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This paper presents a method for developing a malware ontology structure by detecting malware instances on Twitter. The ontology represents a semi-automatic classifier fed by the data extracted from tweets. In particular, the automatic part of the presented methodology relies on a pattern-based approach to detect trigger expressions leading to new information about malware, whilst the manual one covers the evaluation of the results by domain-experts, who also validate the reliability of the semantic relationships within the ontology framework. We present preliminary results on the application of our methodology to tweets extracted from MalwareBazaar database showing how the documents’ collection analysis, through Natural Language Processing (NLP) tasks, can support the knowledge retrieval and documents’ classification procedures for building early warning system of detected malware. Results obtained from this research paper within the time framework of 2023 are referred to the previous version of the current social network X. [ABSTRACT FROM AUTHOR]

Whilst upregulation of type I interferon (IFN) signaling is common across the type I interferonopathies (T1Is), central nervous system (CNS) involvement varies between these disorders, the basis of which remains unclear. We collected cerebrospinal fluid (CSF) and serum from patients with Aicardi-Goutières syndrome (AGS), STING-associated vasculopathy with onset in infancy (SAVI), presumed monogenic T1Is (pT1I), childhood systemic lupus erythematosus with neuropsychiatric features (nSLE), non-IFN-related autoinflammation (AI) and non-inflammatory hydrocephalus (as controls). We measured IFN-alpha protein using digital ELISA. Eighty-two and 63 measurements were recorded respectively in CSF and serum of 42 patients and 6 controls. In an intergroup comparison (taking one sample per individual), median CSF IFN-alpha levels were elevated in AGS, SAVI, pT1I, and nSLE compared to AI and controls, with levels highest in AGS compared to all other groups. In AGS, CSF IFN-alpha concentrations were higher than in paired serum samples. In contrast, serum IFN was consistently higher compared to CSF levels in SAVI, pT1I, and nSLE. Whilst IFN-alpha is present in the CSF and serum of all IFN-related diseases studied here, our data suggest the primary sites of IFN production in the monogenic T1I AGS and SAVI are, respectively, the CNS and the periphery. These results inform the diagnosis of, and future therapeutic approaches to, monogenic and multifactorial T1Is. [ABSTRACT FROM AUTHOR]

The sample collection procedure for SARS-CoV-2 has a strong impact on diagnostic capability, contact tracing approach, ultimately affecting the infection containment performance. This study demonstrates that self-collected nasal-swab has shown to be a valid and well tolerated procedure to SARS-CoV-2 surveillance in a healthcare system. More significantly, no performance adequacy difference was detected in self-administered swabs between healthcare worker (HCW) and non-HCW which allows to speculate that this procedure could be successfully extended to the entire population for mass screening. [ABSTRACT FROM AUTHOR]

A highly accurate, global dipole moment surface (DMS) is calculated for the water molecule using ab initio quantum chemistry methods. The new surface is named LTP2011 and is based on all-electron, internally contracted multireference configuration interaction, including size-extensivity corrections in the aug-cc-pCV6Z basis set. Dipoles are computed as energy derivatives and small corrections due to relativistic effects included. The LTP2011 DMS uses an appropriate functional form that guarantees qualitatively correct behaviour even for most high energies configuration (up to about 60 000 cm-1), including, in particular, along the water dissociation channel. Comparisons with high precision experimental data show agreement within 1% for medium-strength lines. The new DMS and all the ab initio data are made available in the supplementary material. [ABSTRACT FROM AUTHOR]

A valence-only (V) dipole moment surface (DMS) has been computed for water at the internally contracted multireference configuration interaction level using the extended atom-centered correlation-consistent Gaussian basis set aug-cc-pV6Z. Small corrections to these dipole values, resulting from core correlation (C) and relativistic (R) effects, have also been computed and added to the V surface. The resulting DMS surface is hence called CVR. Interestingly, the C and R corrections cancel out each other almost completely over the whole grid of points investigated. The ground-state CVR dipole of H216O is 1.8676 D. This value compares well with the best ab initio one determined in this study, 1.8539±0.0013 D, which in turn agrees well with the measured ground-state dipole moment of water, 1.8546(6) D. Line intensities computed with the help of the CVR DMS shows that the present DMS is highly similar to though slightly more accurate than the best previous DMS of water determined by Schwenke and Partridge [J. Chem. Phys. 113, 16 (2000)]. The influence of the precision of the rovibrational wave functions computed using different potential energy surfaces (PESs) has been investigated and proved to be small, due mostly to the small discrepancies between the best ab initio and empirical PESs of water. Several different measures to test the DMS of water are advanced. The seemingly most sensitive measure is the comparison between the ab initio line intensities and those measured by ultralong pathlength methods which are sensitive to very weak transitions. [ABSTRACT FROM AUTHOR]

An ab initio study of the rotation-vibrational spectrum of the electronic ground state of the (gas-phase) fluoronium ion H 2 F + is presented. A new potential energy surface (PES) and a new dipole moment surface (DMS) were produced and used to compute rotation-vibrational energy levels, line positions and line intensities. Our computations achieve an accuracy of 0.15 cm −1 for the fundamental vibrational frequencies, which is about 50 times more accurate than previous ab initio results. The computed room-temperature line list should facilitate the experimental observations of new H 2 F + lines, in particular of yet unobserved overtone transitions. The H 2 F + molecular ion, which is isoelectronic to water, has a non-linear equilibrium geometry but a low-energy barrier to linearity at about 6000 cm −1 . As a result the effects of so-called quantum monodromy become apparent already at low bending excitations. An analysis of excited bends in terms of quantum monodromy is presented. [ABSTRACT FROM AUTHOR]

In this work we perform a systematic ab initio study of the dipole moment surface (DMS) of H 2 S at various levels of theory and of its effect on the intensities of vibration–rotation transitions; H 2 S intensities are known from the experiment to display anomalies which have so far been difficult to reproduce by theoretical calculations. We use the transition intensities from the HITRAN database of 14 vibrational bands for our comparisons. The intensities of all fundamental bands show strong sensitivity to the ab initio method used for constructing the DMS while hot, overtone and combination bands up to 4000 cm −1 do not. The core-correlation and relativistic effects are found to be important for computed line intensities, for instance affecting the most intense fundamental band ( ν 2 ) by about 20%. Our recommended DMS, called ALYT2, is based on the CCSD(T)/aug-cc-pV(6+d)Z level of theory supplemented by a core-correlation/relativistic corrective surface obtained at the CCSD[T]/aug-cc-pCV5Z-DK level. The corresponding computed intensities agree significantly better (to within 10%) with experimental data taken directly from original papers. Worse agreement (differences of about 25%) is found for those HITRAN intensities obtained from fitted effective dipole models, suggesting the presence of underlying problems in those fits. [ABSTRACT FROM AUTHOR]

Accurate and complete rotational, rotational-vibrational and rotational-vibrational-electronic line lists are calculated for sodium hydride: both the NaH and NaD isotopologues are considered. These line lists cover all ro-vibrational states of the ground (A¹ Σ+) and first excited (X¹ Σ+) electronic states. The calculations use available spectroscopically-determined potential energy curves and new high-quality, ab initio dipole moment curves. Partition functions for both isotopologues are calculated and the effect of quasi-bound states is considered. The resulting line lists are suitable for temperatures up to about 7000 K and are designed for studies of exoplanet atmospheres, brown dwarfs and cool stars. In particular, the NaH A -- X band is found to show a broad absorption feature at about 385 nm which should provide a signature for the molecule. All partition functions, lines and transitions are available as supplementary information to this article and at www.exomol.com. [ABSTRACT FROM AUTHOR]

Accurate and complete rotational, rotational-vibrational and rotational-vibrational-electronic line lists are calculated for sodium hydride: both the NaH and NaD isotopologues are considered. These line lists cover all ro-vibrational states of the ground (X ¹Σ+) and first excited (A ¹Σ+) electronic states. The calculations use available spectroscopically-determined potential energy curves and new high-quality, ab initio dipole moment curves. Partition functions for both isotopologues are calculated and the effect of quasi-bound states is considered. The resulting line lists are suitable for temperatures up to about 7000 K and are designed for studies of exoplanet atmospheres, brown dwarfs and cool stars. In particular, the NaH A - X band is found to show a broad absorption feature at about 385 nm which should provide a signature for the molecule. All partition functions, lines and transitions are available as supplementary information to this article and at www.exomol.com. [ABSTRACT FROM AUTHOR]

The electronic structure of six low-lying electronic states of scandium hydride,X 1Σ+,a 3Δ,b 3Π,A 1Δ,c 3Σ+andB 1Π, is studied using multi-reference configuration interaction as a function of bond length. Diagonal and off-diagonal dipole moment, spin–orbit coupling and electronic angular momentum curves are also computed. The results are benchmarked against experimental measurements and calculations on atomic scandium. The resulting curves are used to compute a line list of molecular rovibronic transitions for45ScH. [ABSTRACT FROM PUBLISHER]

Analysis of the accuracy of two programs widely-used for computing ro-vibrational spectra of diatomic molecules, namely Duo and Level , is presented. Using model systems for which analytic results are available it is shown that compared to Level , Duo gives similar or usually higher accuracy for line intensities, and is accurate for calculations of bound state energies and corresponding wavefunctions. Furthermore, Duo provides matrix elements accurate to about 1 0 − 4 – 1 0 − 5 % relative to the analytic values, which is sufficient for developing of accurate methods for experimental determination of some macroscopic gas features, such as pressure, concentration, temperature, and so on; this level of accuracy can only be achieved with Level by significantly increasing the number of grid points in the calculation. [Display omitted] • Comparison of programs Duo and Level shows both programs give reliable results for model diatomics systems. • Duo shows significantly faster (exponential) convergence for matrix elements. • Duo is also somewhat faster, more flexible and easier to use. [ABSTRACT FROM AUTHOR]

Abstract: New line lists for isotopically substituted water are presented. Most line positions were calculated from experimentally determined energy levels, while all line intensities were computed using an ab initio dipole moment surface. Transitions for which experimental energy levels are unavailable use calculated line positions. These line lists cover the range 0.05–20000cm−1 and are significantly more complete and potentially more accurate than the line lists available via standard databases. All lines with intensities (scaled by isotopologue abundance) greater than 10−29 cm/molecule at 296K are included, augmented by weaker lines originating from pure rotational transitions. The final line lists contain 39918 lines for H2 18O and 27546 for H2 17O and are presented in standard HITRAN format. The number of experimentally determined H2 18O and H2 17O line positions is, respectively, 32970 (83% of the total) and 17073 (62%) and in both cases the average estimated uncertainty is 2×10−4 cm−1. The number of ab initio line intensities with an estimated uncertainty of 1% is 16621 (42%) for H2 18O and 13159 (48%) for H2 17O. [Copyright &y& Elsevier]

Abstract: Pure rotational lines are important for monitoring water concentrations in many environments both in space and on earth. A list of line intensities of rotational transitions for H2 is calculated using variational nuclear-motion wave functions and an ab initio dipole moment surface. This methodology should be equally reliable for both allowed and forbidden rotational transitions. Extensive comparisons are made with available intensity data for these transitions including the HITRAN and JPL databases. Problems are identified with some of these data. A list of 555 allowed and 846 forbidden rotational transition lines within the ground vibrational state is made available. [Copyright &y& Elsevier]

Keywords: food allergy; immunological disorder; pediatrics; TH17 cells; Treg cells EN food allergy immunological disorder pediatrics TH17 cells Treg cells 1833 1834 2 07/14/20 20200701 NES 200701 The historical T-cell dichotomy (T SB H sb 1 versus T SB H sb 2) changed by the identification of T SB H sb 17 and T SB reg sb cells. Among the metabolites that were significantly different, a secondary BA and primary BA were found in pairwise comparisons between nonatopic controls and children with food allergy and asthma, respectively. Food allergy, immunological disorder, pediatrics, TH17 cells, Treg cells. [Extracted from the article]

Aim: To estimate hospitalisation rate and investigate the role of age, prematurity and vaccination status in severe pertussis cases. Methods: We retrospectively evaluated 200 children aged 0–14 years, admitted to the emergency rooms of Meyer Hospital of Florence and Pisa Hospital with a diagnosis of pertussis from 1 October 2010 to 31 January 2020. Results: Children younger than 12 months were 63.0%. Preterm infants were 6.5%. The rate of hospitalisation was 49.0%. Among hospitalised cases, 80.6% were younger than 5 months. Overall, 62.0% were unvaccinated; this percentage increased among hospitalised (73.5%) and preterm subsamples (76.9%). Delays in pertussis vaccination were found in 57.7% of term infants and in 80.0% of preterms. Multivariable analysis confirmed the age under 2 months as the variable at higher risk for hospitalisation (OR 4.49, 95% CI 1.85–10.96, p < 0.001). Being fully vaccinated represented a significant protective factor (OR 0.12, 95% CI 0.04–0.35, p < 0.001). Conclusion: Older classes of age and a complete vaccination, in time with the recommended schedule, are both protective factors for hospitalisation in severe pertussis disease. The widespread vaccination delay frequently observed in preterm children may be the cause for their higher rate of hospitalisation. [ABSTRACT FROM AUTHOR]

Background. Chromosome 22q11.2 Deletion Syndrome (22q11.2DS) is the most frequent microdeletion syndrome and is mainly characterized by congenital cardiac defects, dysmorphic features, hypocalcemia, palatal dysfunction, developmental delay, and impaired immune function due to thymic hypoplasia or aplasia. Thyroid anomalies are frequently reported in patients with 22q11.2DS, although only a few well-structured longitudinal studies about autoimmune thyroid disease (ATD) have been reported. Aim. To longitudinally evaluate the frequency of thyroid anomalies and ATD in patients with 22q11.2DS. Patients and Methods. Pediatric patients with a confirmed genetic diagnosis of 22q11.2DS were recruited and followed up on longitudinally. Clinical, biochemical, and immunological data were collected, as well as thyroid function, autoimmunity, and thyroid sonographic data. Results. The study included 73 children with 22q11.2DS, with a mean follow-up duration of 9.51 ± 5.72 years. In all, 16 of the 73 enrolled patients (21.9%) developed ATD before 18 years of age (mean age 12.92 ± 3.66 years). A total of 20.5% developed Hashimoto's Thyroiditis (HT), of whom 50% required L-thyroxine treatment; 1.4% developed Graves Disease. Thyroid hypoplasia was found in 6/16 patients with ATD and left lobe hypoplasia in 9/16 patients. These features were also found in patients affected by 22q11.2DS without ATD. Among patients who developed ATD, at the first altered ultrasound scan, the most frequent anomalies suggestive of thyroiditis were inhomogeneous echotexture, diffuse or irregular hypo-echogenicity, and vascular overflow. Conclusion. We strongly recommend periodic screening of thyroid function and for autoimmunity in patients affected by 22q11.2DS. Along with blood tests, ultrasound scans of the thyroid gland should be performed periodically since some patients who go on to develop an ATD could have specific anomalies on ultrasound prior to any other anomaly. [ABSTRACT FROM AUTHOR]

Comprehensive line lists for phosphorus monoxide (31P16O) and phosphorus monosulphide (31P32S) in their X 2Π electronic ground state are presented. The line lists are based on new ab initio potential energy (PEC), spin-orbit (SOC) and dipole moment (DMC) curves computed using the MRCI+Q-r method with aug-cc-pwCV5Z and aug-cc-pV5Z basis sets. The nuclear motion equations (i.e. the rovibronic Schrödinger equations for each molecule) are solved using the program DUO. The PECs and SOCs are refined in least-squares fits to available experimental data. Partition functions, Q(T), are computed up to T = 5000 K, the range of validity of the line lists. These line lists are the most comprehensive available for either molecule. The characteristically sharp peak of the Q-branches from the spin-orbit split components gives useful diagnostics for both PO and PS in spectra at infrared wavelengths. These line lists should prove useful for analysing observations and setting up models of environments such as brown dwarfs, low-mass stars, O-rich circumstellar regions and potentially for exoplanetary retrievals. Since PS is yet to be detected in space, the role of the two lowest excited electronic states (α 4Π and B 2Π) are also considered. An approximate line list for the PS X-B electronic transition, which predicts a number of sharp vibrational bands in the near ultraviolet, is also presented. The line lists are available from the CDS (http://cdsarc.u-strasbg.fr) and ExoMol (www.exomol.com) data bases. [ABSTRACT FROM AUTHOR]

Leishmaniasis is a cause of infection associated with hemophagocytic lymphohistiocytosis (HLH). The measurement of the CD8+ CD38high/HLA-DR+ T cells in children presenting with acute onset of shock and multisystem organ failure represents an important parameter to distinguish HLH from sepsis or healthy control. Conclusion: We report a case series of 4 Italian children suffering from HLH secondary to visceral Leishmaniasis in which the lymphocyte subset assay suggests a potential role of CD38high/HLA-DR+ CD8+ T cells as HLH diagnostic biomarkers. What is Known: • Visceral Leishmaniasis is a well-known cause of infection associated with hemophagocytic lymphohistiocytosis (HLH). • The measurement of the CD8+CD38high/HLA-DR+T cells in children presenting with acute onset of shock and multisystem organ failure represents an important diagnostically useful parameter to readily distinguish HLH from sepsis or healthy controls. What is New: • We report a case series of 4 Italian children suffering from HLH secondary to visceral Leishmaniasis in which the lymphocyte subset assay suggests a potential role of CD38high/HLA-DR+CD8+T cells as HLH diagnostic biomarker. • The flow cytometry assay, performed at the disease onset before starting treatment, revealed a mean percentage value of CD38 cells of 36.95% among CD8+T cells. [ABSTRACT FROM AUTHOR]

Introduction: T1DM is the most frequent form of diabetes in children. It has a multifactorial pathogenesis in which genetic, environmental and immunological factors are involved. Among genetic explanations a major role is attributed to second class HLA genes, with the greatest risk associated with the simultaneous presence of the haplotypes DR3DQ2 and DR4DQ8. Based on results obtained in other countries, the aim of this research is to verify a possible association between the haplotype DRB1 * 04: 05-DQA1 * 03-DQB1 * 02 and the onset of T1DM among Italian children with possible genotype-phenotype correlations. Greater knowledge of genes which increase or decrease susceptibility is important for genome analysis. Materials and methods: 165 patients with type 1 diabetes treated at the Diabetology Unit of the Meyer Children's University Hospital, were clinically analyzed. Data relating to age at diagnosis, pancreatic anti-beta cell autoimmunity, comorbidities with date of diagnosis and family history were retrospectively collected from medical data. A case-control study was conducted to investigate the HLA types of the patients compared to a control group of 819 Tuscan donors enrolled in the National Bone Marrow Donor Register. Typing was carried out using the Eurospital "DIABEGEN" kit, currently in use at the immunology laboratory of the Meyer Children's University Hospital. Results: Mean age at diagnosis was 9.3 years; most children (97%) had anti-pancreatic beta cell autoimmunity; the anti-insulin antibody (IAA) was more frequent among children with early clinical disease onset (0–5 years of age). From the case control comparison performed on HLA typing, it emerged that the greatest risk for the development of type 1 diabetes is conferred by the haplotypes DR3DQ2 and DR4DQ8, but in addition to these haplotypes, already known in other countries, we identified another haplotype, DR4DQ2 (DRB1 * 04: 05-DQA1 * 03-DQB1 * 02) which appears to predispose children to type 1 diabetes (p value 2.80E-08) and it is associated with early clinical disease onset (p-value = 0.002). Conclusions: We report a new haplotype which increases susceptibility to type 1 diabetes among Italian children and which is associated with early clinical disease onset. Given the central role attributed to genetic factors in the pathogenesis of T1DM and to the II class HLA genes, this new haplotype ought to be recognized as a risk factor and included in tests routinely carried out to identify patients with a genetic predisposition to type I diabetes in Italy. These findings could have practical implications in research and prevention programs. [ABSTRACT FROM AUTHOR]

Pyogenic bacteria are associated with a wide range of clinical manifestations, ranging from common and relatively mild respiratory and cutaneous infections to life-threatening localized or systemic infections, such as sepsis and profound abscesses. Despite vaccination and the widespread use of effective antibiotic treatment, severe infection is still observed in a subset of affected patients. We aim to summarize the available data regarding inborn errors of immunity that result in a high risk of severe pyogenic infections. Case series, as well as review and original articles on human genetic susceptibility to pyogenic infections were examined. We review host-associated factors resulting in inborn errors of immunity and leading to a susceptibility to pyogenic infections, including deficiency in major components of the immune system (e.g., neutrophils, complement, immunoglobulin, and spleen function) and novel monogenic disorders resulting in specific susceptibility to pyogenic infection. Specifically, innate immune system deficiency involving toll-like receptors and associated signaling typically predispose to a narrow spectrum of bacterial diseases in otherwise healthy people, making a diagnosis more difficult to suspect and confirm. More complex syndromes, such as hyper IgE syndrome, are associated with a high risk of pyogenic infections due to an impairment of the interleukin-6 or -17 signaling, demonstrating the pivotal role of these pathways in controlling bacterial infections. In clinical practice, awareness of such conditions is essential, especially in the pediatric setting, to avoid a potentially fatal diagnostic delay, set the most proper and prompt treatment, and ensure prevention of severe complications. [ABSTRACT FROM AUTHOR]

Mycophenolate mofetil (MMF) is an immunosuppressive drug used for the treatment of autoimmune rheumatological diseases. To test the risk of hypothetical drug-induced hypogammaglobulinemia, the aim of this study was to report the trend of the immunoglobulin (Ig) values and of the infectious diseases in children treated with MMF. This study retrospectively evaluated demographic, clinical, and laboratory data of a cohort of patients affected by a chronic rheumatic disease receiving MMF, followed at the Rheumatology Unit of Meyer Children Hospital, Florence. A total of 29 pediatric patients were enrolled. In patients with normal values of immunoglobulins at the baseline, treatment with MMF resulted in a statistically significant reduction of the IgG levels (p = 0.0058) and in a decrease of IgM levels not reaching statistical significance. The levels of IgA were not affected. During the follow-up, seven patients developed an humoral immune defect. The univariate analysis did not identify any risk factors related to the iatrogenic hypogammaglobulinemia. The infection rate during MMF therapy was significantly higher than the 12-month period before therapy (p = 0.006), while the severe infections did not significantly increase (p = 0.1818), even considering only the patients with hypogammaglobulinemia.Conclusion: In pediatric patients with chronic rheumatic diseases, immunological first level tests and serological analyses to screen the protection against the common childhood pathogens are suggested before starting an immunosuppressive drug. These patients should also complete the vaccination schedule. In patients treated with MMF a strict monitoring of Ig is required during treatment and after discontinuation of the drug.What Is Known: • MMF is an immunosuppressive drug initially used for the treatment of the graft-versus-host disease. • Mycophenolic acid is an inhibitor of inosine-5'-monophosphate dehydrogenase, expressed in lymphocytes; therefore, MMF could impair the immune system function.What Is New: • MMF resulted in a reduction of IgG and an increase of not severe infection rate. • Immunological first level tests, including Ig, lymphocyte subpopulations, and antibody response to vaccines, are suggested in pediatric patients before starting MMF; a strict monitoring of Ig is important before, during, and after MMF treatment. [ABSTRACT FROM AUTHOR]

Keywords: adverse reactions; allergy; hypersensitivity reactions; Pfizer-BioNTech's BNT162B2 vaccine; polyethylene glycol; skin prick test EN adverse reactions allergy hypersensitivity reactions Pfizer-BioNTech's BNT162B2 vaccine polyethylene glycol skin prick test 911 915 5 07/11/22 20220701 NES 220701 Key messages The polyethylene glycol 2000 is the potential cause of allergic reactions to Pfizer-BionTech's BNT162B2. All 7 declared drug allergy history; 3/7 underwent an allergy evaluation before the first dose (two cases) or after an adverse reaction to the first dose (one case). Considering the completed Pfizer-BioNTech BNT162B2 vaccination cycle, 2.4% of Group I (7/290; I p i > .05 vs Group II) and 0.9% (9/1003) of Group II stated post-vaccination effects possibly connected to a hypersensitivity reaction after the first or the second dose of vaccine. [Extracted from the article]

Ataxia telangiectasia (AT) is a rare neurodegenerative genetic disorder due to bi-allelic mutations in the Ataxia Telangiectasia Mutated (ATM) gene. The aim of this paper is to better define the immunological profile over time, the clinical immune-related manifestations at diagnosis and during follow-up, and to attempt a genotype–phenotype correlation of an Italian cohort of AT patients. Retrospective data of 69 AT patients diagnosed between December 1984 and November 2019 were collected from the database of the Italian Primary Immunodeficiency Network. Patients were classified at diagnosis as lymphopenic (Group A) or non-lymphopenic (Group B). Fifty eight out of 69 AT patients (84%) were genetically characterized and distinguished according to the type of mutations in truncating/truncating (TT; 27 patients), non-truncating (NT)/T (28 patients), and NT/NT (5 patients). In 3 patients, only one mutation was detected. Data on age at onset and at diagnosis, cellular and humoral compartment at diagnosis and follow-up, infectious diseases, signs of immune dysregulation, cancer, and survival were analyzed and compared to the genotype. Lymphopenia at diagnosis was related per se to earlier age at onset. Progressive reduction of cellular compartment occurred during the follow-up with a gradual reduction of T and B cell number. Most patients of Group A carried bi-allelic truncating mutations, had a more severe B cell lymphopenia, and a reduced life expectancy. A trend to higher frequency of interstitial lung disease, immune dysregulation, and malignancy was noted in Group B patients. Lymphopenia at the onset and the T/T genotype are associated with a worst clinical course. Several mechanisms may underlie the premature and progressive immune decline in AT subjects. [ABSTRACT FROM AUTHOR]

Accurate rotational-vibrational line lists for 31P14N and 31P15N in their ground electronic states are computed. The line lists are produced using an empirical potential energy curve obtained by fitting to the experimental transition frequencies available in the literature in conjunction with an accurate, high-level ab initio dipole moment curve. In these calculations, the programs DPOTFIT and LEVEL 8.0 were used. The new line lists reproduce the experimental wavenumbers with a root-mean-square error of 0.004 cm-1. The line lists cover the frequency range 0-51 000 cm-1, contain almost 700 000 lines each and extend up to a maximum vibrational level of v = 66 and a maximum rotational level of J = 357. They should be applicable for a large range of temperatures up to, at least, 5000 K. These new line lists are used to simulate spectra for phosphorus nitride at a range of temperatures and are deposited in the Strasbourg data centre. This work is performed as part of the ExoMol project. [ABSTRACT FROM AUTHOR]

Abstract: High-level ab initio electronic structure and variational nuclear motion computations are combined to simulate the spectrum of the water molecule at and above its first dissociation limit. Results of these computations are compared with the related state-selective multi-photon measurements of Grechko et al. [J. Chem. Phys. 138 (2010) 081 103]. Both measured and computed spectra show pronounced structures due to quasi-bound (resonance) states. Traditional resonance features associated with trapping of vibrational or rotational energy of the system are identified and assigned. A strong and broad feature observed slightly above dissociation is found to be associated with direct photodissociation into the continuum. [Copyright &y& Elsevier]

A joint experimental and first-principles quantum chemical study of the vibration-rotation states of the water molecule up to its first dissociation limit is presented. Triple-resonance, quantum state-selective spectroscopy is used to probe the entire ladder of water’s stretching vibrations up to 19 quanta of OH stretch, the last stretching state below dissociation. A new ground state potential energy surface of water is calculated using a large basis set and an all-electron, multireference configuration interaction procedure, which is augmented by relativistic corrections and fitted to a flexible functional form appropriate for a dissociating system. Variational nuclear motion calculations on this surface are used to give vibrational assignments. A total of 44 new vibrational states and 366 rotation-vibration energy levels are characterized; these span the region from 35 508 to 41 126 cm-1 above the vibrational ground state. [ABSTRACT FROM AUTHOR]

• Serotypes 1, 3, 19A and 7F were the most common types in pediatric PPE in the pre-PCV13 era. • Serotypes 1 and 3 decreased by 91.8% and 31.5%, respectively, while serotypes 7F and 19A disappeared in vaccinated children. • The impact of PCV13 might be underestimated due to the improvement of surveillance and diagnostic methods. • A significant shift to non-PCV13 serotypes was not found in PPE during the 12-year follow-up. • Realtime PCR is significantly more sensitive than culture in the diagnosis of PPE. Etiology and serotyping of parapneumonic effusion (PPE) and the impact of vaccination was evaluated over a 12-year period, before and after the PCV13 introduction (2011) for Italian children From 0 to 16 years of age. Five hundred and two children were evaluated; 226 blood and 356 pleural fluid samples were obtained and tested using Realtime-PCR and culture. In the pre-PCV13 era S. pneumoniae was the most frequent pathogen identified (64/90; 71.1%) with a large predominance of serotypes 1 (42.4%), 3 (23.7%), 7F (5.1%) and 19A (11.9%). The impact of vaccination, calculated on children 0–8 years of age, demonstrated a significant reduction of PPE: with an incidence rate of 2.82 (95%CL 2.32–3.41) in the pre-PCV13 era and an age-standardized rate (ASR) of 0.66 (95% CL 0.37–1.99) in the post-PCV13 era, p < 0.0001. No increase in non-PCV13 serotypes was recorded. S. pneumoniae remained the most frequent pathogen identified in the post-PCV13 era in unvaccinated children with an unchanged serotype distribution: respectively 26/66 (39.4%), 25/66 (37.9%), 5/66 (7.6%), and 4/66 (6.1%) for 1, 3, 7F and 19A. On the other hand 7F and 19A disappeared in vaccinated children and serotype 1 and 3 decreased by 91.8% and 31.5%, respectively. Realtime PCR was significantly more sensitive than culture both in pleural fluid (79.7% vs 12.5%) and in blood (17.8% vs 7.4%). In conclusion, our findings indicate that routine immunization with PCV13 has significantly reduced the burden of childhood PPE in vaccinated children, without increasing PPE due to other bacteria and without serotype shift. Moreover, the impact of PCV13 may be underestimated due to the increase in pneumococcal surveillance in Italy. Data has also shown that Real-time PCR is an essential tool to better define the etiology of PPE and to monitor vaccination plans. Longer studies will be necessary to evaluate the role of herd protection in PPE prevention. [ABSTRACT FROM AUTHOR]

Line lists for the sulphur-containing molecules SH (the mercapto radical) and NS are computed as part of the ExoMol project. These line lists consider transitions within the X2Π ground state for 32SH, 33SH, 34SH,36SH and, 32SD, and 14N32S, 14N33S, 14N34S, 14N36S, and 15N32S. Ab initio potential energy (PEC) and spin-orbit coupling (SOC) curves are computed and then improved by fitting to experimentally observed transitions. Fully ab initio dipole moment curves (DMCs) computed at high level of theory are used to produce the final line lists. For SH, our fit gives a root-mean-square (rms) error of 0.03 cm−1 between the observed ( $v$ max = 4, Jmax = 34.5) and calculated transitions wavenumbers; this is extrapolated such that all X2Π rotational-vibrational-electronic (rovibronic) bound states are considered. For 32SH the resulting line list contains about 81 000 transitions and 2300 rovibronic states, considering levels up to $v$ max = 14 and Jmax = 60.5. For NS the refinement used a combination of experimentally determined frequencies and energy levels and led to an rms-fitting error of 0.002 cm−1. Each NS-calculated line list includes around 2.8 million transitions and 31 000 rovibronic states with a vibrational range up to $v$  = 53 and rotational range up to J = 235.5, which covers up to 23 000 cm−1. Both line lists should be complete for temperatures up to 5000 K. Example spectra simulated using this line list are shown and comparisons made to the existing data in the cdms data base. The line lists are available from the CDS (http://cdsarc.u-strasbg.fr) and ExoMol (www.exomol.com) data bases. [ABSTRACT FROM AUTHOR]

Monitoring ozone concentrations in the Earth’s atmosphere using spectroscopic methods is a major activity which undertaken both from the ground and from space. However there are long-running issues of consistency between measurements made at infrared (IR) and ultraviolet (UV) wavelengths. In addition, key O 3 IR bands at 10 µm, 5 µm and 3 µm also yield results which differ by a few percent when used for retrievals. These problems stem from the underlying laboratory measurements of the line intensities. Here we use quantum chemical techniques, first principles electronic structure and variational nuclear-motion calculations, to address this problem. A new high-accuracy ab initio dipole moment surface (DMS) is computed. Several spectroscopically-determined potential energy surfaces (PESs) are constructed by fitting to empirical energy levels in the region below 7000 cm − 1 starting from an ab initio PES. Nuclear motion calculations using these new surfaces allow the unambiguous determination of the intensities of 10 µm band transitions, and the computation of the intensities of 10 µm and 5 µm bands within their experimental error. A decrease in intensities within the 3 µm is predicted which appears consistent with atmospheric retrievals. The PES and DMS form a suitable starting point both for the computation of comprehensive ozone line lists and for future calculations of electronic transition intensities. [ABSTRACT FROM AUTHOR]

Highly accurate ab initio calculations of vibrational and rotational-vibrational energy levels of the HCN/HNC (hydrogen cyanide/hydrogen isocyanide) isomerising system are presented for several isotopologues. All-electron multireference configuration interaction (MRCI) electronic structure calculations were performed using basis sets up to aug-cc-pCV6Z on a grid of 1541 geometries. The ab initio energies were used to produce an analytical potential energy surface (PES) describing the two minima simultaneously. An adiabatic Born-Oppenheimer diagonal correction (BODC) correction surface as well as a relativistic correction surface were also calculated. These surfaces were used to compute vibrational and rotational-vibrational energy levels up to 25 000 cm-1 which reproduce the extensive set of experimentally known HCN/HNC levels with a root-mean-square deviation σ = 1.5 cm-1. We studied the effect of nonadiabatic effects by introducing opportune radial and angular corrections to the nuclear kinetic energy operator. Empirical determination of two nonadiabatic parameters results in observed energies up to 7000 cm-1 for four HCN isotopologues (HCN, DCN, H13CN and HC15N) being reproduced with σ = 0.37 cm-1. The height of the isomerization barrier, the isomerization energy and the dissociation energy were computed using a number of models; our best results are 16 809.4, 5312.8, and 43 729 cm-1, respectively. [ABSTRACT FROM AUTHOR]

The present paper reports room temperature line lists for six asymmetric isotopologues of carbon dioxide: 16 O 12 C 18 O (628), 16 O 12 C 17 O (627), 16 O 13 C 18 O (638), 16 O 13 C 17 O (637), 17 O 12 C 18 O (728) and 17 O 13 C 18 O (738), covering the range 0–8000 cm −1 . Variational rotation-vibration wavefunctions and energy levels are computed using the DVR3D software suite and a high quality semi-empirical potential energy surface (PES), followed by computation of intensities using an ab initio dipole moment surface (DMS). A theoretical procedure for quantifying sensitivity of line intensities to minor distortions of the PES/DMS renders our theoretical model as critically evaluated. Several recent high quality measurements and theoretical approaches are discussed to provide a benchmark of our results against the most accurate available data. Indeed, the thesis of transferability of accuracy among different isotopologues with the use of mass-independent PES is supported by several examples. Thereby, we conclude that the majority of line intensities for strong bands are predicted with sub-percent accuracy. Accurate line positions are generated using an effective Hamiltonian, constructed from the latest experiments. This study completes the list of relevant isotopologues of carbon dioxide; these line lists are available to remote sensing studies and inclusion in databases. [ABSTRACT FROM AUTHOR]

Ab initio calculations of water intensities are becoming mature and are claimed to have 1% accuracy in many cases. Experimental intensities with 1% accuracy can be achieved with some care. An intercomparison of ab initio against experimental water intensities is presented for a variety of infrared bands for H 2 16 O and some for H 2 18 O and H 2 17 O. A new calculated H 2 16 O line list is presented for which uncertainties in the ab initio line intensities are evaluated. Much of the data show agreement within 2% between ab initio and experiment, however, for some bands, notably those involving excitation of some stretching modes, there are larger offsets of up to 8% attributed to ab initio calculation errors but still within the uncertainty of the ab initio calculation. In the ν 1 fundamental band differences of between + 5 % and − 13 % are found which show systematic dependence on wavenumber, Δ K a , and Δ J , again attributable to ab initio calculation errors. In the ν 2 band, intensity-dependent differences up to 2% originate from the analysis of the experimental data. At present experiments are important to validate ab initio calculations but ab initio predictions can be very useful in validating the experiment. As the two procedures display significantly different systematic errors, it is suggested that combining both gives the best results; this study will also facilitate further improvements of the theoretical methodology. [ABSTRACT FROM AUTHOR]

Line lists are presented for six deuterated isotopologues of water vapor namely HD 16 O, HD 17 O, HD 18 O, D 2 16 O, D 2 17 O and D 2 18 O. These line lists are prepared using empirically-determined energy levels, where available, to provide transition frequencies and high-quality ab initio dipole moment surfaces to provide transition intensities. The reliability of the predicted intensities is tested by computing multiple line lists and analyzing the stability of the results. The resulting intensities are expected to be accurate to a few percent for well-behaved, stable transitions. Complete T = 296 K line lists are provided for each species. [ABSTRACT FROM AUTHOR]

H3+ is a ubiquitous and important astronomical species whose spectrum has been observed in the interstellar medium, planets and tentatively in the remnants of supernova SN1897a. Its role as a cooler is important for gas giant planets and exoplanets, and possibly the early Universe. All this makes the spectral properties, cooling function and partition function of H3+ key parameters for astronomical models and analysis. A new high-accuracy, very extensive line list for H3+ called MiZATeP was computed as part of the ExoMol project alongside a temperature-dependent cooling function and partition function as well as lifetimes for excited states. These data are made available in electronic form as supplementary data to this article and at www.exomol.com. [ABSTRACT FROM AUTHOR]

Remote sensing experiments require high-accuracy, preferably sub-percent, line intensities and in response to this need we present computed room temperature line lists for six symmetric isotopologues of carbon dioxide: 13 C 16 O 2 , 14 C 16 O 2 , 12 C 17 O 2 , 12 C 18 O 2 , 13 C 17 O 2 and 13 C 18 O 2 , covering the range 0–8000 cm −1 . Our calculation scheme is based on variational nuclear motion calculations and on a reliability analysis of the generated line intensities. Rotation–vibration wavefunctions and energy levels are computed using the DVR3D software suite and a high quality semi-empirical potential energy surface (PES), followed by computation of intensities using an ab initio dipole moment surface (DMS). Four line lists are computed for each isotopologue to quantify sensitivity to minor distortions of the PES/DMS. Reliable lines are benchmarked against recent state-of-the-art measurements and against the HITRAN2012 database, supporting the claim that the majority of line intensities for strong bands are predicted with sub-percent accuracy. Accurate line positions are generated using an effective Hamiltonian. We recommend the use of these line lists for future remote sensing studies and their inclusion in databases. [ABSTRACT FROM AUTHOR]

In order to promote the development of the passive DOAS technique the Multi Axis DOAS - Comparison campaign for Aerosols and Trace gases (MAD-CAT) was held at the Max Planck Institute for Chemistry in Mainz, Germany from June to October 2013. Here, we systematically compare the differential slant column densities (dSCDs) of nitrous acid (HONO) derived from measurements of seven different instruments. We also compare the tropospheric difference of SCDs (delta SCD) of HONO, namely the difference of the SCDs for the non-zenith observations and the zenith observation of the same elevation sequence. Different research groups analysed the spectra from their own instruments using their individual fit software. All the fit errors of HONO dSCDs from the instruments with cooled large-size detectors are mostly in the range of 0.1 to 0.3 x 1015 molecules cm-2 for an integration time of 1 min. The fit error for the mini MAX-DOAS is around 0.7 x 1015 molecules cm-2. Although the HONO delta SCDs are normally smaller than 6 x 1015 molecules cm-2, consistent time series of HONO delta SCDs are retrieved from the measurements of different instruments. Both fits with a sequential Fraunhofer reference spectrum (FRS) and a daily noon FRS lead to similar consistency. Apart from the mini-MAX-DOAS, the systematic absolute differences of HONO delta SCDs between the instruments are smaller than 0.63 x 1015 molecules cm-2. The correlation coefficients are higher than 0.7 and the slopes of linear regressions deviate from unity by less than 16% for the elevation angle of 1°. The correlations decrease with an increase of elevation angle. All the participants also analysed synthetic spectra using the same baseline DOAS settings to evaluate the systematic errors of HONO results from their respective fit programs. In general the errors are smaller than 0.3 x 1015 molecules cm-2, which is about half of the systematic difference between the real measurements. The differences of HONO delta SCDs between retrieved in the selected three spectral ranges 335-361 nm, 335-373 nm and 335-390 nm are considerable (up to 0.57 x 1015 molecules cm-2) for both real measurements and synthetic spectra. We performed sensitivity studies to quantify the dominant systematic error sources and to find a recommended DOAS setting in the three spectral ranges. The results show that water vapour absorption, temperature and wavelength dependence of O4 absorption, temperature dependence of Ring spectrum, and polynomial and intensity offset correction all together dominate the systematic errors. We recommend a fit range of 335-373 nm for HONO retrievals. In such fit range the total systematic uncertainty from different sources is about 0.87 x 1015 molecules cm-2, much smaller than those in the other two ranges. Meanwhile the systematic bias of the fitted from the simulated real HONO delta SCDs is also smallest in 335-373 nm (about 0.02 x 1015 molecules cm-2). The typical random uncertainty is estimated to be about 0.16 x 1015 molecules cm-2, which is only 25 % of the total systematic uncertainty for most of the instruments in the MAD-CAT campaign. In summary most of the MAX-DOAS instruments can well observe the signals of atmospheric HONO absorption in case of HONO delta SCDs higher than 0.2 x 1015 molecules cm-2. However, systematic uncertainties limit the reliability of the results. [ABSTRACT FROM AUTHOR]

An ab initio potential energy surface (PES) for gas-phase ammonia NH 3 has been computed using the methodology pioneered for water (Polyansky et al., 2013). Multireference configuration interaction calculations are performed at about 50 000 points using the aug-cc-pCVQZ and aug-cc-pCV5Z basis sets and basis set extrapolation. Relativistic and adiabatic surfaces are also computed. The points are fitted to a suitable analytical form, producing the most accurate ab initio PES for this molecule available. The rotation-vibration energy levels are computed using nuclear motion program TROVE in both linearised and curvilinear coordinates. Better convergence is obtained using curvilinear coordinates. Our results are used to assign the visible spectrum of 14 NH 3 recorded by Coy and Lehmann (1986). Rotation-vibration energy levels for the isotopologues NH 2 D, NHD 2 , ND 3 and 15 NH 3 are also given. An ab initio value for the dissociation energy D 0 of 14 NH 3 is also presented. [ABSTRACT FROM AUTHOR]

The ExoMol database ( www.exomol.com ) provides extensive line lists of molecular transitions which are valid over extended temperature ranges. The status of the current release of the database is reviewed and a new data structure is specified. This structure augments the provision of energy levels (and hence transition frequencies) and Einstein A coefficients with other key properties, including lifetimes of individual states, temperature-dependent cooling functions, Landé g -factors, partition functions, cross sections, k -coefficients and transition dipoles with phase relations. Particular attention is paid to the treatment of pressure broadening parameters. The new data structure includes a definition file which provides the necessary information for utilities accessing ExoMol through its application programming interface (API). Prospects for the inclusion of new species into the database are discussed. [ABSTRACT FROM AUTHOR]

Atmospheric carbon dioxide concentrations are being closely monitored by remote sensing experiments which rely on knowing line intensities with an uncertainty of 0.5% or better. We report a theoretical study providing rotation–vibration line intensities substantially within the required accuracy based on the use of a highly accurate ab initio dipole moment surface (DMS). The theoretical model developed is used to compute CO 2 intensities with uncertainty estimates informed by cross comparing line lists calculated using pairs of potential energy surfaces (PES) and DMS׳s of similar high quality. This yields lines sensitivities which are utilized in reliability analysis of our results. The final outcome is compared to recent accurate measurements as well as the HITRAN2012 database. Transition frequencies are obtained from effective Hamiltonian calculations to produce a comprehensive line list covering all 12 C 16 O 2 transitions below 8000 cm − 1 and stronger than 10 − 30 cm /molecule at T = 296 K . [ABSTRACT FROM AUTHOR]

No Abstract. [ABSTRACT FROM AUTHOR]

Atmospheric CO2 concentrations are being closely monitored by remote sensing experiments which rely on knowing line intensities with an uncertainty of 0.5% or better. Most available laboratory measurements have uncertainties much larger than this. We report a joint experimental and theoretical study providing rotation-vibration line intensities with the required accuracy. The ab initio calculations are extendible to all atmospherically important bands of CO2 and to its isotologues. As such, they will form the basis for detailed CO2 spectroscopic line lists for future studies. [ABSTRACT FROM AUTHOR]

Abstract: Triple-resonance vibrational spectroscopy is used to determine the lowest dissociation energy, D 0, for the water isotopologue HD16O as 41239.7±0.2cm−1 and to improve D 0 for H2 16O to 41145.92±0.12cm−1. Ab initio calculations including systematic basis set and electron correlation convergence studies, relativistic and Lamb shift effects as well as corrections beyond the Born–Oppenheimer approximation, agree with the measured values to 1 and 2cm−1 respectively. The improved treatment of high-order correlation terms is key to this high theoretical accuracy. Predicted values for D 0 for the other five major water isotopologues are expected to be correct within 1cm−1. [Copyright &y& Elsevier]

Abstract: This is the third of a series of articles reporting critically evaluated rotational–vibrational line positions, transition intensities, and energy levels, with associated critically reviewed labels and uncertainties, for all the main isotopologues of water. This paper presents experimental line positions, experimental-quality energy levels, and validated labels for rotational–vibrational transitions of the most abundant isotopologue of water, H2 16O. The latest version of the MARVEL (Measured Active Rotational–Vibrational Energy Levels) line-inversion procedure is used to determine the rovibrational energy levels of the electronic ground state of H2 16O from experimentally measured lines, together with their self-consistent uncertainties, for the spectral region up to the first dissociation limit. The spectroscopic network of H2 16O containstwo components, an ortho (o) and a para (p) one. For o-H2 16O and p-H2 16O, experimentally measured, assigned, and labeled transitions were analyzed from more than 100 sources. The measured lines come from one-photon spectra recorded at room temperature in absorption, from hot samples with temperatures up to 3000K recorded in emission, and from multiresonance excitation spectra which sample levels up to dissociation. The total number of transitions considered is 184667 of which 182156 are validated: 68027 between para states and 114129 ortho ones. These transitions give rise to 18486 validated energy levels, of which 10446 and 8040 belong to o-H2 16O and p-H2 16O, respectively. The energy levels, including their labeling with approximate normal-mode and rigid-rotor quantum numbers, have been checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators as well as against previous compilations of energy levels. The extensive list of MARVEL lines and levels obtained are deposited in the supplementary data of this paper, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. [Copyright &y& Elsevier]

Abstract: A new, accurate, global, mass-independent, first-principles potential energy surface (PES) is presented for the ground electronic state of the water molecule. The PES is based on 2200 energy points computed at the all-electron aug-cc-pCV6Z IC-MRCI(8,2) level of electronic structure theory and includes the relativistic one-electron mass-velocity and Darwin corrections. For H2 16O, the PES has a dissociation energy of D 0 = 41109cm−1 and supports 1150 vibrational energy levels up to 41083cm−1. The deviation between the computed and the experimentally measured energy levels is below 15cm−1 for all the states with energies less than 39000cm−1. Characterization of approximate vibrational quantum numbers is performed using several techniques: energy decomposition, wave function plots, normal mode distribution, expectation values of the squares of internal coordinates, and perturbing the bending part of the PES. Vibrational normal mode labels, though often not physically meaningful, have been assigned to all the states below 26500cm−1 and to many more above it, including some highly excited stretching states all the way to dissociation. Issues to do with calculating vibrational band intensities for the higher-lying states are discussed. [Copyright &y& Elsevier]

• A novel in situ dilatometry apparatus allows the control of the applied forces on the electrochemical cell. • Processes occurring at a graphite model electrode are studied in alkylcarbonate-based electrolytes. • Measurements at different applied force emphasize gas evolution phenomena. A new equipment for in situ electrochemical dilatometry is designed and validated by studying the volumetric changes of a model electrode. The contactless measurement system permit to not influence the dilation of the sample during the tests. In addition, different forces can be applied in a selected range. Graphite is selected as model electrode and electrochemical tests in different electrolytes are carried out under different applied forces. The results of the electrodilatometric tests on graphite in EC:DMC- and in PC-based electrolyte reveal not only lithium insertion/deinsertion process, but also the presence of simultaneous phenomena like solvent evaporation, SEI formation and gas evolution. The latter has been detected by applying different forces that affect the gas uptake and release from porous separator. Controlled hydrogen evolution experiments were carried out at different applied forces in order to assess the gassing detection ability of the dilatometer. We demonstrate that with this new equipment it is possible, from thickness variation, to collect information on processes of different nature. Specifically, different applied forces emphasized gas evolution, which is a worth studying phenomenon for increasing battery safety. [Display omitted] [ABSTRACT FROM AUTHOR]