Rehabilitation activities with tablet (REACT) in Parkinson's disease.

INTRODUCTION: There is evidence to demonstrate that plasticity is "use-dependent" and that intensive practice may be necessary to modify neural organization. PURPOSE: The main aim of this work is to investigate the REACT usability, an innovative app, to assist People with Parkinson Disease (PwPD) at home. METHODS: A pilot study has been conducted enrolling 20 consecutive PwPD. Before home rehabilitation activities started, each patient received training on the REACT app and how to use the device and the services in daily practice. Motor and cognitive evaluations were administered to assign personalized exercises, tailored to patients' needs and potential. PwPD carried out REACT home program for 1 month, four times a week. The app included motor exercise and tutorial of activities of daily living (ADL) and functional cognitive stimulation. REACT-app usability was evaluated with the System Usability Scale (SUS). RESULTS: The results from SUS questionnaire were, on average, above the threshold of "good usability" (SUS score > 68), as reported in the literature. The 47% of PwPD that used the app rated the usability of the solution as "excellent." Almost all SUS items reached the reference benchmark (except items 4, 5, and 7). No adverse events occurred. CONCLUSIONS: REACT can be considered a useful and safe tool to support the continuity of care and treatment at home, in PwPD. Larger-scale trials are needed to validate the good acceptance and efficacy of home rehabilitation through technology applications.

Neural alterations underlying executive dysfunction in Parkinson's disease: A systematic review and coordinate-based meta-analysis of functional neuroimaging studies.

Parkinson's Disease's (PD) neuropsychological profile is often characterized by altered performance in executive functions (EF) tasks, with a remarkable impact on patients' quality of life. To date, the available neuroimaging literature lacks conclusive evidence about neural patterns underlying EF deficits in PD. Here, we aimed to synthesize the results of PET/fMRI studies examining the differences in brain activation between PD patients and controls during EF tasks, focusing on the three main EF sub-components: cognitive flexibility, working memory, and response inhibition. We conducted a coordinate-based meta-analysis to assess the converging alterations in brain activity in PD patients compared to controls. We assessed the association between aberrant patterns of activity and the EF sub-domains. We found a significant association between hypoactivation patterns in PD converging at the level of the right inferior frontal gyrus in response inhibition tasks, whereas hypoactivation in the left inferior frontal gyrus was found in association with the cognitive flexibility domain. Our results confirm the existence of neural alterations in PD patients in relation to specific EF sub-domains.

Pay attention: you can fall! The Mini-BESTest scale and the turning duration of the TUG test provide valid balance measures in neurological patients: a prospective study with falls as the balance criterion.

Background: Balance, i.e., the ability not to fall, is often poor in neurological patients and this impairment increases their risk of falling. The Mini-Balance Evaluation System Test (Mini-BESTest), a rating scale, the Timed Up and Go (TUG) test, and gait measures are commonly used to quantify balance. This study assesses the criterion validity of these measures as balance measures. Methods: The probability of being a faller within nine months was used as the balance criterion. The Mini-BESTest, TUG (instrumented with inertial sensors), and walking test were administered before and after inpatient rehabilitation. Multiple and LASSO logistic regressions were used for the analysis. The diagnostic accuracy of the model was assessed with the area under the curve (AUC) of the receiver operating characteristic curve. Mobility measure validity was compared with the Akaike Information Criterion (AIC). Results: Two hundred and fourteen neurological patients (stroke, peripheral neuropathy, or parkinsonism) were recruited. In total, 82 patients fell at least once in the nine-month follow-up. The Mini-BESTest (AUC = 0.69; 95%CI: 0.62-0.76), the duration of the TUG turning phase (AUC = 0.69; 0.62-0.76), and other TUG measures were significant faller predictors in regression models. However, only the turning duration (AIC = 274.0) and Mini-BESTest (AIC = 276.1) substantially improved the prediction of a baseline model, which only included fall risk factors from the medical history (AIC = 281.7). The LASSO procedure selected gender, disease chronicity, urinary incontinence, the Mini-BESTest, and turning duration as optimal faller predictors. Conclusion: The TUG turning duration and the Mini-BESTest predict the chance of being a faller. Their criterion validity as balance measures in neurological patients is substantial.

Action Observation Treatment for Upper Limb Rehabilitation in Patients With Stroke: Protocol for a Multicenter Randomized Controlled Trial.

BACKGROUND: In the last few years, new noninvasive strategies have emerged as rehabilitative treatments for patients with stroke. Action observation treatment (AOT) is a rehabilitation approach based on the properties of the mirror neuron system with a positive impact on modifying cortical activation patterns and improving the upper limb kinematics. AOT involves the dynamic process of observing purposeful actions with the intention of imitating and then practicing those actions. In recent years, several clinical studies suggested the effectiveness of AOT in patients with stroke to improve motor recovery and autonomy in activities of daily living. However, a deeper knowledge of the behavior of the sensorimotor cortex during AOT seems to be essential. OBJECTIVE: The aim of this clinical trial, conducted in 2 neurorehabilitation centers and in patients' homes, is to investigate the effectiveness of AOT in patients with stroke, confirming the translational power of a tailored treatment. Particular emphasis will be placed on the predictive value of neurophysiological biomarkers. In addition, the feasibility and impact of a home-based AOT program will be investigated. METHODS: A 3-arm, assessor-blinded, randomized controlled trial will be performed by enrolling patients with stroke in the chronic stage. A total of 60 participants will be randomly allocated to receive 15 sessions of AOT with different protocols (AOT at the hospital, AOT at home, and sham AOT), 3 sessions per week. The primary outcome will be assessed using the Fugl-Meyer Assessment-Upper Extremity scores. Secondary outcomes will be clinical, biomechanical, and neurophysiological assessment. RESULTS: The study protocol is part of a project (project code GR-2016-02361678) approved and funded by the Italian Ministry of Health. The study began with the recruitment phase in January 2022, and enrollment was expected to end in October 2022. Recruitment is now closed (December 2022). The results of this study are expected to be published in spring 2023. Upon completion of the analyses, we will examine the preliminary effectiveness of the intervention and neurophysiological outcomes. CONCLUSIONS: This study will be used to evaluate the effectiveness of 2 different AOT scenarios (ie, AOT at the hospital and AOT at home) in patients with chronic stroke and to assess the predictive value of neurophysiological biomarkers. Specifically, we will attempt to induce the functional modification of the cortical components by exploiting the features of the mirror neuron system, demonstrating relevant clinical, kinematic, and neurophysiological changes after AOT. With our study, we also want to provide, for the first time in Italy, the AOT home-based program while assessing its feasibility and impact. TRIAL REGISTRATION: ClinicalTrials.gov NCT04047134; https://clinicaltrials.gov/ct2/show/NCT04047134. INTERNATIONAL REGISTERED REPORT IDENTIFIER (IRRID): DERR1-10.2196/42094.

Differential Item Functioning of the Mini-BESTest Balance Measure: A Rasch Analysis Study.

The Mini-Balance Evaluation Systems Test (Mini-BESTest), a 14-item scale, has high content validity for balance assessment. This study further examines the construct validity of the Mini-BESTest with an emphasis on its measurement invariance. The Mini-BESTest was administered to 292 neurological patients in two sessions (before and after rehabilitation) and evaluated with the Rasch analysis (Many-Facet Rating Scale Model: persons, items, sessions). Categories' order and fit to the model were assessed. Next, maps, dimensionality, and differential item functioning (DIF) were examined for construct validity evaluation. DIF was inspected for several clinically important variables, including session, diagnosis, and assistive devices. Mini-BESTest items had ordered categories and fitted the Rasch model. The item map did not flag severe construct underrepresentation. The dimensionality analysis showed that another variable extraneous to balance affected the score of a few items. However, this multidimensionality had only a modest impact on measures. Session did not cause DIF. DIF for assistive devices affected six items and caused a severe measurement artefact. The measurement artefact caused by DIF for diagnosis was negligible. The Mini-BESTest returns interval measures with robust construct validity and measurement invariance. However, caution should be used when comparing Mini-BESTest measures obtained with and without assistive devices.

The Falls Efficacy Scale International is a valid measure to assess the concern about falling and its changes induced by treatments.

OBJECTIVE: To test with the Rasch analysis the psychometric properties of the Falls Efficacy Scale International, a questionnaire for measuring concern about falling. DESIGN: Longitudinal observational study, before-after rehabilitation. SETTING: Inpatient rehabilitation. SUBJECTS: A total of 251 neurological patients with balance impairment. INTERVENTIONS: Physiotherapy and occupational therapy aimed at reducing the risk of falling. MAIN MEASURES: Participants (median age, first-third quartile: 74.0, 65.5-80.5 years; stroke and polyneuropathy: 43% and 21% of the sample, respectively) received a balance assessment (Falls Efficacy Scale International included) pre- and post-rehabilitation. Rasch analysis was used to evaluate the Falls Efficacy Scale International. Differential item functioning, which assesses the measures' stability in different conditions (e.g. before vs. after treatment) and in different groups of individuals, was tested for several variables. RESULTS: Patients suffered a moderate balance impairment (Mini-BESTest median score; first-third quartile: 15; 11-19), mild-moderate concern about falling (Falls Efficacy Scale International: 28; 21-37) and motor disability (Functional Independence Measure, motor domain: 70.0; 57.0-76.5). Falls Efficacy Scale International items fitted the Rasch model (range of infit and outfit mean square statistics: 0.8-1.32 and 0.71-1.45, respectively) and the questionnaire's reliability was satisfactory (0.87). No differential item functioning was found for treatment, gender, age and balance impairment. Differential item functioning was found for diagnosis and disability severity, but it is shown that it is not such as to bias measures. CONCLUSIONS: Falls Efficacy Scale International ordinal scores can be turned into interval measures, i.e. measures of the type of temperature. Being differential item functioning-free for treatment, these measures can be safely used to compare concern about falling before and after rehabilitation, such as when interested in assessing the rehabilitation effectiveness.

Effects of gait rehabilitation on motor coordination in stroke survivors: an UCM-based approach.

Post-stroke locomotion is usually characterized by asymmetrical gait patterns, compensatory movements of trunk and nonparetic limb, altered motor coordination, and wide inter-stride variability. This pilot study was designed to test a twofold hypothesis: post-stroke survivors can exploit the redundancy of the segmental angles to stabilize the 3D footpath trajectory during the swing phase, in accordance with the Uncontrolled Manifold (UCM) theory; an intense rehabilitative treatment improves both motor performance and outcomes of the UCM analysis. Ten stroke survivors underwent two evaluation sessions, before and after a conventional multidisciplinary intensive rehabilitation program, encompassing clinical tests and gait analysis, both overground and on treadmill. In addition, the UCM analysis was implemented to investigate whether variance of segmental angles is structured to minimize the inter-stride variability of the 3D footpath during the swing phase of treadmill locomotion. Both clinical and spatio-temporal parameters improved after the treatment, even if the statistical significance was reached for a limited set of them. The UCM analysis suggested that post-stroke survivors exploit the redundancy of lower limbs segmental angles mainly during the late swing, without significant differences between affected and unaffected sides. Thereafter, the main significant effects of the rehabilitative treatment consisted in strengthening the synergistic organization of the redundant segmental angles involving a more accurate control of the 3D footpath. Concluding, the UCM theory can be a promising tool to appraise the effects of a specific rehabilitative protocol on motor coordination in post-stroke survivors.

Turning and sit-to-walk measures from the instrumented Timed Up and Go test return valid and responsive measures of dynamic balance in Parkinson's disease.

BACKGROUND: Balance impairment is a hallmark of Parkinson's disease with dramatic effects for patients (e.g. falls). Its assessment is thus of paramount importance. The aim of this work is to assess which measures from the instrumented Timed Up and Go test (recorded with inertial sensors) are valid balance measures in Parkinson's disease and evaluate their responsiveness to rehabilitation. METHODS: The Mini-BESTest (a criterion-standard balance measure) and the instrumented Timed Up and Go test (with inertial sensors secured to the trunk) were administered to 20 Parkinson's disease patients before and after inpatient rehabilitation (median [IQR]; 76.5 [8.25] years; 5 females; Hoehn and Yahr stage: 2.5 [0.5]). 81 parameters from the instrumented Timed Up and Go test were evaluated. Multiple factor analysis (a variant of principal component analysis for repeated measurements) and effect sizes were used to assess validity and responsiveness, respectively. FINDINGS: Only the first component of the multiple factor analysis correlated with the Mini-BESTest, and 21 measures from the instrumented Timed Up and Go test had large loadings on this component. However, only three of these 21 measures also directly correlated with the Mini-BESTest (trunk angular velocities from sit-to-walk and turning; r = 0.46 to 0.50, P = 0.021 to 0.038). Sit-to-walk angular velocity showed greater responsiveness than the Mini-BESTest, while turning showed slightly less. INTERPRETATION: Angular velocities from the turning and sit-to-walk phases of the Timed Up and Go test are valid balance measures in Parkinson's disease and are also responsive to rehabilitation.

Experimental and Theoretical Study on the Gas-Phase Reactions of Germyl Radicals with NF3: Homolytic Substitution at the Nitrogen Atom vs Fluorine Abstraction.

In this paper, we report on the unexplored reaction mechanisms of bimolecular homolytic substitution (SH2) between GeH3 radicals and the nitrogen atom of NF3. The SH2 reactions are studied both experimentally and theoretically with ab initio and density functional theory (DFT) calculations. The experimental results of X-ray irradiation of mixtures of GeH4 and NF3 show the formation of GeH3-NF2 and GeH3-F. The trend of product yields as a function of the increase in GeH4 partial pressure in the irradiated mixtures evidences the predominant role of GeH3 radicals. Particularly, the SH2 mechanism can be hypothesized for the reaction between GeH3 radicals and NF3 molecules leading to GeH3-NF2. This mechanism is further confirmed by the increase in GeH3-NF2 yield observed if O2 is added, as a radical scavenger, to the reaction mixture. In agreement with the experimental data, from the calculations performed at the CCSD(T) and G3B3 levels of theory, we observe that the GeH3-NF2 product actually occurs from a bimolecular homolytic substitution by the GeH3 radical, which attacks the N atom of NF3, and this reaction is in competition with the fluorine abstraction reaction leading to GeH3F, even if other mechanisms may be involved in the formation of this product.

Complexes of helium with neutral molecules: Progress toward a quantitative scale of bonding character.

The complexes of helium with nearly 30 neutral molecules (M) were investigated by various techniques of bonding analysis and symmetry-adapted perturbation theory (SAPT). The main investigated function was the local electron energy density H(r), analyzed, in particular, so to estimate the degree of polarization (DoP) of He in the various He(M). As we showed recently (Borocci et al., J. Comput. Chem., 2019, 40, 2318-2328), the DoP is a quantitative index that is generally informative about the role of polarization (induction plus charge transfer [CT]) and dispersion in noncovalent noble gas complexes. As further evidence in this regard, we presently ascertained quantitative correlations between the DoP(He) of the He(M) and indices based on the electron density ρ(r), including the molecular electrostatic potential at the HeM bond critical point, as well as the percentage contributions of induction and dispersion to the SAPT binding energies. Based also on the explicit evaluation of the CT, accomplished through the study of the charge-displacement function, we derived a quantitative scale that ranks the He(M) according to their dispersive, inductive, and CT bonding character. Our taken approach could be conceivably extended to other types of noncovalent complexes.

Responsiveness to rehabilitation of balance and gait impairment in elderly with peripheral neuropathy.

Elderly people with peripheral neuropathy of the lower limbs (PNLL) demonstrate a typical balance and gait impairment because of sensory ataxia. There is evidence that rehabilitation produces important gains on balance and gait. However, responsiveness to rehabilitation of balance and gait measures is unknown in PNLL. Aim of the current work is to evaluate the responsiveness to rehabilitation of balance, gait and sensory ataxia measures in elderly with PNLL. Twenty-five elderly with PNLL attending physiotherapy and occupational therapy during inpatient rehabilitation were recruited. Balance and gait measures (including static posturography, TUG test and the 10 m walking test) were administered on admission and discharge. An accelerometer secured to the trunk was used for TUG recording and static balance assessment. Static balance was tested with open and closed eyes, so as to assess sensory ataxia. Following rehabilitation, patients improved gait [admission vs discharge, mean(SD): 0.86(0.33) vs 0.98(0.32) m/s], TUG [18.7(7.8) vs 15.1(5.2) s] and turning [46.2(15.3) vs 53.3(15.3) °/s]. However, none of 12 static balance parameters derived from trunk acceleration significantly changed. Principal component analysis showed that before training, eyes closed and eyes open balance correlated with orthogonal components (one and two vs. three and four). After training, eyes open and eyes closed balance were more similar to each other being both correlated with component one. Responsiveness to rehabilitation is larger for gait than static balance measured by trunk acceleration. However, exercise can also have a beneficial effect on sensory ataxia by making eyes closed balance more similar to eyes open balance.

Noncovalent Complexes of the Noble-Gas Atoms: Analyzing the Transition from Physical to Chemical Interactions.

The bonding character of the noncovalent complexes of the noble-gas (Ng) atoms ranges from nearly purely dispersive contacts to interactions featuring appreciable contributions of induction and charge transfer. In this study, we discuss a new quantitative index that seems peculiarly informative about these diverse bonding situations. This index was termed as the degree of polarization (DoP) of Ng, as it measures, in essence, the Ng polarization promoted by the binding partner. The definition of the DoP(Ng) relies on the analysis of the local electron energy density H(r), and its physical meaning was best appreciated by studying also the charge-displacement function and the molecular electrostatic potential of the investigated benchmark species, that include nearly 60 Ngs complexes of different bonding character. The DoP(Ng) appears of general applicability, and is also positively correlated with other bonding character indices. © 2019 Wiley Periodicals, Inc.

How do patients improve their timed up and go test? Responsiveness to rehabilitation of the TUG test in elderly neurological patients.

BACKGROUND: The timed up and go (TUG) test is widely used for assessing treatments effectiveness on elderly mobility. Although the TUG test consists of different tasks (e.g. walking and turning), the total TUG duration (TTD) is usually the only outcome measure, with TTD shortening indicating the patient's improvement. RESEARCH QUESTION: Does TTD shortening reflect the improvement of each TUG tasks or does it reflect the improvement of only some of them? METHODS: This retrospective study recruited 120 elderly patients (mean, SD: 76.9, 6.6 years) admitted to inpatient rehabilitation because of an acute or chronic neurological disease (acute patients, AP; chronic patients, CP). TTD and TUG tasks duration was measured on admission and discharge (five trials/session) by means of the instrumental TUG test (ITUG). Likelihood ratios (LRs) were used for inferring TUG tasks improvement from TTD improvement. TTD and TUG tasks have improved if at least four measurements on discharge were shorter than the shortest measurement on admission. RESULTS: TTD improvement per se is not enough to claim that all the TUG tasks have improved (LR+AP = 1.32; LR+CP = 1.85). Conversely, if TTD has not improved, not even a single TUG task has improved (LR-AP = 0.13; LR-CP = 0.19). If TTD has improved, there is at least one TUG task that actually improved (LR+AP = 3.17; LR+CP = 9.54). The improvement of all TUG tasks can be only inferred in the (unusual) event of a large TTD shortening (AP: >39%, LR+AP = 6.26; CP: >30%, LR+CP = 9.0). SIGNIFICANCE: In most cases, TTD improvement is not associated with the improvement of all TUG tasks. Moreover, when TTD has improved there is at least a TUG task that has improved, but that remains unknown. To actually understand how treatments ameliorate patients' mobility, ITUG with TUG task duration measurement should be preferred to TTD.

No evidence of effectiveness of mirror therapy early after stroke: an assessor-blinded randomized controlled trial.

OBJECTIVE: The aim of this study was to investigate the efficacy of mirror therapy on upper-limb recovery in early post-stroke patients. DESIGN: Assessor-blinded randomized controlled trial. SETTING: Inpatient rehabilitation clinic. SUBJECTS: A total of 40 patients with upper-limb impairment due to a first-ever ischaemic or haemorrhagic stroke, within four weeks from the cerebrovascular accident. INTERVENTION: The intervention group received mirror therapy, while the control group received sham therapy. During mirror therapy, patients' sound hand was reflected by a mirror. During sham therapy, an opaque surface replaced the mirror-reflecting surface. Both the mirror therapy and sham therapy groups practised their sound hand with exercises, ranging from the simple elbow flexion-extension to complex tasks (e.g. reaching and grasping). Mirror therapy and sham therapy were added to conventional rehabilitation. MAIN MEASURES: Primary outcome includes Fugl-Meyer upper extremity scale. Secondary outcomes include action research arm test (ARAT) and functional independence measure (FIM) scale. Outcomes were measured at the beginning (T0) and end (T1) of the treatment. RESULTS: At baseline, both groups (sham therapy vs. mirror therapy; mean (SD)) were comparable for Fugl-Meyer (30.9 (23.9) vs. 28.5 (21.8)), ARAT (25.1 (25.5) vs. 23.5 (24)) and FIM (71.0 (20.6) vs. 72.9 (17.8)) scores. At the end of the treatment, both groups significantly improved in the Fugl-Meyer (40.6 (21.3) vs. 38.3 (23.4)), ARAT (31.9 (23.0) vs. 30 (24.1)) and FIM (100.3 (21.9) vs. 99.4 (22.6)) scores. However, at T1, no significant difference was observed between the sham therapy and mirror therapy groups, neither for the Fugl-Meyer, nor for ARAT and FIM scores. CONCLUSION: Compared with sham therapy, mirror therapy did not add additional benefit to upper-limb recovery early after stroke.

Developing new SrI2 and ß-D-fructopyranose-based metal-organic frameworks with nonlinear optical properties.

In the context of personalized medicine, there is a growing interest in materials bearing at the same time diagnostic and therapy functions. This article reports a cheap and easily reproducible procedure to obtain materials with a high potential for these applications. Three new strontium iodide-fructose-based metal-organic frameworks with formulae [Sr(C6H12O6)2]I2, [Sr2(C6H12O6)3(H2O)3]I4·0.5H2O and [Sr(C6H12O6)(H2O)3I]I differing in stoichiometry, symmetry and crystal packing, were obtained and characterized by X-ray diffraction. Bulk quantum simulations show that both the ions and the sugar are crucial in determining the predicted nonlinear response; also, the relative arrangement of various functional groups in the unit cell plays a role in the computed optical properties. Small fragments of the three compounds were selected for in vacuo calculations, proving that the reduced dimensions of the particles have a great influence on the nonlinear optical response. Despite the similar chemical composition of the three compounds, second harmonic generation measurements and in crystal and in vacuo theoretical calculations agree that one of the compounds is a much more efficient second harmonic emitter than the other two, and is thus a suitable candidate for bio-sensor applications.

Criterion validity of the instrumented Timed Up and Go test: A partial least square regression study.

The Timed Up and Go (TUG) test is a common mobility measure in rehabilitation. With the instrumental TUG test (ITUG; i.e. the TUG measured by inertial measurement units, IMUs), several movement measures are newly available. However, the clinical meaning of these new measures is not totally clear. Aim of the current work is to evaluate the validity of different ITUG parameters as a measure of balance. Neurological patients (n = 122; 52 females; 89 older than 65 years) completed the TUG test with IMUs secured to their back. IMUs signals were used to split the TUG test in five phases (sit-to-stand, walk1, turn1, walk2 and turn-and-sit) and twelve movement parameters were obtained. Experienced clinicians administered the Mini-BESTest (MB) scale, a sound balance measure. The partial least square regression (PLSR) was used to explore the association between the ITUG variables and the MB measure. A PLSR model with twelve ITUG variables had satisfactory fit parameters (RMSEP: 11%; R2: 0.41, 95% CI: 0.28-0.54; regression line: 1, 95% CI: 0.78-1.22). Three ITUG variables (i.e. turn1 vertical angular velocity, turn1 duration and turn2 vertical angular velocity) were found to be the most important predictors of the MB measure. A PLSR model with the turning variables only had fit parameters comparable to that of the twelve variables model. Turning parameters from the TUG test are good predictors of the MB scale. The mean angular velocity during turning and the duration of the turning phase are thus proposed as a valid, ratio-level measures of balance in neurological patients.

Synthesis, structure and non-linear optical properties of new isostructural ß-D-fructopyranose alkaline halide metal-organic frameworks: a theoretical and an experimental study.

In this work four metal-organic framework isomorphs, based on fructose and alkali-earth halogenides, were investigated to better understand the effect of the size of the cation and the different polarizability of the anion on the calculated hyperpolarizability and optical susceptibility, which are correlated to non-linear optical properties. The compounds were characterized by X-ray diffraction and the first hyperpolarizability and the second-order susceptibility were obtained from theoretical calculations. Furthermore, a new method to measure the second-harmonic (SH) efficiency on a small quantity of powder at different wavelengths of excitation was optimized and an attempt was made to assess the reduction of the SH intensity for small quantities of nano-crystals, in order to ascertain the possibility of applications in biological systems. The results of this work show that both the intrinsic nature of the anion and the induced dissociation of cations and anions by fructose play a role in the second-harmonic generating properties of such compounds.

Bimolecular Homolytic Substitutions at Nitrogen: An Experimental and Theoretical Study on the Gas-Phase Reactions of Alkyl Radicals with NF3.

The X-ray irradiation of binary mixtures of alkyl iodides R-I (R=CH3 , C2 H5 , or i-C3 H7 radicals) and NF3 produces R-NF2 and R-F. Based on calculations performed at the CCSD(T), MRCI(SD+Q), G3B3, and G3 levels of theory, the former product arises from a bimolecular homolytic substitution reaction (SH 2) by the alkyl radicals R, which attack the N atom of NF3 . This mechanism is consistent with the suppression of R-NF2 by addition of O2 (an efficient alkyl radical scavenger) to the reaction mixture. The R-F product arises from the attack of R to the F atom of NF3 , but additional contributing channels are conceivably involved. The F-atom abstraction is, indeed, considerably more exothermic than the SH 2 reaction, but the involved energy barriers are comparable, and the two processes are comparably fast.

Germyl cations with Ge-S bond: an experimental and theoretical study on the gaseous F(n)Ge(SH)(3-n)+ (n=0-2).

The germyl cations F(2)Ge(SH)(+), FGe(SH)(2)(+) and Ge(SH)(3)(+) were obtained from ionized mixtures of GeF(4) and H(2)S. Ion trap mass spectrometry revealed the occurrence of three consecutive addition-HF elimination reactions between GeF(3)(+), F(2)Ge(SH)(+) and FGe(SH)(2)(+) and H(2)S. The structure and the mechanism of formation of the observed F(n)Ge(SH)(3-n)(+) (n = 0-2) were investigated by ab initio calculations performed at the MP2 and coupled cluster level of theory. It was also possible to note regular trends in the geometries and Lewis acidities of the F(n)Ge(SH)(3-n)(+) (n= 0-3).

Gas-phase reactions of SiH(n)+ (n = 1,2) with NF3: a computational investigation on the detailed mechanistic aspects.

The mechanism of the gas-phase reactions of SiH(n)(+) (n = 1,2) with NF(3) were investigated by ab initio calculations at the MP2 and CAS-MCSCF level of theory. In the reaction of SiH(+), the kinetically relevant intermediates are the two isomeric forms of fluorine-coordinated intermediate HSi-F-NF(2)(+). These species arise from the exoergic attack of SiH(+) to one of the F atoms of NF(3) and undergo two competitive processes, namely an isomerization and subsequent dissociation into SiF(+) + HNF(2) , and a singlet-triplet crossing so to form the spin-forbidden products HSiF(+) + NF(2). The reaction of SiH(2)(+) with NF(3) involves instead the concomitant formation of the nitrogen-coordinated complex H(2)Si-NF(3)(+) and of the fluorine-coordinated complex H(2)Si-F-NF(2)(+). The latter isomer directly dissociates into NF(2)(+) + H(2)SiF, whereas the former species preferably undergoes the passage through a conical intersection point so to form a H(2) SiF-NF(2)(+) isomer, which eventually dissociates into H(2)SiF(+) and NF(2).