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The automotive sector has recently been taking measures to reduce fuel consumption and greenhouse gas emissions for the mobility of ground vehicles. Light-weighting, via material substitution, and the re-designing of components or even a combination of the two, have been identified as a crucial solution. Additive manufacturing (AM) can be used to technologically complement or even replace conventional manufacturing in several industrial fields. The enabling of complexity-for-free (re) designs is inherent in additive manufacturing. It is expected that certain benefits can be achieved from the adoption of re-design techniques, via AM, that rely on topological optimisation, e.g., a reduced use of resources in both the material production and use phases. However, the consequent higher specific energy consumption and the higher embodied impact of feedstock materials could result in unsustainable environmental costs. This paper investigates the case of the light-weighting of an automobile component to quantify the outcomes of the systematic integration of re-designing and material substitution. A bracket, originally cast in iron, has been manufactured by means of a powder bed-based AM technique in AlSi10Mg through an optimized topology. Both manufacturing routes have been evaluated through a comparative Life Cycle Assessment (LCA) within cradle-to-grave boundaries. A 69%-lightweighting has been achieved, and the carbon dioxide emissions and energy demands of both scenarios have been compared. Besides the use-phase-related savings in terms of both energy and carbon footprint due to the lightweighting, the results highlight the environmental trade-offs and prompt the consideration of such a manufacturing process as an integral part of sustainable product development.

In modern optics, materials with large birefringence ({\Delta}n, where n is the refractive index) are sought after for polarization control (e.g. in wave plates, polarizing beam splitters, etc.), nonlinear optics and quantum optics (e.g. for phase matching and production of entangled photons), micromanipulation, and as a platform for unconventional light-matter coupling, such as Dyakonov-like surface polaritons and hyperbolic phonon polaritons. Layered "van der Waals" materials, with strong intra-layer bonding and weak inter-layer bonding, can feature some of the largest optical anisotropy; however, their use in most optical systems is limited because their optic axis is out of the plane of the layers and the layers are weakly attached, making the anisotropy hard to access. Here, we demonstrate that a bulk crystal with subtle periodic modulations in its structure -- Sr9/8TiS3 -- is transparent and positive-uniaxial, with extraordinary index n_e = 4.5 and ordinary index n_o = 2.4 in the mid- to far-infrared. The excess Sr, compared to stoichiometric SrTiS3, results in the formation of TiS6 trigonal-prismatic units that break the infinite chains of face-shared TiS6 octahedra in SrTiS3 into periodic blocks of five TiS6 octahedral units. The additional electrons introduced by the excess Sr subsequently occupy the TiS6 octahedral blocks to form highly oriented and polarizable electron clouds, which selectively boost the extraordinary index n_e and result in record birefringence ({\Delta}n > 2.1 with low loss). The connection between subtle structural modulations and large changes in refractive index suggests new categories of anisotropic materials and also tunable optical materials with large refractive-index modulation and low optical losses., Comment: Main text + supplementary

We report the synthesis and magneto-optical characterization of multifunctional heterometallic 2D MOFs, [TbxEu1−x(MeCOO)(PhCOO)2], that combine luminescence and SMM properties and afford exfoliation by sonication.

In Italy Alexandrium minutum is recurrently found at low concentrations in mussel farming areas, such as the Western Adriatic and the Sardinia coasts; mussels positive to PSP toxins have occasionally been detected but rarely exceeded the legal limit for commercial sale. Conversely, in South Italy, the Sicilian coast represents a hot spot of A. minutum blooms, repeatedly occurring in high densities. This study shows the presence of extensive blooms detected for the first time on the Jonian coast of Calabria at Roccella Jonica; the first bloom occurred in 2018, followed by a larger event in 2020. Both blooms occurred in March in the harbour dockyard, an area not monitored for toxic algae due to the absence of mussel farms. The blooms caused a yellow/brown water discoloration, but no PSP symptoms were reported. In order to understand if these blooms can cause harmful consequences, five Alexandrium strains were isolated from the 2018 event for molecular identification at the species level and analysis of the toxin content and profile. All strains were confirmed to belong to the A. minutum group and produce PSP toxins, with four out of five clones displaying higher toxin levels. The toxin profile displayed slight differences among strains, however, GTX 1,4 were the prevalent analogues, as previously observed in the Mediterranean region. Despite A. minutum blooms being rare events historically, intensive toxic blooms are increasing, especially on the South Italian coasts. This poses some concerns and highlights the need for better monitoring and management of the new identified spot and of nearby areas.

A highly enantioselective aza-Darzens reaction (up to 99% ee) catalyzed by an enantiopure supramolecular host has been discovered. To understand the role of host structure on reaction outcome, nine new gallium(III)-based enantiopure supramolecular assemblies were prepared via substitution of the external chiral amide. Despite the distal nature of the substitution in these catalysts, changes in enantioselectivity (61 to 90% ee) in the aziridine product were observed. The enantioselectivities were correlated to the flexibility of the supramolecular host scaffold as measured by the kinetics of exchange of a model cationic guest. This correlation led to the development of a best-in-class catalyst by substituting the gallium(III)-based host with one based on indium(III), which generated the most flexible and selective catalyst.

Background/aim To evaluate the impact of sarcopenia in muscle invasive bladder cancer (MIBC) elderly patients submitted to curative radiotherapy. Patients and methods Patients received radiotherapy between 2013 and 2018, and the skeletal muscle index was calculated to classify them as sarcopenic or non-sarcopenic. Primary endpoints were overall survival (OS), cancer specific survival (CSS), 90-day mortality and toxicity. Results A total of 28 patients with a median age of 85 years met our inclusion criteria and 8 of them were sarcopenic. With a median prescribed dose of 61 Gy and a median follow-up of 24.5 months, OS rates in the sarcopenic and non-sarcopenic groups were 100% and 84.4% at 3 months, 57.1% and 56.6% at 12 months, 38.1% and 50.3% at 24 months and 38.1% and 33.5% at 48 months, respectively; the CSS rates were 100% and 94.1% at 3 months and 68.6% and 88.2% at 12, 24 and 48 months, respectively. The actuarial 90-day mortality rate was 17.9% for the whole cohort, and 20% and 12.5% for the non-sarcopenic and sarcopenic groups, respectively. The radio-induced toxicity was similar in both groups. Conclusion Sarcopenia cannot be considered a negative prognostic factor for MIBC elderly patients treated with external beam radiotherapy. Irradiation is therefore a feasible and effective choice for these patients, especially if unfit for surgery.

In this article, the author, based on concrete factual material, explores the specifics of modern migration processes considered within an urban area localized in Palermo (Sicily). In the context of this complex heterotopic space, resorting to the conceptual apparatus of M. Foucault, this kind of rhizome, if we operate with the concepts of J. Deleuze and F.Guattari, the author analyzes the actions of various actors of power – local and transnational – which dominate in this closed socio-urban environment, outlined by the framework of certain city blocks, – formal and informal, institutionalized and not, state and extra-state, legal and illegal, political, social, ecclesiastical, economic, criminal, the objects of projection and manifestation of which are migrants (primarily illegal) concentrated in these urban areas, who coexist there with the local population. The author also studies reactions of “newcomers” to the factors that affect them, including their ways of understanding and familiarizing with of their new place of residence as a micro- and the macrocosm, in all the diversity and complexity of the social connections that permeate this habitat and the factors that affect it.

We present the case of a patient with vaginal mucosal melanoma who underwent complete remission after immunotherapy and ‘0-7-21’ radiotherapy regimen (24 Gy/3 fractions/21 days). An 80-year-old woman had a biopsy of a voluminous vaginal lesion and received a histological diagnosis of melanoma with angiomatoid aspects. The patient underwent immunotherapy with pembrolizumab 2 mg/kg every 3 weeks and was sent to our attention for planning radiotherapy as the extent of the lesion did not make it susceptible to surgery. Considering the concomitant administration of pembrolizumab, we chose to treat this patient with a modulated intensity radiation therapy technique delivering a hypofractionated dose of 24 Gy in 3 fractions delivered on days 0, 7, and 21. We observed a complete clinical remission of the melanoma 12 months after radiotherapy and she has been alive for 18 months with no clinical signs of local recurrence.

Gambling has increasingly become a problem in adolescence over the last 20 years. Previous research has failed to identify exactly the level of involvement of adolescents in gambling, yet a relevant presence of addictive behaviors was noticed.This narrative review highlights the implications of adolescent gambling, taking into consideration the main risk and protection factors aimed at limiting gambling activity, as well as the main links with the impulse-control disorder, addiction, and behavioral addiction.The review process was conducted through Medline, Scopus, Web of Science and Google Scholar search engines. The considered keywords were "Gambling" AND "Adolescence," "Behavioral addiction," AND "Adolescence." The articles related to gambling and adolescence in the last 20 years were included in compliance with inclusion and exclusion criteria, to perform a consistent analysis of the phenomenon and the related maintenance factors.Starting from 1067 articles, 107 were selected to denote the main thematic areas involved in the gambling problem. The online search was completed on December 13, 2019.The narrative review of literature can facilitate the analysis of gambling problems in adolescence, as the main studies in the last 20 years showed the complexity of the problem, the links between addiction, and the most effective methods of prevention and treatment.

Layered transition-metal dichalcogenides (TMDCs) host a plethora of interesting physical phenomena ranging from charge order to superconductivity. By introducing magnetic ions into 2H−TA2 (T=Nb, Ta; A=S, Se), the material forms a family of magnetic intercalated TMDCs MxTA2 (M=3d transition metal). Recently, Fe1/3+δNbS2 has been found to possess intriguing resistance switching and magnetic memory effects coupled to the Néel temperature of TN∼45 K [Maniv et al., Nat. Phys. 17, 525 (2021); Sci. Adv. 7, eabd8452 (2021)]. We present comprehensive single crystal neutron diffraction measurements on underintercalated (δ∼−0.01), stoichiometric, and overintercalated (δ∼0.01) samples. Magnetic defects are usually considered to suppress magnetic correlations and, concomitantly, transition temperatures. Instead, we observe highly tunable magnetic long-ranged states as the Fe concentration is varied from underintercalated to overintercalated, that is, from Fe vacancies to Fe interstitials. The under- and overintercalated samples reveal distinct antiferromagnetic stripe and zigzag orders, associated with wave vectors k1=(0.5,0,0) and k2=(0.25,0.5,0), respectively. The stoichiometric sample shows two successive magnetic phase transitions for these two wave vectors with an unusual rise-and-fall feature in the intensities connected to k1. We ascribe this sensitive tunability to the competing next-nearest neighbor exchange interactions and the oscillatory nature of the Ruderman-Kittel-Kasuya-Yosida mechanism. We discuss experimental observations that relate to the observed intriguing switching resistance behaviors. Our discovery of a magnetic defect tuning of the magnetic structure in bulk crystals Fe1/3+δNbS2 provides a possible new avenue to implement controllable antiferromagnetic spintronic devices., Physical Review X, 12 (2), ISSN:2160-3308

OBJECTIVE: Several studies addressed the psychological and physical consequences of caregiving. Literature suggests that the majority of caregivers would benefit from a psychological support. Despite this evidence, lots of caregivers are reluctant in seeking psychological help. The aim of the present study is to identify the sociodemographic characteristics and the psychological motivations of caregivers who request a support, in terms of gender, age, occupation, type of recipient pathology, perceived burden and experienced emotions. METHOD: Two hundred ninety-three caregivers, 70.4% females, aged between 20 and 80 years, were interviewed with a Questionnaire for Caregiver and the Caregiver Burden Inventory (CBI). RESULTS: Findings show that factors associated with caregivers help-seeking are not the objective ones (time spent in care, age, occupation), with the exeption for gender. The reasons are rather traceable in the type of pathology (physical vs. mental), the level of burden and the negative affects experienced. CONCLUSIONS: Focusing on the demand analysis could contribute in the clinical practice to better specify the objectives of the psychological and psychotherapeutic interventions.

Objective: Work-related stress typically occurs due to particularly challenging dynamics, risks and pressure. Prolonged exposure to stress may cause serious consequences on psychophysical well-being. The current study was conducted to reexamine the clinical instruments useful for evaluating the risk factors and to examine two closely linked dimensions, which may constitute protective factors such as coping strategies and satisfaction. Method: Through a narrative review of the scientific literature of the last 5 years, carried out through the PubMed, Web of Science and Scopus databases, the most relevant clinical instruments used in the evaluation of stress, job satisfaction and coping strategies were examined. Results: Based on the considered inclusion criteria, 142 articles were selected, and 10 of the most used psycho-diagnostic instruments were identified for the evaluation of the three dimensions. The selected assessment instruments were deeply discussed in order to highlight strengths and limitations. Conclusions: A variety of studies used a range of psycho-diagnostic tools in order to measure stress, coping strategies and job satisfaction. However, their integration is necessary to guarantee a complete evaluation protocol.

Stereotactic body radiation therapy in patients with spine metastases maximizes local tumor control and preserves neurologic function. A novel approach could be the use of stereotactic body radiation therapy with simultaneous integrated boost delivering modality. The aim of the present study is to report our experience in the treatment of spine metastases using a frameless radiosurgery system delivering stereotactic body radiation therapy–simultaneous integrated boost technique. The primary endpoints were the pain control and the time to local progression; the secondary ones were the overall survival and toxicity. A total of 20 patients with spine metastases and 22 metastatic sites were treated in our center with stereotactic body radiation therapy–simultaneous integrated boost between December 2007 and July 2018. Stereotactic body radiation therapy–simultaneous integrated boost treatments were delivered doses of 8 to 10 Gy in 1 fraction to isodose line of 50%. The median follow-up was 35 months (range: 12-110). The median time to local progression for all patients was not reached and the actuarial 1-, 2-, and 3-years local free progression rate was 86.36%. In 17 of 20 patients, a complete pain remission was observed and 3 of 20 patients had a partial pain remission (complete pain remission + partial pain remission: 100%). The median overall survival was 38 months (range 12-83). None of the patients experienced neither radiation adverse events (grade 1-4) nor reported pain flair reaction. None of the patients included in our series experienced vertebral compression fracture. Spine radiosurgery with stereotactic body radiation therapy–simultaneous integrated boost is safe. The use of this modality in spine metastases patients provides an excellent local control.

Background: Different treatments have been developed and used to control symptoms and improve quality of life in patients with digestive diseases and disorders. Although the use of drugs or alternative approaches has improved symptom severity in some but not all patients, often these improvements were not sustainable. Objectives: An open label clinical study was initiated to determine if oral capsules containing a dietary supplement of herbs and oils (GI RegenerateTM) could reduce self-reported gastrointestinal symptoms and improve quality of life (QOL) indicators in patients with gastrointestinal conditions. Methods: Participants included 50 patients (40 females and 10 males) of mean age of 51.1 ± 12.7 years (range, 24 - 77 years) with a diagnosis of a gastrointestinal disorder or gastrointestinal symptoms. These patients consumed five soft-gels containing the test supplement 30 minutes before each meal for 90 days. Symptoms were evaluated by medical staff, and patient health status was self-reported using a validated quality of life questionnaire (Quality of Life Digestive Survey) designed for functional digestive disorders. Exit interviews (Patient Global Impression of Change, PGIC) were conducted by the medical staff. Results: Participants in the study responded with improved symptom severities and QOL scores to the test dietary supplement within the 90 day period; most improvements occurred within 20 days on the test dietary supplement. By the end of the study there were significant overall global improvements in the symptoms and QOL health surveys (p = 0.0183), with significant improvements in symptom discomfort (p = 0.0004), daily activities (p = 0.029) and anxiety (p = 0.018). In contrast, there were insignificant improvements in diet (p = 0.398), sleep (p = 0.136), health perception (p = 0.686), coping with the disease (p = 0.309) and impact of stress (p = 0.785). Using the PGIC exit interview that measured each patient’s impression of overall global change in symptoms and QOL these data also indicated overall significant improvements in symptoms and in satisfaction with the test supplement (moderately better improvements in symptoms and QOL or score of 4.8 ± 0.169, p 50 years) versus younger (TM natural dietary supplement safely and significantly reduced gastrointestinal symptoms and improved quality of life in subjects with a broad spectrum of gastrointestinal disorders and symptoms.

Our experience with transsexual individuals in healthcare is based on a psychological path, where the needs expressed by subjects are considered in the perspective of the life-course. Comprehension and attention on psychological figures are considered as the expression of identity, desires and life projects. The current evolutions of the phenomenon open doors to the possibility to reduce the distance between sexual and gender identity, also considering the social role and all the interactions that Gender Dysphoric people have in their social interactions. This work has considered important guidelines suggested by APA, to share our experience on the themes of identity, affectivity and psychological phenomena involved in the clinical relationship. This occasion provided by puntOorg International Journal (PIJ), allows us to share our perspective, which can be considered as the intention to compare methods and practices.

Here we report the first series of in-plane thorium(IV), uranium(IV), and neptunium(IV) expanded porphyrin complexes. These actinide (An) complexes were synthesized using a hexa-aza porphyrin analogue, termed dipyriamethyrin, and the nonaqueous An(IV) precursors, ThCl

Brassica rupestris Raf. is a species native to South Italy, extremely rich in vitamins, fibers, and bioactive compounds with phytoterapic properties and may represent a resource for pharmaceutical and nutraceutical industries. Thus, our aim was to evaluate if and which soil properties affected the accumulation of secondary metabolites in B. rupestris. Knowledge of the causes of plant metabolism changes in a specific area may represent an important economic opportunity. We analyzed soils (physical and chemical parameters) in two different localities of B. rupestris growth and leaves (biocompounds and antioxidant activity) of B. rupestris grown over them to identify the soil factors that drove their phytochemical production and antioxidant power. Soil properties influenced the contents but not the types of the bioactive compounds in B. rupestris. No significant correlation was found between soil physical parameters and phytochemicals in Brassica leaves. Conversely, soil chemical and biochemical properties influenced the total antioxidant capacity and the synthesis of carotenoids and glucosinolates. Soil organic matter (SOM), dehydrogenase activity (DH), fluorescein diacetate hydrolysis (FDA), microbial biomass carbon (MBC), and humic acid/fulvic acid ratio (HA/FA) were the most important soil factors influencing the amount of phytochemicals in B. rupestris. A strict relationship between soil properties and metabolic profile of B. rupestris was found. The synthesis of specific classes of metabolites in B. rupestris is a direct response to soil biochemical conditions.

Hydrogen has been shown in several clinical trials to be completely safe without adverse events and there are no warnings in the literature of its toxicity or adverse effects during long-term exposure. Molecular hydrogen has proven useful and convenient as a novel antioxidant and modifier of gene expression in many conditions where oxidative stress and changes in gene expression result in cellular damage. Our intracellular biomarker studies have shown that a hydrogenized water drink formula containing 2.6 ppm dissolved hydrogen was able to penetrate cellular membranes and function as an antioxidant in human liver cells (HePG2) utilizing the Cellular Antioxidant Assay (CAA). This assay uses the protection of a florescent probe as a marker for cellular damage by reactive oxygen species (ROS), such as peroxyl radical, and compares this to the known antioxidant standard, Quercetin. Using this system oxidative damage was reduced in a dose-dependent manner. One ml of hydrogenized water was found to possess antioxidant capacity equivalent to 0.05 µmole of quercetin. When examined in a human colon cell line (Caco-2 cells), hydrogenized water demonstrated a dose- and time-dependent permeability inhibition of an intracellular fluorescent glucose derivative (2-NBDG), indicating decreased glucose uptake. In another study, the impact of hydrogenized water on Akt phosphorylation (Ser473), a biomarker for insulin signaling, was monitored in human skeletal muscle cells. The hydrogenized water treatment markedly elevated the level of phosphorylation of Akt (Ser473) in a dose-dependent manner. The anti-aging effects of hydrogenized water were examined utilizing SIRT1 expression as a biomarker of aging in human umbilical cells (HUVECs). Hydrogenized water increased dose-dependent SIRT1 gene expression. Hydrogenized water also increased telomerase activity (an anti-aging biomarker in HUVEC cells) up to 148% when cells were treated with media containing 25% hydrogenized water formula. Increased telomerase activity caused by hydrogenized water may be able to protect telomeres from degradation, suggesting the possible use of hydrogenized water in therapeutic interventions of age-related diseases. These studies show that commercial hydrogenized water improved the levels or activities of a few intracellular biomarkers specific for antioxidant activity, glucose uptake, insulin signaling and SIRT 1 and telomerase activities. Industrial Relevance: The molecular hydrogen used in this study indicates that certain commercial sources of hydrogenized water can provide similar antioxidant and gene expression modifications seen in other sources of molecular hydrogen. The biomarkers evaluated here lend well to hydrogenized water’s biological activity relating to health conditions and aging.

Hydrogenized water is known to have protective effects on cells and tissues, mainly through its antioxidant activities. Here we examined the protective effects of a commercial source of hydrogenized water on cultured human brain cells. Hydrogenized water was able to protect brain cells from oxidative stress and glutamate toxicity. At H2 concentrations above 0.01 mM the glutathione levels increased in cultured brain cells. The level of glutathione rose from approximately 500 to approximately 850 μM at the maximum dose of hydrogenized water with an EC50 of approximately 0.030 mM. Hydrogenized water was also able to enhance the signaling pathway for oxidative stress response mediated by Nrf2 (Nuclear factor erythroid 2 like factor). Treatment of cells with hydrogenized water at concentrations above 0.01 mM H2 induced activation of Nrf2 (EC50 approximately 0.05 mM). Hydrogenized water was also able to protect brain cells against glutamate toxicity. Using a DNA damage response element, (γH2AX, to monitor the damage of glutamate toxicity we found that concentrations of H2 above 0.01 mM protected cells from glutamate damage with an EC50 of approximately 0.05 mM H2. These in vitro results demonstrated that hydrogenized water can protect brain cells against common types of damage from oxidative stress and glutamate toxicity.

Objectives. To assess relationships among burden, compassion, and well-being and health among an active group of caregivers. Methods. 301 caregivers with female prevalence (F = 61.1%, M = 38.9%) and ages between 18 and 84 years old (average = 38.72; SD 13.36) participated. Evaluation was carried using standardized instruments to assess: Burdens (CBI), dimensions related to Compassion and Burnout (ProQOL-5), State of Well-being (Who-5) and particular health-related domains (Emotional state, Physical health, Depressive Polarity, Dysphoric Polarity-SF-36). Correlational analyses and multivariate linear regressions were performed. Results. Positive correlations emerged between Burdens and Compassion Fatigue, Well-being and Satisfaction; inverse correlations emerged among Well-being and Burnout, Compassion Satisfaction and Emotional State, with the exception of Time Dependence. Multivariate linear regression indicated relations among Compassion Fatigue with Depression and Social Burden, Compassion Satisfaction with Depressive Polarity and Dysphoria and Burnout with Social Burden. Conclusions. Caregivers’ work presents various risks, with negative outcomes that need to be addressed for this group of professionals. These risks present a professional and human development opportunity.

Background: The pathological reality of diabetes and the incidents in following the prescribed therapies have been considered and are still a serious and relevant problem in the health sector. Objective: This review aims at highlighting the importance of clinical psychological phenomena that underlie the notion of therapies. Methods: The review was conducted through search engines such as PubMed, Medline, Web of Science and Google Scholar. The articles related to compliance, adherence, concordance, empowerment and the self-management of diabetes were included, in order to highlight the possible similarities and differences that these terms bring with them in them management of diabetes. Results: Starting from 252 initial publications, 101 articles were selected that highlighted the practical implications that each term has compared to the others. Conclusion: The review can represent a bridge between the medical approach and clinical psychology, in which integration can suggest paths aiming at improving patients’ existential conditions and adaptation.

In Mediterranean countries the olive oil industry produces, yearly, a huge quantity of pollutant wastes in a short time that are phytotoxic for their high content of phenols and wax that affect soil and groundwater quality. With the use of biological processes, we can transform these wastes into fertilizers for a sustainable agriculture. We used three different methods anaerobic digestion, aerobic digestion, and crude agricultural waste management system to produce organic fertilizers. The obtained compounds were chemically analysed to verify if their characteristics fell into the marketability limits permitted by the current Italian regulation. Their effects on soil were subsequently assessed. Results evidenced that all the by-products obtained were suitable as fertilizers. They were able to increase soil organic matter, microbial biomass, and nutrients with beneficial effects on soil fertility, but at different extent. The best effects were in the order: compost, olive pomace-sulphur-bentonite pelletized and digestate. Considering that the three different methodologies dispose different amounts of olive pomace (90% in aerobic digestion, 12% in anaerobic digestion and 5% in sulphur bentonite pelletized) in different time (4months for compost, 1month for anaerobic digestion and 1day for sulphur-bentonite pelletized) and processing set-up, each method can be differently competitive for environment and/or agriculture. Aerobic digestion has economic advantage over other alternatives and has the greatest fertilizer effect even if the production time is longer than the other two. Digestate, coming from anaerobic digestion, reduces the environmental impact of greenhouse gas emissions it is rich in nutrients and can be obtained in a shorter time than compost. Olive pomace-sulphur-bentonite pelletized represents a crude waste management systems that reduce greenhouse gas emission in the atmosphere producing fertilizers able to generate, mainly in alkaline soils, a soluble zone of nutrients while minimizing leaching losses to the environment.

Plasmonic dimer cavities can induce extreme electric-field hot spots that allow one to access ultrastrong coupling regimes using Raman-type spectroscopy on single vibrating molecules. Using a generalized master equation, we study resonant Raman scattering in the strong coupling regime of cavity quantum electrodynamics, when also in the vibrational ultrastrong coupling regime, leading to ``phonon-dressed polaritons.'' The master equation rigorously includes spectral baths for the cavity and vibrational degrees of freedom, as well as a pure dephasing bath for the resonant two-level system, which play a significant role. Employing realistic parameters for gold dimer cavity modes, we investigate the emission spectra in several characteristic strong coupling regimes, leading to extremely rich spectral resonances due to an interplay of phonon-modified polariton states and bath-induced resonances. We also show explicitly the failure of the standard master equation in these quantum nonlinear regimes.

Topochemical polymerization reactions hold the promise of producing ultra-high molecular weight crystalline polymers. However, the totality of topochemical polymerization reactions has failed to produce ultra-high molecular weight polymers that are both soluble and display variable functionality, which are restrained by the crystal-packing and reactivity requirements on their respective monomers in the solid state. Herein, we demonstrate the topochemical polymerization reaction of a family of para-azaquinodimethane compounds that undergo facile visible light and thermally initiated polymerization in the solid state, allowing for the first determination of a topochemical polymer crystal structure resolved via the cryoelectron microscopy technique of microcrystal electron diffraction. The topochemical polymerization reaction also displays excellent functional group tolerance, accommodating both solubilizing side chains and reactive groups that allow for post-polymerization functionalization. The thus-produced soluble ultra-high molecular weight polymers display superior capacitive energy storage properties. This study overcomes several synthetic and characterization challenges amongst topochemical polymerization reactions, representing a critical step toward their broader application., Topochemical polymerization reactions produce ultra-high molecular weight crystalline polymers. Here the authors show a family of para-azaquinodimethane compounds that undergo facile visible light and thermally initiated polymerization in the solid state and the crystal structure has been resolved via cryoelectron microscopy.

The development of a water-soluble iridium catalyst enables the trifluoromethylation of polar small molecules and peptides in DMSO solution or aqueous media. The reaction was optimized in a microtiter plate format under ambient air, using commercial Langlois reagent as a CF3 radical source, blue LEDs for excitation, and using DPBS as solvent to provide up to 60% CF3- peptide.

Uranium nitride complexes are attractive targets for chemists as molecular models for the bonding, reactivity, and magnetic properties of next-generation nuclear fuels, but these molecules are uncommon and can be difficult to isolate due to their high reactivity. Here, we describe the synthesis of three new multinuclear uranium nitride complexes, [U(BCMA)2]2(μ-N)(μ-κ1:κ1-BCMA) (7), [(U(BIMA)2)2(μ-N)(μ-NiPr)(K2(μ-η3:η3-CH2CHNiPr)]2 (8), and [U(BIMA)2]2(μ-N)(μ-κ1:κ1-BIMA) (9) (BCMA = N,N-bis(cyclohexyl)methylamidinate, BIMA = N,N-bis(iso-propyl)methylamidinate), from U(III) and U(IV) amidinate precursors. By varying the amidinate ligand substituents and azide source, we were able to influence the composition and size of these nitride complexes. 15N isotopic labeling experiments confirmed the bridging nitride moieties in 7-9 were formed via two-electron reduction of azide. The tetra-uranium cluster 8 was isolated in 99% yield via reductive cleavage of the amidinate ligands; this unusual molecule contains nitrogen-based ligands with formal 1-, 2-, and 3- charges. Additionally, chemical oxidation of the U(IV) precursor U(N3)(BCMA)3 yielded the cationic U(V) species [U(N3)(BCMA)3][OTf]. Magnetic susceptibility measurements confirmed a U(IV) oxidation state for the uranium centers in the three nitride-bridged complexes and provided a comparison of magnetic behavior in the structurally related U(III)-U(IV)-U(V) series U(BCMA)3, U(N3)(BCMA)3, and [U(N3)(BCMA)3][OTf]. At 240 K, the magnetic moments in this series decreased with increasing oxidation state, i.e., U(III) > U(IV) > U(V); this trend follows the decreasing number of 5f valence electrons along this series.

Uranium nitride complexes are attractive targets for chemists as molecular models for the bonding, reactivity, and magnetic properties of next-generation nuclear fuels, but these molecules are uncommon and can be difficult to isolate due to their high reactivity. Here, we describe the synthesis of three new multinuclear uranium nitride complexes, [U(BCMA)2]2(μ-N)(μ-κ1:κ1-BCMA) (7), [(U(BIMA)2)2(μ-N)(μ-NiPr)(K2(μ-η3:η3-CH2CHNiPr)]2 (8), and [U(BIMA)2]2(μ-N)(μ-κ1:κ1-BIMA) (9) (BCMA = N,N-bis(cyclohexyl)methylamidinate, BIMA = N,N-bis(iso-propyl)methylamidinate), from U(III) and U(IV) amidinate precursors. By varying the amidinate ligand substituents and azide source, we were able to influence the composition and size of these nitride complexes. 15N isotopic labeling experiments confirmed the bridging nitride moieties in 7-9 were formed via two-electron reduction of azide. The tetra-uranium cluster 8 was isolated in 99% yield via reductive cleavage of the amidinate ligands; this unusual molecule contains nitrogen-based ligands with formal 1-, 2-, and 3- charges. Additionally, chemical oxidation of the U(IV) precursor U(N3)(BCMA)3 yielded the cationic U(V) species [U(N3)(BCMA)3][OTf]. Magnetic susceptibility measurements confirmed a U(IV) oxidation state for the uranium centers in the three nitride-bridged complexes and provided a comparison of magnetic behavior in the structurally related U(III)-U(IV)-U(V) series U(BCMA)3, U(N3)(BCMA)3, and [U(N3)(BCMA)3][OTf]. At 240 K, the magnetic moments in this series decreased with increasing oxidation state, i.e., U(III) > U(IV) > U(V); this trend follows the decreasing number of 5f valence electrons along this series.

At present, economic and technological design criteria for products and processes should be matched with the minimization of environmental impact objectives. Manufacturing, material production, and product design are strictly connected stages. The choice of a production system over another could result in significant material and energy/resource savings, particularly if the component has been properly designed for manufacturing. In this scenario, Additive Manufacturing, which has been identified as a potential disruptive technology, gained an increasing interest for the creation of complex metal parts. The paper focuses on the tools, based on the holistic modelling of additive and subtractive approaches, which could be used to identify the production route allowing the lowest energy demand or CO2 emissions. The models account for the main process variables as well as the impacts due to the re-design for AM for the creation of components made of Ti-6Al-4 V.

This article belongs to the Special Issue 2D Magnetic Molecular Materials., The synthesis of a terbium-based 2D metal–organic framework (MOF), of formula [Tb(MeCOO)(PhCOO)2] (1), a crystalline material formed by neutral nanosheets held together by Van der Waals interactions, is presented. The material can be easily exfoliated by sonication and deposited onto different substrates. Uniform distributions of Tb-2D MOF flakes onto silicon were obtained by spin-coating. We report the luminescent and magnetic properties of the deposited flakes compared with those of the bulk. Complex 1 is luminescent in the visible and has a sizeable quantum yield of QY = 61% upon excitation at 280 nm. Photoluminescence measurements performed using a micro-Raman set up allowed us to characterize the luminescent spectra of individual flakes on silicon. Magnetization measurements of flakes-on-silicon with the applied magnetic field in-plane and out-of-plane display anisotropy. Ac susceptibility measurements show that 1 in bulk exhibits field-induced slow relaxation of the magnetization through two relaxation paths and the slowest one, with a relaxation time of τlf ≈ 0.5 s, is assigned to a direct process mechanism. The reported exfoliation of lanthanide 2D-MOFs onto substrates is an attractive approach for the development of multifunctional materials and devices for different applications., This research was funded by the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, Grant Nos. MAT2017-83468-R; PGC2018-098630-B-I00 (ECS)) and from the regional Government of Aragon (E12-20R RASMIA project).

Background: The health professionals are involved in the paths of care for patients with different medical conditions. Their life is frequently characterized by psychopathological outcomes so that it is possible to identify consistent burdens. Besides the possibility to develop pathological outcomes, some protective factors such as resilience play a fundamental role in facilitating the adaptation process and the management of maladaptive patterns. Personal characteristics and specific indexes such as burdens and resilience are essential variables useful to study in-depth ongoing conditions and possible interventions. The study was aimed at highlighting the presence and the relations among factors as personal variables, burdens, and resilience, to understand health professionals' specific structure and functions.Methods: The observation group was composed of 210 participants, 55 males (26.2%), and 155 females (73.8%), aged from 18 to 30 years old with a mean age of 25.92 years old (SD = 3.33). The study considered personal characteristics of the subjects, such as age, gender, years of study, days of work per week, hours of work per week, and years of work. Our study had been conducted with the use of measures related to burdens (Caregivers Burden Inventory) and resilience (Resilience Scale for Adults).Results: The performed analyses consisted of descriptive statistics, correlations, and regressions among the considered variables. Several significant correlations emerged among personal characteristics, CBI, and RSA variables. Specifically, age and work commitment indexes appeared to be significantly related to the development of burdens, differently from the years of study. Significant correlations emerged among personal and RSA variables, indicating precise directions for both domains. Age and gender were identified as predictors to perform multivariate regression analyses concerning CBI factors. Significant dependence relations emerged with reference to all CBI variables.Conclusion: Pathological outcomes and resilience factors represent two sides of the health professionals' experiences, also known as “invisible patients.” Greater knowledge about present conditions and future possibilities is a well-known need in literature so that the current analyses considered fundamental factors. In line with state of the art, future studies are needed in order to deepen elusive phenomena underlying maladjustment.

Single-crystal X-ray structures were obtained for the copper and μ-oxodiiron complexes of 2,3,7,8,12,13,17,18-octafluoro-5,10,15-triphenylcorrole, hereafter denoted as Cu[F8TPC] and {Fe[F8TPC]}2O. A comparison with the crystal structures of other undecasubstituted Cu corroles, including those with H, Ar, Br, I, and CF3 as β-substituents, showed that the degree of saddling increases in the order: H ≲ F < Ar ≲ Br ≲ I < CF3. In other words, Cu[F8TPC] is marginally more saddled than β-unsubstituted Cu triarylcorroles, but substantially less saddled than Cu undecaarylcorroles, β-octabromo-meso-triarylcorroles, and β-octaiodo-meso-triarylcorroles, and far less saddled than Cu β-octakis(trifluoromethyl)-meso-triarylcorroles. As for {Fe[F8TPC]}2O, the moderate quality of the structure did not allow us to draw firm conclusions in regard to bond length alternations in the corrole skeleton and hence also the question of ligand noninnocence. The Fe-O bond distances, 1.712(8) and 1.724(8), however, are essentially identical to those observed for {Fe[TPFPC]}2O, where TPFPC3- is the trianion of 5,10,15-tris(pentafluorophenyl)corrole, suggesting that a partially noninnocent electronic structural description may be applicable for both compounds.

Exposure of bis-amidinate and -guanidinate supported thorium dialkyl complexes to dioxygen results in facile oxygen atom insertion and formation of the corresponding thorium bis(alkoxide) species. Preliminary mechanistic studies suggest a radical propagation mechanism is operative. All new complexes were fully characterized by 1H and 13C NMR spectroscopy, IR, EA and X-ray crystallography.

Membrane Lipid Replacement is the use of functional oral supplements containing cell membrane glycerolphospholipids and antioxidants to safely replace damaged membrane lipids that accumulate during aging and in various chronic and acute diseases. Most if not all clinical conditions and aging are characterized by membrane phospholipid oxidative damage, resulting in loss of membrane and cellular function. Clinical trials have shown the benefits of Membrane Lipid Replacement supplements in replenishing damaged membrane lipids and restoring mitochondrial function, resulting in reductions in fatigue in aged subjects and patients with a variety of clinical diagnoses. Recent observations have indicated that Membrane Lipid Replacement can be a useful natural supplement strategy in a variety of conditions: chronic fatigue, such as found in many diseases and disorders; fatiguing illnesses (fibromyalgia and chronic fatigue syndrome); chronic infections (Lyme disease and mycoplasmal infections); cardiovascular diseases; obesity, metabolic syndrome and diabetes; neurodegenerative diseases (Alzheimer’s disease); neurobehavioral diseases (autism spectrum disorders); fertility diseases; chemical contamination (Gulf War illnesses); and cancers (breast, colorectal and other cancers). Membrane Lipid Replacement provides general membrane nutritional support during aging and illness to improve membrane function and overall health without risk of adverse effects.

Introduction: Previous studies indicated that lipids and nanostructured materials may improve the uptake of nutrients with moderate bioabsorption properties. Objectives: This study evaluated the effects of Membrane Lipid Replacement with NTFactor® Lipids (NTFL) on bioabsorption of three poorly to moderately absorbed nutrients (quercetin, curcumin and coenzyme Q10) utilizing the Caco-2 epithelial cell permeability model. Methods: Transfer across a Caco-2 epithelial cell layer has become a reference standard in the pharmaceutical and nutraceutical industries for in vitro prediction of in vivo human intestinal absorption and bioavailability of orally administered substances. The degree of bioabsorption of the test materials was assessed by monitoring the concentrations of the test materials on each side of the Caco-2 monolayers by liquid chromatography and mass spectroscopy (LCMS/MS analysis).Results: When NTFL was added to each of the three test nutrients, there was increased absorption and transfer across a Caco-2 cell layer in a dose-dependent manner for the three nutrients. When compared individually, CoQ10 with NTFL showed the most significant increase in absorption (2.01-times more compared to controls without NTFL, p=0.0011) at a concentration of NTFL of 10 mg/mL. NTFL also increased absorption and transfer across a Caco-2 cell layer of the other test nutrients, but these results did not achieve the same level of significance. Discussion: A variety of Oral membrane lipid replacement supplements with NTFL, such as various vitamins, minerals and nutrients, have been designed to reduce fatigue, improve health conditions, and protect cellular and especially mitochondrial membranes from damage. Here we used NTFL to demonstrate improvements in absorption and bioavailability of three nutrients. Conclusion: Using the Caco-2 bioabsorption and bioavailability in vitro model we found that NTFL could enhance absorption, bioavailability and uptake of nutrients while providing its own clinically demonstrated health benefits. Keywords: Phospholipids, Membrane Lipid Replacement, CoQ10, curcumin, quercetin, bioavailability, absorption, permeability, Caco2, bio-uptake, bioabsorption, glycerolphospholipids, intestinal absorption

Background:The study proposes a psychodynamic analysis of the traumatic role of mental images, that can be expressed by many conditions; in phenomenology, the psychic relationship is meant as the relationship between subject and object. The analysis is aimed at understanding how representations are relevant.Objective:Representations are distinguished as the possibility of intrinsic trauma and as inherently deferred in the conflict between sexual-biological identity and gender-psychological identity; our work aims to highlight how internal images affect adaptation processes.Method:The analysis involves the study of 10 Rorschach protocols of Gender Dysphoria subjects in Male to Female transition; the protocols are analyzed through the studies of N. Raush de Traubenberg, with reference to the Self and Body; a psycho-traumatological and phenomenological analysis of imaginal experiences will be proposed.Results:From the analysis emerges the presence of Self and Body representations affected by a partial and fragmentary prevalence of contents, the presence of psychotraumatic phenomena associated to the processes of introjection and identification of mental representations.Conclusion:The knowledge of the presence of affected representations and psycho-traumatological outcomes would be useful for a psychodiagnostic and psychotherapeutic purpose, intended for the implementation of the adaptation process.

Waste composting is a process which is spreading worldwide to reduce waste disposal in landfill. The composting technical currents give little attention to the type and chemical composition of biomass that are mixed not considering that these can affect quality and maturity of the compost produced. In addition, during the composting process the amount of oxygen and temperature are generally only monitored but not set up. Our hypothesis is that composts, prepared from different organic wastes, can be chemically different with consequent different fertilizer properties. Stability and quality of composts are dependent on multivariate parameters such as raw material source, proportions used, composting procedure, and maturation time. Starting from this consideration a composting experiment was carried out to evaluate if were the raw materials (chemical composition, mixture and ratio), or the composting conditions and time, to influence the maturity or the quality of composts. We prepared four composts starting from different combinations and ratios of vegetable residues and/or olive pomace. After 120 days, the four composts were physically, chemically and biologically characterized to evaluate maturity degree, stability and quality of the products obtained under the same composting conditions and time. Their ability, as soil improver, was evaluated assessing soil chemical and biochemical properties 90 days after the compost addition. Here we show that the chemical composition of raw materials and the set up parameters of composting processes can have a different weight in influencing compost stability and quality. Our results evidenced that during the composting process all the composts had a similar percentage of C/N ratio reduction and all of them achieved an acceptable maturity degree. The composts produced by olive pomace showed the highest degree of maturity as demonstrated by T value and organic matter loss, both indices of compost stability. Conversely the composts coming from green vegetable residues were richest in nutrients and phenols and had the highest CSC all indices of better quality. In this work we identified two composts able to increase carbon stock, and water holding capacity parameters that positively influence soil structure, and two compost able to increase the amount of soil microbial biomass, their activity and soil biodiversity, improving soil biological fertility. These results highlighted that compost maturity doesn't mean compost quality, suggesting that compost maturity is mainly linked to composting setup parameters, while compost quality is mainly linked to chemical composition. FDA and DHA activities have been identified as markers for assessing the quality of amended soils.

Resume Objectif Cet article tente d’apporter une clarification du rapport entre la pathologie des organes et les images des organes connexes. Dans ce type de construction c’est comme si l’esprit se retrouvait en face d’une pareidolie a genese interne. Comme l’inadaptation, les pareidolies subissent des transformations quand l’organe est endommage ; on pense que le sujet a une distorsion dans la production des images. Dans ce travail, nous avons compare deux maladies tres differentes : une maladie de la peau (psoriasis) et une maladie du cœur (coronaropathie). Voici l’hypothese que nous proposons. Methode La methode qui se rapproche le plus de notre but interpretatif est celle de Rorschach, d’apres les etudes de Rauch de Traubenberg a travers lesquelles il est possible de comprendre la representation du Soi et du corps. Cette methode, en dehors des simples buts nosographiques, s’approche bien de la complexite subjective de la souffrance somatique et donc psychique du psoriasis et des patients cardiaques. Resultats L’aspect inadapte de la souffrance mentale suscitee par les objets psychiques endommages se degage de l’analyse des protocoles des groupes d’observation. Ceci est comprehensible par une representation du soi et du corps. Les sujets psoriasiques sont plus compromis dans la representation du Soi, tandis que les sujets ayant subi un infarctus ont une plus grande fragmentation de la representation du corps. Discussion Malgre la difference de la representation des organes endommages et les specificites dans les differentes grilles, il semble clair que la tentative de representation, influencee par l’organe endommage, a des effets d’inadaptation. Conclusions Les resultats suggerent que les possibilites de generer des representations du monde interieur sont fortement influencees par des problemes somatiques, invalidants en termes existentiels.

Although the manufacturing process of structural members has been improved over the last decades, inherent geometric imperfections in slender beam-columns cannot be avoided altogether. Such imperfections largely affect the buckling behavior of the beam by modifying (reducing) the actual critical load in comparison with the theoretically perfect beam idealization. Whereas the deterministic characterization of such imperfections is a rather difficult task that should be performed from case to case, a more general approach would require dealing with imperfections within a probabilistic framework, i.e., treating them as random fields. The aim of this paper is to provide a simple but effective method to characterize probabilistically the response of imperfect beam-column elements based on the stochastic description of the imperfections. The proposed method assumes that the imperfections are expressed through series expansion wherein the critical shapes of the corresponding perfect beam represent the series polynomials. Once the continuum deflection field and the random imperfection field are discretized, some simple closed-form relationships between the imperfection parameters and the main response quantities (e.g. beam deflection and critical load) are established. In contrast to other methods, any type of boundary conditions can be incorporated without computational effort. A few boundary conditions are numerically investigated that clarify how the proposed method can be usefully employed to characterize the buckling response of imperfect beam-column elements probabilistically.

Objectives: A preliminary, open label study was initiated to determine if oral wafers containing a combination of membrane glycerolphospholipids and controlled-release caffeine could reduce self-reported pain, fatigue, and gastrointestinal symptoms and improve quality of life (QOL) indicators in fibromyalgia patients. Methods: Pain, fatigue and other symptoms were determined using validated, patient survey forms completed over an 8-day test period and compared to baseline values. Participants included 21 patients (15 females and 6 males) of average age of 48.5 ± 9.8 years with a diagnosis of fibromyalgia. These patients consumed four daily chewable wafers containing glycerolphospholipids (4.8 g) and one controlled-released caffeine (184 mg) wafer that maintained caffeine levels at approximately one cup of coffee for over 8 h. Results: Participants in the study responded to the combination test supplement within days. By the end of the study there were significant overall improvements (36.1%, p < 0.001), reductions in pain (27.2%, p < 0.001), fatigue (37.8%, p < 0.001), gastrointestinal symptoms (54.7%, p < 0.001) and improved ability to complete tasks and participate in activities (quality of life indicators) (39.1%, p < 0.001). Regression analysis of the data using a generalized mixed-effects model and calculating R2 values indicated that reductions in pain, fatigue and gastrointestinal symptoms and improvements in quality of life indicators were consistent, and occurred with a low degree of variance. Males responded slightly better to the combination supplement than females but for most parameters these differences were not significant. Conclusions: The combination membrane lipid replacement glycerolphospholipid supplement with controlled-release caffeine was safe and effective and significantly reduced pain, fatigue and gastrointestinal symptoms as well as improved QOL indicators in fibromyalgia patients.

Reaction of the first homoleptic U(iii) guanidinate complex with diphenyldiazomethane results in two-electron oxidation of U(iii) to U(v) and isolation of a U(v) hydrazido complex. Corresponding U(v) imido, U(v) oxo, and U(iv) azido complexes were also synthesized for structural comparison.

The reactivity of the thorium monoalkyl complex Th(CH2SiMe3)(BIMA)3 [1, BIMA = MeC(NiPr)2] with various small molecules is described. While steric congestion prohibits the insertion of N,N′-diisopropylcarbodiimide into the Th–C bond in 1, the first thorium tetrakis(amidinate) complex, Th(BIMA)4 (2), is synthesized via an alternative salt metathesis route. Insertion of p-tolyl azide leads to the triazenido complex Th[(p-tolyl)NNN(CH2SiMe3)-κ2N1,2](BIMA)3 (3), which then undergoes thermal decomposition to the amido species Th[(p-tolyl)N(SiMe3)](BIMA)3 (4). The reaction of 1 with 2,6-dimethylphenylisocyanide results in the thorium iminoacyl complex Th[η2-(CN)-2,6-Me2-C6H3(CH2SiMe3)](BIMA)3 (5), while the reaction with isoelectronic CO leads to the products Th[OC(CH2)SiMe3](BIMA)3 (6) and Th[OC(NiPr)C(CH2SiMe3)(C(Me)N(iPr))O-κ2O,O′](BIMA)2 (7), the latter being the result of CO coupling and insertion into an amidinate ligand. Protonolysis is achieved with several substrates, producing amido (9), aryloxide (10), phosphido (11a,b), acetylide (12), and cationic (13) complexes. Ligand exchange with 9-borabicyclo[3.3.1]nonane (9-BBN) results in formation of the thorium borohydride complex (BIMA)3Th(μ-H)2[B(C8H14)] (14). Complex 1 also reacts under photolytic conditions to eliminate SiMe4 and produce Th(BIMA)2(BIMA*) [15, BIMA* = (iPr)NC(CH2)N(iPr)], featuring a rare example of a dianionic amidinate ligand. Complexes 2, 3, 5, 6, 11a, and 12–15 were characterized by 1H and 13C{1H} NMR spectroscopy, FTIR, EA, melting point and X-ray crystallography. All other complexes were identified by one or more of these spectroscopic techniques.