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The recently synthesized monolayer fullerene network in a quasi-hexagonal phase (qHP-C60) exhibits superior electron mobility and optoelectronic properties compared to molecular fullerene (C60), making it highly promising for a variety of applications. However, the microscopic carrier dynamics of qHP-C60 remain unclear, particularly in realistic environments, which are of significant importance for applications in optoelectronic devices. Unfortunately, traditional ab initio methods are prohibitive for capturing the real-time carrier dynamics of such large systems due to their high computational cost. In this work, we present the first real-time electron-nuclear dynamics study of qHP-C60 using velocity-gauge density functional tight binding, which enables us to perform several picoseconds of excited-state electron-nuclear dynamics simulations for nanoscale systems with periodic boundary conditions. When applied to C60, qHP-C60, and their solvated counterparts, we demonstrate that water/moisture significantly increases the electron-hole recombination time in C60 but has little impact on qHP-C60. Our excited-state electron-nuclear dynamics calculations show that qHP-C60 is extremely unique and enable exploration of time-resolved dynamics for understanding excited-state processes of large systems in complex, solvated environments.

We present a new software module, QRCODE (Quantum Research for Calculating Optically Driven Excitations), for massively parallelized real-time time-dependent density functional theory (RT-TDDFT) calculations of periodic systems in the open-source Qbox software package. Our approach utilizes a custom implementation of a fast Fourier transformation scheme that significantly reduces inter-node message passing interface (MPI) communication of the major computational kernel and shows impressive scaling up to 16,344 CPU cores. In addition to improving computational performance, QRCODE contains a suite of various time propagators for accurate RT-TDDFT calculations. As benchmark applications of QRCODE, we calculate the current density and optical absorption spectra of hexagonal boron nitride (h-BN) and photo-driven reaction dynamics of the ozone-oxygen reaction. We also calculate the second and higher harmonic generation of monolayer and multi-layer boron nitride structures as examples of large material systems. Our optimized implementation of RT-TDDFT in QRCODE enables large-scale calculations of real-time electron dynamics of chemical and material systems with enhanced computational performance and impressive scaling across several thousand CPU cores.

Abstract We present the first investigation of unusual nonlinear Hall effects in twisted multilayer 2D materials. Contrary to expectations, our study shows that these nonlinear effects are not merely extensions of their monolayer counterparts. Instead, we find that stacking order and pairwise interactions between neighboring layers, mediated by Berry curvatures, play a pivotal role in shaping their collective nonlinear optical response. By combining large-scale Real-Time Time-Dependent Density Functional Theory (RT-TDDFT) simulations with model Hamiltonian analyses, we demonstrate a remarkable second-harmonic transverse response in hexagonal boron nitride four-layers, even in cases where the total Berry curvature cancels out. Furthermore, our symmetry analysis of the layered structures provides a simplified framework for predicting nonlinear responses in multilayer materials in general. Our investigation challenges the prevailing understanding of nonlinear optical responses in layered materials and opens new avenues for the design and development of advanced materials with tailored optical properties.

Abstract The discovery of ~80 K superconductivity in nickelate La3Ni2O7 under pressure has ignited intense interest. Here, we present a comprehensive first-principles study of the electron-phonon (e-ph) coupling in La3Ni2O7 and its implications on the observed superconductivity. Our results conclude that the e-ph coupling is too weak (with a coupling constant λ ≲ 0.5) to account for the high T c , albeit interesting many-electron correlation effects exist. While Coulomb interactions (via G W self-energy and Hubbard U) enhance the e-ph coupling strength, electron doping (oxygen vacancies) introduces no major changes. Additionally, different structural phases display varying characteristics near the Fermi level, but do not alter the conclusion. The e-ph coupling landscape of La3Ni2O7 is intrinsically different from that of infinite-layer nickelates. These findings suggest that a phonon-mediated mechanism is unlikely to be responsible for the observed superconductivity in La3Ni2O7, pointing instead to an unconventional nature.

Excitons are prevalent in semiconductors and insulators, and their binding energies are critical for optoelectronic applications. The state-of-the-art method for first-principles calculations of excitons in extended systems is the ab initio GW-Bethe-Salpeter equation (BSE) approach, which can require a fine sampling of reciprocal space to accurately resolve solid-state exciton properties. Here we show, for a range of semiconductors and insulators, that the commonly employed approach of uniformly sampling the Brillouin zone can lead to underconverged exciton binding energies, as impractical grid sizes are required to achieve adequate convergence. We further show that nonuniform sampling of the Brillouin zone, focused on the region of reciprocal space where the exciton wave function resides, enables efficient rapid numerical convergence of exciton binding energies at a given level of theory. We propose a well-defined convergence procedure, which can be carried out at relatively low computational cost and which in some cases leads to a correction of previous best theoretical estimates by almost a factor of 2, qualitatively changing the predicted exciton physics. These results call for the adoption of nonuniform sampling methods for ab initio GW-BSE calculations and for revisiting previously computed values for exciton binding energies of many systems.

We present a new velocity-gauge real-time, time-dependent density functional tight-binding (VG-rtTDDFTB) implementation in the open-source DFTB+ software package (https://dftbplus.org) for probing electronic excitations in large, condensed matter systems. Our VG-rtTDDFTB approach enables real-time electron dynamics simulations of large, periodic, condensed matter systems containing thousands of atoms with a favorable computational scaling as a function of system size. We provide computational details and benchmark calculations to demonstrate its accuracy and computational parallelizability on a variety of large material systems. As a representative example, we calculate laser-induced electron dynamics in a 512-atom amorphous silicon supercell to highlight the large periodic systems that can be examined with our implementation. Taken together, our VG-rtTDDFTB approach enables new electron dynamics simulations of complex systems that require large periodic supercells, such as crystal defects, complex surfaces, nanowires, and amorphous materials.

The COVID-19 pandemic has left an indelible mark globally, presenting numerous challenges to public health. This crisis, while disruptive and impactful, has provided a unique opportunity to gather precious clinical data extensively. In this observational, case-control study, we utilized data collected at the Azienda Sanitaria Universitaria Friuli Centrale, Italy, to comprehensively characterize the immuno-inflammatory features in COVID-19 patients. Specifically, we employed multicolor flow cytometry, cytokine assays, and inflammatory biomarkers to elucidate the interplay between the infectious agent and the host’s immune status. We characterized immuno-inflammatory profiles within the first 72 hours of hospital admission, stratified by age, disease severity, and time elapsed since symptom onset. Our findings indicate that patients admitted to the hospital shortly after symptom onset exhibit a distinct pattern compared to those who arrive later, characterized by a more active immune response and heightened cytokine activity, but lower markers of tissue damage. We used univariate and multivariate logistic regression models to identify informative markers for outcome severity. Predictors incorporating the immuno-inflammatory features significantly outperformed standard baselines, identifying up to 59% of patients with positive outcomes while maintaining a false omission rate as low as 4%. Overall, our study sheds light on the immuno-inflammatory aspects observed in COVID-19 patients prior to vaccination, providing insights for guiding the clinical management of first-time infections by a novel virus.

Electron/hole transfer mechanisms in DNA and polynucleotide structures continue to garner considerable interest as emerging charge-transport systems and molecular electronics. To shed mechanistic insight into these electronic properties, we carried out large-scale density functional theory (DFT) calculations (up to 650 atoms) to systematically analyze the structural and electron/hole transport properties of fully periodic single- and double-stranded DNA. We examined the performance of various exchange-correlation functionals (LDA, BLYP, B3LYP, and B3LYP-D) and found that single-stranded thymine (T) and cytosine (C) are predominantly hole conductors, whereas single-stranded adenine (A) and guanine (G) are better electron conductors. For double-stranded DNA structures, the periodic A-T and G-C electronic band structures undergo a significant renormalization, which causes hole transport to only occur on the A and G nucleobases. Our calculations (1) provide new benchmarks for periodic nucleobase structures using dispersion-corrected hybrid functionals with large basis sets and (2) highlight the importance of dispersion effects for obtaining accurate geometries and electron/hole mobilities in these extended systems.

Background: Depressive and negative symptoms are related to poor functional outcomes in schizophrenia. Cognitive deficits, reduced brain cortical thickness and volumes, and inflammation may contribute to depressive and negative symptoms, but pharmacological treatment and disease progression may confound the associations. Methods: We evaluated whether higher plasma interleukin 6 (IL-6) levels would be associated with more severe negative or depressive symptoms in schizophrenia and explored illness stage utilizing early (BeneMin [Benefit of Minocycline on Negative Symptoms of Psychosis: Extent and Mechanism], n = 201, 72.8% male) and established (iRELATE [Immune Response & Social Cognition in Schizophrenia], n = 94, 67.3% male) schizophrenia cohorts. Using structural equation modeling in a subsample (iRELATE: n = 42, 69.0% male; BeneMin: n = 102, 76.5% male) with data on structural brain metrics (cortical thickness and volume), general cognitive performance, and plasma IL-6 levels, we assessed the interrelationships between these variables on depressive and negative symptom severity in early and established schizophrenia samples combined and in early schizophrenia only. All analyses were adjusted for sex, age, and chlorpromazine equivalent dose. Results: Higher plasma IL-6 levels were related to more severe depressive symptoms in early schizophrenia (p .05). Higher plasma IL-6 levels and lower general cognitive performance were associated with reduced brain metrics (p < .05). Conclusions: Our results indicate that higher plasma IL-6 levels may be differently associated with the severity of depressive and negative symptoms dependent on the illness stage. Future work identifying elevated levels of inflammation in larger samples may allow stratification and personalized intervention by subgroups who are at risk of poor outcomes.

We present a new implementation of real-time time-dependent density functional theory (RT-TDDFT) for calculating excited-state dynamics of periodic systems in the open-source Python-based PySCF software package. Our implementation uses Gaussian basis functions in a velocity gauge formalism and can be applied to periodic surfaces, condensed-phase, and molecular systems. As representative benchmark applications, we present optical absorption calculations of various molecular and bulk systems and a real-time simulation of field-induced dynamics of a (ZnO)4 molecular cluster on a periodic graphene sheet. We present representative calculations on optical response of solids to infinitesimal external fields as well as real-time charge-transfer dynamics induced by strong pulsed laser fields. Due to the widespread use of the Python language, our RT-TDDFT implementation can be easily modified and provides a new capability in the PySCF code for real-time excited-state calculations of chemical and material systems.

Background: The long-COVID syndrome is characterised by a plethora of symptoms. Given its social and economic impact, many studies have stressed the urgency of proposing innovative strategies other than hospital settings. In this double-blinded, randomised, case–control trial, we investigate the effects of sulphur thermal water inhalations, rich in H2S, compared to distilled water inhalations on symptoms, inflammatory markers and nasal microbiome in long-COVID patients. Methods: About 30 outpatients aged 18–75 with positive diagnosis for long-COVID were randomised in two groups undergoing 12 consecutive days of inhalations. The active group (STW) received sulphur thermal water inhalations whereas the placebo group received inhalations of sterile distilled non-pyrogenic water (SDW). Each participant was tested prior treatment at day 1 (T0), after the inhalations at day 14 (T1) and at 3 months follow-up (T2). At each time point, blood tests, nasal swabs for microbiome sampling, pulmonary functionality tests (PFTs) and pro-inflammatory marker measure were performed. Results: The scores obtained in the administered tests (6MWT, Borg score and SGRQ) at T0 showed a significant variation in the STW group, at T1 and T2. Serum cytokine levels and other inflammatory biomarkers reported a statistically significant decrease. Some specific parameters of PFTs showed ameliorations in the STW group only. Changes in the STW nasopharyngeal microbiota composition were noticed, especially from T0 to T2. Conclusions: Inhalations of sulphur thermal water exerted objective and subjective improvements on participants affected by long-COVID. Significant reduction of inflammatory markers, dyspnoea scores and quantitative and qualitative changes in the nasopharyngeal microbiome were also assessed.

Este artigo tem como objetivo investigar como o estagiário do curso de licenciatura em música constrói compreensões sobre a função de ensinar música na educação básica. Fundamentando-se nos estudos de Maria do Céu Roldão sobre profissionalidade docente, foi desenvolvido por meio de análise documental, tendo como material empírico o portfólio de estágio de um licenciando em música, composto por oito relatórios. Os resultados indicam que a compreensão do estagiário se constrói ao longo do tempo, a partir de encontros no campo de estágio, com alunos, professoras e escola, do encontro consigo mesmo e dos encontros coletivos de orientação na universidade. Quanto mais encontros no campo de estágio, maior a possibilidade de construir entendimentos mais amplos, mas as transformações da compreensão do estagiário dependem da ampliação de saberes e do acionamento de geradores de especificidade do conhecimento docente, conduzidos pela orientação. É, portanto, a partir da interação entre o espaço de atuação profissional e a universidade que a função de ensinar música na educação básica vai sendo compreendida em sua complexidade.

Investigamos a influência da depressão materna (DM) nas dimensões comunicativas e motoras do neurodesenvolvimento infantil, por meio de um estudo longitudinal e descritivo. Foram avaliadas 1.555 díades mãe-bebê de duas cidades brasileiras com características sociodemográficas discrepantes: Ribeirão Preto (RP) (N=663) e São Luís (SL) (N=892). A DM durante a gravidez e no segundo ano de vida da criança foi avaliada, respectivamente, através da Escala de Depressão do Centro de Estudos Epidemiológicos-CES-D (≥24) e da Escala de Depressão Pós-natal de Edinburg-EPDS (≥12). O desenvolvimento infantil foi avaliado por meio do teste de triagem da Escala Bayley (BSID-III), quando as crianças tinham entre 12 e 24 meses de idade. Houve associação entre DM no segundo ano de vida da criança e comprometimento na dimensão Comunicação Receptiva do desenvolvimento da linguagem, principalmente quando a análise incluiu depressão durante a gravidez e variáveis sociodemográficas. Tal associação foi encontrada apenas no município com piores indicadores sociodemográficos. Nossos achados corroboraram a influência da DM no segundo ano de vida da criança no neurodesenvolvimento infantil, especificamente na dimensão Comunicação Receptiva do Desenvolvimento da Linguagem em SL. Além disso, os resultados sugeriram um possível papel das variáveisambientais e socioeconômicas nessa associação, chamando a atenção para o monitoramento do pré-natal e programas de intervenção para mães que vivem em contextos socioeconômicos desfavoráveis.

Background: Thrombotic thrombocytopenic purpura, particularly its immune-mediated variant (iTTP), necessitates accurate diagnostic approaches for effective management. Objectives: To compare a chemiluminescence immunoassay (CLIA) and an enzyme-linked immunosorbent assay (ELISA) for testing ADAMTS-13 activity and detecting anti–ADAMTS-13 autoantibodies (AAbs) in patients with iTTP. Methods: This study involved 31 paired samples from 12 iTTP patients. ADAMTS-13 activity was measured using the HemosIL AcuStar (Instrumentation Laboratory, CLIA) and Technozym (Technoclone) activity assay (ELISA). The presence of AAbs was assessed using Technozym ADAMTS-13-INH assay (ELISA) and HemosIL AcuStar activity (CLIA) within a Bethesda assay following mixing with normal pool plasma. von Willebrand factor (VWF) multimers were analyzed using the HYDRASYS-2 SCAN system and the HYDRAGEL 5- or 11-VW Multimer kits (Sebia). VWF activity levels were measured with the HemosIL AcuStar VWF:GPIbR on the ACL AcuStar Analyzer (IL). Results: For ADAMTS-13 activity, a strong linear relationship and no bias between CLIA and ELISA were confirmed (slope = 1.01 [0.91, 1.11], intercept = 0.00 [−0.47, 0]). However, significant discrepancies were found in AAb detection during remission phases with ADAMTS-13 activity between 10% and 50%, with CLIA and ELISA showing significant divergence (P < .001, Cohen’s g = 0.34). Consistently, VWF multimers and activity levels exhibited significantly different values between remission samples with ADAMTS-13 activity below 50% and above 50%. In longitudinal analysis of patients with multiple iTTP relapses, positivity to CLIA appears to precede ELISA in predicting exacerbations. Conclusion: While CLIA and ELISA might be interchangeable for assessing ADAMTS-13 activity, they are not equivalent for detecting AAbs, particularly in patients in clinical remission with ADAMTS-13 activity between 10% and 50%.

Interlayer organic cations in quasi-two-dimensional halide perovskites are a versatile tuning vehicle for the optoelectronic properties of these complex systems, but chemical intuition for this design route is yet to be established. Here, we use density functional theory, the GW approximation, and the Bethe-Salpeter equation approach to understand the contribution of the organic cation to the quasiparticle band gap and exciton binding energy of layered perovskites. We show that organic cations in quasi-two-dimensional perovskites contribute significantly to the dielectric screening in these systems, countering quantum confinement effects on the quasiparticle band gap and the exciton binding energy. Using a simple electrostatics model inspired by parallel-plate capacitors, we decouple the organic cation and inorganic layer contributions to the effective dielectric constants and show that dielectric properties of layered perovskites are broadly tunable via the interlayer cation, providing a direct means of tuning photophysical properties for a variety of applications.

Background and Aims: Hypoalbuminemia, as defined by serum albumin (SA) levels ≤35 g/L, is associated to venous and arterial thrombosis in general population and in patients at risk of cardiovascular disease. It is unknown if SA ≤35 g/L is also associated to portal vein thrombosis (PVT) in cirrhosis. Methods: Cirrhotic patients enrolled in the Portal vein thrombosis Relevance On Liver cirrhosis: Italian Venous thrombotic Events Registry (PRO-LIVER) study (n = 753), were followed-up for 2 years to assess the risk of PVT, that was diagnosed by Doppler ultrasonography. Child-Pugh classes, Model for End-Stage Liver Disease score, presence of hepatocellular carcinoma and laboratory variables including SA, D-dimer, and high-sensitivity C-reactive protein (hs-CRP) were measured at baseline. Results: SA ≤35 g/L was detected in 52% of patients. A logistic multivariate regression analysis showed that higher Child-Pugh class, hepatocellular carcinoma and thrombocytopenia were significantly associated to SA ≤35 g/L. In a subgroup of patients where data regarding hs-CRP and D-dimer were available, SA ≤35 g/L was inversely associated with hs-CRP and D-dimer. During the follow-up, a total of 61 patients experienced PVT. A Kaplan Meier survival analysis showed SA ≤35 g/L was associated to increased risk of PVT compared to SA >35 g/L (P = .005). A multivariate Cox proportional hazards regression analysis showed that male sex, lower platelet count, and SA ≤35 g/L remained associated to PVT after adjusting for confounding factors. Conclusion: Cirrhotic patients with SA ≤35 g/L are at higher risk of experiencing PVT compared to those with SA >35 g/L and could be considered as potential candidates to anticoagulant prophylaxis for PVT prevention.

Abstract Seismic reflection (2D/3D), borehole and bathymetric data are used to recognize a new gravitational complex in the Gulf of Squillace, Southern Italy, named the Squillace Complex. The complex has a NE-striking headwall connected to a basal detachment formed between Messinian evaporites and Tortonian shales. Its sense of movement changes to a W–E direction in the toe region. In plan view, the Squillace Complex is marked by the presence of sinuous and continuous seafloor scarps, just a few kilometers offshore, over an elongated morphological high. Seismic-well ties reveal that the complex was initiated in the Zanclean (~ 4 Ma) and continued its movement into the Gelasian (~ 2.1 Ma) at an average rate of 1.9 mm/year. Movement slowed down in the Calabrian (middle Pleistocene) and continued until the present day at a lower rate of 0.1 mm/year. Gravitational collapse of the Squillace Complex correlates with discrete contractional/transpressional events affecting the Calabrian region, which caused basin shortening and the temporary arrest of Calabrian Arc migration. These episodes resulted in tectonic uplift in the study area after 0.45 Ma (Late Pleistocene). Conversely, the complex’s slower movement recorded since the Calabrian (middle Pleistocene) is associated with slab rollback of the Ionian plate under the Calabrian Arc.

BackgroundIn this study, we explored the accuracy of two new sepsis biomarkers, monocyte distribution width (MDW) and presepsin (PSP), compared to traditional ones, C-reactive protein (CRP) and Procalcitonin (PCT), to identify sepsis and predict intra-hospital mortality by analyzing their kinetic at different time points during hospitalization stay.MethodsWe enrolled 104 patients admitted to the intensive care unit (ICU) of University Hospital “Paolo Giaccone”, Palermo. Among these, 30 (29%) had a clinical diagnosis of sepsis. MDW, PCT, CRP, and PSP were evaluated at admission (T0), after 24 h (T24), 48 h (T48), 72 h (T72), at day 5 (T5), and at discharge (TD).ResultsPatients with sepsis displayed higher levels of PCT and PSP than patients without sepsis at each timepoint; differently, CRP displayed statistically significant differences only at T0, while MDW only at T0 and T24. Patients with increasing levels of PSP displayed lower median survival time than patients with decreasing levels; differences reached statistical significance only at 48 h (20 vs. 29 days, log rank test, p = 0.046). Interestingly, PSP was an independent predictor of ICU mortality at 48 and 72 h after hospital admission. Also, the kinetic of PSP had prognostic value, with increased values at 48 h after admission being associated with reduced survival.ConclusionOur findings support the role of PSP and its kinetic as a predictor of ICU mortality.

Objectives: Gene-environment interactions increase the risk of psychosis. The objective of this study was to investigate gene-gene and gene-environment interactions in psychosis, including single nucleotide variants (SNVs) of dopamine-2 receptor (D2R), N-methyl-d-aspartate receptor (NMDAR), and cannabinoid receptor type 1 (CB1R), lifetime cannabis use, and childhood trauma. Methods: Twenty-three SNVs of genes encoding D2R (DRD2: rs1799978, rs7131056, rs6275), NMDAR (GRIN1: rs4880213, rs11146020; GRIN2A: rs1420040, rs11866328; GRIN2B: rs890, rs2098469, rs7298664), and CB1R (CNR1: rs806380, rs806379, rs1049353, rs6454674, rs1535255, rs2023239, rs12720071, rs6928499, rs806374, rs7766029, rs806378, rs10485170, rs9450898) were genotyped in 143 first-episode psychosis patients (FEPp) and 286 community-based controls by Illumina HumanCoreExome-24 BeadChip. Gene-gene and gene-environment associations were assessed using nonparametric Multifactor Dimensionality Reduction software. Results: Single-locus analyses among the 23 SNVs for psychosis and gene-gene interactions were not significant (p > 0.05 for all comparisons); however, both environmental risk factors showed an association with psychosis (p < 0.001). Moreover, gene-environment interactions were significant for an SNV in CNR1 and cannabis use. The best-performing model was the combination of CNR1 rs12720071 and lifetime cannabis use (p < 0.001), suggesting an increased risk of psychosis. Conclusion: Our study supports the hypothesis of gene-environment interactions for psychosis involving T-allele carriers of CNR1 SNVs, childhood trauma, and cannabis use.

Dementia is an age-related syndrome characterized by the progressive deterioration of cognition and capacity for independent living. Diabetes is often associated with cognitive decline and shares similar pathophysiological mechanisms with dementia, such as systemic inflammation, oxidative stress, insulin resistance, and advanced glycation end-products formation. Therefore, adequate diabetes management may reduce the risk of cognitive decline, especially in patients with other comorbidities and risk factors. The sodium glucose cotransporter inhibitors (SGLT2i) regulate renal glucose reabsorption by blocking the SGLT2 cotransporters located in the proximal tubules, causing glycosuria and intraglomerular pressure reduction. Their use helps to lower blood pressure by modifying sodium and water homeostasis; these drugs are also commonly used in the treatment of heart failure and chronic kidney disease, while recently, a potential neuroprotective role in the central nervous system has been suggested. The aim of our scoping review is to analyze current evidence about the potential neuroprotective effects of SGLT2i in adult patients. We performed a scoping literature review to evaluate the effect of SGLT2i on dementia, mild cognitive impairment (MCI) and Alzheimer’s disease incidence and progression. The screening process was performed through different searches on PubMed and EMBASE, evaluating original works published up to January 2024. In conclusion, the use of SGLT2i could be associated with a neuroprotective effect in patients with diabetes, reducing the incidence or the progression of MCI and dementia. Further prospective studies are needed to validate this hypothesis and to evaluate the effectiveness of this class of drugs in normal glycemic profile patients.