Quantitative performance analysis and comparison of optimal-continuum Gaussian basis sets for high-harmonic generation spectra.

Quantum-chemistry methods in the time domain with Gaussian basis sets are increasingly used to compute high-harmonic generation (HHG) spectra of atomic and molecular systems. The quality of these approaches is limited by the accuracy of Gaussian basis sets to describe continuum energy states. In the literature, optimal-continuum Gaussian basis sets have been proposed: Kaufmann et al. [J. Phys. B: At., Mol. Opt. Phys. 22, 2223 (1989)], Wozniak et al. [J. Chem. Phys. 154, 094111 (2021)], Nestmann and Peyerimhoff [J. Phys. B: At., Mol. Opt. Phys. 23, L773 (1990)], Faure et al. [Comput. Phys. Commun. 144, 224 (2002)], and Krause et al. [J. Chem. Phys. 140, 174113 (2014)]. In this work, we have compared the performances of these basis sets to simulate HHG spectra of H atom at different laser intensities. We have also investigated different strategies to balance basis sets with these continuum functions, together with the role of angular momentum. To quantify the performance of the different basis sets, we introduce local and global HHG descriptors. Comparisons with the grid and exact calculations are also provided.

Electronic circular dichroism from real-time propagation in state space.

In this paper, we propose to compute the electronic circular dichroism (ECD) spectra of chiral molecules using a real-time propagation of the time-dependent Schrödinger equation (TDSE) in the space of electronic field-free eigenstates, by coupling TDSE with a given treatment of the electronic structure of the target. The time-dependent induced magnetic moment is used to compute the ECD spectrum from an explicit electric perturbation. The full matrix representing the transition magnetic moment in the space of electronic states is generated from that among pairs of molecular orbitals. In the present work, we show the ECD spectra of methyloxirane, of several conformers of L-alanine, and of the Λ-Co(acac)3 complex, computed from a singly excited ansatz of time-dependent density functional theory eigenstates. The time-domain ECD spectra properly reproduce the frequency-domain ones obtained in the linear-response regime and quantitatively agree with the available experimental data. Moreover, the time-domain approach to ECD allows us to naturally go beyond the ground-state rotationally averaged ECD spectrum, which is the standard outcome of the linear-response theory, e.g., by computing the ECD spectra from electronic excited states.

The Conformational Dynamics of the Ligands Determines the Electronic Circular Dichroism of the Chiral Au38(SC2H4Ph)24 Cluster.

Effects of the conformational dynamics of 2-PET protective ligands on the electronic circular dichroism (ECD) of the chiral Au38(SC2H4Ph)24 cluster are investigated. We adopt a computational protocol in which ECD spectra are calculated via the first principle polTDDFT approach on a series of conformations extracted from MD simulations by using Essential Dynamics (ED) analysis, and then properly weighted to predict the final spectrum. We find that the experimental spectral features are well reproduced, whereas significant discrepancies arise when the spectrum is calculated using the experimental X-ray structure. This result unambiguously demonstrates the need to account for the conformational effects in the ECD modeling of chiral nanoclusters. The present procedure proved to be able of capturing the essential conformational features of the dynamic Au38(SC2H4Ph)24 system, opening the possibility to model the ECD of soluble chiral nanoclusters in a realistic way.

Observation of Rayleigh-Lamb waves generated by the 2022 Hunga-Tonga volcanic eruption with the POLA detectors at Ny-Ålesund.

The eruption of the Hunga-Tonga volcano in the South Pacific Ocean on January 15, 2022, at about 4:15 UTC, generated a violent explosion, which created atmospheric pressure disturbances in the form of Rayleigh-Lamb waves detected all over the globe. Here we discuss the observation of the Hunga-Tonga shock-wave performed at the Ny-Ålesund Research Station on the Spitsbergen island, by the detectors of the PolarquEEEst experiment and their ancillary sensors. Online pressure data as well as the results of dedicated offline analysis are presented and discussed in details. Results include wave arrival times, wave amplitude measurements and wave velocity calculation. We observed five passages of the shock wave with a significance larger than 3 [Formula: see text] and an amplitude up to 1 hPa. The average propagation velocity resulted to be (308 ± 0.6) m/s. Possible effects of the atmospheric pressure variation associated with the shock-wave multiple passages on the cosmic-ray rate at ground level are also investigated. We did not find any significant evidence of this effect.

Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe-Salpeter Equation Formalisms.

In this work, a theoretical and computational set of tools to study and analyze time-resolved electron dynamics in molecules, under the influence of one or more external pulses, is presented. By coupling electronic-structure methods with the resolution of the time-dependent Schrödinger equation, we developed and implemented the time-resolved induced density of the electronic wavepacket, the time-resolved formulation of the differential projection density of states (ΔPDOS), and of transition contribution map (TCM) to look at the single-electron orbital occupation and localization change in time. Moreover, to further quantify the possible charge transfer, we also defined the energy-integrated ΔPDOS and the fragment-projected TCM. We have used time-dependent density-functional theory (TDDFT), as implemented in ADF software, and the Bethe-Salpeter equation, as provided by MolGW package, for the description of the electronic excited states. This suite of postprocessing tools also provides the time evolution of the electronic states of the system of interest. To illustrate the usefulness of these postprocessing tools, excited-state populations have been computed for HBDI (the chromophore of GFP) and DNQDI molecules interacting with a sequence of two pulses. Time-resolved descriptors have been applied to study the time-resolved electron dynamics of HBDI, DNQDI, LiCN (being a model system for dipole switching upon highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) electronic excitation), and Ag22. The computational analysis tools presented in this article can be employed to help the interpretation of fast and ultrafast spectroscopies on molecular, supramolecular, and composite systems.

Hybrid theoretical models for molecular nanoplasmonics.

The multidisciplinary nature of the research in molecular nanoplasmonics, i.e., the use of plasmonic nanostructures to enhance, control, or suppress properties of molecules interacting with light, led to contributions from different theory communities over the years, with the aim of understanding, interpreting, and predicting the physical and chemical phenomena occurring at molecular- and nano-scale in the presence of light. Multiscale hybrid techniques, using a different level of description for the molecule and the plasmonic nanosystems, permit a reliable representation of the atomistic details and of collective features, such as plasmons, in such complex systems. Here, we focus on a selected set of topics of current interest in molecular plasmonics (control of electronic excitations in light-harvesting systems, polaritonic chemistry, hot-carrier generation, and plasmon-enhanced catalysis). We discuss how their description may benefit from a hybrid modeling approach and what are the main challenges for the application of such models. In doing so, we also provide an introduction to such models and to the selected topics, as well as general discussions on their theoretical descriptions.

Age estimation by measuring open apices in teeth: a new formula for two samples of South African black and white children.

In this cross-sectional study, the accuracy of Cameriere's European formula was tested and a new specific model was developed for two samples of black and white South African children with known age and sex. For these purposes, 970 children of black South African ethnicity (girls 491, boys 479) and 974 with European ethnicity, living in South Africa (girls 493, boys 481), were retrospectively analyzed. The application of the European formula showed that there is a trend in the error estimates: the ages of the younger children are overestimated and those of the older children are underestimated, in both white and black children. A new model, based on the relationship between the apical width and the tooth length (maturity index) of the seven permanent mandibular teeth, was therefore constructed. The new developed equation for the South African population was able to explain 76% of total variance in white girls and 80% in white boys' subgroup. On the other side, the model explained 76% of total variance in black girls and 78% in the black boys' subgroup. The mean absolute error of the residuals (residuals = predicted age minus observed age) ranged from 0.718 to 0.769 years, with the interquartile range (IQRres) ranging from 1.19 to 1.31 years. Differently from the Cameriere's European formula, the plot did not tend to underestimate the chronological age significantly as the age increases. Cameriere's maturity index is reproducible in both samples of South African black and white children, for forensic purposes, and the Bayesian calibration approach is useful for a more accurate and precise estimation.

Spider Zygoma: a new implant rehabilitation technique for atrophic maxilla.

OAtrophic maxilla is a challenge in dental implant surgery, and new strategies are needed. We present a new minimally-invasive approach, called "Spider Zygoma", consisting of implant-supported prosthesis with the addition of customized maxillofacial plates and screws on surface of zygomatic bone. A 3D-model of the edentulous upper jaw was used as preoperative model. Two customized bone plates were created and used as guide for placement of implants and zygomatic screws. Although this is only a pilot study, this new surgical technique seems to be safe and accurate, confirmed by the maintenance of good aesthetic and functional results after 5-year follow-up.

Manipulating azobenzene photoisomerization through strong light-molecule coupling.

The formation of hybrid light-molecule states (polaritons) offers a new strategy to manipulate the photochemistry of molecules. To fully exploit its potential, one needs to build a toolbox of polaritonic phenomenologies that supplement those of standard photochemistry. By means of a state-of-the-art computational photochemistry approach extended to the strong-coupling regime, here we disclose various mechanisms peculiar of polaritonic chemistry: coherent population oscillations between polaritons, quenching by trapping in dead-end polaritonic states and the alteration of the photochemical reaction pathway and quantum yields. We focus on azobenzene photoisomerization, that encompasses the essential features of complex photochemical reactions such as the presence of conical intersections and reaction coordinates involving multiple internal modes. In the strong coupling regime, a polaritonic conical intersection arises and we characterize its role in the photochemical process. Our chemically detailed simulations provide a framework to rationalize how the strong coupling impacts the photochemistry of realistic molecules.

Third molar maturity index (I3M) for assessing age of majority: study of a black South African sample.

AIMS: The evaluation of the cutoff value of I3M = 0.08 for discriminating black South African minors from adults, and its relationship with chronological age. MATERIAL AND METHODS: A sample of 833 panoramic radiographs of healthy black South African subjects (500 females and 333 males), in the age range of 14 to 24 years (mean age 17.67 years in females and 17.42 years in males), was retrospectively evaluated. RESULTS: ICC values were 99.10% (95% CI 97.70 to 99.70%) and 99.20% (95% CI 98.00 to 99.60%), for the intra- and inter-observer reliability, respectively. I3M decreased as the real age gradually increased in both sexes. According to the logistic regression model, the variable sex was not significant when the probability that an individual is 18 years or older was calculated. The I3M = 0.08 was valuable in discriminating between adults and minors. The overall accuracy (ACC = fraction of accurately classified subjects) is 0.90 (95% CI 0.87-0.91); the proportion of correctly classified subjects (Se = sensitivity) is 0.80 (95% CI 0.76-0.84), and specificity (Sp) is 0.95 (95% CI 0.93-0.97). The PPV (predictive positive value) is 0.96 (95% CI 0.95-0.97), and the negative predictive value is 0.76 (95% CI 0.72-0.80). CONCLUSION: The results show that I3M is a valuable method to distinguish subjects who are around legal adult age in South Africa.

Oral health conditions of the elderly in Ancona: a population-based study.

AIM: Information currently available regarding the oral health of elderly people is poor, especially in Italy. The aim of this study was to evaluate oral health conditions in older people in the city of Ancona, Italy. The usefulness of a dedicated medical record, specifically designed for older people, was tested. METHODS: A total of 124 elderly subjects aged between 65 and 95 years, all autonomous and self-sufficient, were recruited for this study. The specific medical/dental record, designed for older people, was used to collect data and was divided into three parts. The first part lists the patient's demographics. The second part was devoted to general medical history. The third part includes the dental history and the dental visit. As regards the oral conditions, injury to the soft tissues, degree of oral hygiene, presence of caries, periodontal diseases, missing teeth, presence of the prosthesis, and presence of xerostomia, were noticed. RESULTS: Among the examined subjects 53% were male and 47% were female. The most prevalent medical condition was hypertension (64.5%); 74.2% of the examined population took up to 3 drugs/day, while the 25.8% more than 3 drugs/day. Only 9.6% of patients had soft tissues lesions and only 33.3% had sufficient oral hygiene; 45.1% of patients suffered decayed teeth; 44% of patients had fewer than 8 missing teeth, the 33.4% had the number of missing teeth including between 9 and 15, and 22.6% had more than 16 missing teeth. Only 7 patients were completely edentulous; 32.3% of the patients had fixed partial dentures, 17.7% had removable partial dentures, 22.6% had both fixed partial dentures and removable partial dentures, 4% removable total dentures and 23.4% do not have any dentures. Only 29.1% patients had xerostomia. CONCLUSION: The most important data from this study are the following: 1) the majority of elderly patients is hypertensive; 2) the majority of elderly patients take up to 3 drugs/day; 3) the majority of elderly patients has insufficient oral hygiene; 4) the majority of elderly patients do not have removable dentures but fixed dentures. Therefore, it is important to preserve and take care of the teeth of the older people, especially of the autonomous and self-sufficient elderly patients. Further visits are therefore necessary in order to make a complete epidemiological study in Ancona.

Comprehensive investigation in patients affected by sperm macrocephaly and globozoospermia.

The aim of this study was to provide a comprehensive genetic/phenotypic characterization of subjects suffering infertility owing to sperm macrocephaly (n = 3) or globozoospermia (n = 9) and to investigate whether the patients' genetic status was correlated with the alteration of various sperm parameters. AURKC was sequenced in case of sperm macrocephaly while the DPY19L2 status has been analyzed by multiple approaches including a novel qPCR-based copy number assay in case of globozoospermia. Globozoospermic patients were also analyzed for SPACA1, a novel candidate gene herein tested for the first time in humans. The effect of the patients' genetic status was interrogated by implementing the molecular screening with the characterization of several sperm parameters: (i) routine sperm analysis, integrated with transmission electron microscopy; (ii) sperm fluorescent in situ hybridization (FISH) analysis; (iii) sperm DNA fragmentation (DF) analysis. Moreover, for the first time, we performed microsatellite instability analysis as a marker of genome instability in men with sperm macrocephaly and globozoospermia. Finally, artificial reproductive technology (ART) history has been reported for those patients who underwent the treatment. Macrocephalic patients had an AURKC mutation and >89% tetraploid, highly fragmented spermatozoa. DPY19L2 was mutated in all patients with >80% globozoospermia: the two homozygous deleted men and the compound heterozygous showed the severest phenotype (90-100%). The newly developed qPCR method was fully validated and has the potential of detecting also yet undiscovered deletions. DPY19L2 status is unlikely related to FISH anomalies and DF, although globozoospermic men showed a higher disomy rate and DF compared with internal reference values. No patient was mutated for SPACA1. Our data support the general agreement on the negative correlation between macro/globozoospermia and conventional intracytoplasmic sperm injection outcomes. Microsatellites were stable in all patients analyzed. The comprehensive picture provided on these severe phenotypes causing infertility is of relevance in the management of patients undergoing ART.

IFN-ß and multiple sclerosis: from etiology to therapy and back.

Several immunomodulatory treatments are currently available for relapsing-remitting forms of multiple sclerosis (RRMS). Interferon beta (IFN) was the first therapeutic intervention able to modify the course of the disease and it is still the most used first-line treatment in RRMS. Though two decades have passed since IFN-ß was introduced in the management of MS, it remains a valid approach because of its good benefit/risk profile. This is witnessed by new efforts of pharmaceutical industry to improve this line: a PEGylated form of subcutaneous IFN-ß 1a, (Plegridy(®)) with a longer half-life, has been recently approved in RRMS. This review will survey the various stages of the use of type I IFN in MS, with special attention to the effect of the treatment on the supposed viral etiologic factors associated to the disease. The antiviral activities of IFN (that initially prompted its use as immunomodulatory agent in MS), and the mounting evidences in favor of a viral etiology in MS, allowed us to outline a re-appraisal from etiology to therapy and back.

n-3 LC-PUFA deposition efficiency and appetite-regulating hormones are modulated by the dietary lipid source during rainbow trout grow-out and finishing periods.

Largely attributable to concerns surrounding sustainability, the utilisation of omega-3 long-chain polyunsaturated fatty acid-rich (n-3 LC-PUFA) fish oils in aquafeeds for farmed fish species is an increasingly concerning issue. Therefore, strategies to maximise the deposition efficiency of these key health beneficial fatty acids are being investigated. The present study examined the effects of four vegetable-based dietary lipid sources (linseed, olive, palm and sunflower oil) on the deposition efficiency of n-3 LC-PUFA and the circulating blood plasma concentrations of the appetite-regulating hormones, leptin and ghrelin, during the grow-out and finishing phases in rainbow trout culture. Minimal detrimental effects were noted in fish performance; however, major modifications were apparent in tissue fatty acid compositions, which generally reflected that of the diet. These modifications diminished somewhat following the fish oil finishing phase, but longer-lasting effects remained evident. The fatty acid composition of the alternative oils was demonstrated to have a modulatory effect on the deposition efficiency of n-3 LC-PUFA and on the key endocrine hormones involved in appetite regulation, growth and feed intake during both the grow-out and finishing phases. In particular, n-6 PUFA (sunflower oil diet) appeared to 'spare' the catabolism of n-3 LC-PUFA and, as such, resulted in the highest retention of these fatty acids, ultimately highlighting new nutritional approaches to maximise the maintenance of the qualitative benefits of fish oils when they are used in feeds for aquaculture species.

Fibre-reinforced composite crowns luted to implant abutments via electroformed primary copings: an in vitro retention study.

AIM: The aim of this study was to investigate the retention values and mode of failure of metal crowns and fibre-reinforced composite crowns. METHODS: Seventy-five implants and the corresponding abutments were used. After the galvanic copings were fabricated, the specimens were distributed into three groups: in group A traditional metal crowns were realized, whereas in groups B and C fibre-reinforced composite crowns were made. In group B the same resin based cement used in group A was employed for luting the fibre-reinforced composite crowns to the galvanic copings, while in group C a dedicated self-adhesive composite cement was used. All galvanic coping/crown assemblies were cemented onto abutments with Panavia 21 cement. Specimens were subjected to a pull-out test; median retentive values and standard deviations were calculated. RESULTS: All samples in the group A showed separation at the abutment-galvanic cap interface. All samples in the group B showed decementation at galvanic cap-crown interface. In 13 samples of the group C the decementation occurred at the abutment-galvanic cap interface and in 12 samples of this group the decementation occurred at the galvanic cap-crown interface. The mean retention value was 659.1 N±162.9 for group A, 304.7 N±101.4 for B and 635.4 N±155.9 for C. Differences between groups A/B and B/C are statistically significant (t-student test, P<0.01), while is not statistically different between groups A/C. CONCLUSION: When a self-adhesive composite cement is used, fibre-reinforced composite single crowns and conventional metal crowns show similar retentive performance.

Differential regulation of miR-21 and miR-146a by Epstein-Barr virus-encoded EBNA2.

The discovery of microRNA (miR) represents a novel paradigm in RNA-based regulation of gene expression and their dysregulation has become a hallmark of many a tumor. In virally associated cancers, the host-pathogen interaction could involve alteration in miR expression. Epstein-Barr virus (EBV)-encoded EBNA2 is indispensable for the capacity of the virus to transform B cells in vitro. Here, we studied how it affects cellular miRs. Extensive miR profiling of the virus-infected and EBNA2-transfected B lymphoma cells revealed that oncomiR miR-21 is positively regulated by this viral protein. Conversely, Burkitt's lymphoma (BL) cell lines infected with EBNA2 lacking P3HR1 strain did not show any increase in miR-21. EBNA2 increased phosphorylation of AKT and this was directly correlated with increased miR-21. In contrast, miR-146a was downregulated by EBNA2 in B lymphoma cells. Low miR-146a expression correlates with an elevated level of IRAK1 and type I interferon in EBNA2 transfectants. Taken together, the present data suggest that EBNA2 might contribute to EBV-induced B-cell transformation by altering miR expression and in particular by increasing oncomiR-like miR-21 and by affecting the antiviral responses of the innate immune system through downregulation of its key regulator miR-146a.

A state observer for the Virgo inverted pendulum.

We report an application of Kalman filtering to the inverted pendulum (IP) of the Virgo gravitational wave interferometer. Using subspace method system identification techniques, we calculated a linear mechanical model of Virgo IP from experimental transfer functions. We then developed a Kalman filter, based on the obtained state space representation, that estimates from open loop time domain data, the state variables of the system. This allows the observation (and eventually control) of every resonance mode of the IP mechanical structure independently.

Type I interferon and Toll-like receptor expression characterizes inflammatory myopathies.

OBJECTIVES: Juvenile dermatomyositis (JDM), adult dermatomyositis, and polymyositis (PM) are idiopathic inflammatory myopathies (IIMs) characterized by muscle infiltration and specific muscle fiber alterations. They are thought to have an autoimmune etiology, but triggering factors, and how immunologic attack induces muscle weakness, remain unknown. Recent evidence suggests a key role for type I interferon (IFN)-mediated innate immunity in dermatomyositis, which we explored in JDM, dermatomyositis, and PM by gene expression profiling, and other methods. METHODS: Ten IIM and 5 control muscle biopsies were assessed for expression of approximately 16,000 genes by microarray; 37 additional IIM, 10 dystrophinopathic, and 14 nonmyopathic control muscles were studied for type I IFN-dependent genes, and Toll-like receptor (TLR) expression by immunochemistry and PCR. RESULTS: Type I IFN-dependent transcripts were significantly upregulated in IIM muscles compared to controls; in JDM the most expressed were ISG15 (408-fold), IFIT3 (261-fold), MX1 (99-fold), and IRF7 (37-fold). IFN-ß (but not IFN-α) transcripts were upregulated in PM as well as dermatomyositis/JDM. TLR3 was upregulated particularly in JDM, being localized on vascular endothelial cells, muscle infiltrating cells (mainly myeloid dendritic cells), and regenerating myofibers; TLR7 and TLR9 proteins were present in IIM (prominently in PM), mainly on cell infiltrates, particularly plasma cells, and on some injured myofibers. CONCLUSIONS: IFN-ß and type I IFN-induced molecules are involved in PM as well as JDM/dermatomyositis. Endosomal TLRs (effectors of innate immunity) are also involved (but differently) in the 3 conditions, further suggesting viral involvement, although TLR activation could be secondary to tissue damage.

[Prevention of postoperative abdominal adhesions in gynecological surgery. Consensus paper of an Italian gynecologists' task force on adhesions]. / Aderenze addominali postoperatorie e loro prevenzione in chirurgia ginecologica. Documento di consenso si una "task force" di ginecologi italiani sulle aderenze.

Adhesions are the most frequent complication of abdominopelvic surgery, causing important short- and long-term problems, including infertility, chronic pelvic pain and a lifetime risk of small bowel obstruction. They also complicate future surgery with considerable morbidity and expense, and an important mortality risk. They pose serious quality of life issues for many patients with associated social and healthcare costs. Despite advances in surgical techniques, the healthcare burden of adhesion-related complications has not changed in recent years. Adhesiolysis remains the main treatment although adhesions reform in most patients. There is rising evidence, however, that surgeons can take important steps to reduce the impact of adhesions. A task force of Italian gynecologists with a specialist interest in adhesions having reviewed the current evidence on adhesions and considered the opportunities to reduce adhesions in Italy, have approved a collective consensus position. This consensus paper provides a comprehensive overview of adhesions and their consequences and practical proposals for actions that gynecological surgeons in Italy should take. As well as improvements in surgical technique, developments in adhesion-reduction strategies and new agents offer a realistic possibility of reducing adhesion formation and improving outcomes for patients. They should be adopted particularly in high risk surgery and in patients with adhesiogenic conditions. Patients also need to be better informed of the risks of adhesions.

In-vacuum Faraday isolation remote tuning.

In-vacuum Faraday isolators (FIs) are used in gravitational wave interferometers to prevent the disturbance caused by light reflected back to the input port from the interferometer itself. The efficiency of the optical isolation is becoming more critical with the increase of laser input power. An in-vacuum FI, used in a gravitational wave experiment (Virgo), has a 20 mm clear aperture and is illuminated by an almost 20 W incoming beam, having a diameter of about 5 mm. When going in vacuum at 10(-6) mbar, a degradation of the isolation exceeding 10 dB was observed. A remotely controlled system using a motorized lambda=2 waveplate inserted between the first polarizer and the Faraday rotator has proven its capability to restore the optical isolation to a value close to the one set up in air.