Theoretical study of the finite temperature spectroscopy in van der Waals clusters. III Solvated Chromophore as an effective diatomics

The absorption spectroscopy of calcium-doped argon clusters is described in terms of an effective diatomics molecule Ca-(Ar_n), in the framework of semiclassical vertical transitions. We show how, upon choosing a suitable reaction coordinate, the effective finite-temperature equilibrium properties can be obtained for the ground- and excited-surfaces from the potential of mean force (PMF). An extension of the recent multiple range random-walk method is used to calculate the PMF over continuous intervals of distances. The absorption spectra calculated using this single-coordinate description are found to be in good agreement with the spectra obtained from high-statistics Monte Carlo data, in various situations. For CaAr$_{13}$, we compare the performances of two different choices of the reaction coordinate. For CaAr_37, the method is seen to be accurate enough to distinguish between different low-energy structures. Finally, the idea of casting the initial many-body problem into a single degree of freedom problem is tested on the spectroscopy of calcium in bulk solid argon.Comment: 8 pages, 9 figure

Bidentate ligation of magnesium by 1,2-dimethoxyethane in the gas phase

International audienceThe 1:1 Mg[centered ellipsis]1,2-dimethoxyethane (Mg-DXE) complexes are studied experimentally and theoretically. They are generated by a laser ablation source in a supersonic expansion. They are studied spectroscopically by resonance two-photon ionization. Density functional theory/Becke three-dimensional Lee, Yang, and Parr and ab initio calculations using the MOLPRO quantum chemistry package are performed to document their ground and excited states in a series of geometry ranging from monodentate to bidentate ligation of Mg by the O atoms of DXE. An absorption band is observed in the 27 800–30 500 cm−1 range, which, thanks to the calculations, is attributed to the bidentate complex. The structure of the band is discussed in terms of the excitation of electronic states of the complex correlating adiabatically to the 3s3p 1P and 3s4s 1S states of Mg at large separation between Mg and DXE

Dynamics of excited tetrakis(dimethyl amino)ethylene solvated by argon atoms

The supersonic expansion of a mixture of the title molecule (TDMAE) with argon generates a beam carrying a log-normal distribution of TDAME(Ar)n clusters, broadly centered at . The femtosecond pump–probe technique is used to investigate the excited state dynamics of these clusters up to a 220 ps delay between the pump and the probe. This documents the effect of the argon environment on the TDMAE dynamics. The TDMAE molecule is excited in the valence state V within the cluster by the pump laser at 266 nm. It undergoes deformation in the excited potential energy surface that brings the initial wavepacket to a conical intersection (CI), where the electronic configuration of the molecule switches to a zwitterionic configuration Z. Compared to the behaviour of free TDMAE, the effect of the argon environment is a slow down of the wavepacket movement and an increase of the time scale of the V–Z energy transfer from 300 to 400±50 fs. This slow down effect, that we call a chistera effect, differs from a standard cage effect. Here, the deforming molecule does not experience a hard sphere collision with the argon cage, rather it pushes it away. Furthermore, umbrella oscillations of the dimethylamino groups are excited when the initial wavepacket passes the CI region. Because of the argon environment, the sharp 250 fs oscillation period of the free molecules is transformed into a broad structure of 40 fs width (FWHM) centred at about 240 fs. In addition, breathing oscillations of the argon environment with respect to the TDMAE molecule are observed with a period of 410±40 fs. Finally, long delays between the pump and the probe lasers allow us to investigate the nonradiative energy transfer from the Z electronic configuration of TDMAE(Ar)n to a charge transfer state. The effect of the evaporation of argon atoms in the neutral and the ionised clusters has been taken into account, as its time scale accompanies that of the observed phenomena

Femtosecond Dynamics of Isolated Phenylcarbenes

International audienceUnderstanding the primary photophysical processes in molecules is essential for interpreting their photochemistry, because molecules rarely react from the initially excited electronic state. In this study the ultrafast excited-state dynamics of chlorophenylcarbene (CPC) and trifluoromethylphenylcarbene (TFPC), two species that are considered as models for carbene dynamics, were investigated by femtosecond time-resolved pump probe spectroscopy in the gas phase. Their dynamics was followed in real time by time-resolved photoionization and photoelectron imaging. CPC was excited at 265 nm into the 3 1A′ state, corresponding to excitation from a π-orbital of the aromatic ring into the LUMO. The LUMO contains a contribution of the p-orbital at the carbene center. Three time constants are apparent in the photoelectron images: A fast decay process with τ1 ≈ 40 fs, a second time constant of τ2 ≈ 350 fs, and an additional time constant of τ3 ≈ 1 ps. The third time constant is only visible in the time-dependence of low kinetic energy electrons. Due to the dense manifold of excited states between 3.9 and 5 eV, known from ab initio calculations, the recorded time-resolved electron images show broad and unstructured bands. A clear population transfer between the states thus can not directly be observed. The fast deactivation process is linked to either a population transfer between the strongly coupled excited states between 3.9 and 5.0 eV or the movement of the produced wave packet out of the Franck−Condon region. Since the third long time constant is only visible for photoelectrons at low kinetic energy, evidence is given that this time constant corresponds to the lifetime of the lowest excited A 1A′ state. The remaining time constant reflects a deactivation of the manifold of states in the range 3.9−5.0 eV down to the A 1A′ state

Practitioner and researcher perspectives on the utility of ecological momentary assessment in mental health care:A survey study

Background: Ecological momentary assessment (EMA) is a scientific self-monitoring method to capture individuals' daily life experiences. Early on, EMA has been suggested to have the potential to improve mental health care. However, it remains unclear if and how EMA should be implemented. This requires an in-depth investigation of how practitioners and researchers view the implementation of EMA. Objective: Explore the perspectives of mental health practitioners and EMA researchers on the utility of EMA for mental health care. Methods: Practitioners (n = 89; psychiatrists, psychologists, psychiatric nurses) and EMA researchers (n = 62) completed a survey about EMA in clinical practice. This survey addressed EMA goals for practitioner and patient, requirements regarding clinical use of EMA, and (dis)advantages of EMA compared to treatment-as-usual. t-Tests were used to determine agreement with each statement and whether practitioners' and researchers' views differed significantly. Linear regression was used to explore predictors of goals and preferences (e.g., EMA experience). Results: Practitioners and researchers considered EMA to be a useful clinical tool for diverse stages of care. They indicated EMA to be most useful for gaining insight into the context specificity of symptoms (55.0 %), whereas receiving alerts when symptoms increase was rated the least useful (11.3 %, alerts is in 95 % of bootstrap iterations between rank 8 and 10). Compared to treatment-as-usual, EMA was considered easier to use (M = 4.87, t = 5.30, p < .001) and interpret (M = 4.52, t = 3.61, p < .001), but also more burdensome for the patient (M = 4.48, t = 3.17, p < .001). Although participants preferred personalization of the EMA diary, they also suggested that EMA should cost practitioners and patients limited time. The preference for creating personalized EMA was related to the level of experience with EMA. Finally, they highlighted the need for practitioner training and patient full-time access to the EMA feedback. Conclusions: This survey study demonstrated that practitioners and researchers expect EMA to have added value for mental health care. Concrete recommendations for implementation of EMA are formulated. This may inform the development of specific clinical applications and user-friendly EMA software

m-Path:An easy-to-use and highly tailorable platform for ecological momentary assessment and intervention in behavioral research and clinical practice

In this paper, we present m-Path (www.m-Path.io), an online platform that provides an easy-to-use and highly tailorable framework for implementing smartphone-based ecological momentary assessment (EMA) and intervention (EMI) in both research and clinical practice in the context of blended care. Because real-time monitoring and intervention in people's everyday lives have unparalleled benefits compared to traditional data collection techniques (e.g., retrospective surveys or lab-based experiments), EMA and EMI have become popular in recent years. Although a surge in the use of these methods has led to a myriad of EMA and EMI applications, many existing platforms only focus on a single aspect of daily life data collection (e.g., assessment vs. intervention, active self-report vs. passive mobile sensing, research-dedicated vs. clinically-oriented tools). With m-Path, we aim to integrate all of these facets into a single platform, as it is exactly this all-in-one approach that fosters the clinical utility of accumulated scientific knowledge. To this end, we offer a comprehensive platform to set up complex and highly adjustable EMA and EMI designs with advanced functionalities, using an intuitive point-and click web interface that is accessible for researchers and clinicians with limited programming skills. We discuss the strengths of daily life data collection and intervention in general and m-Path in particular. We describe the regular workflow to set up an EMA or EMI design within the m-Path framework, and summarize both the basic functionalities and more advanced features of our software

Transition State Spectroscopy of the Photoinduced Ca + CH3F Reaction. 2. Experimental and Ab Initio Studies of the Free Ca***FCH3 Complex

International audienceThe Ca* + CH3F CaF* + CH3 reaction was photoinduced in 1:1 Ca***CH3F complexes formed in a supersonic expansion. The transition state of the reaction was explored by monitoring the electronically excited product, CaF, while scanning the laser that turns on the reaction. Moreover, the electronic structure of the Ca***FCH3 system was studied using ab initio methods by associating a pseudopotential description of the [Ca2+] and [F7+] cores, a core polarization operator on calcium, an extensive Gaussian basis and a treatment of the electronic problem at the CCSD(T) (ground state) and RSPT2 (excited states) level. In this contribution we present experimental results for the free complex and a comparison with the results of a previous experiment where the Ca***CH3F complexes are deposited at the surface of large argon clusters. The ab initio calculations allowed an interpretation of the experimental data in terms of two reaction mechanisms, one involving a partial charge transfer state, the other involving the excitation of the C-F stretch in the CH3F moiety prior to charge transfer

Widespread dysregulation of MiRNAs by MYCN amplification and chromosomal imbalances in neuroblastoma: association of miRNA expression with survival

MiRNAs regulate gene expression at a post-transcriptional level and their dysregulation can play major roles in the pathogenesis of many different forms of cancer, including neuroblastoma, an often fatal paediatric cancer originating from precursor cells of the sympathetic nervous system. We have analyzed a set of neuroblastoma (n = 145) that is broadly representative of the genetic subtypes of this disease for miRNA expression (430 loci by stem-loop RT qPCR) and for DNA copy number alterations (array CGH) to assess miRNA involvement in disease pathogenesis. The tumors were stratified and then randomly split into a training set (n = 96) and a validation set (n = 49) for data analysis. Thirty-seven miRNAs were significantly over-or under-expressed in MYCN amplified tumors relative to MYCN single copy tumors, indicating a potential role for the MYCN transcription factor in either the direct or indirect dysregulation of these loci. In addition, we also determined that there was a highly significant correlation between miRNA expression levels and DNA copy number, indicating a role for large-scale genomic imbalances in the dysregulation of miRNA expression. In order to directly assess whether miRNA expression was predictive of clinical outcome, we used the Random Forest classifier to identify miRNAs that were most significantly associated with poor overall patient survival and developed a 15 miRNA signature that was predictive of overall survival with 72.7% sensitivity and 86.5% specificity in the validation set of tumors. We conclude that there is widespread dysregulation of miRNA expression in neuroblastoma tumors caused by both over-expression of the MYCN transcription factor and by large-scale chromosomal imbalances. MiRNA expression patterns are also predicative of clinical outcome, highlighting the potential for miRNA mediated diagnostics and therapeutics

Laser Spectroscopic Studies of the E 1£+ State of the MgO Molecule

The E1Σ+ ‘Rydberg' state of 24Mg16O has been characterized by two-color resonance-enhanced two-photon ionization (R2PI) spectroscopy in the 36 000–40 000 cm−1 region. Several rotationally resolved bands, assigned consistently to 24Mg16O(E1Σ+←X1Σ+) vibronic transitions, have been analyzed. The effective Bv′(v′=0−8) constants determined exhibit an unusual variation with v′. Possible causes of this variation are discussed. Estimated spectroscopic constants for the E1Σ+ state are reported

Pain management after elective craniotomy: A systematic review with procedure-specific postoperative pain management (PROSPECT) recommendations.

BACKGROUND Pain after craniotomy can be intense and its management is often suboptimal. OBJECTIVES We aimed to evaluate the available literature and develop recommendations for optimal pain management after craniotomy. DESIGN A systematic review using procedure-specific postoperative pain management (PROSPECT) methodology was undertaken. DATA SOURCES Randomised controlled trials and systematic reviews published in English from 1 January 2010 to 30 June 2021 assessing pain after craniotomy using analgesic, anaesthetic or surgical interventions were identified from MEDLINE, Embase and Cochrane Databases. ELIGIBILITY CRITERIA Each randomised controlled trial (RCT) and systematic review was critically evaluated and included only if met the PROSPECT requirements. Included studies were evaluated for clinically relevant differences in pain scores, use of nonopioid analgesics, such as paracetamol and NSAIDs, and current clinical relevance. RESULTS Out of 126 eligible studies identified, 53 RCTs and seven systematic review or meta-analyses met the inclusion criteria. Pre-operative and intra-operative interventions that improved postoperative pain were paracetamol, NSAIDs, intravenous dexmedetomidine infusion, regional analgesia techniques, including incision-site infiltration, scalp nerve block and acupuncture. Limited evidence was found for flupirtine, intra-operative magnesium sulphate infusion, intra-operative lidocaine infusion, infiltration adjuvants (hyaluronidase, dexamethasone and α-adrenergic agonist added to local anaesthetic solution). No evidence was found for metamizole, postoperative subcutaneous sumatriptan, pre-operative oral vitamin D, bilateral maxillary block or superficial cervical plexus block. CONCLUSIONS The analgesic regimen for craniotomy should include paracetamol, NSAIDs, intravenous dexmedetomidine infusion and a regional analgesic technique (either incision-site infiltration or scalp nerve block), with opioids as rescue analgesics. Further RCTs are required to confirm the influence of the recommended analgesic regimen on postoperative pain relief