Explicit Modelling of Spectral Bandshapes by a Mixed Quantum-Classical Approach: Solvent Order and Temperature Effects in the Optical Spectra of Distryrylbenzene.

The absorption and emission spectral shapes of a flexible organic probe,  the distyrylbenzene (DSB) dye, are simulated accounting for the effect of different environments of increasing complexity, ranging from a homogeneous, low-molecular-weight solvent, to a long-chain alkane, and, eventually, a channel-forming organic matrix.  Each embedding is treated explicitly, adopting a mixed quantum-classical approach, the Adiabatic Molecular Dynamics -- generalized vertical Hessian (Ad-MD|gVH) model, which allows a direct simulation of the environment-induced constraining effects on the vibronic spectral shapes.  In such a theoretical framework, the stiff modes of the dye are described at a quantum level within the harmonic approximation, including Duschinsky mixing effects, while flexible degrees of freedom of the solute (e.g. torsions) and those of the solvent are treated classically by means of molecular dynamics sampling. Such a setup is shown to reproduce the distinct effects exerted by the different environments in varied thermodynamic conditions.  Besides allowing for a first-principles rationale on the supramolecular mechanism leading to the experimental spectral features, this result represents the first successful application of the Ad-MD|gVH method to complex embeddings and supports its potential application to other heterogeneous environments, such as for instance pigment-protein complexes or organic dyes adsorbed into metal-organic frameworks.

Dynamic effects on the nonlinear optical properties of donor acceptor stenhouse adducts: insights from combined MD + QM simulations.

The second-order nonlinear optical (NLO) responses of a donor-acceptor stenhouse adduct (DASA) are investigated by using a computational approach combining molecular dynamics simulations and density functional theory (DFT) calculations. Specific force fields for the open and closed photoswitching forms are first parameterized and validated according to the Joyce protocol, in order to finely reproduce the geometrical features and potential energy surfaces of both isomers in chloroform solution. Then, DFT calculations are performed on structural snapshots extracted at regular time steps of the MD trajectories to address the influence of the thermalized conformational dynamics on the NLO responses related to hyper-Rayleigh scattering (HRS) experiments. We show that accounting for the structural dynamics largely enhances the HRS hyperpolarizability (ßHRS) compared to DFT calculations considering solely equilibrium geometries, and greatly improves the agreement with experimental measurements. Furthermore, we show that the NLO responses of the NLO-active open form are correlated with the bond order alternation along the triene bridge connecting the donor and acceptor moieties, which is rationalized using simple essential state models.

Subtypes of avoidant/restrictive food intake disorder in children and adolescents: a latent class analysis.

Background: The Diagnostic and Statistical Manual of Mental Disorders, fifth edition (DSM-5) describes three primary avoidant/restrictive food intake disorder (ARFID) subtypes including sensory sensitivity, lack of interest in food or eating, and fear of aversive consequences. Studies exploring these subtypes have yielded varying results. We used latent class analysis (LCA) based on the psychopathology of ARFID in a sample of children and adolescents to empirically identify classes. Methods: We carried out a surveillance study of ARFID in collaboration with the British Paediatric Surveillance Unit (BPSU) and the Child and Adolescent Psychiatry Surveillance System (CAPSS) in the United Kingdom and the Republic of Ireland from 1st of March 2021 to 31st of March 2022. Paediatricians and child and adolescent psychiatrists were contacted monthly to report newly diagnosed cases of ARFID electronically and complete a detailed clinical questionnaire. Cases aged 5-18 years were included. LCA was performed specifying 1-6 classes and likelihood-based tests for model selection. The Bayesian Information Criterion (BIC), the Akaike Information Criterion (AIC) and the Sample-Size Adjusted BIC were used to determine the most parsimonious model. Analysis of variance (ANOVA) and χ2 tests were used to compare the characteristics of the identified classes. A multinomial logistic regression (MLR) was performed to investigate predicting factors for the latent classes. Findings: We identified 319 children and adolescents with ARFID. LCA revealed four distinct classes which were labelled as Fear subtype, Lack of Interest subtype, Sensory subtype, and Combined subtype. The probability of being classified as these were 7.2% (n = 23), 25.1% (n = 80), 29.5% (n = 94) and 38.2% (n = 122), respectively. Age at diagnosis, sex, weight loss, distress associated with eating, and autism spectrum disorder diagnosis were identified as predictors of class membership. Interpretation: LCA identified four different classes in a sample of children and adolescents with ARFID. The Combined Subtype, a mixed presentation was the most common. The other three classes resembled the subtypes described in the literature. Clinicians should be aware of these different presentations of ARFID as they may benefit from different clinical interventions. Funding: This study was funded by the Former EMS Ltd (charity number 1098725, registered October 9th 2017).

Spanish Cross-Cultural Adaptation and Validation of the Kerlan-Jobe Orthopaedic Clinic Shoulder and Elbow Score.

CONTEXT: There are no available questionnaires in Spanish that assess the function and performance of shoulder and elbow in overhead sports. The Kerlan-Jobe Orthopaedic Clinic (KJOC) score is a reference tool for this purpose. We aimed to cross-culturally adapt and investigate its measurement properties in Spanish overhead athletes. DESIGN: Cross-cultural adaptation followed the steps of direct translation, back translation, comprehensibility analysis, and review by the Committee of Experts. Then, symptomatic and asymptomatic overhead athletes were invited to complete an electronic version of the Spanish adaptation (KJOC-Sp). The structural validity was evaluated through an exploratory factor analysis with principal axis factoring. Hypotheses were tested for known-groups and convergent validity, studying the correlation with the Shoulder Pain and Disability Index and the Disabilities of the Arm, Shoulder, and Hand Sports Module questionnaires in symptomatic athletes. Cronbach alpha was calculated for internal consistency and intraclass correlation coefficient (ICC)2,1 for test-retest reliability. Floor and ceiling effects and time to completion were also calculated. RESULTS: The KJOC-Sp maintained the content of the original version and was adapted to the new population. One hundred participants (41 females and 59 males) with a mean age of 22.4 (5.9) years participated in the study of measurement properties. The factor analysis revealed a 1-factor solution. Symptomatic participants scored significantly lower than asymptomatic, with a large effect size (P < .001; r = .67). Correlations were of -.60 (P < .05) with the Shoulder and Pain Disability Index questionnaire and -0.66 (P < .05) with the Disabilities of the Arm, Shoulder, and Hand Sports Module questionnaire. Cronbach alpha was .98 (95% confidence interval, .97-.98) and the ICC2,1 was .96 (95% confidence interval .93-.98). No floor or ceiling effects were observed among the symptomatic athletes, while mean time to completion was 121 seconds. CONCLUSION: The KJOC-Sp is equivalent to the original score, aside from valid and reliable, without floor or ceiling effects in symptomatic athletes and with a low time consumption.

Quantum-Classical Protocol for Efficient Characterization of Absorption Lineshape and Fluorescence Quenching upon Aggregation: The Case of Zinc Phthalocyanine Dyes.

A quantum-classical protocol that incorporates Jahn-Teller vibronic coupling effects and cluster analysis of molecular dynamics simulations is reported, providing a tool for simulations of absorption spectra and ultrafast nonadiabatic dynamics in large molecular photosystems undergoing aggregation in solution. Employing zinc phthalocyanine dyes as target systems, we demonstrated that the proposed protocol provided fundamental information on vibronic, electronic couplings and thermal dynamical effects that mostly contribute to the absorption spectra lineshape and the fluorescence quenching processes upon dye aggregation. Decomposing the various effects arising upon dimer formation, the structure-property relations associated with their optical responses have been deciphered at atomistic resolution.

Non-Phenomenological Description of the Time-Resolved Emission in Solution with Quantum-Classical Vibronic Approaches-Application to Coumarin C153 in Methanol.

We report a joint experimental and theoretical work on the steady-state spectroscopy and time-resolved emission of the coumarin C153 dye in methanol. The lowest energy excited state of this molecule is characterized by an intramolecular charge transfer thus leading to remarkable shifts of the time-resolved emission spectra, dictated by the methanol reorganization dynamics. We selected this system as a prototypical test case for the first application of a novel computational protocol aimed at the prediction of transient emission spectral shapes, including both vibronic and solvent effects, without applying any phenomenological broadening. It combines a recently developed quantum-classical approach, the adiabatic molecular dynamics generalized vertical Hessian method (Ad-MD|gVH), with nonequilibrium molecular dynamics simulations. For the steady-state spectra we show that the Ad-MD|gVH approach is able to reproduce quite accurately the spectral shapes and the Stokes shift, while a ∼0.15 eV error is found on the prediction of the solvent shift going from gas phase to methanol. The spectral shape of the time-resolved emission signals is, overall, well reproduced, although the simulated spectra are slightly too broad and asymmetric at low energies with respect to experiments. As far as the spectral shift is concerned, the calculated spectra from 4 ps to 100 ps are in excellent agreement with experiments, correctly predicting the end of the solvent reorganization after about 20 ps. On the other hand, before 4 ps solvent dynamics is predicted to be too fast in the simulations and, in the sub-ps timescale, the uncertainty due to the experimental time resolution (300 fs) makes the comparison less straightforward. Finally, analysis of the reorganization of the first solvation shell surrounding the excited solute, based on atomic radial distribution functions and orientational correlations, indicates a fast solvent response (≈100 fs) characterized by the strengthening of the carbonyl-methanol hydrogen bond interactions, followed by the solvent reorientation, occurring on the ps timescale, to maximize local dipolar interactions.

The Resonance Raman Spectrum of Cytosine in Water: Analysis of the Effect of Specific Solute-Solvent Interactions and Non-Adiabatic Couplings.

In this contribution, we report a computational study of the vibrational Resonance Raman (vRR) spectra of cytosine in water, on the grounds of potential energy surfaces (PES) computed by time-dependent density functional theory (TD-DFT) and CAM-B3LYP and PBE0 functionals. Cytosine is interesting because it is characterized by several close-lying and coupled electronic states, challenging the approach commonly used to compute the vRR for systems where the excitation frequency is in quasi-resonance with a single state. We adopt two recently developed time-dependent approaches, based either on quantum dynamical numerical propagations of vibronic wavepackets on coupled PES or on analytical correlation functions for cases in which inter-state couplings were neglected. In this way, we compute the vRR spectra, considering the quasi-resonance with the eight lowest-energy excited states, disentangling the role of their inter-state couplings from the mere interference of their different contributions to the transition polarizability. We show that these effects are only moderate in the excitation energy range explored by experiments, where the spectral patterns can be rationalized from the simple analysis of displacements of the equilibrium positions along the different states. Conversely, at higher energies, interference and inter-state couplings play a major role, and the adoption of a fully non-adiabatic approach is strongly recommended. We also investigate the effect of specific solute-solvent interactions on the vRR spectra, by considering a cluster of cytosine, hydrogen-bonded by six water molecules, and embedded in a polarizable continuum. We show that their inclusion remarkably improves the agreement with the experiments, mainly altering the composition of the normal modes, in terms of internal valence coordinates. We also document cases, mostly for low-frequency modes, in which a cluster model is not sufficient, and more elaborate mixed quantum classical approaches, in explicit solvent models, need to be applied.

Vibrationally resolved two-photon electronic spectra including vibrational pre-excitation: Theory and application to VIPER spectroscopy with two-photon excitation.

Following up on our previous work on vibrationally resolved electronic absorption spectra including the effect of vibrational pre-excitation [von Cosel et al., J. Chem. Phys. 147, 164116 (2017)], we present a combined theoretical and experimental study of two-photon-induced vibronic transitions in polyatomic molecules that are probed in the VIbrationally Promoted Electronic Resonance experiment using two-photon excitation (2P-VIPER). In order to compute vibronic spectra, we employ time-independent and time-dependent methods based on the evaluation of Franck-Condon overlap integrals and Fourier transformations of time-domain correlation functions, respectively. The time-independent approach uses a generalized version of the FCclasses method, while the time-dependent approach relies on the analytical evaluation of Gaussian moments within the harmonic approximation, including Duschinsky rotation effects. For the Coumarin 6 dye, two-dimensional 2P-VIPER experiments involving excitation to the lowest-lying singlet excited state (S1) are presented and compared with corresponding one-photon VIPER spectra. In both cases, coumarin ring modes and a CO stretch mode show VIPER activity, albeit with different relative intensities. Selective pre-excitation of these modes leads to a pronounced redshift of the low-frequency edge of the electronic absorption spectrum, which is a prerequisite for the VIPER experiment. Theoretical analysis underscores the role of interference between Franck-Condon and Herzberg-Teller effects in the two-photon experiment, which is at the root of the observed intensity distribution.

Unraveling the contributions to the spectral shape of flexible dyes in solution: insights on the absorption spectrum of an oxyluciferin analogue.

We present a computational investigation of the absorption spectrum in water of 5,5-spirocyclopropyl-oxyluciferin (5,5-CprOxyLH), an analogue of the emitter compound responsible for the bioluminescence in fireflies. Several factors participate in determining the 5,5-CprOxyLH's spectral shape: (i) the contribution of the four close-energy excited states, which show significant non-adiabatic couplings, (ii) the flexible molecular structure and (iii) the specific interactions established with the surrounding environment, which strongly couple the protic solvent dynamics with the dye's spectral response. To tackle the challenge to capture and dissect the role of all these effects we preliminarily investigate the role of non-adiabatic couplings with quantum dynamics simulations and a linear vibronic coupling model in the gas phase. Then, we account for both the molecular flexibility and solvent interactions by resorting to a mixed quantum classical protocol, named Adiabatic Molecular Dynamics generalized Vertical Gradient (Ad-MD|gVG), which is built on a method recently proposed by some of us. It is rooted in the partition between stiff degrees of freedom of the dye, accounted for at the vibronic level within the harmonic approximation, and flexible degrees of freedom of the solute (and of the solvent), described classically through a sampling based on Molecular Dynamics (MD). Ad-MD|gVG avoids spurious effects arising in the excited state Hessians due to non-adiabatic couplings, and can therefore be applied to account for the contributions of the first four excited states to the 5,5-CprOxyLH absorption spectrum. The final simulated spectrum is in very good agreement with the experiment, especially when the MD is driven by a refined quantum-mechanically derived force-field. More importantly, the origin of each separate contribution to the spectral shape is appropriately accounted for, paving the way to future applications of the method to more complex systems or alternative spectroscopies, as emission or circular dichroism.

What do we know about the epidemiology of avoidant/restrictive food intake disorder in children and adolescents? A systematic review of the literature.

BACKGROUND: Avoidant/restrictive food intake disorder (ARFID) was a new diagnosis in DSM-5. This systematic review explores what is known to date about the epidemiology of ARFID in children and adolescents. METHOD: Embase, Medline and PsycInfo were used to identify studies meeting inclusion criteria. PRISMA guidelines were followed. RESULTS: Thirty studies met inclusion criteria, with most coming from specialised eating disorder services where prevalence rates were 5%-22.5%. Three studies from specialist feeding clinics showed the highest prevalence rates, ranging from 32% to 64%. Studies from non-clinical samples reported ARFID prevalence estimates ranging from 0.3% to 15.5%. One study, using national surveillance methodology, reported the incidence of ARFID in children and adolescents reaching clinical care to be 2.02 per 100,000 patients. Psychiatric comorbidity was common, especially anxiety disorders (9.1%-72%) and autism spectrum disorder (8.2%-54.75%). CONCLUSION: The current literature on the epidemiology of ARFID in children and adolescents is limited. Studies are heterogeneous with regard to setting and sample characteristics, with a wide range of prevalence estimates. Further studies, especially using surveillance methodology, will help to better understand the nature of this disorder and estimate clinical service needs.

FCclasses3: Vibrationally-resolved spectra simulated at the edge of the harmonic approximation.

We introduce FCclasses3, a code to carry out vibronic simulations of electronic spectra and nonradiative rates, based on the harmonic approximation. Key new features are: implementation of the full family of vertical and adiabatic harmonic models, vibrational analysis in curvilinear coordinates, extension to several electronic spectroscopies and implementation of time-dependent approaches. The use of curvilinear valence internal coordinates allows the adoption of quadratic model potential energy surfaces (PES) of the initial and final states expanded at arbitrary configurations. Moreover, the implementation of suitable projectors provides a robust framework for defining reduced-dimensionality models by sorting flexible coordinates out of the harmonic subset, so that they can then be treated at anharmonic level, or with mixed quantum classical approaches. A set of tools to facilitate input preparation and output analysis is also provided. We show the program at work in the simulation of different spectra (one and two-photon absorption, emission and resonance Raman) and internal conversion rate of a typical rigid molecule, anthracene. Then, we focus on absorption and emission spectra of a series of flexible polyphenyl molecules, highlighting the relevance of some of the newly implemented features. The code is freely available at http://www.iccom.cnr.it/en/fcclasses/.

Life-threatening obsessive-compulsive disorder precipitated by the COVID-19 pandemic in an adolescent.

The COVID-19 pandemic starting in 2020 has had massive mental health consequences worldwide. It has caused generalised fear and anxiety about catching, spreading and suffering from the virus. This article describes a fictionalised patient's presentation of life-threatening obsessive-compulsive disorder (OCD) associated with fears of catching COVID-19. The fears resulted in refusal to eat and drink, with subsequent weight loss that required paediatric admission. The scenario portrays the association between COVID-19 and life-threatening OCD symptoms and goes on to illustrate the patient's good response to standard OCD treatments.

Nonadiabatic Vibrational Resonance Raman Spectra from Quantum Dynamics Propagations with LVC Models. Application to Thymine.

We present a viable protocol to compute vibrational resonance Raman (vRR) spectra for systems with several close-lying and potentially coupled electronic states. It is based on the parametrization of linear vibronic coupling (LVC) models from time-dependent density functional theory (TD-DFT) calculations and quantum dynamics propagations of vibronic wavepackets with the multilayer version of the multiconfiguration time-dependent Hartree (ML-MCTDH) method. Our approach is applied to thymine considering seven coupled electronic states, comprising the three lowest bright states, and all vibrational coordinates. Computed vRR at different excitation wavelengths are in good agreement with the available experimental data. Up to 250 nm the signal is dominated by the lowest HOMO → LUMO transition, whereas at 233 nm, in the valley between the two lowest energy absorption bands, the contributions of all the three bright states, and their interferences and couplings, are important. Inclusion of solvent (water) effects improves the agreement with experiment, reproducing the coalescence of vibrational bands due to CC and C═O stretchings. With our approach we disentangle and assess the effect of interferences between the contribution of different quasi-resonant states to the transition polarizability and the effect of interstate couplings. Our findings strongly suggest that in cases of close-lying and potentially coupled states a simple inclusion of interference effects is not sufficient, and a fully nonadiabatic computation should instead be performed. We also document that for systems with strong couplings and quasi-degenerate states, the use of HT perturbative approach, not designed for these cases, may lead to large artifacts.

Turn on Fluorescence Sensing of Zn2+ Based on Fused Isoindole-Imidazole Scaffold.

Optical chemosensors caused a revolution in the field of sensing due to their high specificity, sensitivity, and fast detection features. Imidazole derivatives have offered promising features in the literature as they bear suitable donor/acceptor groups for the selective analytes in the skeleton. In this work, an isoindole-imidazole containing a Schiff base chemosensor (1-{3-[(2-Diethylamino-ethylimino)-methyl]-2-hydroxy-5-methyl-phenyl}-2H-imidazo[5,1-a]isoindole-3,5-dione) was designed and synthesized. The complete sensing phenomena have been investigated by means of UV-Vis, fluorescence, lifetime measurement, FT-IR, NMR and ESI-MS spectroscopic techniques. The optical properties of the synthesized ligand were investigated in 3:7 HEPES buffer:DMSO medium and found to be highly selective and sensitive toward Zn2+ ion through a fluorescence turn-on response with detection limit of 0.073 µm. Furthermore, this response is effective in gel form also. The competition studies reveal that the response of the probe for Zn2+ ion is unaffected by other relevant metal ions. The stoichiometric binding study was performed utilizing Job's method which indicated a 1:1 sensor-Zn2+ ensemble. Computational calculations were performed to pinpoint the mechanism of sensing.

Online Information on Painful Sexual Dysfunction in Women: Quality Analysis of Websites in SPANISH about Dyspareunia, Vaginismus and Vulvodynia.

The objective of this study was to evaluate the content, quality, and readability of websites containing information on dyspareunia, vaginismus, and vulvodynia in Spanish. Web pages were retrieved entering the terms "dyspareunia", "vaginismus", and "vulvodynia" in Google, Yahoo!, and Bing search engines. Two researchers employed the DISCERN and Bermúdez-Tamayo questionnaires to analyze the content and quality of the websites, and the INFLESZ scale to evaluate their readability. IBM SPSS® version 25 statistical software was employed for data analysis. The internet search yielded 262 websites, 91 of which were included after applying the selection criteria. Websites with information on dyspareunia obtained median scores of 24 (30-21) in the DISCERN, 38 (41.0-35.5) in the Bermúdez-Tamayo, and 55.3 (57.2-50.9) in the INFLESZ tools. The results for websites on vaginismus revealed median scores of 23.5 (30-20) in the DISCERN, 37 (42-35) in the Bermúdez-Tamayo, and 52.9 (55.6-46.4) in the INFLESZ. Finally, the median scores for vulvodynia sites was 25.5 (30-20) in the DISCERN, 38 (43-33.7) in the Bermúdez-Tamayo, and 54.2 (57.3-47.2) in the INFLESZ. These outcomes indicate that the quality of information in these websites is very low, while the overall quality of the web pages is moderate. Sites on vaginismus and vulvodynia were "somewhat difficult" to read, while readability was "normal" for websites on dyspareunia. Healthcare professionals should be aware of the shortcomings of these websites and address them through therapeutic education with resources containing updated, quality information. This raises the need for health professionals to generate these resources themselves or for experts and/or scientific societies in the field to check the quality and timeliness of the contents, regardless of whether or not the websites are endorsed with quality seals.

Effectiveness of Therapeutic Exercise and Patient Education on Cancer-Related Fatigue in Breast Cancer Survivors: A Randomised, Single-Blind, Controlled Trial with a 6-Month Follow-Up.

This study aimed to determine the effectiveness of therapeutic exercise plus patient therapeutic education on perceived fatigue, functional capacity and pain in breast cancer survivors with cancer-related fatigue. A randomised, single-blind, clinical trial was conducted with a total of 80 breast cancer survivors who presented cancer-related fatigue. Women were randomised into a supervised therapeutic exercise group (STE-G) (n = 40) or an unsupervised exercise group (UE-G) (n = 40). Both interventions included patient therapeutic education and were delivered in three sessions per week over eight weeks. The main outcome was perceived fatigue as assessed by the Spanish version of the Functional Assessment of Chronic Illness Therapy-Fatigue subscale (FACIT-F). Other evaluated outcomes were pain measured on a visual analogue scale, and distance measured using the 6-Minute Walk Test. Data were collected at baseline, immediately post-intervention, and at three and six months after baseline. Significantly greater improvements across all variables were observed in the STE-G throughout the entire follow-up period with the exception of pain. Conclusions: A supervised therapeutic exercise program plus patient therapeutic education significantly reduce perceived fatigue and increase functional capacity in breast cancer survivors suffering from cancer-related fatigue compared to an unsupervised physical exercise program based on individual preferences with patient therapeutic education.

Changes in shoulder outcomes using ultrasonographic assessment of breast cancer survivors: a prospective longitudinal study with 6-month follow-up.

This study aimed to describe changes in supraspinatus tendon thickness, acromiohumeral distance, and the presence of fluid in the subacromial bursa as measured by ultrasound, as well as shoulder range of motion and strength, perceived shoulder disability, and health-related quality of life in women before and after breast cancer treatment. Women who underwent surgery for unilateral breast cancer who did not suffer from shoulder pain or difficulty performing activities of daily living in the 6 months prior to surgery were included. One pre-surgical (A0) and three post-surgical assessments at 7-10 days (A1), 3 months (A2), and 6 months (A3) after surgery were carried out. The thickness of the supraspinatus tendon on the affected side decreased between post-surgical (A1) and 6-month (A3) follow-up assessments (p = 0.029), although the minimal detectable change was not reached. The active range of motion of the affected shoulder decreased after surgery. Strength changes were observed in both shoulders after surgery. The intensity of shoulder pain increased between post-surgical and 6-month follow-up assessments. Shoulder function was decreased at the post-surgical assessment and increased throughout the follow-ups. Health-related quality of life declined after surgery. A trend of decreasing thickness of the supraspinatus tendon of the affected shoulder was observed. Detecting these possible structural changes early would allow for early or preventive treatment.

Ab Initio Partition Functions and Thermodynamic Quantities for the Molecular Hydrogen Isotopologues.

In this work, we calculate the partition functions and thermodynamic quantities of molecular hydrogen isotopologues using the rovibrational energy levels provided by the highly accurate ab initio adiabatic potential energy functions recently determined by Pachucki and Komasa (Pachucki, K.; Komasa, J. J. Chem. Phys. 2014, 141, 224103). The partition functions are calculated by including all bound energy levels of the isotopologues, up to their dissociation limits, plus the quasi-bound levels lying below the centrifugal potential barriers. For the homonuclear isotopologues, H2, D2, and T2, we also determine the partition functions and thermodynamic quantities of the normal mixtures using the statistical treatment recently proposed by Colonna et al. (Colonna, G.; D'Angola, A.; Capitelli, M. Int. J. Hydrogen Energy 2012, 37, 9656) based on the definition of the partition function of the mixture, which avoids inconsistencies in the values of the thermodynamic quantities depending directly on the internal partition function, in the high-temperature limit.

Postural Sensorimotor Control on Anorectal Pressures and Pelvic Floor Muscle Tone and Strength: Effects of a Single 5P® LOGSURF Session. A Cross-Sectional Preliminary Study.

Pelvic floor dysfunction (PFD) is a functional condition present most frequently in women. Despite pelvic floor muscle training being considered by the International Continence Society (ICS) as the first-line treatment in uncomplicated urinary incontinence, other more comprehensive postural methods as 5P® LOGSURF have emerged. This preliminary cross-sectional study explores the effects of a single 5P® LOGSURF session on pelvic floor muscle (PFM) tone and strength (MVC), resting anal tone, intrarectal pressure, and deep abdominal muscles activation. Thirty women were included (11 without PFD and 19 with PFD). Primary outcome measures were PFM tone, PFM MVC and resting anal tone and secondary measures outcomes were intrarectal pressure and deep abdominal activation. All outcome measures were collected before, throughout and after a single 30' 5P® LOGSURF session. The findings from this study suggest that PFM tone (PFD group: p = 0.09, d = 0.72; non-PFD group: p = 0.003, d = 0.49) and PFM MVC (PFD group: p = 0.016; non-PFD group: p = 0.005) decreased in both groups after a single 5P® LOGSURF session, with a medium effect size for women with PFD. Contrarily, deep abdominal muscle MVC increased (PFD group: p < 0.001; non-PFD group: p = 0.03). Intrarectal pressure and resting anal tone decreased in both groups throughout the session. These results suggest that 5P® LOGSURF method may be interesting if is performed by women with mild symptoms of PFD or healthy women to achieve a decrease in PFM tone in women who manifested pain to intracavitary techniques or practices. Further research with higher sample sizes and long-term are necessary for generalizing.

Assessment Tools of Patient Competences: The Spanish Version of the R-NPQ and Three Practical Cases in Women with Breast Cancer and Persistent Pain.

Persistent pain following treatment for breast cancer (PPBCT) is a prevalent and complex clinical issue. Education together with physiotherapy have been shown to lessen pain and disability in chronic pain. Although the evaluation of the patient's competences is a major part of the educational program, the published educational programs rarely describe the tools used to assess competences, especially regarding those related to decision-making and problem-solving. The aim of this study was to provide two competences assessment tools: the cross-cultural adaptation and validation of the Spanish version of the Revised Neurophysiology of Pain Questionnaire (R-NPQ) and practical cases of women with PPBCT. The Spanish cross-cultural adaptation was conducted following recognized criteria. Measurement properties testing included an analysis of construct validity (known-groups approach), reliability (internal consistency and test-retest reliability), responsiveness, interpretability, and feasibility. To promote a tool that would allow evaluation of the educational program competences, a group of experts developed three cases extracted from real contexts by means of an iterative process. A total of 80 women with PPBCT (mean age 56 years) and 81 physiotherapy students (mean age 20 years) participated in the measurement properties analysis. The three developed cases were presented to the same 80 women with PPBCT before and after the educational program. As we expected, students showed a significantly higher score (p < 0.001) than did women with PPBCT in the R-NPQ questionnaire, with a large effect size (d = 2.49), demonstrating good construct validity. The Cronbach alpha was 0.90 (95% CI, 0.87-0.92) and the intraclass correlation coefficient was 0.82 (95% CI, 0.73-0.88). A large effect size (5.2) was found, as we expected, between baseline and post-treatment scores, suggesting adequate responsiveness. In addition, identifying and analyzing, decision making, communicating needs, knowing how to manage, and problem-solving skills were evaluated through the three practical cases. Most women (88.75%) reached the highest level in the assessment rubric of the proposed practical cases. The Spanish R-NPQ is a comprehensible, valid, reliable, and responsive tool for Spanish women with PPBCT. The practical cases are a useful competence assessment tool and were well accepted by women with PPBCT. Further studies are needed to investigate more competence assessment tools and to investigate whether the achievement of different levels of competences has an effect on health behaviors.