CCL18, CHI3L1, ANG2, IL-6 systemic levels are associated with the extent of lung damage and radiomic features in SARS-CoV-2 infection.

OBJECTIVE AND DESIGN: We aimed to identify cytokines whose concentrations are related to lung damage, radiomic features, and clinical outcomes in COVID-19 patients. MATERIAL OR SUBJECTS: Two hundred twenty-six patients with SARS-CoV-2 infection and chest computed tomography (CT) images were enrolled. METHODS: CCL18, CHI3L1/YKL-40, GAL3, ANG2, IP-10, IL-10, TNFα, IL-6, soluble gp130, soluble IL-6R were quantified in plasma samples using Luminex assays. The Mann-Whitney U test, the Kruskal-Wallis test, correlation and regression analyses were performed. Mediation analyses were used to investigate the possible causal relationships between cytokines, lung damage, and outcomes. AVIEW lung cancer screening software, pyradiomics, and XGBoost classifier were used for radiomic feature analyses. RESULTS: CCL18, CHI3L1, and ANG2 systemic levels mainly reflected the extent of lung injury. Increased levels of every cytokine, but particularly of IL-6, were associated with the three outcomes: hospitalization, mechanical ventilation, and death. Soluble IL-6R showed a slight protective effect on death. The effect of age on COVID-19 outcomes was partially mediated by cytokine levels, while CT scores considerably mediated the effect of cytokine levels on outcomes. Radiomic-feature-based models confirmed the association between lung imaging characteristics and CCL18 and CHI3L1. CONCLUSION: Data suggest a causal link between cytokines (risk factor), lung damage (mediator), and COVID-19 outcomes.

A computational study of the negative LiIn modified anode and its interaction with ß-Li3PS4 solid-electrolyte for battery applications.

All-solid-state lithium batteries (ASSLBs) have sparked interest due to their far superior energy density compared to current commercial material, but the heightened reactivity of the negative Li electrode can compromise the long-term cyclability of the cell, calling for the introduction of passivating layers or alloy anodes. In this article, we aim to explain the outstanding stability of LiIn alloy-based anodes over extended cycling by comparing its bulk and interface properties to Li-metal. Using density functional theory, we conducted an in-depth analysis of the LiIn surfaces' formation and subsequent structural stability in interfaces with the solid electrolyte ß-Li3PS4. Several LiIn facets are shown to possess sufficient structural stability, with the (110) surface being the most stable. The stable interfaces established with the ß-Li3PS4(100) surface featured favorable adhesion energy, low strain energy, and little reconstruction. By comparing these interface properties with the bulk properties of Li-metal and LiIn, we highlighted the influence of the cohesion energy, Fermi energy level, and band position of the two materials in the long-term stability of their anodes under battery conditions.

Integrated Approach of Life Cycle Assessment and Experimental Design in the Study of a Model Organic Reaction: New Perspectives in Renewable Vanillin-Derived Chemicals.

This work is focused on performing a quantitative assessment of the environmental impacts associated with an organic synthesis reaction, optimized using an experimental design approach. A nucleophilic substitution reaction was selected, employing vanillin as the substrate, a phenolic compound widely used in the food industry and of pharmaceutical interest, considering its antioxidant and antitumoral potential. To carry out the reaction, three different solvents have been chosen, namely acetonitrile (ACN), acetone (Ace), and dimethylformamide (DMF). The syntheses were planned with the aid of a multivariate experimental design to estimate the best reaction conditions, which simultaneously allow a high product yield and a reduced environmental impact as computed by Life Cycle Assessment (LCA) methodology. The experimental results highlighted that the reactions carried out in DMF resulted in higher yields with respect to ACN and Ace; these reactions were also the ones with lower environmental impacts. The multilinear regression models allowed us to identify the optimal experimental conditions able to guarantee the highest reaction yields and lowest environmental impacts for the studied reaction. The identified optimal experimental conditions were also validated by experimentally conducting the reaction in those conditions, which indeed led to the highest yield (i.e., 93%) and the lowest environmental impacts among the performed experiments. This work proposes, for the first time, an integrated approach of DoE and LCA applied to an organic reaction with the aim of considering both conventional metrics, such as reaction yield, and unconventional ones, such as environmental impacts, during its lab-scale optimization.

Stability and Formation of the Li3PS4/Li, Li3PS4/Li2S, and Li2S/Li Interfaces: A Theoretical Study.

Solid electrolytes have shown superior behavior and many advantages over liquid electrolytes, including simplicity in battery design. However, some chemical and structural instability problems arise when solid electrolytes form a direct interface with the negative Li-metal electrode. In particular, it was recognized that the interface between the ß-Li3PS4 crystal and lithium anode is quite unstable and tends to promote structural defects that inhibit the correct functioning of the device. As a possible way out of this problem, we propose a material, Li2S, as a passivating coating for the Li/ß-Li3PS4 interface. We investigated the mutual affinity between Li/Li2S and Li2S/ß-Li3PS4 interfaces by DFT methods and investigated the structural stability through the adhesion energy and mechanical stress. Furthermore, a topological analysis of the electron density identified preferential paths for the migration of Li ions.

From symmetry breaking in the bulk to phase transitions at the surface: a quantum-mechanical exploration of Li6PS5Cl argyrodite superionic conductor.

Lithium superionic conductor electrolytes may enable the safe use of metallic lithium anodes in all-solid-state batteries. The key to a successful application is a high Li conductivity in the electrolyte material, to be achieved through the maintenance of intimate contact with the electrodes and the knowledge of the chemical nature of that contact. In this manuscript, we tackle this issue by a theoretical ab initio approach. Focusing on the Li6PS5Cl, a thiophosphate with high ionic conductivity, we carry on thorough modeling of the surfaces together with the prediction of the thermal and elastic behaviour. Our investigation leads to some new findings: the bulk structure, as reported in the literature, appears to be metastable, with spontaneous symmetry breaking. Moreover, the relevant stoichiometric surfaces identified for stable and metastable crystal structures are not up-down symmetry related and they expose from one side Li2S and LiCl. Surface reconstructions can be interpreted as local phase transitions. We also predict entirely ab initio the morphology of crystallites, charge, and electrostatic potential at surfaces, together with the effect of temperature on structural properties and the elastic behaviour of this material. Such findings may constitute the relevant groundwork for a better understanding of ionic transport in Li-ion conductors at the electrolyte/anode and electrolyte/cathode interfaces.

A Review of Mechanical and Chemical Sensors for Automotive Li-Ion Battery Systems.

The electrification of passenger cars is one of the most effective approaches to reduce noxious emissions in urban areas and, if the electricity is produced using renewable sources, to mitigate the global warming. This profound change of paradigm in the transport sector requires the use of Li-ion battery packages as energy storage systems to substitute conventional fossil fuels. An automotive battery package is a complex system that has to respect several constraints: high energy and power densities, long calendar and cycle lives, electrical and thermal safety, crash-worthiness, and recyclability. To comply with all these requirements, battery systems integrate a battery management system (BMS) connected to an complex network of electric and thermal sensors. On the other hand, since Li-ion cells can suffer from degradation phenomena with consequent generation of gaseous emissions or determine dimensional changes of the cell packaging, chemical and mechanical sensors should be integrated in modern automotive battery packages to guarantee the safe operation of the system. Mechanical and chemical sensors for automotive batteries require further developments to reach the requested robustness and reliability; in this review, an overview of the current state of art on such sensors will be proposed.

The value of computed tomography in assessing the risk of death in COVID-19 patients presenting to the emergency room.

OBJECTIVE: The aims of this study were to develop a multiparametric prognostic model for death in COVID-19 patients and to assess the incremental value of CT disease extension over clinical parameters. METHODS: Consecutive patients who presented to all five of the emergency rooms of the Reggio Emilia province between February 27 and March 23, 2020, for suspected COVID-19, underwent chest CT, and had a positive swab within 10 days were included in this retrospective study. Age, sex, comorbidities, days from symptom onset, and laboratory data were retrieved from institutional information systems. CT disease extension was visually graded as < 20%, 20-39%, 40-59%, or ≥ 60%. The association between clinical and CT variables with death was estimated with univariable and multivariable Cox proportional hazards models; model performance was assessed using k-fold cross-validation for the area under the ROC curve (cvAUC). RESULTS: Of the 866 included patients (median age 59.8, women 39.2%), 93 (10.74%) died. Clinical variables significantly associated with death in multivariable model were age, male sex, HDL cholesterol, dementia, heart failure, vascular diseases, time from symptom onset, neutrophils, LDH, and oxygen saturation level. CT disease extension was also independently associated with death (HR = 7.56, 95% CI = 3.49; 16.38 for ≥ 60% extension). cvAUCs were 0.927 (bootstrap bias-corrected 95% CI = 0.899-0.947) for the clinical model and 0.936 (bootstrap bias-corrected 95% CI = 0.912-0.953) when adding CT extension. CONCLUSIONS: A prognostic model based on clinical variables is highly accurate in predicting death in COVID-19 patients. Adding CT disease extension to the model scarcely improves its accuracy. KEY POINTS: • Early identification of COVID-19 patients at higher risk of disease progression and death is crucial; the role of CT scan in defining prognosis is unclear. • A clinical model based on age, sex, comorbidities, days from symptom onset, and laboratory results was highly accurate in predicting death in COVID-19 patients presenting to the emergency room. • Disease extension assessed with CT was independently associated with death when added to the model but did not produce a valuable increase in accuracy.

Management of Asbestos Containing Materials: A Detailed LCA Comparison of Different Scenarios Comprising First Time Asbestos Characterization Factor Proposal.

This work addresses the complex issue of asbestos containing materials (ACMs) management, by focusing on the scenario of six municipalities comprised in the Reggio Emilia province of Emilia Romagna Italian region. Particularly, the life cycle assessment (LCA) methodology was applied in order to assess in a quantitative and reliable manner the human toxicity as well as the ecotoxicity impacts associated with all of the different phases of ACMs management. The latter comprises mapping of ACMs, creation of a risk map for defining priority of intervention, encapsulation and removal of ACMs, as well as the as obtained asbestos containing waste (ACW) end of life. Particularly, a thermal inertisation treatment performed in a continuous industrial furnace was considered as the innovative end of life scenario to be compared with what actually was provided by the legislation of many countries worldwide, that is, the disposal of ACW in a controlled landfill for hazardous wastes. A characterization factor for asbestos fibers released both in outdoor air and in occupational setting was proposed for the first time and included in the USEtox 2.0 impact assessment method. This allowed us to reliably and quantitatively highlight that inertisation treatments should be the preferred solutions to be adopted by local and national authorities, especially if the obtained inert material finds application as secondary raw materials, thus contributing to a decrease in the environmental damage (limited to its toxicological contributions) to be associated with asbestos management.

The NV-N+ charged pair in diamond: a quantum-mechanical investigation.

The NV-N+ charged pair in diamond has been investigated by using a Gaussian-type basis set, the B3LYP functional, the supercell scheme and the CRYSTAL code. It turns out that: (i) when the distance between the two defects is larger than 6-7 Å, the properties of the double defect are the superposition of the properties of the individual defects. (ii) The energy required for the reaction NV0 + Ns→ NV- + N+ is roughly -1.3 eV at about 12 Å, irrespective of the basis set and functional adopted, and remains negative at any larger distance. (iii) These results support the observation of a charge transfer mechanism through a Ns→ NV0 donation occurring in the ground state, through a tunnelling process, without irradiation. (iv) The IR spectrum of the two subunits is characterized by specific peaks, that might be used as fingerprints. (v) Calculation of electrostatic interaction permitted an estimate of the effective charge of the defects.

Interstitial defects in diamond: A quantum mechanical simulation of their EPR constants and vibrational spectra.

The local geometry, electronic structure, and vibrational features of three vicinal double interstitial defects in diamond, ICIC, ICIN, and ININ, are investigated and compared with those of three "simple" ⟨100⟩ interstitial defects, ICC, ICN, and INN, previously reported by Salustro et al. [Phys. Chem. Chem. Phys. 20, 16615 (2018)], using a similar quantum mechanical approach based on the B3LYP functional constructed from Gaussian-type basis sets, within a supercell scheme, as implemented in the CRYSTAL code. For the first time, the Fermi contact term and hyperfine coupling tensor B of the four open shell structures, ICIC, ICIN, ICC, and ICN, are evaluated and compared with the available experimental EPR data. For the two double interstitial defects, the agreement with experiment is good, whereas that for the single interstitials is found to be very poor, for which a likely reason is the incorrect attribution of the EPR spectra to uncertain atomic details of the micro-structure of the samples. The infrared spectra of the three double interstitial defects exhibit at least two peaks that can be used for their characterization.

The CRYSTAL code, 1976-2020 and beyond, a long story.

CRYSTAL is a periodic ab initio code that uses a Gaussian-type basis set to express crystalline orbitals (i.e., Bloch functions). The use of atom-centered basis functions allows treating 3D (crystals), 2D (slabs), 1D (polymers), and 0D (molecules) systems on the same grounds. In turn, all-electron calculations are inherently permitted along with pseudopotential strategies. A variety of density functionals are implemented, including global and range-separated hybrids of various natures and, as an extreme case, Hartree-Fock (HF). The cost for HF or hybrids is only about 3-5 times higher than when using the local density approximation or the generalized gradient approximation. Symmetry is fully exploited at all steps of the calculation. Many tools are available to modify the structure as given in input and simplify the construction of complicated objects, such as slabs, nanotubes, molecules, and clusters. Many tensorial properties can be evaluated by using a single input keyword: elastic, piezoelectric, photoelastic, dielectric, first and second hyperpolarizabilities, etc. The calculation of infrared and Raman spectra is available, and the intensities are computed analytically. Automated tools are available for the generation of the relevant configurations of solid solutions and/or disordered systems. Three versions of the code exist: serial, parallel, and massive-parallel. In the second one, the most relevant matrices are duplicated on each core, whereas in the third one, the Fock matrix is distributed for diagonalization. All the relevant vectors are dynamically allocated and deallocated after use, making the code very agile. CRYSTAL can be used efficiently on high performance computing machines up to thousands of cores.

Serum Copeptin levels in the emergency department predict major clinical outcomes in adult trauma patients.

BACKGROUND: Early prognostication in trauma patients is challenging, but particularly important. We wanted to explore the ability of copeptin, the C-terminal fragment of arginine vasopressin, to identify major trauma, defined as Injury Severity Score (ISS) > 15, in a heterogeneous cohort of trauma patients and to compare its performances with lactate. We also evaluated copeptin performance in predicting other clinical outcomes: mortality, hospital admission, blood transfusion, emergency surgery, and Intensive Care Unit (ICU) admission. METHODS: This single center, pragmatic, prospective observational study was conducted at Arcispedale Santa Maria Nuova, a level II trauma center in Reggio Emilia, Italy. Copeptin determination was obtained on Emergency Department (ED) arrival, together with venous lactate. Different outcomes were measured including ISS, Revised Trauma Score (RTS), hospital and ICU admission, blood transfusion, emergency surgery, and mortality. RESULTS: One hundred and twenty five adult trauma patients admitted to the ED between June 2017 and March 2018. Copeptin showed a good ability to identify patients with ISS > 15 (AUC 0.819). Similar good performances were recorded also in predicting other outcomes. Copeptin was significantly superior to lactate in identifying patients with ISS > 15 (P 0.0015), and in predicting hospital admission (P 0.0002) and blood transfusion (P 0.016). Comparable results were observed in a subgroup of patients with RTS 7.84. CONCLUSIONS: In a heterogeneous group of trauma patients, a single copeptin determination at the time of ED admission proved to be an accurate biomarker, statistically superior to lactate for the identification of major trauma, hospital admission, and blood transfusion, while no statistical difference was observed for ICU admission and emergency surgery. These results, if confirmed, may support a role for copeptin during early management of trauma patients.

Nitrogen substitutional defects in silicon. A quantum mechanical investigation of the structural, electronic and vibrational properties.

The vibrational infrared (IR) and Raman spectra of seven substitutional defects in bulk silicon are computed, by using the quantum mechanical CRYSTAL code, the supercell scheme, an all electron Gaussian type basis set and the B3LYP functional. The relative stability of various spin states has been evaluated, the geometry optimized, the electronic structure analyzed. The IR and Raman intensities have been evaluated analitically. In all cases the IR spectrum is dominated by a single N peak (or by two or three peaks with very close wavenumbers), whose intensity is at least 20 times larger than the one of any other peak. These peaks fall in the 645-712 cm-1 interval, and a shift of few cm-1 is observed from case to case. The Raman spectrum of all defects is dominated by an extremely intense peak at about 530 cm-1, resulting from the (weak) perturbation of the peak of pristine silicon.

On the Models for the Investigation of Charged Defects in Solids: The Case of the VN- Defect in Diamond.

Local charged defects in periodic systems are usually investigated by adopting the supercell charge compensated (CC) model, which consists of two main ingredients: (i) the periodic supercell, hopefully large enough to reduce to negligible values the interaction among defects belonging to different cells; (ii) a background of uniform compensating charge that restores the neutrality of the supercell and then avoids the "Coulomb catastrophe". Here, an alternative approach is proposed and compared to CC, the double defect (DD) model, in which another point defect is introduced in the supercell that provides (or accept) the electron to be transferred (subtracted) to the defect of interest. The DD model requires obviously a (much) larger supercell than CC, and the effect of the relative position of the two defects must be explored. A third possible option, the cluster approach, is not discussed here. The two models have been compared with reference to the VN- defect; for DD, the positive compensating charge is provided by a P atom. Three cubic supercells of increasing size (containing 216, 512, and 1000 atoms) and up to eight relative VN--P+ defect-defect positions have been considered. The comparison extends to the equilibrium geometry around the defect, band structure, charge and spin distribution, IR and Raman vibrational spectra, and electron paramagnetic resonance constants. It turns out that the CC and DD models provide very similar results for all of these properties, in particular when the P+ compensating defect is not too close to VN-.

Vibrational spectroscopy of hydrogens in diamond: a quantum mechanical treatment.

The electronic and vibrational features of the VHn (n = 1 to 4) family of defects in diamond (hydrogen atoms saturating the dangling bonds of the atoms surrounding a vacancy) are investigated at the quantum mechanical level by using the periodic supercell approach, an all electron Gaussian type basis set, hybrid functionals, and the Crystal code. Most of the results have been collected for supercells containing 64 atoms; however, in order to explore the effect of the defect concentration on both the IR and Raman spectra, supercells containing 216, 512 and 1000 atoms have also been considered in the VH4 case. For each system, all the possible spin states are considered; their relative stability, band structure, charge and spin density distributions are thoroughly described. All the investigated systems present specific IR and Raman spectra, with vibrational spectroscopic features that can in principle be used as fingerprints for their characterization. This is particularly true for the C-H stretching, that ranges between 2500 and 4400 cm-1. The stretching modes are strongly affected by anharmonicity that has been evaluated in this work; it turns out to be extremely sensitive to the H load and spin state of the system, and ranges from -335 cm-1 for VH1 to +85 cm-1 for VH4. All of the investigated defects have very low C-H stretching IR intensity, so that they essentially appear as silent, the exception being VH1. The situation is different for the Raman spectra: the stretching modes of all defects do have similar large intensity; unfortunately here it is the experimental evidence that is lacking.

Characterization of the B-Center Defect in Diamond through the Vibrational Spectrum: A Quantum-Mechanical Approach.

The B-center in diamond, which consists of a vacancy whose four first nearest-neighbors are nitrogen atoms, has been investigated at the quantum-mechanical level with an all-electron Gaussian-type basis set, hybrid functionals, and the periodic supercell approach. To simulate various defect concentrations, four cubic supercells have been considered, containing (before the creation of the vacancy) 64, 216, 512, and 1000 atoms, respectively. Whereas the B-center does not affect the Raman spectrum of diamond, several intense peaks appear in the IR spectrum, which should permit us to identify this defect. It turns out that of the seven peaks proposed by Sutherland in 1954, located at 328, 780, 1003, 1171, 1332, 1372, and 1426 cm-1, and frequently mentioned as fingerprints of the B center, the first one and the last three do not appear in the simulated spectrum at any concentration. The graphical animation of the modes confirms the attribution of the remaining three and also permits investigation of the nature of the full set of modes.

Calibration of 57Fe Mössbauer constants by first principles.

Electron density and eigenvalues of the 3 × 3 matrix of the electric field gradients at the (57)Fe nuclei positions have been evaluated with the periodic ab initio CRYSTAL code for a wide range of crystalline compounds, adopting different computational approaches (Hartree-Fock, gradient corrected and hybrids functionals). The robust calibration procedure, involving experimental isomer shifts and quadrupolar splittings, yields reliable Mössbauer parameters, i.e. the isomer shift constant (α) and the nuclear quadrupolar moment (Q). Dependence of the results on the Hamiltonian is explored and well suited localized basis sets for periodic calculations are provided.

Water dissociation on MnO(1 × 1)/Ag(100).

In this work we utilize experimental and simulation techniques to examine the molecular level interaction of water with a MnO(1 × 1) thin film deposited onto Ag(100). The formation of MnO(1 × 1)/Ag(100) was characterized by low energy electron diffraction and scanning tunneling microscopy. Density functional theory (DFT) shows MnO(1 × 1) is thermodynamically more stable than MnO(2 × 1) by ∼0.4 eV per MnO. Upon exposure to 2.5 Torr water vapor at room temperature, X-ray photoemission spectroscopy results show extensive surface hydroxylation attributed to reactivity at MnO(1 × 1) terrace sites. DFT calculations of a water monomer on MnO(1 × 1)/Ag(100) show the dissociated form is energetically more favorable than molecular adsorption, with a hydroxylation activation barrier 0.4 eV per H2O. These results are discussed and contrasted with previous studies of MgO/Ag(100) which show a stark difference in behavior for water dissociation.

Combined experimental and theoretical investigation of the hemi-squaraine/TiO2 interface for dye sensitized solar cells.

A simple hemi-squaraine dye (CT1) has been studied as a TiO2 sensitizer for application in dye sensitized solar cells (DSCs) by means of a combined experimental and theoretical investigation. This molecule is a prototype dye presenting an innovative anchoring group: the squaric acid moiety. Ab initio calculations based on Density Functional Theory (DFT) predict that this acid spontaneously deprotonates at the anatase (101) surface forming chemical bonds that are stronger than the ones formed by other linkers (e.g. cathecol and isonicotinic acid). Moreover an analysis of the electronic structure of the hybrid interface reveals the formation of a type II heterostructure ensuring adiabatic electron transfer from the molecule to the oxide. DSCs containing hemi-squaraine dyes were assembled, characterized and their performances compared to state of the art cells. Experimental results (large incident photon-to-electron conversion efficiency and an efficiency of 3.54%) confirmed the theoretical prediction that even a simple hemi-squaraine is an effective sensitizer for TiO2. Our study paves the way to the design of more efficient sensitizers based on a squaric acid linker and specifically engineered to absorb light in a larger part of the visible range.

Computational Understanding of Delithiation, Overlithiation, and Transport Properties in Disordered Cubic Rock-Salt Type Li2TiS3.

Lithium-titanium-sulfur cathodes have gained attention because of their unique properties and have been studied for their application in lithium-ion batteries. They offer different advantages such as lower cost, higher safety, and higher energy density with respect to commonly adopted transition metal oxides. Moreover, this family of compounds is free from critical raw materials such as cobalt and nickel. For cathode materials, a crucial aspect is evaluating the evolution and behavior of the structure and properties during the cycling process, which means simulating the system under lithium extraction and insertion. Structural optimization, electronic band structures, density of states, and Raman spectra were simulated, looking for fingerprints and peculiar aspects related to the delithiation and overlithiation process. Lithium transport properties were also investigated through the nudged elastic band methodology. This allowed us to evaluate the diffusion coefficient of lithium, which is a crucial parameter for cathode performance evaluation.