Fast rate dual-comb spectrometer in the water-transparent 7.5-11.5†µm region.

We introduce a dual-comb spectrometer based on erbium fiber oscillators at 250 MHz that operates in the 7.5-11.5 µm spectral range over optical bandwidths up to 9 THz with a multi-kHz acquisition rate. Over an observation bandwidth of 0.8 THz, the signal-to-noise ratio per spectral point reaches 168 Hz0.5 at an acquisition rate of 26 kHz, which allows the investigation of transient processes in the gas phase at high temporal resolution. The system also represents an attractive solution for multi-species atmospheric gas detection in open paths due to the water transparency of the spectral window, the use of thermo-electrically cooled detectors, and the out-of-loop phase correction of the interferograms.

Vibronic Coupling Drives the Ultrafast Internal Conversion in a Functionalized Free-Base Porphyrin.

Internal conversion (IC) is a common radiationless transition in polyatomic molecules. Theory predicts that molecular vibrations assist IC between excited states, and ultrafast experiments can provide insight into their structure-function relationship. Here we elucidate the dynamics of the vibrational modes driving the IC process within the Q band of a functionalized porphyrin molecule. Through a combination of ultrafast multidimensional spectroscopies and theoretical modeling, we observe a 60 fs Qy-Qx IC and demonstrate that it is driven by the interplay among multiple high-frequency modes. Notably, we identify 1510 cm-1 as the leading tuning mode that brings the porphyrin to an optimal geometry for energy surface crossing. By employing coherent wave packet analysis, we highlight a set of short-lived vibrations (1200-1400 cm-1), promoting the IC within ≈60 fs. Furthermore, we identify one coupling mode (1350 cm-1) that is responsible for vibronic mixing within the Q states. Our findings indicate that porphyrin-core functionalization modulates IC effectively, offering new opportunities in photocatalysis and optoelectronics.

Mini-Z validation for burnout and stress evaluation: an observational study.

BACKGROUND: The Mini-Z is a questionnaire created to evaluate the levels of burnout in healthcare workers. It consists of 10 items rated using a 5-point Likert scale and one open question. It explores three outcomes (burnout, stress and satisfaction) and seven drivers of burnout (work control, work chaos, teamwork, values alignment with leadership, documentation time pressure, EMR use at home, and EMR proficiency). The aim of this study is to validate the Italian version of the Mini-Z, comparing it with the other most used scales. MATERIALS AND METHODS: We recruited a sample of 120 healthcare professionals and administered all three questionnaires to each of them, after which we compared the answers and the scores of the results. A cross-sectional study among healthcare workers was conducted from May to July 2022. An online questionnaire was sent, by e-mail, to 120 healthcare workers (60.8% male, 39.2% female), aged between 18 and 60 years old (26.8% between 25 and 38 years old). They were invited to answer to an anonymous survey, consisting of three assessment instruments: Copenhagen Burnout Inventory (CBI), Maslach Burnout Inventory (MBI) and Mini-Z Inventory 2.0. The Mini-Z 2.0 is a new and easier tool to assess burnout syndrome, actually validated only in English. It was translated into Italian by reverse translation. Cronbach's Alpha coefficient, a statistical index, was used to assess its reliability. The last phase of the study compared the Mini-Z, the CBI and the MBI, by means of Pearson's coefficient, to highlight the Mini-Z's ability to be used for Burnout assessment. RESULTS: The analysis of the results showed that 18.3% of the interviewed healthcare professionals scored equal (2.5%) or higher (15.8%) than 40. The average percentage value was 33.35%, with a standard deviation of 6.3%. This emphasises, therefore, that this portion of employees is more or less satisfied with their working environment. The remaining portion of employees, on the other hand, 81.7%, scored below 40, emphasising an unpleasant and unjoyful working environment. DISCUSSION AND CONCLUSIONS: Burnout is very common among employees and especially among healthcare workers and a routine assessment seems to be necessary to be able to prevent the syndrome. The Italian version of the Mini-Z includes ten items, is more user-friendly and aims to assess not only Burnout subscales, as in the previous tests, but also well-being factors and has applied a rigorous approach, including forward translation, back translation and cognitive debriefing.

Stimulus-triggered task conflict affects task-selection errors in task switching: A Bayesian multinomial processing tree modeling approach.

In the present study, we used a modeling approach for measuring task conflict in task switching, assessing the probability of selecting the correct task via multinomial processing tree (MPT) modeling. With this method, task conflict and response conflict can be independently assessed as the probability of selecting the correct task and the probability of selecting the correct response within a given task, respectively. These probabilities can be estimated on the basis of response accuracy in the different experimental conditions. In two task-switching experiments, we used bivalent stimuli and manipulated irrelevant-task difficulty by varying the saliency of the stimulus feature belonging to the irrelevant task. The more salient the task-irrelevant stimulus feature, the more salient the irrelevant task, leading to more task conflict. Consistent with this assumption, we observed that task conflict, but not response conflict, was larger when the task-irrelevant stimulus feature was made more salient. Furthermore, both task conflict and response conflict were larger when the task switched than when the task was repeated. On a methodological level, the present results demonstrate that MPT modeling is a useful approach for measuring task conflict in task switching and for dissociating it from within-task response conflict. Furthermore, the present results inform theories of task switching by showing that the task-irrelevant feature tends to activate the irrelevant task set rather than being associated with a specific response option via a direct stimulus-response route. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

Examining the cognitive processes underlying resumption costs in task-interruption contexts: Decay or inhibition of suspended task goals?

To examine whether an ongoing primary task is inhibited when switching to an interruption task, we implemented the n - 2 backward inhibition paradigm into a task-interruption setting. In two experiments, subjects performed two primary tasks (block-wise manipulation) consisting of a predefined sequence of three subtasks. The primary tasks differed regarding whether the last subtask switched or repeated relative to the penultimate subtask, resulting in n - 1 switch subtasks (e.g., ABC) and n - 1 repetition subtasks (e.g., ACC) as the last subtask of the primary task. Occasionally, an interruption task was introduced before the last subtask of a primary task, changing the last subtask of the primary task from a n - 1 switch subtask to a n - 2 switch subtask (e.g., AB → secondary task → C) and from a n - 1 repetition subtask to a n - 2 repetition subtask (e.g., AC → secondary task → C). In two experiments with different degrees of response-set overlap between the interruption task and the subtasks of the primary task, we observed that switching back from the interruption task to the primary task resulted in n - 2 switch costs in the first subtask after the interruption (i.e., worse performance in n - 2 switch subtasks than in n - 2 repetition subtasks). This n - 2 switch cost was replicated in a third experiment in which we used a predefined sequence of four subtasks instead of three subtasks. Our finding of n - 2 switch costs suggest that the last subtask performed before the interruption remains activated when switching to the interruption task.

Measurement principles for quantum spectroscopy of molecular materials with entangled photons.

Nonlinear spectroscopy with quantum entangled photons is an emerging field of research that holds the promise to achieve superior signal-to-noise ratio and effectively isolate many-body interactions. Photon sources used for this purpose, however, lack the frequency tunability and spectral bandwidth demanded by contemporary molecular materials. Here, we present design strategies for efficient spontaneous parametric downconversion to generate biphoton states with adequate spectral bandwidth and at visible wavelengths. Importantly, we demonstrate, by suitable design of the nonlinear optical interaction, the scope to engineer the degree of spectral correlations between the photons of the pair. We also present an experimental methodology to effectively characterize such spectral correlations. Importantly, we believe that such a characterization tool can be effectively adapted as a spectroscopy platform to optically probe system-bath interactions in materials.

Local and global control adjustments to stimulus-based task conflict in task switching.

A prominent feature of cognitive control is that its deployment is regulated depending on the environmental circumstances. Control upregulation has been widely documented in response-conflict paradigms where congruency effects are reduced both following incongruent trials, and in blocks where incongruent trials are the majority. In two pre-registered task-switching experiments, we investigated whether similar flexible mechanisms are also available when dealing with stimulus-based task conflict. Building up on previous Stroop studies, task conflict was measured as the difference in performance between bivalent congruent and univalent trials, which we name the "valency effect." If cognitive control is upregulated analogously to what observed with response conflict, valency effects should be reduced following bivalent trials and in majority-bivalent blocks. Furthermore, as cognitive control upregulation has been proposed to be task specific, we assessed whether switching to a new task eliminates the expected modulations of task. The results broadly matched our predictions. First, we observed a reduction of the valency effect following bivalent trials similar to the well-known congruency sequence effect, demonstrating similar patterns of flexible control adjustment to task and response conflict. This valency sequence effect was limited to task repetitions, indicating that local control adjustments are task specific. Furthermore, task conflict was reduced in majority-bivalent blocks, similar to the proportion-congruency effect. This finding extends previous Stroop studies suggesting that control is recruited proactively when dealing with stimulus-based task. The proportion valency effect was limited to task-switch trials, leaving open the question on the precise mechanisms behind sustained control adjustments.

Evaluation of the Factors Associated with Reinfections towards SARS-CoV-2 Using a Case Control Design.

OBJECTIVE: The risk of reinfection with SARS-CoV-2 has been rapidly increased with the circulation of concerns about variants. So, the aim of our study was to evaluate the factors that increase the risk of this reinfection in healthcare workers compared to those who have never been positive and those who have had only one positivity. METHODS: A case-control study was carried out at the Teaching Hospital Policlinico Umberto I in Rome, Sapienza University of Rome, in the period between 6 March 2020 and 3 June 2022. Cases are healthcare workers who have developed a reinfection with the SARS-CoV-2 virus, while controls were either healthcare workers who tested positive once or those who have never tested positive for SARS-CoV-2. RESULTS: 134 cases and 267 controls were recruited. Female gender is associated with a higher odds of developing reinfection (OR: 2.42; 95% CI: 1.38-4.25). Moreover, moderate or high alcohol consumption is associated with higher odds of reinfection (OR: 1.49; 95% CI: 1.19-1.87). Diabetes is also associated with higher odds of reinfection (OR: 3.45; 95% CI: 1.41-8.46). Finally, subjects with increased red blood cell counts have higher odds of reinfection (OR: 1.69; 95% CI: 1.21-2.25). CONCLUSION: From the prevention point of view, these findings indicate that particular attention should be paid to subjects with diabetes mellitus, women and alcoholic drinkers. These results could also suggest that contact tracing represents a fundamental approach model against the SARS-CoV-2 pandemic, together with the health information of participants.

Synergistic Effect between SARS-CoV-2 Wave and COVID-19 Vaccination on the Occurrence of Mild Symptoms in Healthcare Workers.

BACKGROUND: Since the beginning of the pandemic, five variants of epidemiological interest have been identified, each of them with its pattern of symptomology and disease severity. The aim of this study is to analyze the role of vaccination status in modulating the pattern of symptomatology associated with COVID-19 infection during four waves. METHODS: Data from the surveillance activity of healthcare workers were used to carry out descriptive analysis, association analyses and multivariable analysis. A synergism analysis between vaccination status and symptomatology during the waves was performed. RESULTS: Females were found at a higher risk of developing symptoms. Four SARS-CoV-2 waves were identified. Pharyngitis and rhinitis were more frequent during the fourth wave and among vaccinated subjects while cough, fever, flu syndrome, headache, anosmia, ageusia, arthralgia/arthritis and myalgia were more frequent during the first three waves and among unvaccinated subjects. A correlation was found between vaccination and the different waves in terms of developing pharyngitis and rhinitis. CONCLUSION: Vaccination status and viruses' mutations had a synergic effect in the mitigation of the symptomatology caused by SARS-CoV-2 in healthcare workers.

Multivalent calix[4]arene-based mannosylated dendrons as new FimH ligands and inhibitors.

We report the synthesis and biological characterization of a novel class of multivalent glycoconjugates as hit compounds for the design of new antiadhesive therapies against urogenital tract infections (UTIs) caused by uropathogenic E. coli strains (UPEC). The first step of UTIs is the molecular recognition of high mannose N-glycan expressed on the surface of urothelial cells by the bacterial lectin FimH, allowing the pathogen adhesion required for mammalian cell invasion. The inhibition of FimH-mediated interactions is thus a validated strategy for the treatment of UTIs. To this purpose, we designed and synthesized d-mannose multivalent dendrons supported on a calixarene core introducing a significant structural change from a previously described family of dendrimers bearing the same dendrons units on a flexible pentaerythritol scaffold core. The new molecular architecture increased the inhibitory potency against FimH-mediated adhesion processes by about 16 times, as assessed by yeast agglutination assay. Moreover, the direct molecular interaction of the new compounds with FimH protein was assessed by on-cell NMR experiments acquired in the presence of UPEC cells.

Plurality of excitons in Ruddlesden-Popper metal halides and the role of the B-site metal cation.

We investigate the effect of metal cation substition on the excitonic structure and dynamics in a prototypical Ruddlesden-Popper metal halide. Through an in-depth spectroscopic and theoretical analysis, we identify the presence of multiple resonances in the optical spectra of a phenethyl ammonium tin iodide, a tin-based RPMH. Based on ab initio calculations, we assign these resonances to distinct exciton series that originate from the splitting of the conduction band due to spin-orbit coupling. While the splitting energy in the tin based system is low enough to enable the observation of the higher lying exciton in the visible-range spectrum of the material, the higher splitting energy in the lead counterpart prevents the emergence of such a feature. We elucidate the critical role played by the higher lying excitonic state in the ultrafast carrier thermalization dynamics.

What Are the Determinants of the Quality of Systematic Reviews in the International Journals of Occupational Medicine? A Methodological Study Review of Published Literature.

Objective: The aim of this study was to evaluate the methodological quality of systematic reviews published in occupational medicine journals from 2014 to 2021. Methods: Papers edited between 2014 and 2021 in the 14 open access journals with the highest impact were assessed for their quality. Studies were included if they were systematic reviews and meta-analyses, and if they were published in English. Results: The study included 335 studies. Among these, 149 were meta-analyses and 186 were systematic reviews. The values of the AMSTAR-2 score range between three and fourteen with a mean value of 9.85 (SD = 2.37). The factors that significantly and directly associate to a higher AMSTAR-2 score were impact factor (p = 0.003), number of consulted research databases (p = 0.011), declaration of PRISMA statement (p = 0.003), year of publication (p < 0.001) and performing a meta-analysis (p < 0.001).The R² values from the multivariate analysis showed that the AMSTAR-2 score could be predicted by the inclusion of these parameters by up to 23%. Conclusions: This study suggests a quality assessment methodology that could help readers in a fast identification of good systematic reviews or meta-analyses. Future studies should analyze more journals without applying language restrictions and consider a wider range of years of publication in order to give a more robust evidence for results.

Disentangling task-selection failures from task-execution failures in task switching: an assessment of different paradigms.

Differentiating errors on the basis of the distinct cognitive mechanisms that may have generated them has provided neuropsychologists with useful diagnostic tools. For example, perseverative errors arising from the inability of the patient to set a new criterion for responding are considered one of the hallmarks of cognitive inflexibility. Similarly, in the task-switching paradigm it is possible to distinguish between task-confusion errors, produced by a failure in task selection, and response-confusion errors, arising when the correct task is selected, but the wrong response is given. Nonetheless, only a few studies so far have exploited the existence of different kinds of errors in multitasking situations to inform theories of cognitive flexibility. In the present study, we set out to use a variety of methodologies employed so far in the literature for disentangling errors due to task-selection failure from errors due to task-execution failure. In three experiments, we assessed the capacity of each method to produce error categories that can be mapped as clearly as possible to the cognitive mechanism(s) underlying them using multinomial processing tree modelling. Subsequently, the distinction between task- and response-confusion errors was used to test their differential impact on inhibitory mechanisms in task switching as measured by N-2 repetition costs. Our results are encouraging regarding the possibility of correctly detecting response- and task-selection failures, thus allowing us to assess their differential impact on N-2 repetition costs.

Prevention and Epidemiological, Clinical, and Economic Issues of COVID-19: Far More Than a Respiratory Disease.

The Journal of Clinical Medicine has published many papers on coronavirus disease 2019 (COVID-19), and it is now clear that this is not simply a respiratory disease [...].

Modulating Singlet Fission by Scanning through Vibronic Resonances in Pentacene-Based Blends.

Vibronic coupling has been proposed to play a decisive role in promoting ultrafast singlet fission (SF), the conversion of a singlet exciton into two triplet excitons. Its inherent complexity is challenging to explore, both from a theoretical and an experimental point of view, due to the variety of potentially relevant vibrational modes. Here, we report a study on blends of the prototypical SF chromophore pentacene in which we engineer the polarizability of the molecular environment to scan the energy of the excited singlet state (S1) continuously over a narrow energy range, covering vibrational sublevels of the triplet-pair state (1(TT)). Using femtosecond transient absorption spectroscopy, we probe the dependence of the SF rate on energetic resonance between vibronic states and, by comparison with simulation, identify vibrational modes near 1150 cm-1 as key in facilitating ultrafast SF in pentacene.

High-resolution crystal structure of a 20 kDa superfluorinated gold nanocluster.

Crystallization of atomically precise nanoclusters is gaining increasing attention, due to the opportunity of elucidating both intracluster and intercluster packing modes, and exploiting the functionality of the resulting highly pure crystallized materials. Herein, we report the design and single-crystal X-ray structure of a superfluorinated 20 kDa gold nanocluster, with an Au25 core coated by a shell of multi-branched highly fluorinated thiols (SF27) resulting in almost 500 fluorine atoms, i.e., ([Au25(SF27)18]0). The cluster shows a switchable solubility in the fluorous phase. X-ray analysis and computational studies reveal the key role of both intracluster and intercluster F···F contacts in driving [Au25(SF27)18]0 crystal packing and stabilization, highlighting the ability of multi-branched fluorinated thiols to endow atomically precise nanoclusters with remarkable crystallogenic behavior.

Chemically-Controlled Ultrafast Photothermal Response in Plasmonic Nanostructured Assemblies.

Plasmonic nanoparticles are renowned as efficient heaters due to their capability to resonantly absorb and concentrate electromagnetic radiation, trigger excitation of highly energetic (hot) carriers, and locally convert their excess energy into heat via ultrafast nonradiative relaxation processes. Furthermore, in assembly configurations (i.e., suprastructures), collective effects can even enhance the heating performance. Here, we report on the dynamics of photothermal conversion and the related nonlinear optical response from water-soluble nanoeggs consisting of a Au nanocrystal assembly trapped in a water-soluble shell of ferrite nanocrystals (also called colloidosome) of ∼250-300 nm in size. This nanoegg configuration of the plasmonic assembly enables control of the size of the gold suprastructure core by changing the Au concentration in the chemical synthesis. Different metal concentrations are analyzed by means of ultrafast pump-probe spectroscopy and semiclassical modeling of photothermal dynamics from the onset of hot-carrier photogeneration (few picosecond time scale) to the heating of the matrix ligands in the suprastructure core (hundreds of nanoseconds). Results show the possibility to design and tailor the photothermal properties of the nanoeggs by acting on the core size and indicate superior performances (both in terms of peak temperatures and thermalization speed) compared to conventional (unstructured) nanoheaters of comparable size and chemical composition.

Errors in task switching: Investigating error aftereffects in a N-2 repetition cost paradigm.

Studies of switching between tasks and studies of error commission have both provided solid behavioral measures of executive control. Nonetheless, a gap remains between these strands of research. In three experiments we sought to reduce this gap by assessing the impact of task errors on N-2 repetition costs, an effect supposedly related to task-set inhibition. Based on previous literature reporting a task-switch benefit following task errors, due to incidental learning of the erroneously executed task-set, we predicted N-2 repetition costs to be decreased after task errors in Trial N-2, relative to correct responses. Furthermore, we predicted this effect to be present only when corrective control mechanisms would not have the time to build up on the post-error trial (i.e., following fast post-error trial only). This hypothesis was tested in a three-tasks paradigm using incongruent stimuli, under the assumption that errors on such trials are partly due to task confusions. Consistent with our predictions, N-2 repetition costs following N-2 errors were found to be reduced when responses in Trial N-1 were fast but were present when the N-1 response was slow. Taken together, our results suggest that task execution leads to associative strengthening of the corresponding task-set, irrespective of response accuracy, and that such automatic strengthening can be counteracted by slowly acting control mechanisms. (PsycInfo Database Record (c) 2022 APA, all rights reserved).

Permanent Dipole Moments Enhance Electronic Coupling and Singlet Fission in Pentacene.

Singlet fission (SF), the photophysical process in which one singlet exciton is transformed into two triplets, depends inter alia on the coupling of electronic states. Here, we use fluorination and the resulting changes in partial charge distribution across the chromophore backbone as a particularly powerful tool to control this parameter in pentacene. We find that the introduction of a permanent dipole moment leads to an enhanced coupling of Frenkel exciton and charge transfer states and to an increased SF rate which we probed using ultrafast transient absorption spectroscopy. These findings are contrasted with H-aggregate formation and a significantly reduced triplet-pair state lifetime in a fluorinated pentacene for which the different partial charge distribution leads to a negligible dipole moment.