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Nel corso della lunga campagna militare che Alfonso il Magnanimo condusse per la conquista di Napoli e del Mezzogiorno (1421-23 e 1435-42), la Sicilia svolse un ruolo fondamentale per il finanziamento della guerra, soprattutto grazie alle risorse provenienti dal regio demanio, ovvero quelle frutto delle imposte indirette e del commercio del grano. Per vie delle crescenti e urgenti esigenze economiche della Corona, nell¿ultima fase del conflitto Alfonso il Magnanimo ricorse in maniera più intensa alla tassazione diretta, promovendo nel contempo diverse altre strategie fiscali alternative. Tale processo, come si discute in questo articolo, emerse con particolare forza nel 1441-42, quando il sovrano elaborò un inedito programma fiscale per fare fronte al pagamento della condotta di Niccolò Piccinino e di diverse lettere di cambio. Da una parte, si richiese alle città demaniali e baronali dell¿isola il pagamento di una esosa composizione per i loro supposti crimini di usura, estendendo poi tale richiesta economica a tutti i sudditi del regno nella forma di una subventio generalis; dall¿altra parte, si provvide all¿imposizione di un prestito forzoso ad alcuni membri delle élite politiche, urbane e religiose dell¿isola., L’elaborazione di questo saggio è stata possibile grazie ai contributi del programma Beatriu de Pinós (n. 2018 BP 00274), finanziato dalla Direcció General de Recerca de la Generalitat de Catalunya e dall’Unione Europea mediante il programma COFUND (contratto n. 801370) delle Marie-Skłodowska-Curie actions, nel contesto di «Horizon 2020», nonché del progetto di ricerca Movimiento y movilidad en el Mediterráneo medieval. Personas, términos y conceptos, finanziato dal Ministerio de Ciencia, Innovación y Universidades (MICIU) del governo spagnolo (PGC2018-094502-B-I00). Il contributo si inserisce nel quadro delle ricerche realizzate dal gruppo di ricerca La Corona catalanoaragonesa, l'Islam i el món mediterrani medieval (CAIMMed), riconosciuto dalla Generalitat de Catalunya (2017 SGR 109).

Objectives. The mounting of the plaster casts on articulator procedure is routinely performed in orthognathic surgery to assess canting of the maxillary occlusal plane, but the currently used protocols and reference plane could be source of errors which affect reliability. Nowadays the assessment of canting of the maxillary occlusal plane could be also performed with an entirely digital protocol. Aim of the study was to propose a method to evaluate canting in patients affected by Unilateral Condylar Hyperplasia, comparing the measurements performed on digital models matched on CBCT with those made on traditional articulator. Materials and methods. A retrospective cross-sectional study was designed on 20 patients affected by vertical Unilateral Condylar Hyperplasia treated in the Units of Orthodontics and Maxillo-Facial Surgery. The canting of the maxillary occlusal plane was measured on plaster casts mounted on the conventional articulator and the measures were compared with those made on digital models matched on CBCT, according the protocol developed in our Unit. Molar, canine and basal difference were measured. To compare the two protocols and to test the agreement, we performed descriptive statistics, comparison between means and Bland Altman analysis. P value was set at 0.05. Results. Statistic comparison demonstrated agreement between measurements performed with the digital protocol and conventional physical method. Conclusion. Measurements of canting with digital protocol are comparable to the physical standard method. A total digital protocol allows faster availability and storage of patient's data and better communication between orthodontist and maxillo-facial surgeon, especially in patients affected by three-dimensional malocclusions.

Crystallization of alkaline earth metal carbonates from water is important for biomineralization and environmental geochemistry. Here, large-scale computer simulations are a useful approach to complement experimental studies by providing atomistic insights and even by quantitatively determining the thermodynamics of individual steps. However, this is dependent on the existence of force field models that are sufficiently accurate while being computationally efficient enough to sample complex systems. Here, we introduce a revised force field for aqueous alkaline earth metal carbonates that reproduces both the solubilities of the crystalline anhydrous minerals, as well as the hydration free energies of the ions. The model is also designed to run efficiently on graphical processing units thereby reducing the cost of such simulations. The performance of the revised force field is compared against previous results for important properties relevant to crystallization, including ion-pairing and mineral–water interfacial structure and dynamics. This article is part of a discussion meeting issue ‘Supercomputing simulations of advanced materials’.

Mitoviruses in the family Mitoviridae are the mitochondria-replicating “naked RNA viruses” with genomes encoding only the replicase RNA-dependent RNA polymerase (RdRp) and prevalent across fungi, plants, and invertebrates. Arbuscular mycorrhizal fungi in the subphylum Glomeromycotina are obligate plant symbionts that deliver water and nutrients to the host. We discovered distinct mitoviruses in glomeromycotinian fungi, namely “large duamitovirus,” encoding unusually large RdRp with a unique N-terminal motif that is endogenized in some host genomes. More than 400 viral sequences similar to the large duamitoviruses are present in metatranscriptome databases. They are globally distributed in soil ecosystems, consistent with the cosmopolitan distribution of glomeromycotinian fungi, and formed the most basal clade of the Mitoviridae in phylogenetic analysis. Given that glomeromycotinian fungi are the only confirmed hosts of these viruses, we propose the hypothesis that large duamitoviruses are the most ancestral lineage of the Mitoviridae that have been maintained exclusively in glomeromycotinian fungi.

Crystallisation of alkaline earth metal carbonates from water is important for biomineralisation and environmental geochemistry. Here large-scale computer simulations are a useful approach to complement experimental studies by providing atomistic insights and even by quantitatively determining the thermodynamics of individual steps. However, this is dependent on the existence of force field models that are sufficiently accurate while being computationally efficient enough to sample complex systems. Here we introduce a revised force field for aqueous alkaline earth metal carbonates that reproduces both the solubilities of the crystalline anhydrous minerals, as well as the hydration free energies of the ions. The model is also designed to run efficiently on GPUs thereby reducing the cost of such simulations. The performance of the revised force field is compared against previous results for important properties relevant to crystallisation, including ion-pairing and mineral-water interfacial structure and dynamics.

In this study, the adaption of the recently published molecular GFN-FF for periodic boundary conditions (pGFN-FF) is described through the use of neighbor lists combined with appropriate charge sums to handle any dimensionality from 1D polymers to 2D surfaces and 3D solids. Numerical integration over the Brillouin zone for the calculation of π bond orders of periodic fragments is also included. Aside from adapting the GFN-FF method to handle periodicity, improvements to the method are proposed in regard to the calculation of topological charges through the inclusion of a screened Coulomb term that leads to more physical charges and avoids a number of pathological cases. Short-range damping of three-body dispersion is also included to avoid collapse of some structures. Analytic second derivatives are also formulated with respect to both Cartesian and strain variables, including prescreening of terms to accelerate the dispersion/coordination number contribution to the Hessian. The modified pGFN-FF scheme is then applied to a wide range of different materials in order to examine how well this universal model performs.

Carbon nanodots, a class of carbon nano-allotropes, have been synthesized through different routes and methods from a wide range of precursors. The selected precursor, synthetic method, and conditions can strongly alter the physicochemical properties of the resulting material and their intended applications. Herein, carbon nanodots (CNDs) have been synthesized from d-glucose by combining pyrolysis and chemical oxidation methods. The effect of the pyrolysis temperature, equivalents of oxidizing agent, and refluxing time were studied on the product and quantum yield. In the optimum conditions (pyrolysis temperature of 300 °C, 4.41 equiv of H

In the last decade, the use of graphene supported on solid surfaces has broadened its scope and applications, and graphene has acquire a promising role as a major component of high-performance electronic devices. In this context, the chemical modification of graphene has become essential. In particular, covalent modification offers key benefits, including controllability, stability, and the facility to be integrated into manufacturing operations. In this Review, we critically comment on the latest advances in the covalent modification of supported graphene on substrates. We analyze the different chemical modifications with special attention to radical reactions. In this context, we review the latest achievements in reactivity control, tailoring electronic properties, and introducing active functionalities. Finally, we extended our analysis to other emerging 2D materials supported on surfaces, such as transition metal dichalcogenides, transition metal oxides, and elemental analogs of graphene.

Carbon dots are emerging in the nanotechnology field as the newest class of fluorescent probes, owing to their high water-solubility, good chemical and photo-stability and tunable photoluminescence. The ability of metal cations to quench carbon dots fluorescence is already well known. Anyway, a dedicated study directed to the rational design of the optimal carbon dot probe is still missing. Herein we present a novel synthetic method for the production of carbon nanodots from an economic and environmental polluting starting material: olive solid wastes. The obtained carbon dots are efficiently quenched in presence of Fe3+, allowing the cation detection. Starting from a comprehensive study on their quenching mechanism, we have been able to develop effective strategies to modulate the sensing properties of these carbon dots. The sensitivity and linear range of the probe have been tuned by modulating the surface functionalization of the nanoparticles. The selectivity toward Fe3+ has been improved by growing around the dots a porous microsphere of ion imprinted polymer. The results highlighted in this work demonstrate that the carbon dots sensing properties can be modulated to meet the requirement of the users, allowing the design of tailored probes for a wide range of applications.

Nano-bionics have the potential of revolutionizing modern medicine. Among nano-bionic devices, body sensors allow to monitor in real-time the health of patients, to achieve personalized medicine, and even to restore or enhance human functions. The advent of two-dimensional (2D) materials is facilitating the manufacturing of miniaturized and ultrathin bioelectronics, that can be easily integrated in the human body. Their unique electronic properties allow to efficiently transduce physical and chemical stimuli into electric current. Their flexibility and nanometric thickness facilitate the adaption and adhesion to human body. The low opacity permits to obtain transparent devices. The good cellular adhesion and reduced cytotoxicity are advantageous for the integration of the devices in vivo. Herein we review the latest and more significant examples of 2D material-based sensors for health monitoring, describing their architectures, sensing mechanisms, advantages and, as well, the challenges and drawbacks that hampers their translation into commercial clinical devices.

Enzymes are ideal receptors for biosensors since they offer excellent selectivity and high catalytic activity. However, once removed from their native environment, enzymes present a short lifespan determining a huge drawback for their application in bio-analytical systems. The use of appropriate immobilization matrices is an effective strategy to preserve enzymatic activity. In this work, an enzymatic amperometric biosensor is designed by entrapping lactate oxidase into a protein-based immobilization matrix, formed by the self-assembly of engineered repeat proteins. Electrochemically exfoliated graphene, functionalized with cobalt phthalocyanine, is employed as electroactive material and transducer of the sensor. Due to the extraordinary enzymatic stabilization provided by the engineered protein film, the device sensitivity is preserved for more than 6 months at room temperature. Furthermore, the presented biosensor can detect lactate with outstanding performance in terms of sensitivity, repeatability, and reproducibility.

Objective Pierre Robin Sequence (PRS) is a heterogeneous pathological condition characterized by the coexistence of micrognathia, glossoptosis, and cleft palate, resulting in upper airway tract obstruction. Among the treatment modalities, the orthodontic approach is one part of the comprehensive care of those patients and will be present in the treatment modalities during all the growth period of the child. Methods All patients with PRS observed in the period 2013-2017 were treated with a definite functional approach. The results were retrospectively analyzed with regard to functional outcome, total treatment time, and number of plates provided for a single patient. Results In all the patients, the indicated treatment protocol has been applied as early impression and plate supply, stimulation of bottle feeding with the use of the plate, eventual substitution of the plate if no more adequate to the transverse and sagittal growth of the palate, and continuing the use until the surgical closure of the cleft. All the patients showed a positive outcome to the proposed treatment approach, evaluated with regard to the incidence of feeding improvement and weight gain, to the limit for the surgical phase, in the absence of adverse effects. Conclusion The use of a functional obturator plate, removing functional alterations to mandibular growth, reduces and, in some cases, eliminates the need for surgical intervention. As also stated in the literature, if despite the presence of the plate nutritional problems persist, immediate different surgical approaches, mainly mandibular osteodistraction, become necessary.

The management of patients suffering from class III due to syndromic craniosynostosis requires a multidisciplinary team to prevent and correct the complex clinical features related to the syndrome. Among the main clinical features, the midface hypoplasia requires surgical advancement with a rigid external distraction device. The comparison of pre- and postdistraction lateral cephalometries is often difficult in these patients, because the craniofacial advancement mobilizes the landmarks routinely used in cephalometry. Aim of this study is to evaluate occlusal, maxillary, and facial changes obtained after the midface osteodistraction using as reference the PM plane, that does not undergo postsurgical spatial modifications.The before and after surgery lateral X-rays of 12 patients were compared to test the cephalometric protocol: 10 angles and 11 linear distances were evaluated.The cephalometric comparison before and after osteodistractions of syndromic class III, using as reference the Enlow's PM plane, has confirmed the data present in current literature, consisting in forward and downward movements of facial middle 3rd, with clockwise rotation of the splanchnocranium and increase of the facial heights. The use of the PM plane as reference could be the solution to problems that have been an obstacle for the study of occlusal and facial changes in patients affected by craniofacial dysostosis.

An important goal of higher education is to shape the behavior of future citizens by influencing conscious students.The work is aimed at presenting the methodology for assessing “competencies in the field of sustainable development” acquired during university studies in non-formal and informal learning contexts. Given the absence of a framework, but following the criteria established by the “Council Recommendation of 20thDecember 2012 on the validation of non-formal and informal learning” (2012/C 398/01), a model called “Higher Education for Sustainability Competencies” (HE4SC) has been developed. Starting from the 17 Sustainable Development Goals by United Nations, the model allows evaluating the theoretical and practical knowledge achieved by students through their university educational path and environment. The main idea of the proposed model is to translate the Sustainable Development Goals into “sustainability competences” of individuals, developed in non-formal and informal learning contexts. In defining the model, it is important to single out a “sponsor” of sustainability, that will guarantee the activities that can support the acquisition of competencies by students; identify the Sustainable Development Goals more appropriate for the specific analysis; make classification of “competencies in the field of sustainable development” for the chosen goals; determine the level that is considered acceptable for each “competence in sustainable development” in accordance with the scheme of the European Qualifications Framework. While underestimating the contribution of the university environment and ways to improve the transfer of knowledge, skills and competencies, a balance between “sustainability competencies” can be achieved through the HE4SC model.

Since graphene was exfoliated in 2004, two-dimensional (2D) materials have received great attention due to their physical and chemical properties associated with their nanosized thickness and the correlated quantum size effect. 2D planes allow the confinement of charge carriers, heat, and photons, leading to the remarkable electronic and optical properties of these materials. The Faraday Discussion "Chemistry of 2-dimensional materials: beyond graphene" has been an incredible showcase for a variety of highly interesting contributions in the field. This conference comprised a large number of aspects of the topic: from their synthesis and the study of their optical and physical properties to their numerous applications. These concluding remarks aim to capture the recent developments in 2D materials chemistry and physics that were presented and debated during this Faraday Discussion, and more generally in the research field in recent years. Particular attention will be paid to aspects like the synthesis of the materials, their toxicity and biodegradation, and some of their major applications in catalysis, as well as Li-ion batteries, water filtration and sensing. In addition we aim to highlight future challenges that still need to be addressed.

The detection of cancer biomarkers at an early stage of tumor development is vital for effective diagnosis and treatment of cancer. Current diagnostic tools can often detect cancer only when the biomarker levels are already too high, so that the tumors have spread and treatments are less effective. It is urgent therefore to develop highly sensitive assays for the detection of such biomarkers at the lowest possible concentration. In this context, we developed a sandwich immunoassay based on surface-enhanced Raman scattering (SERS) for the ultrasensitive detection of α-fetoprotein (AFP), which is typically present in human serum as a biomarker indicative of early stages of hepatocellular carcinoma. In the immunoassay design, molybdenum disulfide (MoS2) modified with a monoclonal antibody was used as a capture probe for AFP. A secondary antibody linked to an SERS-encoded nanoparticle was employed as the Raman signal reporter, that is, the transducer for AFP detection. The sandwich immunocomplex “capture probe/target/SERS tag” was deposited on a silicon wafer and decorated with silver-coated gold nanocubes to increase the density of “hot spots” on the surface of the immunosensor. The developed SERS immunosensor exhibits a wide linear detection range (1 pg mL–1 to 10 ng mL–1) with a limit of detection as low as 0.03 pg mL–1 toward AFP with good reproducibility (RSD < 6%) and stability. These parameters demonstrate that the proposed immunosensor has the potential to be used as an analytical platform for the detection of early-stage cancer biomarkers in clinical applications.

In the last twenty years, anthropologists, archivists, and historians have dedicated increased attention to the study of archives as objects of research themselves. In so doing, scholars have predominantly examined the emergence and transformations of archives during the early modern age, focusing mostly on political and diplomatic depositories. They have tended to neglect financial archives, which is unfortunate, as—alongside judicial archives—they were probably the largest documentary repositories of the pre-modern world and those that first faced the problem of managing huge masses of documentation. This article discusses the formation and development of the Kingdom of Sicily’s financial archives in the later Middle Ages, arguing that this repository evolved into a collecting archive by the early fifteenth-century, when it preserved not only the records and accounts produced by the central financial administration, but also those from a number of territorial officers and magistracies. This archival turn, I suggest, originated from the fact that the Crown of Aragon’s rulers constantly needed increased incomes to fund bureaucracies and warfare and exercise patronage, and thus needed financial information organized, at hand, and under their control. After briefly discussing the emergence of the financial archive in the thirteenth-century, this essay traces the Crown’s attempts to create a stable repository for storing financial records and accounts and its continuous struggles to prevent documentation from being scattered and dispersed. Finally, it examines the successful strategy that King Alfonso V of Aragon (1416–58), called the Magnanimous, pursued to organize financial documentation and concentrate records and accounts produced by financial administration into a stable building. The essay pays particular attention to the material aspects of preserving records, e.g., the restoration of buildings, construction of chests, and preparation of secure locks that were integral to the emergence of collecting archives for financial documents in the later Middle Ages., This work was supported by the Beatriu de Pinós programme (2018 BP 00274), funded by the Direcció General de Recerca de la Generalitat de Catalunya and by the European Union through the COFUND programme (contract no. 801370) for Marie-Skłodowska-Curie actions in the “Horizon 2020” programme, and and by the research project ‘Movement and mobility in the medieval Mediterranean. People, terms, and concepts (PGC2018-094502-B-I00), funded by the Spanish Ministry of the Science, Innovation and Universities (MICINN). Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature.

The detection of cancer biomarkers at an early stage of tumor development is vital for effective diagnosis and treatment of cancer. Current diagnostic tools can often detect cancer only when the biomarker levels are already too high, so that the tumors have spread and treatments are less effective. It is urgent therefore to develop highly sensitive assays for the detection of such biomarkers at the lowest possible concentration. In this context, we developed a sandwich immunoassay based on surface-enhanced Raman scattering (SERS) for the ultrasensitive detection of alpha-fetoprotein (AFP), which is typically present in human serum as a biomarker indicative of early stages of hepatocellular carcinoma. In the immunoassay design, molybdenum disulfide (MoS2) modified with a monoclonal antibody was used as a capture probe for AFP. A secondary antibody linked to an SERS-encoded nanoparticle was employed as the Raman signal reporter, that is, the transducer for AFP detection. The sandwich immunocomplex "capture probe/target/SERS tag" was deposited on a silicon wafer and decorated with silver-coated gold nanocubes to increase the density of "hot spots" on the surface of the immunosensor. The developed SERS immunosensor exhibits a wide linear detection range (1 pg mL(-1) to 10 ng mL(-1)) with a limit of detection as low as 0.03 pg mL(-1) toward AFP with good reproducibility (RSD < 6%) and stability. These parameters demonstrate that the proposed immunosensor has the potential to be used as an analytical platform for the detection of early-stage cancer biomarkers in clinical applications E.E. is grateful for a fellowship from the Scientific and Technological Research Council of Turkey (TUBITAK). A.C. and A.S. thank MINECO for their research grant (Juan de la Cierva.Incorporacion/no. IJCI-2016-31113, Juan de la Cierva. Formacion/no. FJC2018-036777-I, respectively). We thank Dr. Judith Langer for support in the interpretation of SERS results. This work was supported by the European Union's Horizon 2020 research and innovation program under Grant Agreements 785219 and 881603 Graphene Flagship. L.M.L.-M. acknowledges funding from the European Research Council (ERC-AdG-2017#787510). M.P., as the recipient of the AXA Bionanotechnology Chair, is grateful to the AXA Research Fund for financial support. This work was performed under the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency.grant no. MDM-20170720

Gene expression analysis is a broadly used and powerful technique in many fields of biological research. The expression pattern of specific marker genes provides an insight into complex regulatory networks and leads to the identification of relevant genes associated to specific biological processes, such as arbuscular mycorrhizal symbiosis. Among the existing gene expression analysis toolbox, reverse transcriptase coupled to quantitative polymerase chain reaction (qRT-PCR) is considered the gold standard for accurate, sensitive, fast, and relatively inexpensive measurement. However, for a correct identification of differentially expressed genes, appropriate controls are required in order to minimize nonspecific variations associated with intrinsic technical variability. In this chapter, we recommend a number of tips to use qRT-PCR analysis in mycorrhizal roots and fungal mycelium.

This article argues that the late-medieval Catalan-Aragonese kings and their viceroys relied on record-keeping as a practical means of government, in essence for controlling the Kingdom of Sicily f...

PurposeThe purpose of this paper is to build a theoretic and practical framework, based on agile project management, to support the decision-making process in order to help companies in optimizing the reengineering production processes and improve management costs.Design/methodology/approachThis paper seeks to propose an agile Reengineering Performance Model (ARPM) for managing projects of reengineering of processes and applies it in a real case study concerning a water bottling plant.FindingsThe proposed model should serve as a valuable tool to facilitate a successful business process reengineering design in the project management and intends to assist companies as they operate projects of transferring and optimizing production lines. Thanks to the use of ARPM tools, it is easy to modify the evolution of the project, with the possibility of extending or enhancing the application if necessary.Research limitations/implicationsThe main limits of the ARPM model are: it requires close collaboration among team; it is rather intense for developers; and it is necessary flexibility to change course as needed and to ensure delivery of the right product.Practical implicationsThe main implications of the authors’ work for research and business are to propose a structured methodological approach, rigorous but simple, suitable to implement in any companies.Originality/valueThe novelty of the approach is to apply the agile approach not for software development but in a manufacturing company.

In recent years, the most common need for companies consists in an increasingly efficient business process management and its continuous improvement. Companies are achieving this goal by implementing innovative approaches targeted on the individual project requirements. In this scenario, the present research aims to investigate, through a real pilot project, the benefits of implementing the agile project management (APM) framework based on a multi tools approach in order to re-engineering a business process (BPR). A real case study concerning a manufacturing plant is analyzed, in order to assess and highlight the effectiveness of the proposed model.

Density functional theory (DFT) with semiempirical dispersion corrections (DFT-D2) has been used to calculate the binding energy of a CO2 molecule on the calcite {10.4} surface for different positions and orientations. This generated potential energy landscape was then used to parametrize a classical force field. From this, we used metadynamics (MTD) to derive free energy profiles at 300 and 350 K for CO2 binding to calcite, CO2 binding with Ca2+, and pairing of two CO2 molecules, all for aqueous conditions. We subsequently performed classical molecular dynamics (MD) simulations of CO2 and water on the {10.4} surface at pressures and temperatures relevant for CO2 geological storage. Density profiles show characteristic structured water layering at the calcite surface and two distinct phases of water and CO2. We have also calculated the densities of the CO2-rich and water-rich phases and thereby determined the mutual solubilities. For all the pressures and temperatures in the studied range, CO2 was unable ...

SUMMARY We attempted to transfect six recently characterized virus species to protoplasts of Penicillium janczewskii and Chryphonectria parasitica. None of the recovered P. janczewskii colonies was positive for the transfected viruses, but Penicillium aurantiogriseum partiti-like virus 1 (PaPLV1) was detected in three distinct regenerated C. parasitica colonies. We screened the phenotype of the infected strains in up to 45 different conditions combining different media, salinity and temperatures: our results show that the infected strains grow slower than the virus- free in most of the tested conditions with the exception of halophilic stress in a specific nutrient combination media. We proceeded to characterize molecularly the population of distinct isolates of PaPLV1 infected C. parasitica through RNAseq: comparison to the viral population present in the original host -P. auratiogriseum- showed that two isolates accumulated non-synonymous mutations suggesting adaptation to the new host. RNAseq analyses identified a second genomic RNA segment and northern blot of RNA extracted from purified virus suspensions allowed establishing that PaPLV1 is at least bipartite in nature and that it forms isometric virions of circa 36-38 nm in diameter. In light of these new acquisitions, we discuss the taxonomic placement of PaPLV1 inside the Partitiviridae. This article is protected by copyright. All rights reserved.

Glyco-gold nanoparticles combine in a single entity the peculiar properties of gold nanoparticles with the biological activity of carbohydrates. The result is an exciting nanosystem, able to mimic the natural multivalent presentation of saccharide moieties and to exploit the peculiar optical properties of the metallic core. In this review, we present recent advances on glyco-gold nanoparticle applications in different biological fields, highlighting the key parameters which inspire the glyco nanoparticle design.

Safety is one of the most important issues in modern industrial plants and industrial activities. The Safety Engineering role is to ensure acceptable safety levels of production systems, not only t...

Ferrol, N.; Lanfranco, L. (Eds.) 2020 Arbuscular Mycorrhizal Fungi. Methods and Protocols. Vol 2146. pp. 257. ISBN 978 1 0716-0602-5, Gene expression analysis is a broadly used and powerful technique in many fields of biological research. The expression pattern of specific marker genes provides an insight into complex regulatory networks and leads to the identification of relevant genes associated to specific biological processes, such as arbuscular mycorrhizal symbiosis. Among the existing gene expression analysis toolbox, reverse transcriptase coupled to quantitative polymerase chain reaction (qRT-PCR) is considered the gold standard for accurate, sensitive, fast, and relatively inexpensive measurement. However, for a correct identification of differentially expressed genes, appropriate controls are required in order to minimize nonspecific variations associated with intrinsic technical variability. In this chapter, we recommend a number of tips to use qRT-PCR analysis in mycorrhizal roots and fungal mycelium.

In late medieval Sicily, the 'conservator' and the 'magistri rationales' conducted two separate but intertwined reviews of the accounts annually produced by the various monetary officers operating in the fragmented financial administration of the island. Whereas the control exercised by the 'magna curia rationum' followed the traditional procedure based on the audit of the accounts at the end of the administrative year, the conservator introduced an innovative revision practice that continued into the modern era. Through thorough inspection of the financial records, the 'conservatoria'’s staff were able to verify if the actual revenues and expenditures of the various officers in charge of collecting and delivering moneys and goods on behalf of the Crown were consistent with the budget that had been produced at the beginning of the year. The monitoring activity of the 'conservator' was possible thanks to the development since 1414 of an ingenious information management technology that combined bookkeeping and record-keeping methods. The material result of this intellectual development was the creation of a system through which the 'conservatoria'’s staff could organise an unprecedented amount of information, including any privilege, letter, decree, or any other documentation concerning the royal patrimony of the kingdom of Sicily into a book system of series and subseries dedicated to various specific financial matters. Among the various book series of the 'conservator', the so-called books of the accounts stand out as its most significant tools of administrative and financial knowledge. In essence, these books allowed the 'conservatoria'’s staff to produce annual accounts parallel to those officially prepared by the treasurer and the other principal financial officers of the realm. This system of information management gave the authorities – the Aragonese monarchs and the Sicilian viceroys on their behalf – the unique opportunity to collect detailed knowledge of the financial condition of the kingdom, even before the 'magistri rationales' conducted their formal auditing after the conclusion of the administrative year. In a composite polity such as the late medieval Crown of Aragon, whose territories were scattered across the Western Mediterranean, the many series of books of the 'conservator' thus resulted in a formidable governmental tool through which the monarchs could exercise their authority from afar on one of their dominions: the kingdom of Sicily. This vast financial and bureaucratic knowledge proved crucial for allocating the revenues and expenditures of the island according to the monarchs’ needs, in essence for supporting the expensive campaign for the conquest of Naples and the later Aragonese wars in Italy and in the Mediterranean basin.

Assessment of the risks and environmental impacts of carbon geosequestration requires knowledge about the wetting behavior of mineral surfaces in the presence of CO2 and the pore fluids. In this context, the interfacial tension (IFT) between CO2 and the aqueous fluid and the contact angle, theta, with the pore mineral surfaces are the two key parameters that control the capillary pressure in the pores of the candidate host rock. Knowledge of these two parameters and their dependence on the local conditions of pressure, temperature and salinity is essential for the correct prediction of structural and residual trapping. We have performed classical molecular dynamics simulations to predict the CO2–water IFT and the CO2–water–calcite contact angle. The IFT results are consistent with previous simulations, where simple point charge water models have been shown to underestimate the water surface tension, thus affecting the simulated IFT values. When combined with the EPM2 CO2 model, the SPC/Fw water model indeed underestimates the IFT in the low pressure region at all temperatures studied. On the other hand, at high pressure and low temperature, the IFT is overestimated by ~5 mN/m. Literature data regarding the water contact angle on calcite are contradictory. Using our new set of force field parameters, we performed NVT simulations at 323 K and 20 MPa to calculate the contact angle of a water droplet on the calcite {10.4} surface in a CO2 atmosphere. We performed simulations for both spherical and cylindrical droplet configurations for different initial radii, to study the size dependence of the water contact angle on calcite in the presence of CO2. Our results suggest that the contact angle of a cylindrical water droplet on calcite {10.4}, in the presence of CO2, is independent of droplet size, for droplets with a radius of 50 Å or more. On the contrary, spherical droplets make a contact angle that is strongly influenced by their size. At the largest size explored in this study, both spherical and cylindrical droplets converge to the same contact angle, 38 degrees, indicating that calcite is strongly wetted by water.

Background Small RNAs (sRNAs) are short non-coding RNA molecules (20–30 nt) that regulate gene expression at transcriptional or post-transcriptional levels in many eukaryotic organisms, through a mechanism known as RNA interference (RNAi). Recent studies have highlighted that they are also involved in cross-kingdom communication: sRNAs can move across the contact surfaces from “donor” to “receiver” organisms and, once in the host cells of the receiver, they can target specific mRNAs, leading to a modulation of host metabolic pathways and defense responses. Very little is known about RNAi mechanism and sRNAs occurrence in Arbuscular Mycorrhizal Fungi (AMF), an important component of the plant root microbiota that provide several benefits to host plants, such as improved mineral uptake and tolerance to biotic and abiotic stress. Results Taking advantage of the available genomic resources for the AMF Rhizophagus irregularis we described its putative RNAi machinery, which is characterized by a single Dicer-like (DCL) gene and an unusual expansion of Argonaute-like (AGO-like) and RNA-dependent RNA polymerase (RdRp) gene families. In silico investigations of previously published transcriptomic data and experimental assays carried out in this work provided evidence of gene expression for most of the identified sequences. Focusing on the symbiosis between R. irregularis and the model plant Medicago truncatula, we characterized the fungal sRNA population, highlighting the occurrence of an active sRNA-generating pathway and the presence of microRNA-like sequences. In silico analyses, supported by host plant degradome data, revealed that several fungal sRNAs have the potential to target M. truncatula transcripts, including some specific mRNA already shown to be modulated in roots upon AMF colonization. Conclusions The identification of RNAi-related genes, together with the characterization of the sRNAs population, suggest that R. irregularis is equipped with a functional sRNA-generating pathway. Moreover, the in silico analysis predicted 237 plant transcripts as putative targets of specific fungal sRNAs suggesting that cross-kingdom post-transcriptional gene silencing may occur during AMF colonization. Electronic supplementary material The online version of this article (10.1186/s12864-019-5561-0) contains supplementary material, which is available to authorized users.

This paper analyses both the attributes of carsharing transport modes (station-based and free-floating) and their relationship with other transport modes. Users' and stakeholders’ perspectives are synthesized from in-depth interviews in Spain. The elicitation of the comparative advantages of the two carsharing modes with respect to public transport and private vehicles helps identifying factors such as availability of parking, road pricing and convenience that drive the complementary and substitution property of carsharing with other transport modes. Interviews show the limited complementarity of carsharing with public transport, as well as the limited substitutability with private vehicles. Potential policy instruments to make carsharing coexist with public transport are discussed. The authors acknowledge support from the European Union Horizon 2020 research and innovations programme under grant agreement N?727524, Project: ?Enabling the Energy Union through understanding the drivers of individual and collective energy choices, in Europe?. This research is also supported by the Spanish State Research Agency through Mar?a de Maeztu Excellence Unit accreditation 2018?2022 (Ref. MDM-2017-0714); and by the Basque Government through the BERC 2018?2021 program. Alberto Ansuategi gratefully acknowledges financial support from the Spanish Ministry of Science and Innovation (grant RTI2018-093352-B-100) and the UPV/EHU (grant GIC18/29). Ibon Galarraga also wishes to acknowledge the financial support from the Government of Spain and the European Regional Development Fund through grant RTI2018-093692-B-I00.

Reliability target definition is a crucial aspect of any reliability analysis. In literature, there are two types of analysis. The first one, called ‘bottom-up’, goes back to the system's target using data of units through a fault tree analysis. Reliability data of components could be only partially available, particularly in the case of innovative systems. In the second type of analysis, called ‘top-down’, starting from similar systems, the target of each unit is defined, by applying allocation techniques. Also, in this case, reliability data of similar systems might not be available, and the choice of the most appropriate technique could be tricky. The purpose of the present research is to combine the advantages of both usual approaches. The newly developed approach is based on the integrated factors method, whose values are adjusted trough a multicriteria method, the analytic hierarchy process, depending on the importance of each factor and each unit. The innovation of the proposed model consists in its dynamism, as most of the literature methods use constant weights for the factors involved in reliability allocation. No method takes into account the assignment of a different level of significance (weight) to different units of the system, simultaneously with the considered factors. The developed approach has been applied on an aerospace prototype system. The results show the goodness of the new method and its ability to overcome the problems noted in literature. Copyright © 2017 John Wiley & Sons, Ltd.

Knowledge about the interaction between fluids and solids and the interfacial tension (IFT) that results is important for predicting behavior and properties in industrial systems and in nature, such as in rock formations before, during, and after CO2 injection for long-term storage. Many authors have studied the effect of the environmental variables on the IFT in the CO2–H2O system. However, experimental measurements above CO2 supercritical conditions are scarce and sometimes contradictory. Molecular modeling is a valuable tool for complementing experimental IFT determination, and it can help us interpret results and gain insight under conditions where experiments are difficult or impossible. Here, we report predictions for CO2–water interfacial tension performed using density functional theory (DFT) combined with the COSMO-RS implicit solvent model. We predicted the IFT dependence as a function of pressure (0–50 MPa), temperature (273–383 K), and salinity (0–5 M NaCl). The results agree well with literat...

In the biomedical applications of nanoparticles (NPs), the proper choice of surface chemistry is a crucial aspect in their design. The nature of the coating can heavily impact the interaction of NPs with biomolecules, affect the state of aggregation, and ultimately determine their biological fate. As such, protein corona formation and the aggregation behaviour of gold NPs (Au NPs) are studied here. Au NPs are prepared with four distinct surface functionalisations, namely mercaptosuccinic acid (MSA), N-4-thiobutyroil glucosamine, HS-PEG(5000) and HS-alkyl-PEG(600). Corona formation, aggregation, and the intracellular behaviour of the Au NPs are then investigated by means of Fluorescence Correlation Spectroscopy (FCS) in cell culture media and in live cells. To evaluate the state of aggregation and the formation of a protein corona, the Au NPs are incubated in cell media and the diffusion coefficient is determined via FCS. The in vitro behaviour is compared with the level of aggregation of the NPs in cells. Diffusion times of the NPs are estimated at different positions in the cell after a one hour incubation period. It is found that the majority of MSA and glucose-Au NPs are present inside the cell as slowly diffusing species with diffusion times (tau(D)) greater than 6000 mu s (hydrodynamic diameter > 250 nm). PEGylated Au NPs adsorb a small amount of protein and manifest low agglomeration both in media and in living cells. In particular, the HS-alkyl-PEG(600) coating shows an excellent correlation between lower protein adsorption, 4-fold lower compared to the MSA coated NPs, and limited intracellular aggregation. In the case of single HS-alkylPEG(600) coated NPs, it is found that typical intracellular tD values range from 500 to 1500 mu s, indicating that these particles display reduced aggregation in the intracellular environment.

The development of new molecules able to efficiently act as long-circulating computed tomography (CT) contrast agents is one of the most crucial topics in the biomedical field. In the last years, the chance to manipulate materials at the nano-size level gave new boost to this research, with the specific aim to design innovative nanoprobes. Gold nanoparticles (AuNPs) have showed unique X-rays attenuation properties which, combined with their easy surface functionalization, makes them ideal candidates for the next generation of contrast agents. In this paper, we present a rational and facile approach to synthesize engineered and water-stable AuNPs, achieving concentrated colloidal solution with high Hounsfield Units (HU). An accurate control of reagents ratio allowed us to design AuNPs with different shapes, from symmetrical to anisotropic morphology, in a convenient ‘one-pot’ fashion. Their activity as efficient and reliable CT contrast agents has been evaluated and compared. Moreover, glucosamine-functionalized gold nanoparticles have been developed ([Au] = 31.20 mg/mL; HU = 2453), in order to obtain a CT contrast agent able to combine spatial resolution with metabolic information. Copyright © 2016 John Wiley & Sons, Ltd.

Hetero-nanoparticles represent an important family of composite nanomaterials that in the past years are attracting ever-growing interest. Here, we report a new strategy for the synthesis of water dispersible cobalt ferrite nano particles (CoxFe3-xO4 NPs) decorated with ultrasmall (2-3 nm). gold nanoparticles (Au NPs). The synthetic procedure is based on the use of 2,3-meso-dimercaptosuccinic acid (DMSA), which plays a double role. First, it transfers cobalt ferrite NPs from the organic phase to aqueous media. Second, the DMSA reductive power promotes the in situ nucleation of gold NPs in proximity of the magnetic NP surface. Following this procedure, we achieved a water dispersible nanosystem (CoxFe3-xO4-DMSA-Au NPs) which combines the cobalt ferrite magnetic properties with the catalytic features of ultrasmall Au NPs. We showed that CoxFe3-xO4-DMSA-Au NPs act as an efficient nanocatalyst to reduce 4-nitrophenol to 4-aminophenol and that they can be magnetically recovered and recycled. It is noteworthy that such nanosystem is more catalytically active than Au NPs with equal size. Finally, a complete structural and chemical characterization of the hetero-NPs is provided.

From the late medieval period the Crown of Aragon was at the forefront of archival innovation. Culminating in the establishment of the Royal Archive of Barcelona in 1318, this development was not, as is traditionally stated, a mere imitation of external models but the result of an innovative historical process that had its roots in local history and reflected the structure of the Aragonese monarchy. As a result of the later enlargement and decentralization of the Crown, and especially after the advent of the House of Trastámara in 1414, the Aragonese developed an extensive system for record-keeping across the Mediterranean. By focusing on what I describe as a complex archival network, this article analyses a series of administrative developments, which are generally studied in isolation, as interrelated responses to similar needs across disparate and far-flung territories. The results differed within the Iberian dominions (Aragon, Majorca and Valencia) and in the Italian kingdoms of Sicily and Naples, with Sardinia somewhere in between. For all these differences, however, the establishment of a number of financial archives shows that this network had an especially crucial role in defending the royal patrimony in all the territories under the rule of the Crown of Aragon. The authorities also tried to use archives as tools for exercising pressure upon local political elites, as demonstrated, for instance, by the systematic inquiry into feudal possessions and pecuniary rights instigated by King Ferdinand II in early sixteenth-century Sicily. The outcome, however, was totally unexpected.

In 1412 Sicily lost its independence and became part of the Crown of Aragon. To rule the island, the new monarchs developed a system of long-distance government, through the action of local viceroys. But how did this system work in practice? This article engages with the lively historiographical debate about late medieval Sicily and more generally the Aragonese conglomerate by examining the series of libri quictacionum (‘books of quittances’) produced by the financial office, the Conservatoria regii patrimonii. It shows that the management of information – by means of a new genre of documents, an innovative record-keeping system and an apparatus of marginal annotations – became crucial in establishing effective government at a distance and in strengthening royal control over Sicilian institutions and officers. Moreover, these books and the documents they encompass highlight the social dynamics of the island and the emergence of an urban class: the Aragonese promoted the inclusion of the principal ...

Over the course of the fifteenth century, the Kingdom of Sicily faced significant institutional and administrative changes, originating from the need, on the part of the Aragonese sovereigns, to rule the island from afar. These developments resulted not only in the establishment of a new financial office (the conservator regii patrimonii), but also in innovations in the methods used for producing and recording documents, which in turn are reflected in the structures of the archival bindings and other material features that survive to this day. Through the analysis of material elements from the mise en page of the documents to their temporary filing systems and binding structures, this article focuses on the relationship between text and paratext in late-medieval Sicily, and casts light upon the carefully-crafted material forms of the document throughout its lifespan. In short, the Sicilian case study demonstrates how apparently mere material aspects played a crucial role for the government of a trans-Mediterranean monarchy such as the Crown of Aragon, as they allowed its kings – and their bureaucratic staff – to classify, organize, and use a growing amount of information in a way that fulfilled their administrative needs..

Purpose Cone-beam computed tomography (CBCT) is widely used for 3-dimensional assessments of cranio-maxillofacial relationships, especially in patients undergoing orthognathic surgery. We have introduced, for reference in CBCT cephalometry, an anatomical mid-sagittal plane (MSP) identified by the nasion, the midpoint between the posterior clinoid processes of the sella turcica, and the basion. The MSP is an updated version of the median plane previously used at our institution for 2D posterior-anterior cephalometry. This study was conducted to test the accuracy of the CBCT measures compared to those obtained using standard posterior-anterior cephalometry. Materials and methods Two operators measured the inter-zygomatic distance on 15 CBCT scans using the MSP as a reference plane, and the CBCT measurements were compared with measurements made on patients' posterior-anterior cephalograms. The statistical analysis evaluated the absolute and percentage differences between the 3D and 2D measurements. Results As demonstrated by the absolute mean difference (roughly 1 mm) and the percentage difference (less than 3%), the MSP showed good accuracy on CBCT compared to the 2D plane, especially for measurements of the left side. However, the CBCT measurements showed a high standard deviation, indicating major variability and low precision. Conclusion The anatomical MSP can be used as a reliable reference plane for transverse measurements in 3D cephalometry in cases of symmetrical or asymmetrical malocclusion. In patients who suffer from distortions of the skull base, the identification of landmarks might be difficult and the MSP could be unreliable. Becoming familiar with the relevant software could reduce errors and improve reliability.

In the present work, starting from well-known methodologies, a new reliability allocation method [critical flow method (CFM)] has been proposed. We focused on the most important conventional methods and discussed their limitations in order to motivate the current research. The results show the main common problem of the most conventional reliability allocation methods: they are developed for complex systems with series configurations but not for series–parallel ones. The consequence is an increase of the required units' reliability (series configuration) in order to guarantee the reliability system target. Actually, the design and manufacturing of a subsystem with an extremely low failure rate would consume a considerable amount of economic resources. The proposed method can solve the shortcomings of the conventional methods with a new reliability approach useful to series–parallel configurations in order to obtain an important cost saving. The CFM has been applied to a liquid nitrogen cooling installation in a thermonuclear system, with many series–parallel configurations in order to guarantee the whole safety system. The proposed technique can be applied to working complex systems, and, in general, in the design phase of new installations. By comparing the CFM application results with real parameters, the new technique has been validated. The computational results clearly demonstrate the advantages of the proposed method. In particular, by applying the method to series–parallel configurations, it allocates failure rates higher than conventional methods, with a component cost reduction. Copyright © 2015 John Wiley & Sons, Ltd.