Anticancer diiron aminocarbyne complexes with labile N-donor ligands.

The novel diiron amine complexes [FeCp(CO)(NHR')(μ-CO){μ-CN(Me)(Cy)}]CFSO [R' = H, 3; Cy, 4; CHCHNH, 5; CHCHNMe, 6; CHCH(4-CHOMe), 7; CHCH(4-CHOH), 8; Cp = η-CH, Cy = CH = cyclohexyl] were synthesized in 49-92 % yields from [FeCp(CO)(μ-CO){μ-CN(Me)(Cy)}]CFSO, 1a, using a straightforward two-step procedure. They were characterized by IR and multinuclear NMR spectroscopy, and the structure of 7 was confirmed through X-ray diffraction analysis. Complexes 3-8 and the acetonitrile adducts [FeCp(CO)(NCMe)(μ-CO){μ-CN(Me)(R)}]CFSO (R = Cy, 2a; Me, 2b; Xyl = 2,6-CHMe, 2c) were assessed for their water solubility, octanol-water partition coefficient and stability in physiological-like solutions.

Challenges and opportunities for digital twins in precision medicine from a complex systems perspective.

Digital twins (DTs) in precision medicine are increasingly viable, propelled by extensive data collection and advancements in artificial intelligence (AI), alongside traditional biomedical methodologies. We argue that including mechanistic simulations that produce behavior based on explicitly defined biological hypotheses and multiscale mechanisms is beneficial. It enables the exploration of diverse therapeutic strategies and supports dynamic clinical decision-making through insights from network science, quantitative biology, and digital medicine.

Atypical Regional Accent in Autistic Children: A Perception Study.

Autistic children are frequently said to speak with accents that markedly differ from those of their linguistic communities. To date, these anecdotal reports have never been tested or explained. We ran two perception studies using short audio recordings of autistic and typically developing children from the Campania region in Italy.

Nanoscale polarization transient gratings.

Light manipulation at the nanoscale is essential both for fundamental science and modern technology. The quest to shorter lengthscales, however, requires the use of light wavelengths beyond the visible. In particular, in the extreme ultraviolet regime these manipulation capabilities are hampered by the lack of efficient optics, especially for polarization control.

Orbital and suborbital temperature variability in the central Mediterranean across the Pliocene/Pleistocene transition.

A high-resolution record of central Mediterranean Sea Surface Temperatures (SSTs) based on the alkenone UK'37 index and planktic δ18O values for the surface-dweller G. ruber has been reconstructed across the Pliocene/Pleistocene transition at Monte San Nicola (Sicily), reference area for the GSSP (Global Boundary Stratotype Section and Point) of the Gelasian Stage. Spectral analyses indicate that the SST record is predominantly paced by a cyclicity in the ~47 kyr time domain, consistent with the obliquity driven glacial-interglacial variability that is expected to dominate in the interval of relevance.

Unusual Reaction of Isocyanides with Aromatic Aldehydes Catalyzed by a Supramolecular Capsule.

The supramolecular resorcinarene hexameric capsule efficiently promotes the unprecedented reaction between isocyanides and electron-deficient aromatic aldehydes leading to the formation of imines and carbon monoxide. The mechanism of the reaction was investigated via isotope labelling, kinetic analysis of the reaction, computational studies and the independent synthesis of a proposed intermediate. Control experiments indicate that the formation of the key aziridinone intermediate is limited to the cavity of the capsule.

Terahertz metamaterials for light-driven magnetism.

We describe the design of two types of metamaterials aimed at enhancing terahertz field pulses that can be used to control the magnetic state in condensed matter systems. The first structure is a so-called "dragonfly" antenna, able to realize a five-fold enhancement of the impinging terahertz magnetic field, while preserving its broadband features. For currently available state-of-the-art table top sources, this leads to peak magnetic fields exceeding 1 T.

Unveiling the Composition of La Pajarita PVAc-Based Paints in Joan Miró's Studio and in Three Artworks from the 1970s.

In this study, we present the first characterisation of the polyvinyl acetate (PVAc) paints of commercial Spanish brand La Pajarita preserved in the studios of Joan Miró (1893-1983) in Mallorca, Spain. Investigation of several black and white paint samples using complementary analytical techniques (XRD, SEM-EDX, FTIR, and Py-GC-MS) allowed for the identification of pigments and binding media in studio materials, as well as in three artworks dating from the 1970s. Through comparative analysis, it was possible to find significant similarities between the composition of La Pajarita paints conserved in cans in the artist's studio with black and white painted layers from three artworks by Miró.

Impact of COVID-19 vaccination on preventive behavior: The importance of confounder adjustment in observational studies.

The COVID-19 pandemic has underscored the critical role of observational studies in evaluating the effectiveness of public health strategies. However, although many studies have explored the true impact of vaccination on preventive behavior, their results may be skewed by potential biases and confounding variables. This study examines the application of covariate adjustment and propensity score (PS) estimation, particularly through inverse probability treatment weighting (IPTW), to assess their performance in reducing bias in a framework featuring ordinal outcomes and cumulative logistic regression models, as commonly used in observational studies related to social sciences and psychology.

Light-assisted carbon dioxide reduction in an automated photoreactor system coupled to carbonylation chemistry.

Continuous-flow methodologies offer promising avenues for sustainable processing due to their precise process control, scalability, and efficient heat and mass transfer. The small dimensions of continuous-flow reactors render them highly suitable for light-assisted reactions, as can be encountered in carbon dioxide hydrogenations. In this study, we present a reactor system emphasizing reproducibility, modularity, and automation, facilitating streamlined screening of conditions and catalysts for these processes.

From the highway to receiving water bodies: identification and simultaneous quantification of small microplastics (< 100 µm) in highway stormwater runoff.

Highway stormwater (HSW) runoff is among the environment's most important sources of microplastics. This study aimed to characterize via vibrational spectroscopy and quantify SMPs (small microplastics < 100 µm) in HSW runoff from a trafficked highway entering a facility equipped with a filtration system and in those flowing out to the receiving water body near agricultural activities. Samples of the inlet runoff (from the highway) and outlet runoff (the discharge into the environment) were collected in different periods to investigate potential seasonal and spatial differences.

Synergistic interfacial electronic modulation of topotactically developed bimetallic CoNiP on NiS nanorods for enhanced alkaline hydrogen evolution reaction.

Designing hybrid transition metal phosphosulfide electrocatalysts is critical for the hydrogen evolution reaction (HER). We propose a novel approach by designing a hierarchical structure of cobalt phosphide (CoP) and nickel phosphide (NiP) nanoparticles topotactically developed on nickel sulfide (NiS) nanorods (CoNiP/NiS) a sulfuration-phosphorization strategy using conductive 3D nickel foam. Hierarchical heterostructured nanorods were achieved without the need for template removal steps or the assistance of surfactants.

Predictors of Poor Mental Health Outcomes in Healthcare Workers during COVID-19: A Two Waves Study.

This cross-sectional study aimed to identify potential predictors of poor mental health outcomes among healthcare workers in two different waves of the COVID-19 emergency in Italy. An online survey collected data from N = 557 healthcare workers (21-77 years). The study predictors were sociodemographic characteristics, occupational status, factors related to the work environment, COVID-19-related adverse events, and lifetime traumatic events.

Selective Labeling of Small Microplastics with SERS-Tags Based on Gold Nanostars: Method Optimization Using Polystyrene Beads and Application in Environmental Samples.

Microplastics pollution is being unanimously recognized as a global concern in all environments. Routine analysis protocols foresee that samples, which are supposed to contain up to hundreds of microplastics, are eventually collected on nanoporous filters and inspected by microspectroscopy techniques like micro-FTIR or micro-Raman. All particles, whether made of plastic or not, must be inspected one by one to detect and count microplastics.

The effect of parental health shocks on living arrangements and employment.

This study investigates the impacts of health shocks among older individuals on the dynamics of their living arrangements in Europe and the United States. Exploiting unpredicted health shocks, we use an event-study difference-in-differences approach to demonstrate that health shocks increase difficulties with activities of daily living and instrumental activities of daily living, thereby increasing the need for care. Our findings indicate that health shocks raise the probability of nursing home residency and co-residence with adult children by 0.

Inflammation related to inhalation of nano and micron sized iron oxides: a systematic review.

Inhalation exposure to iron oxide occurs in many workplaces and respirable aerosols occur during thermal processes (e.g. welding, casting) or during abrasion of iron and steel products (e.

Unravelling dispersion forces in liquid-phase enantioseparation. Part II: Planar chiral 1-(iodoethynyl)-3-arylferrocenes.

Background: In the first part of our study on possible contribution of dispersion forces in liquid-phase enantioseparations, the enantioseparation of the axially chiral 3,3'-dibromo-5,5'-bis-ferrocenylethynyl-4,4'-bipyridine with an amylose tris(3,5-dimethylphenylcarbamate)-based chiral column appeared reasonably consistent with a picture of the enantioselective recognition based on the interplay between hydrogen bond (HB), π-π stacking and dispersion interactions.

Results: In the second part of this study, we evaluated the impact of analyte and chiral stationary phase (CSP) structure, mobile phase and temperature on the enantioseparations of planar chiral 1-(iodoethynyl)-3-arylferrocenes (3-aryl = phenyl, 2-naphthyl, 4-methylphenyl, 4-t-butylphenyl) with polysaccharide-based chiral columns. The main aim of the present study was to understand the molecular bases of the high affinity observed for the second eluted (R)-enantiomer of some of these analytes toward amylose phenylcarbamate-based selectors when methanol-containing mixtures were used as mobile phases.

A Physics-Informed Neural Network approach for compartmental epidemiological models.

Compartmental models provide simple and efficient tools to analyze the relevant transmission processes during an outbreak, to produce short-term forecasts or transmission scenarios, and to assess the impact of vaccination campaigns. However, their calibration is not straightforward, since many factors contribute to the rapid change of the transmission dynamics. For example, there might be changes in the individual awareness, the imposition of non-pharmacological interventions and the emergence of new variants.