Early attentional processing and cortical remapping strategies of tactile stimuli in adults with an early and late-onset visual impairment: A cross-sectional study.

Neuroplastic changes appear in people with visual impairment (VI) and they show greater tactile abilities. Improvements in performance could be associated with the development of enhanced early attentional processes based on neuroplasticity. Currently, the various early attentional and cortical remapping strategies that are utilized by people with early (EB) and late-onset blindness (LB) remain unclear. Thus, more research is required to develop effective rehabilitation programs and substitution devices. Our objective was to explore the differences in spatial tactile brain processing in adults with EB, LB and a sighted control group (CG). In this cross-sectional study 27 participants with VI were categorized into EB (n = 14) and LB (n = 13) groups. They were then compared with a CG (n = 15). A vibrotactile device and event-related potentials (ERPs) were utilized while participants performed a spatial tactile line recognition task. The P100 latency and cortical areas of maximal activity were analyzed during the task. The three groups had no statistical differences in P100 latency (p>0.05). All subjects showed significant activation in the right superior frontal areas. Only individuals with VI activated the left superior frontal regions. In EB subjects, a higher activation was found in the mid-frontal and occipital areas. A higher activation of the mid-frontal, anterior cingulate cortex and orbitofrontal zones was observed in LB participants. Compared to the CG, LB individuals showed greater activity in the left orbitofrontal zone, while EB exhibited greater activity in the right superior parietal cortex. The EB had greater activity in the left orbitofrontal region compared to the LB. People with VI may not have faster early attentional processing. EB subjects activate the occipital lobe and right superior parietal cortex during tactile stimulation because of an early lack of visual stimuli and a multimodal information processing. In individuals with LB and EB the orbitofrontal area is activated, suggesting greater emotional processing.

Physical activity to reduce the burden of frailty after menopause: effectiveness and adherence rate of a resource saving exercise plan.

OBJECTIVE: Frailty may be increased by menopause. Physical activity has been proposed to reduce frailty, but poor adherence and cost limit effectiveness. We aimed to investigate both the effectiveness against the frailty burden and the adherence rate of a multicomponent physical activity scheme partially managed by the participating women themselves. METHODS: Prospective controlled study consisting of a twice-weekly group physical activity scheme divided into two consecutive periods, one supervised by a health professional (12 wk) and the other supervised by the women themselves (36 wk). Group cohesion and mutual support during the patient-only period were aided by social networking via smartphones. Community-dwelling postmenopausal women were divided into a physical activity group (PAG = 126) and a usual activity control group (UAG = 126), both assessed at baseline and at the end of the study. Participants self-assigned to one of the two study arms. RESULTS: Overall, women in the PAG were more likely to improve their frailty status (60.2% vs 42.6%, P < 0.05). The frailty reversal rate from prefrail to robust was significantly higher in the PAG than in the UAG (34.04 vs 8.00%, P < 0.05). Logistic regression confirmed that women in the PAG were more likely to improve their frailty phenotype (odds ratio [OR], 9.12; 95% confidence interval [CI], 3.45-31.52; P < 0.001). Adherence, defined by participants attending 75% of sessions, was attained by 56.35% of women at 48 wk. CONCLUSION: A physical activity scheme implemented to improve frailty proved effective and attained acceptable adherence. Conditions in the peer-supervised 36-wk phase may increase sustainability.

Validity of an android device for assessing mobility in people with chronic stroke and hemiparesis: a cross-sectional study.

BACKGROUND: Incorporating instrument measurements into clinical assessments can improve the accuracy of results when assessing mobility related to activities of daily living. This can assist clinicians in making evidence-based decisions. In this context, kinematic measures are considered essential for the assessment of sensorimotor recovery after stroke. The aim of this study was to assess the validity of using an Android device to evaluate kinematic data during the performance of a standardized mobility test in people with chronic stroke and hemiparesis. METHODS: This is a cross-sectional study including 36 individuals with chronic stroke and hemiparesis and 33 age-matched healthy subjects. A simple smartphone attached to the lumbar spine with an elastic band was used to measure participants' kinematics during a standardized mobility test by using the inertial sensor embedded in it. This test includes postural control, walking, turning and sitting down, and standing up. Differences between stroke and non-stroke participants in the kinematic parameters obtained after data sensor processing were studied, as well as in the total execution and reaction times. Also, the relationship between the kinematic parameters and the community ambulation ability, degree of disability and functional mobility of individuals with stroke was studied. RESULTS: Compared to controls, participants with chronic stroke showed a larger medial-lateral displacement (p = 0.022) in bipedal stance, a higher medial-lateral range (p < 0.001) and a lower cranio-caudal range (p = 0.024) when walking, and lower turn-to-sit power (p = 0.001), turn-to-sit jerk (p = 0.026) and sit-to-stand jerk (p = 0.001) when assessing turn-to-sit-to-stand. Medial-lateral range and total execution time significantly correlated with all the clinical tests (p < 0.005), and resulted significantly different between independent and limited community ambulation patients (p = 0.042 and p = 0.006, respectively) as well as stroke participants with significant disability or slight/moderate disability (p = 0.024 and p = 0.041, respectively). CONCLUSION: This study reports a valid, single, quick and easy-to-use test for assessing kinematic parameters in chronic stroke survivors by using a standardized mobility test with a smartphone. This measurement could provide valid clinical information on reaction time and kinematic parameters of postural control and gait, which can help in planning better intervention approaches.

Improving assessment of procedural skills in health sciences education: a validation study of a rubrics system in neurophysiotherapy.

BACKGROUND: The development of procedural skills is essential in health sciences education. Rubrics can be useful for learning and assessing these skills. To this end, a set of rubrics were developed in case of neurophysiotherapy maneuvers for undergraduates. Although students found the rubrics to be valid and useful in previous courses, the analysis of the practical exam results showed the need to change them in order to improve their validity and reliability, especially when used for summative purposes. After reviewing the rubrics, this paper analyzes their validity and reliability for promoting the learning of neurophysiotherapy maneuvers and assessing the acquisition of the procedural skills they involve. METHODS: In this cross-sectional and psychometric study, six experts and 142 undergraduate students of a neurophysiotherapy subject from a Spanish university participated. The rubrics' validity (content and structural) and reliability (inter-rater and internal consistency) were analyzed. The students' scores in the subject practical exam derived from the application of the rubrics, as well as the rubrics' criteria difficulty and discrimination indices were also determined. RESULTS: The rubrics´ content validity was found to be adequate (Content Validity Index > 0.90). These showed a unidimensional structure, and an acceptable internal consistency (α = 0.71) and inter-rater reliability (Fleiss' ƙ=0.44, ICC = 0.94). The scores of the subject practical exam practically covered the entire range of possible theoretical scores, showing all the criterion medium-low to medium difficulty indices - except for the one related to the physical therapist position-. All the criterion exhibited adequate discrimination indices (rpbis > 0.39), as did the rubric as a whole (Ferguson's δ = 0.86). Students highlighted the rubrics´ usefulness for learning the maneuvers, as well as their validity and reliability for formative and summative assessment. CONCLUSIONS: The changed rubrics constitute a valid and reliable instrument for evaluating the execution quality of neurophysiotherapy maneuvers from a summative evaluation viewpoint. This study facilitates the development of rubrics aimed at promoting different practical skills in health-science education.

Assessing Stroke-Related Sarcopenia in Chronic Stroke: Identification of Clinical Assessment Tools-A Pilot Study.

Stroke-related sarcopenia has recently been defined as the muscle atrophy consequent to stroke and assessing it following the guidelines with simple clinical tools is crucial in chronic stroke survivors. The aim of this study was to determine the characteristics of patient-friendly instruments sarcopenia in a chronic stroke sample (SG) compared to non-stroke counterparts (CG). Each participant underwent a single assessment which consisted of: SARC-F questionnaire, assessment of muscle strength (hand grip and five-times sit-to-stand test, 5STS), the calf circumference (CC) of both legs, the short physical performance battery (SPPB), and the 10 m walk test. A total of 68 participants were included (SG, n = 34 and CG, n = 34). All variables showed statistical differences (p < 0.05) between the SG and the CG, except handgrip although it showed lower values for SG. The values of the 5STS (16.26 s) and the SPPB (7 points) were below to the cutoff values for the SG. The five-times sit-to-stand test, SPPB, and gait speed can lead clinicians to detect stroke-related sarcopenia. Maximum handgrip shows a trend of low values for men and women in the SG, however, CC did not detect sarcopenia in our sample.

The Parietal Lobe in Alzheimer's Disease and Blindness.

The progressive aging of the population will notably increase the burden of those diseases which leads to a disabling situation, such as Alzheimer's disease (AD) and ophthalmological diseases that cause a visual impairment (VI). Eye diseases that cause a VI raise neuroplastic processes in the parietal lobe. Meanwhile, the aforementioned lobe suffers a severe decline throughout AD. From this perspective, diving deeper into the particularities of the parietal lobe is of paramount importance. In this article, we discuss the functions of the parietal lobe, review the parietal anatomical and pathophysiological peculiarities in AD, and also describe some of the changes in the parietal region that occur after VI. Although the alterations in the hippocampus and the temporal lobe have been well documented in AD, the alterations of the parietal lobe have been less thoroughly explored. Recent neuroimaging studies have revealed that some metabolic and perfusion impairments along with a reduction of the white and grey matter could take place in the parietal lobe during AD. Conversely, it has been speculated that blinding ocular diseases induce a remodeling of the parietal region which is observable through the improvement of the integration of multimodal stimuli and in the increase of the volume of this cortical region. Based on current findings concerning the parietal lobe in both pathologies, we hypothesize that the increased activity of the parietal lobe in people with VI may diminish the neurodegeneration of this brain region in those who are visually impaired by oculardiseases.

Non-use of information and communication technology as a predictor of frailty in postmenopausal midlife and older women.

BACKGROUND: Frailty is a clinically discernible state in which decreased physiological reserve and function result in a reduced ability to cope with stressors. Information and communication technology (ICT) has been proposed as an aid to help with frailty, yet the use of ICT by older people, particularly women, is an understudied area. AIM: To analyze the association between use of ICT (specifically internet functions and social media) and frailty status in postmenopausal midlife and elderly women. METHODS: A cross-sectional study was designed to investigate whether frailty status is related to ICT use in postmenopausal midlife and older women. Community-dwelling women attending primary health care centers for health checks were invited to participate in the study. Postmenopausal status was the only inclusion criterion, whereas limitations that could interfere with use of ICT were exclusion criteria. The Fried phenotype was used to assess frailty. Four types of ICT use were examined: the internet for e-mail, the internet for other functions, and social media (WhatsApp or Facebook). Chi-square test and multivariate multinomial regression analysis were used to examine the association between frailty status and ICT use. RESULTS: We included 409 women (age = 67.45 ± 7.81 years, mean ± SD), who were frail (n = 135, 33.01%), pre-frail (n = 159, 38.87%), or robust (n  =  115, 28.11%). Frailty status was significantly and inversely associated with any ICT use, showing a strong association with use of WhatsApp (P < 0.001) and internet searches (P < 0.001). ICT non-use was a predictor of frailty, while ICT users were more likely to be robust (OR 10.62; 95% [CI], 5.34-21.10) or pre-frail (OR 9.03; [CI], 95% 5.18-15.74). CONCLUSION: Postmenopausal midlife and older women not using ICT were more likely to be frail.

Association of Barriers, Fear of Falling and Fatigue with Objectively Measured Physical Activity and Sedentary Behavior in Chronic Stroke.

Understanding the fostering factors of physical activity (PA) and sedentary behavior (SB) in post-stroke chronic survivors is critical to address preventive and health interventions. This cross-sectional study aimed to analyze the association of barriers to PA, fear of falling and severity of fatigue encountered by stroke chronic survivors with device-measured PA and SB. Ambulatory community-dwelling post-stroke subjects (≥six months from stroke onset) were evaluated and answered the Barriers to Physical Activity after Stroke Scale (BAPAS), Short Falls Efficacy Scale-International (Short FES-I) and Fatigue Severity Scale (FSS). SB and PA were measured with an Actigraph GT3X+ accelerometer for ≥seven consecutive days. Stepwise multiple linear regression analysis was employed to identify factors associated with PA and SB. Fifty-seven participants (58.2 ± 11.1 years, 37 men) met the accelerometer wear-time criteria (three days, ≥eight h/day). The physical BAPAS score explained 28.7% of the variance of the prolonged sedentary time (ß = 0.547; p < 0.001). Additionally, the walking speed (ß = 0.452) together with physical BAPAS (ß = -0.319) explained 37.9% of the moderate-to-vigorous PA time (p < 0.001). In chronic post-stroke survivors, not only the walking speed but, also, the perceived physical barriers to PA are accounted for the SB and PA. Interventions to reverse SB and to involve subjects post-stroke in higher levels of PA should consider these factors.

A new methodology based on functional principal component analysis to study postural stability post-stroke.

BACKGROUND: A major goal in stroke rehabilitation is the establishment of more effective physical therapy techniques to recover postural stability. Functional Principal Component Analysis provides greater insight into recovery trends. However, when missing values exist, obtaining functional data presents some difficulties. The purpose of this study was to reveal an alternative technique for obtaining the Functional Principal Components without requiring the conversion to functional data beforehand and to investigate this methodology to determine the effect of specific physical therapy techniques in balance recovery trends in elderly subjects with hemiplegia post-stroke. METHODS: A randomized controlled pilot trial was developed. Thirty inpatients post-stroke were included. Control and target groups were treated with the same conventional physical therapy protocol based on functional criteria, but specific techniques were added to the target group depending on the subjects' functional level. Postural stability during standing was quantified by posturography. The assessments were performed once a month from the moment the participants were able to stand up to six months post-stroke. FINDINGS: The target group showed a significant improvement in postural control recovery trend six months after stroke that was not present in the control group. Some of the assessed parameters revealed significant differences between treatment groups (P < 0.05). INTERPRETATION: The proposed methodology allows Functional Principal Component Analysis to be performed when data is scarce. Moreover, it allowed the dynamics of recovery of two different treatment groups to be determined, showing that the techniques added in the target group increased postural stability compared to the base protocol.

How Methylation Modifies the Photophysics of the Native All- trans-Retinal Protonated Schiff Base: A CASPT2/MD Study in Gas Phase and in Methanol.

A comparison between the free-energy surfaces of the all- trans-retinal protonated Schiff base (RPSB) and its 10-methylated derivative in gas phase and methanol solution is performed at CASSCF//CASSCF and CASPT2//CASSCF levels. Solvent effects were included using the average solvent electrostatic potential from molecular dynamics method. This is a QM/MM (quantum mechanics/molecular mechanics) method that makes use of the mean field approximation. It is found that the methyl group bonded to C10 produces noticeable changes in the solution free-energy profile of the S1 excited state, mainly in the relative stability of the minimum energy conical intersections (MECIs) with respect to the Franck-Condon (FC) point. The conical intersections yielding the 9- cis and 11- cis isomers are stabilized while that yielding the 13- cis isomer is destabilized; in fact, it becomes inaccessible by excitation to S1. Furthermore, the planar S1 minimum is not present in the methylated compound. The solvent notably stabilizes the S2 excited state at the FC geometry. Therefore, if the S2 state has an effect on the photoisomerization dynamics, it must be because it permits the RPSB population to branch around the FC point. All these changes combine to speed up the photoisomerization in the 10-methylated compound with respect to the native compound.

Immediate Changes After Manual Therapy in Patients With Persistent, Nonspecific Back Pain: A Randomized Controlled Trial.

CONTEXT: Thoracic manipulation decreases pain and disability. However, when such manipulation is contraindicated, the use of other manual techniques based on the regional interdependence of the thoracic spine, upper ribs, and shoulders is an alternative approach. OBJECTIVE: The study intended to investigate the immediate changes resulting from 3 manual therapy treatments on spinal mobility, flexibility, comfort, and pain perception in patients with persistent, nonspecific back pain as well as changes in their sense of physical well-being and their perception of change after treatment. DESIGN: The study was a randomized, double-blind, controlled trial. SETTING: The study took place in the Department of Physiotherapy of the Faculty of Physiotherapy at the University of Valencia (Valencia, Spain). PARTICIPANTS: Participants were 112 individuals from the community-56.6% female, with a mean age of 21.8 ± 0.2 y-who had persistent, nonspecific back pain. INTERVENTION: Participants were randomly assigned to 1 of 3 groups, receiving (1) neurolymphatic therapy (NL group), (2) articulatory spinal manual therapy (AS group), or (3) articulatory costal manual therapy (AC group). OUTCOME MEASURES: Cervical mobility, lumbar flexibility, comfort, pain perception, and physical well-being were assessed at baseline and immediately postintervention. Perception of change was evaluated postintervention. RESULTS: Between baseline and postintervention, the AC group showed a significant increase in cervical flexion (P = .010), whereas the NL and AS groups improved in lumbar flexibility, P = .047 and P = .012, respectively. For that period, significant changes were found in lumbar comfort for the AS group (P < .001) and the NL group (P < .026) and in thoracic comfort (P < .001) for the AC group. All groups improved in physical well-being and pain perception (P < .05). Changes in thoracic comfort, lumbar comfort, and physical well-being differed among the groups, with some differences being statistically significant. CONCLUSIONS: All treatments improved pain perception and increased physical well-being. The NL and AS treatments were more effective in lumbar flexibility, the AC treatment in cervical flexion and thoracic comfort, and the NL treatment in lumbar comfort.

QM/MM Study of Substituent and Solvent Effects on the Excited State Dynamics of the Photoactive Yellow Protein Chromophore.

Substituent and solvent effects on the excited state dynamics of the Photoactive Yellow Protein chromophore are studied using the average solvent electrostatic potential from molecular dynamics (ASEP/MD) method. Four molecular models were considered: the ester and thioester derivatives of the p-coumaric acid anion and their methylated derivatives. We found that the solvent produces dramatic modifications on the free energy profile of the S1 state: 1) Two twisted structures that are minima in the gas phase could not be located in aqueous solution. 2) Conical intersections (CIs) associated with the rotation of the single bond adjacent to the phenyl group are found for the four derivatives in water solution but only for thio derivatives in the gas phase. 3) The relative stability of minima and CIs is reverted with respect to the gas phase values, affecting the prevalent de-excitation paths. As a consequence of these changes, three competitive de-excitation channels are open in aqueous solution: the fluorescence emission from a planar minimum on S1, the trans-cis photoisomerization through a CI that involves the rotation of the vinyl double bond, and the nonradiative, nonreactive, de-excitation through the CI associated with the rotation of the single bond adjacent to the phenyl group. In the gas phase, the minima are the structures with the lower energy, while in solution these are the conical intersections. In solution, the de-excitation prevalent path seems to be the photoisomerization for oxo compounds, while thio compounds return to the initial trans ground state without emission.

Pilot randomized controlled trial to assess a physical therapy program on upper extremity function to counteract inactivity in chronic stroke.

BACKGROUND: In chronic stroke, feasible physical therapy (PT) programs are needed to promote function throughout life. OBJECTIVE: This randomized controlled pilot trial investigated the feasibility and effect of a PT program composed of strengthening exercises with elastic bands and bimanual functional training, with clearly defined doses based on the rate of perceived exertion (Borg scale), to counteract inactivity in chronic stroke. METHODS: Fifteen subjects > 6 month post-stroke were randomized to three-month of UE function training (UE group), or to lower extremity function training (LE group). At baseline (T0), post-intervention (T1) and three-month follow-up (T2) assessment included the Fugl-Meyer Assessment scale (FMA), Wolf Motor Function test (WMFT), grip strength, and muscle tone. Feasibility was also evaluated. RESULTS: The mixed-model ANOVAs revealed a significant interaction between the time and group factors for FMA (p < .001) and WMFT (p = .009). The UE group improved upper extremity function and motor recovery significantly more than the LE group. There was no significant interaction between treatment group and change in grip strength over time (p = .217). No between-group differences (p > .05) were found in muscle tone. In the UE group, the attendance rate was ≥85% for 71.4% of subjects and 85.7% showed high satisfaction. No adverse events were recorded. After treatment, adherence to the program was higher in the UE group. CONCLUSIONS: The suggested PT program may be useful to improve the paretic UE function and motor recovery in chronic stroke. Moreover, it may be helpful to facilitate lifelong active involvement of stroke subjects in exercise.

A new QM/MM method oriented to the study of ionic liquids.

The interest on room temperature ionic liquids has grown in the last decades because of their use as all-purpose solvent and their low environmental impact. In the present work, a new theoretical procedure is developed to study pure ionic liquids within the framework of the quantum mechanics/molecular mechanics method. Each type of ion (cation or anion) is considered as an independent entity quantum mechanically described that follows a differentiated path in the liquid. The method permits, through an iterative procedure, the full coupling between the polarized charge distribution of the ions and the liquid structure around them. The procedure has been tested with 1-ethyl-3-methylimidazolium tetrafluoroborate. It was found that, similar to non-polar liquids and as a consequence of the low value of the reaction field, the cation and anion charge distributions are hardly polarized by the rest of molecules in the liquid. Their structure is characterized by an alternance between anion and cation shells as evidenced by the coincidence of the first maximum of the anion-anion and cation-cation radial distribution functions with the first minimum of the anion-cation. Some degree of stacking between the cations is also found.

A new methodology for Functional Principal Component Analysis from scarce data. Application to stroke rehabilitation.

Functional Principal Component Analysis (FPCA) is an increasingly used methodology for analysis of biomedical data. This methodology aims to obtain Functional Principal Components (FPCs) from Functional Data (time dependent functions). However, in biomedical data, the most common scenario of this analysis is from discrete time values. Standard procedures for FPCA require obtaining the functional data from these discrete values before extracting the FPCs. The problem appears when there are missing values in a non-negligible sample of subjects, especially at the beginning or the end of the study, because this approach can compromise the analysis due to the need to extrapolate or dismiss subjects with missing values. In this paper, we present an alternative methodology extracting the FPCs directly from the sampled data, avoiding the need to have functional data before extracting them. We demonstrate the feasibility of our approach from real data obtained from the analysis of balance recovery after stroke. Finally, we demonstrate that FPCA can obtain differences between groups when these differences are more related to the dynamics of the process than data values at given points.

Tratamiento combinado aplicado en parálisis cerebral infantil: presentación de un caso / Combined treatment applied in cerebral palsy: case report

Introducción. Es importante determinar una fisioterapia adecuada para las personas que presentan discapacidad de por vida, como es el caso de la parálisis cerebral (PC). El objetivo fue estudiar el efecto de la aplicación de terapia física combinada en las habilidades motoras gruesas. Descripción del caso. Se describe el caso clínico de una niña de 12 años diagnosticada de tetraparesia espástica tras PC y con déficit en las funciones cognitivas. Intervención. Durante 35 semanas se aplicó terapia física combinada que incluyó estiramientos, entrenamiento de la fuerza, equilibrio, trabajo de marcha en suspensión parcial y terapia miofascial. La evaluación se ha llevado a cabo al inicio y al final del tratamiento con el Gross Motor Function Measure (GMFM).Resultados y discusión: Se han observado mejorías clínicas en las dimensiones evaluadas con el GMFM. En el caso de la ‘bipedestación’ (de 17,95 por ciento al inicio a28,21 por ciento al final) y en la dimensión ‘caminar,correr y saltar’ (de 5,56 por ciento al inicio a 19,44 por ciento al final). Si bien las técnicas fisioterápicas utilizadas han demostrado ser útiles aplicadas de forma aislada, hemos observado que su uso combinado mejora la función motora gruesa en el caso presentado.

Background and Purpose. For people suffering from a lifelong disability such as cerebral palsy (CP), establishing an appropriate physiotherapy treatment is of great concern. The aim was to study the effect on gross motor skills of the application of a combined physical therapy. Case description. A case report of a 12-year-old female patient with a diagnosis of spastic tetraparesis after CP, who also showed a cognitive function disorder, is reported. Intervention. A combined physical therapy treatment was applied during 35 weeks. The protocol consisted of stretching, training of muscle resistance, balance, reeducation of gait in partial suspensión and myofascial therapy. Baseline and postintervention assessments were carried out by means of the Gross Motor Function Measure (GMFM). Results and discussion: A clinical improvement was observed in those dimensions of the GMFM which were lower rated at baseline. The dimension ‘standing’ (from 17,95 percent pre-intervention to 28,21 percent post-intervention) and the dimension ‘walking, running and jumping’ (from 5,56 percent pre-intervention to 19,44 percent postintervention). Though the proposed physiotherapy techniques have been shown to be useful separately, when combined, it was observed that the gross motor function clinically improved in our patient.

Theoretical study of solvent effects on the ground and low-lying excited free energy surfaces of a push-pull substituted azobenzene.

The ground and low-lying excited free energy surfaces of 4-amino-4'-cyano azobenzene, a molecule that has been proposed as building block for chiroptical switches, are studied in gas phase and a variety of solvents (benzene, chloroform, acetone, and water). Solvent effects on the absorption and emission spectra and on the cis-trans thermal and photo isomerizations are analyzed using two levels of calculation: TD-DFT and CASPT2/CASSCF. The solvent effects are introduced using a polarizable continuum model and a QM/MM method, which permits one to highlight the role played by specific interactions. We found that, in gas phase and in agreement with the results found for other azobenzenes, the thermal cis-trans isomerization follows a rotation-assisted inversion mechanism where the inversion angle must reach values close to 180° but where the rotation angle can take almost any value. On the contrary, in polar solvents the mechanism is controlled by the rotation of the CN═NC angle. The change in the mechanism is mainly related to a better solvation of the nitrogen atoms of the azo group in the rotational transition state. The photoisomerization follows a rotational pathway both in gas phase and in polar and nonpolar solvents. The solvent introduces only small modifications in the nπ* free energy surface (S1), but it has a larger effect on the ππ* surface (S2) that, in polar solvents, gets closer to S1. In fact, the S2 band of the absorption spectrum is red-shifted 0.27 eV for the trans isomer and 0.17 eV for the cis. In the emission spectrum the trend is similar: only S2 is appreciably affected by the solvent, but in this case a blue shift is found.

Functional principal component analysis as a new methodology for the analysis of the impact of two rehabilitation protocols in functional recovery after stroke.

BACKGROUND: This study addressed the problem of evaluating the effectiveness of two protocols of physiotherapy for functional recovery after stroke. In particular, the study explored the use of Functional Principal Component Analysis (FPCA), a multivariate data analysis in order to assess and clarify the process of regaining independence after stroke. METHODS: A randomized double-blind controlled trial was performed. Thirteen subjects with residual hemiparesis after a single stroke episode were measured in both in- and outpatient settings at a district hospital. All subjects were able to walk before suffering the stroke and were hemodynamically stable within the first week after stroke. Control and target groups were treated with conventional physiotherapy for stroke, but specific techniques were added for treatment of the target group depending on patients' functional levels.Independence level was assessed with the Barthel Index (BI) throughout 7 evolution stages (hemodynamic stability, beginning of standing, beginning of physical therapy sessions in the physiotherapy ward and monthly assessment for 6 months after stroke). RESULTS: FPCA was applied for data analysis. Statistically significant differences were found in the dynamics of the recovery process between the two physiotherapy protocols. The target group showed a trend of improvement six months after stroke that was not present in the control group. CONCLUSIONS: FPCA is a method which may be used to provide greater insight into the analysis of the rehabilitation process than that provided by conventional parametric methods. So, by using the whole curves as basic data parameters, subtle differences in the rehabilitation process can be found.FPCA represents a future aid for the fine analysis of similar physiotherapy techniques, when applied in subjects with a huge variability of functional recovery, as in the case of post-stroke patients.

Solvent Effects on the Structure and Spectroscopy of the Emitting States of 1-Phenylpyrrole.

Theoretical calculations of absorption and fluorescence properties of 1-phenylpyrrole have been performed, at the CASPT2//CASSCF level, in the gas phase and in acetonitrile solution, using in the latter case the ASEP/MD method. In addition to a locally excited state, it was also possible to identify a candidate intramolecular charge transfer state that could explain the second red-shifted fluorescence band that appears in polar solvents. In the gas phase, the charge transfer state is found to lie higher in energy than the locally excited state and the Franck-Condon absorption state, making it unlikely to be reached under these conditions. In acetonitrile solution, the charge transfer state is stabilized and lies much closer to the locally excited state, becoming accessible after absorption. The results indicate that the free-energy surface of the charge transfer state is very flat in solution, and several geometries are possible, ranging from almost planar to twisted and bent. Solvent caging and transition probabilities favor emission from structures with a small twist angle between the rings and without a pyramidal atom.

Solvent Effects on the Radiative and Nonradiative Decay of a Model of the Rhodopsin Chromophore.

The radiative and nonradiative decay of a model with five double bonds of the 11-cis-retinal protonated Schiff base was studied both in vacuum and in methanol solution using an extended version of the averaged solvent electrostatic potential from molecular dynamics data (ASEP/MD) method that allows the location of crossing points between free energy surfaces both in equilibrium and in frozen solvent conditions. The multireference quantum method CASSCF was used for the description of the states of interest, while the solvent structure was obtained from molecular dynamics simulations. Electron dynamic correlation corrections to the energy were included at CASPT2 level. Unlike in gas phase, where only two states seem to be implicated, in methanol solution, three states are necessary to describe the photoisomerization process. At the Franck-Condon point the S1 and S2 states are almost degenerate; consequently, the S1 surface has a region with an ionic character ((1)Bu-like) and another one with a covalent character ((2)Ag-like). Emission from the ionic minima is responsible for the low-frequency part of the fluorescence band, while emission from the covalent minima originates the high-frequency part. The ionic minimum is separated from the conical intersection yielding the all-trans isomer by an energy barrier that was estimated in 0.7 kcal/mol. The geometry of the optimized conical intersection was found at a torsion angle of the central double bond close to 90° both in vacuum and in methanol solution. This large torsion in addition to the accompanying charge displacements forces a strong solvent reorganization during the de-excitation process which slows down the photoisomerization kinetics in methanol with respect to the gas phase. Solvent fluctuations modulate the minima depth and the barrier height and could explain the multiexponential relaxation time observed in the experiments.