widely used in medieval manuscripts and easel paintings for its rich yellow colour and transparency. The experimental spectra of apigenin and luteolin upon addition of increasing [Al(3+)] show a general red-shift of the lowest absorption bands of both flavonoids spectra, associated with the presence of two and three isosbestic points for apigenin and luteolin, respectively. The molecular geometries of all the Al-apigenin and -luteolin complexes have been optimized, followed by calculation of the formation Gibbs free energies and UV-vis absorption spectra. The comparison between the computed absorption spectra of the Al-flavonoid complexes and the experimental ones corresponding to various limit [Al(3+)] concentrations has been used to discriminate between the possible complexation modes as well as the stoichiometry ratio. We have thus been able to associate specific Al-apigenin (-luteolin) complexes with the experimental absorption spectra as a function of the [Al(3+)] concentration, thus providing insights into the aluminium complexation of these hydroxyflavonoids and most importantly into the weld lake composition.

Cyclometalated Ir(III) complexes with substituted 1,10-phenanthrolines: a new class of efficient cationic organometallic second-order NLO chromophores.

Cyclometalated cationic Ir(III) complexes with substituted 1,10-phenanthrolines (1,10-phen), such as [Ir(ppy)(2)(5-R-1,10-phen)]Y (ppy=cyclometalated 2-phenylpyridine; R=NO(2), H, Me, NMe(2); Y(-)=PF(6) (-), C(12)H(25)SO(3) (-), I(-)) and [Ir(ppy)(2)(4-R,7-R-1,10-phen)]Y (R=Me, Ph) are characterized by a significant second-order optical non linearity (measured by the electrical field induced second harmonic generation (EFISH) technique). This nonlinearity is controlled by MLCT processes from the cyclometalated Ir(III), acting as a donor push system, to pi* orbitals of the phenanthroline, acting as an acceptor pull system. Substitution of cyclometalated 2-phenylpyridine by the more pi delocalized 2-phenylquinoline (pq) or benzo[h]quinoline (bzq) or by the sulfur-containing 4,5-diphenyl-2-methyl-thiazole (dpmf) does not significantly affect the mubeta absolute value, which instead is affected by the nature of the R substituents on the phenanthroline, the higher value being associated with the electron-withdrawing NO(2) group. By using a combined experimental (the EFISH technique and (1)H and (19)F PGSE NMR spectroscopy) and theoretical (DFT, time-dependent-DFT (TDDFT), sum over states (SOS) approach) investigation, evidence is obtained that ion pairing, which is controlled by the nature of the counterion and by the concentration, may significantly affect the mubeta values of these cationic NLO chromophores. In CH(2)Cl(2), concentration-dependent high absolute values of mubeta are obtained for [Ir(ppy)(2)(5-NO(2)-1,10-phen)]Y if Y is a weakly interacting anion, such as PF(6) (-), whereas with a counterion, such as C(12)H(25)SO(3) (-) or I(-), which form tight ion-pairs, the absolute value of mubeta is lower and quite independent of the concentration. This mubeta trend is partially due to the perturbation of the counterion on the LUMO pi* levels of the phenanthroline. The correlation between the mubeta value and dilution shows that the effect of concentration is a factor that must be taken into careful consideration.

An Efficient Parallel All-Electron Four-Component Dirac-Kohn-Sham Program Using a Distributed Matrix Approach.

We show that all-electron relativistic four-component Dirac-Kohn-Sham (DKS) computations, using G-spinor basis sets and state-of-the-art density fitting algorithms, can be efficiently parallelized and applied to large molecular systems, including large clusters of heavy atoms. The performance of the parallel implementation of the DKS module of the program BERTHA is illustrated and analyzed by some test calculations on several gold clusters up to Au32, showing that calculations with more than 25 000 basis functions (i.e., DKS matrices on the order of 10 GB) are now feasible. As a first application of this novel implementation, we investigate the interaction of the atom Hg with the Au20 cluster.

Proteomic strategies for the identification of proteinaceous binders in paintings.

The identification of proteinaceous components in paintings remains a challenging task for several reasons. In addition to the minute amount of sample available, complex and variable chemical composition of the paints themselves, possible simultaneous presence of several binders and contaminants, and degradation of the original materials due to aging and pollution are complicating factors. We proposed proteomic strategies for the identification of proteins in binders of paintings that can be adapted to overcome the requirements and difficulties presented by specific samples. In particular, we worked on (1) the development of a minimally invasive method based on the direct tryptic cleavage of the sample without protein extraction; (2) the use of microwave to enhance the enzymatic digestion yield, followed by the analysis of the peptide mixtures by nanoLC-MS/MS with electrospray ionization (ESI). Moreover, as an additional tool to tackle the problem of contaminating proteins, we exploited the possibility of generating an exclusion list of the mass signals that in a first run had been fragmented and that the mass spectrometer had to ignore for fragmentation in a subsequent run. The methods, tested on model samples, allowed the identification of milk proteins in a sample from paintings attributed to Cimabue and Giotto, thirteenth-century Italian masters, decorating the vaults of the upper church in the Basilica of St. Francis in Assisi, Italy.

Absorption and emission of the apigenin and luteolin flavonoids: a TDDFT investigation.

The absorption and emission properties of the two components of the yellow color extracted from weld (Reseda luteola L.), apigenin and luteolin, have been extensively investigated by means of DFT and TDDFT calculations. Our calculations reproduce the absorption spectra of both flavonoids in good agreement with the experimental data and allow us to assign the transitions giving rise to the main spectral features. For apigenin, we have also computed the electronic spectrum of the monodeprotonated species, providing a rationale for the red-shift of the experimental spectrum with increasing pH. The fluorescence emission of both apigenin and luteolin has then been investigated. Excited-state TDDFT geometry optimizations have highlighted an excited-state intramolecular proton transfer (ESIPT) from the 5-hydroxyl to the 4-carbonyl oxygen of the substituted benzopyrone moiety. By computing the potential energy curves at the ground and excited states as a function of an approximate proton transfer coordinate for apigenin, we have been able to trace an ESIPT pathway and thus explain the double emission observed experimentally.

In situ non-invasive investigation on the painting techniques of early Meissen Stoneware.

In situ, non-invasive investigations by means of portable X-ray fluorescence and fibre optic reflectance mid-infrared (mid-FTIR) spectroscopy of painted Böttger Stoneware objects have been carried out through the MOLAB transnational access to the Porcelain Collection of the Staatliche Kunstsammlungen in Dresden. It has been possible to gather information regarding the composition of the black glaze by applying a principal component analysis to the elemental analysis to distinguish between the variations of lead, iron and manganese compositions of each glaze. It has been furthermore feasible to combine molecular spectroscopy for characterization of the constituent painting materials, namely lead white as cerusite and hydrocerusite, the use of cinnabar, azurite and Prussian blue leading to a better knowledge of the state of conservation and utility of certain pigments that may give rise to chronology of the decorative artwork. The identification of oxalates namely whedellite and moolooite are assigned as degradation products relative to the decorative areas.

First-principles investigations on the functionalization of chiral and non-chiral carbon nanotubes by Diels-Alder cycloaddition reactions.

Functionalization of single-walled carbon nanotubes through cycloaddition reactions constitutes an effective route to obtain novel nanostructured materials with interesting properties. In this paper, we perform density functional theory calculations on Diels-Alder reactions at the sidewall of armchair, zigzag and chiral nanotubes by applying finite-length models of carbon nanotubes based on Clar's theory of the aromatic sextet. The analysis of binding energies and molecular orbitals suggests a prevalence of local factors, related to the structural and electronic properties at the coordinating site, in controlling the overall energetics of cycloaddition reactions. Our results can be expected to have strong implications in the development of rational strategies for the functionalization of carbon nanotubes of any stereochemistry.

Cr(CO)3-activated Diels-Alder reaction on single-wall carbon nanotubes: a DFT investigation.

Breaking barriers: In agreement with experimental evidence, it was found by means of high-level DFT calculations that the Cr(CO)(3) metal fragment considerably reduces the reaction energy barrier-for both the concerted and stepwise reaction mechanisms (see graphic)-of the Diels-Alder reaction of butadiene on (5,5) carbon nanotubes.The reaction mechanism and the effect of Cr(CO)(3) on the Diels-Alder reaction of butadiene on (5,5) carbon nanotube sidewalls have been investigated by high-level DFT calculations. We investigated both concerted and stepwise reaction pathways on closed-shell and open-shell potential-energy surfaces. In agreement with recent experimental evidence, we found the Cr(CO)(3) metal fragment to considerably reduce the reaction energy barrier, both for the concerted and stepwise reaction mechanisms. The latter mechanism, previously found to be higher in energy with traditional substrates, appears to compete with the concerted mechanism on the carbon nanotube sidewalls. An analysis of the frontier molecular orbitals on the pristine and Cr(CO)(3)-complexed carbon nanotubes allowed us to identify the reason for this inverted reactivity pattern and the role of the transition metal on the addition of the diene.

A non-invasive XRF study supported by multivariate statistical analysis and reflectance FTIR to assess the composition of modern painting materials.

The palette used in two paintings by Paul Cézanne, L'étang des soeurs dated c. 1875 and La route tournante, made in the last year of his life (1902), were analyzed using non-invasive spectroscopic methods. X-ray fluorescence combined with principal components analysis (PCA) and supported by reflectance near- and mid-FTIR was shown to be a powerful analytical tool to draw conclusions about the chemical identification of inorganic materials in paintings. Pigments and fillers such us Thénard's blue, Prussian blue, red ochre, kaolin, vermilion, lead white, zinc white and barium sulphate, were identified. Evidence for three different pigments, namely a copper arsenite pigment, chrome green (a mixture of chrome yellow and Prussian blue) and viridian has been obtained by the PCA analysis of elemental compositions of green hues.

Poisson-transformed density fitting in relativistic four-component Dirac-Kohn-Sham theory.

We present recent developments in the implementation of the density fitting approach for the Coulomb interaction within the four-component formulation of relativistic density functional theory [Belpassi et al., J. Chem. Phys. 124, 124104 (2006)]. In particular, we make use of the Poisson equation to generate suitable auxiliary basis sets and simplify the electron repulsion integrals [Manby and Knowles, Phys. Rev. Lett. 87, 163001 (2001)]. We propose a particularly simple and efficient method for the generation of accurate Poisson auxiliary basis sets, based on already available standard Coulomb fitting sets. Just as is found in the nonrelativistic case, we show that the number of standard auxiliary fitting functions that need to be added to the Poisson-generated functions in order to achieve a fitting accuracy equal or, in some cases, better than that of the standard procedure is remarkably small. The efficiency of the present implementation is demonstrated in a detailed study of the spectroscopic properties and energetics of several gold containing systems, including the Au dimer and the CsAu molecule. The extraction reaction of a H(2)O molecule from a Au(H(2)O)(9) (+) cluster is also calculated as an example of mixed heavy-light-atom molecular systems. The scaling behavior of the algorithm implemented is illustrated for some closed shell gold clusters up to Au(5) (+). The increased sparsity of the Coulomb matrices involved in the Poisson fitting is identified, as are potential computational applications and the use of the Poisson fitting for the relativistic exchange-correlation problem.