Reply to Inzitari et al. Comment on "Blancafort Alias et al. A Multi-Domain Group-Based Intervention to Promote Physical Activity, Healthy Nutrition, and Psychological Wellbeing in Older People with Losses in Intrinsic Capacity: AMICOPE Development Study. Int. J. Environ. Res. Public Health 2021, 18, 5979".

This is a reply to the comment by Inzitari et al [...].

A Multi-Domain Group-Based Intervention to Promote Physical Activity, Healthy Nutrition, and Psychological Wellbeing in Older People with Losses in Intrinsic Capacity: AMICOPE Development Study.

The World Health Organization has developed the Integrated Care of Older People (ICOPE) strategy, a program based on the measurement of intrinsic capacity (IC) as "the composite of all physical and mental attributes on which an individual can draw". Multicomponent interventions appear to be the most effective approach to enhance IC and to prevent frailty and disability since adapted physical activity is the preventive intervention that has shown the most evidence in the treatment of frailty and risk of falls. Our paper describes the development of a multi-domain group-based intervention addressed to older people living in the community, aimed at improving and/or maintaining intrinsic capacity by means of promoting physical activity, healthy nutrition, and psychological wellbeing in older people. The process of intervention development is described following the Guidance for reporting intervention development studies in health research (GUIDED). The result of this study is the AMICOPE intervention (Aptitude Multi-domain group-based intervention to improve and/or maintain IC in Older PEople) built upon the ICOPE framework and described following the Template for Intervention Description and Replication (TIDieR) guidelines. The intervention consists of 12 face-to-face sessions held weekly for 2.5 h over three months and facilitated by a pair of health and social care professionals. This study represents the first stage of the UK Medical Research Council framework for developing and evaluating a complex intervention. The next step should be carrying out a feasibility study for the AMICOPE intervention and, at a later stage, assessing the effectiveness in a randomized controlled trial.

Deactivation of Excited States in Transition-Metal Complexes: Insight from Computational Chemistry.

Investigation of the excited-state decay dynamics of transition-metal systems is a crucial step for the development of photoswitchable molecular based materials with applications in growing fields as energy conversion, data storage, or molecular devices. The photophysics of these systems is an entangled problem arising from the interplay of electronic and geometrical rearrangements that take place on a short time scale. Several factors play a role in the process: various electronic states of different spin and chemical character are involved, the system undergoes important structural variations and several nonradiative processes can occur. Computational chemistry is a useful tool to get insight into the microscopic description of the photophysics of these materials, since it provides unique information about the character of the electronic spin states involved, the energetics and time evolution of the system. In this review article, we present an overview of the state of the art methodologies available to address the several aspects that have to be incorporated to properly describe the deactivation of excited states in transition-metal complexes. The most recent developments in theoretical methods are discussed and illustrated with examples.

Switching the Spin-Crossover Phenomenon by Ligand Design on Imidazole-Diazineiron(II) Complexes.

The iron(II) complexes of two structural isomers of 2-(1 H-imidazol-2-yl)diazine reveal how ligand design can be a successful strategy to control the electronic and magnetic properties of complexes by fine-tuning their ligand field. The two isomers only differ in the position of a single diazinic nitrogen atom, having either a pyrazine (Z) or a pyrimidine (M) moiety. However, [Fe(M)3](ClO4)2 is a spin-crossover complex with a spin transition at 241 K, whereas [Fe(Z)3](ClO4)2 has a stable magnetic behavior between 2 and 300 K. This is corroborated by temperature-dependent Mössbauer spectra showing the presence of a quintet and a singlet state in equilibrium. The temperature-dependent single-crystal X-ray diffraction results relate the spin-crossover observed in [Fe(M)3](ClO4)2 to changes in the bond distances and angles of the coordination sphere of iron(II), hinting at a stronger σ donation of ligand Z in comparison to ligand M. The UV/vis spectra of both complexes are solved by means of the multiconfigurational wave-function-based method CASPT2 and confirm their different spin multiplicities at room temperature, as observed in the Mössbauer spectra. Calculations show larger stabilization of the singlet state in [Fe(Z)3]2+ than in [Fe(M)3]2+, stemming from the slightly stronger ligand field of the former (506 cm-1 in the singlet). This relatively weak effect is indeed capable of changing the spin multiplicity of the complexes and causes the appearance of the spin transition in the M complex.

Theoretical evidence for the direct 3MLCT-HS deactivation in the light-induced spin crossover of Fe(ii)-polypyridyl complexes.

Spin-orbit couplings have been calculated in twenty snapshots of a molecular dynamics trajectory of [Fe(bpy)3]2+ to address the importance of geometrical distortions and second-order spin-orbit coupling on the intersystem crossing rate constants in the light-induced spin crossover process. It was found that the effective spin-orbit coupling between the 3MLCT and 5T2 state is much larger than the direct coupling in the symmetric structure, which opens the possibility of a direct 3MLCT-5T2 deactivation without the intervention of triplet metal-centered states. Based on the calculated deactivation times, we conclude that both the direct pathway and the one involving intermediate triplet states are active in the ultrafast population of the metastable HS state, bringing in agreement two experimental observations that advocate for either deactivation mechanism. This resolves a long-standing dispute about the deactivation mechanism of Fe(ii)-polypyridyl complexes in particular, and about light-induced magnetism in transition metal complexes in general.

Dinuclear Iron(II) Spin-Crossover Compounds: A Theoretical Study.

The structures and spin-state energetics of two di-iron(II) complexes based on thiadiazole and oxadiazole ligands in different crystals were studied by using density functional theory and second-order perturbation theory based on the density matrix renormalization group approach (DMRG-CASPT2). When taking into account all different contributions to the relative energy, our theoretical approach is capable of providing results that are in excellent agreement with established experimental data. In all cases, we correctly describe the ground state of the complexes as well as predict their spin-crossover behavior. A comparison between the two complexes in the gas phase and in different crystals shows how the structures change by moving from the gas phase to different crystals and reveals a large impact of the crystal stabilization on the relative spin-state energy. This theoretical work also demonstrates the applicability of the DMRG-CASPT2 approach to quantitatively study the spin-state energetics of multinuclear transition-metal complexes.

Effect of Second-Order Spin-Orbit Coupling on the Interaction between Spin States in Spin-Crossover Systems.

The second-order spin-orbit coupling is evaluated in two transition-metal complexes to establish the effect on the deactivation mechanism of the excited low-spin state in systems that undergo spin transitions under the influence of light. We compare the standard perturbational approach to calculate the second-order interaction with a variational strategy based on the effective Hamiltonian theory and show that the former one can only be applied in some special cases and even then gives results that largely overestimate the interaction. The combined effect of geometry distortions and second-order spin-orbit coupling leads to sizeable interactions for states that are nearly uncoupled in the symmetric (average) structure of the complex. This opens the possibility of a direct deactivation from the singlet and triplet states of the metal-to-ligand charge-transfer manifold to the final high-spin state as suggested from the interpretation of experimental data but so far not supported by theoretical descriptions of the light-induced spin crossover.

The SITLESS project: exercise referral schemes enhanced by self-management strategies to battle sedentary behaviour in older adults: study protocol for a randomised controlled trial.

BACKGROUND: Older adults are the fastest growing segment of the world's population. Recent evidence indicates that excessive sitting time is harmful to health, independent of meeting the recommended moderate to vigorous physical activity (PA) guidelines. The SITLESS project aims to determine whether exercise referral schemes (ERS) can be enhanced by self-management strategies (SMSs) to reduce sedentary behaviour (SB), increase PA and improve health, quality of life and function in the long term, as well as psychosocial outcomes in community-dwelling older European citizens from four countries, within a three-armed pragmatic randomised controlled trial, compared with ERS alone and also with general recommendations about PA. METHODS: A total of 1338 older adults will be included in this study, recruited from four European countries through different existing primary prevention pathways. Participants will be randomly allocated into an ERS of 16 weeks (32 sessions, 45-60 min per session), ERS enhanced by seven sessions of SMSs and four telephone prompts, or a control group. Outcomes will be assessed at baseline, month 4 (end of ERS intervention), month 16 (12 months post intervention) and month 22 (18 months post intervention). Primary outcomes will include measures of SB (time spent sedentary) and PA (counts per minute). Secondary outcomes will include muscle and physical function, health economics' related outcomes, anthropometry, quality of life, social networks, anxiety and depressive symptoms, disability, fear of falling, executive function and fatigue. A process evaluation will be conducted throughout the trial. The full analysis set will follow an intention-to-treat principle and will include all randomised participants for whom a baseline assessment is conducted. The study hypothesis will be tested with mixed linear models with repeated measures, to assess changes in the main outcomes (SB and PA) over time (baseline to month 22) and between study arms. DISCUSSION: The findings of this study may help inform the design and implementation of more effective interventions to reduce SB and increase PA levels, and hence improve long-term health outcomes in the older adult population. SITLESS aims to support policy-makers in deciding how or whether ERS should be further implemented or restructured in order to increase its adherence, impact and cost-effectiveness. TRIAL REGISTRATION: ClinicalTrials.gov, NCT02629666 . Registered 19 November 2015.

Spin State Energetics in First-Row Transition Metal Complexes: Contribution of (3s3p) Correlation and Its Description by Second-Order Perturbation Theory.

This paper presents an in-depth study of the performance of multiconfigurational second-order perturbation theory (CASPT2, NEVPT2) in describing spin state energetics in first-row transition metal (TM) systems, including bare TM ions, TM ions in a field of point charges (TM/PC), and an extensive series of TM complexes, where the main focus lies on the (3s3p) correlation contribution to the relative energies of different spin states. To the best of our knowledge, this is the first systematic NEVPT2 investigation of TM spin state energetics. CASPT2 has been employed in several previous studies but was regularly found to be biased toward high spin states. The bias was attributed to a too low value of the so-called IPEA shift ϵ, an empirical correction in the CASPT2 zeroth-order Hamiltonian with a standard value of 0.25 hartree. Based on comparisons with experiment (TM ions) and calculations with the multireference configuration interaction (TM ions and TM/PC systems) and coupled-cluster (TM complexes) methods, we demonstrate in this work that standard CASPT2 works well for valence correlation and that its bias toward high-spin states is caused by an erratic description of (3s3p) correlation effects. The latter problem only occurs for spin transitions involving a ligand field (de)excitation, not in bare TM ions. At the same time the (3s3p) correlation contribution also becomes strongly ϵ dependent. The error can be reduced by increasing ϵ but only at the expense of deteriorating the CASPT2 description of valence correlation in the TM complexes. The alternative NEVPT2 method works well for bare TM and TM/PC systems, but its results for the TM complexes are disappointing, with large errors both for the valence and (3s3p) correlation contributions to the relative energies of different spin states.

Spin State Energetics and Oxyl Character of Mn-Oxo Porphyrins by Multiconfigurational ab Initio Calculations: Implications on Reactivity.

Important electromeric states in manganese-oxo porphyrins MnO(P)(+) and MnO(PF4)(+) (porphyrinato or meso-tetrafluoroporphyrinato) have been investigated with correlated ab initio methods (CASPT2, RASPT2), focusing on their possible role in multistate reactivity patterns in oxygen transfer (OAT) reactions. Due to the lack of oxyl character, the Mn(V) singlet ground state is kinetically inert. OAT reactions should therefore rather proceed through thermally accessible triplet and quintet states that have a more pronounced oxyl character. Two states have been identified as possible candidates: a Mn(V) triplet state and a Mn(IV)O(L(•)a2u)(+) quintet state. The latter state is high-lying in MnO(P)(+) but is stabilized by the substitutions of H by F at the meso carbons (where the a2u orbital has a significant amplitude). Oxyl character and Mn-O bond weakening in these two states stems from the fact that the Mn-O π* orbitals become singly (triplet) or doubly occupied (quintet). Moreover, an important role for the reactivity of the triplet state is also likely to be played by the π bond that has an empty π* orbital, because of the manifest diradical character of this π bond, revealed by the CASSCF wave function. Interestingly, the diradical character of this bond increases when the Mn-O bond is stretched, while the singly occupied π* orbital looses its oxygen radical contribution. The RASPT2 results were also used as a benchmark for the description of excited state energetics and Mn-O oxyl character with a wide range of pure and hybrid density functionals. With the latter functionals both the Mn(V) → Mn(IV) promotion energy and the diradical character of the π bond (with empty π*) are found to be extremely dependent on the contribution of exact exchange. For this reason, pure functionals are to be preferred.

Electronic reorganization triggered by electron transfer: the intervalence charge transfer of a Fe³âº/Fe²âº bimetallic complex.

The key role of the molecular orbitals in describing electron transfer processes is put in evidence for the intervalence charge transfer (IVCT) of a synthetic nonheme binuclear mixed-valence Fe(3+)/Fe(2+) compound. The electronic reorganization induced by the IVCT can be quantified by controlling the adaptation of the molecular orbitals to the charge transfer process. We evaluate the transition energy and its polarization effects on the molecular orbitals by means of ab initio calculations. The resulting energetic profile of the IVCT shows strong similarities to the Marcus' model, suggesting a response behaviour of the ensemble of electrons analogue to that of the solvent. We quantify the extent of the electronic reorganization induced by the IVCT process to be 11.74 eV, a very large effect that induces the crossing of states reducing the total energy of the transfer to 0.89 eV.

The effect of thermal motion on the electron localization in metal-to-ligand charge transfer excitations in [Fe(bpy)3](2+).

Accurate electronic structure calculations of the lowest excited states have been performed on twenty snapshots of a molecular dynamics simulation of [Fe(bpy)3](2+) dissolved in water. The thermal motion distorts the structure of the complex from its average D3 symmetry, causing the localization on one bipyridine ligand of the excited electron in the metal-to-ligand charge transfer (MLCT) state. The excitation energy is about 0.25 eV lower than that for the delocalized description of the MLCT state and is in good agreement with experiments. The composition of the MLCT band is carefully analyzed and the effect of thermal motion on the mechanism of light-induced spin crossover is discussed.

Charge transfer processes: the role of optimized molecular orbitals.

The influence of the molecular orbitals on charge transfer (CT) reactions is analyzed through wave function-based calculations. Characteristic CT processes in the organic radical 2,5-di-tert-butyl-6-oxophenalenoxyl linked with tetrathiafulvalene and the inorganic crystalline material LaMnO3 show that changes in the inner shells must be explicitly taken into account. Such electronic reorganization can lead to a reduction of the CT vertical transition energy up to 66%. A state-specific approach accessible through an adapted CASSCF (complete active space self-consistent field) methodology is capable of reaching good agreement with the experimental spectroscopy of CT processes. A partitioning of the relaxation energy in terms of valence- and inner-shells is offered and sheds light on their relative importance. This work paves the way to the intimate description of redox reactions using quantum chemistry methods.

Multidimensional network structures and versatile magnetic properties of intermolecular compounds of a radical-anion ligand, [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 1,1-dioxide.

The crystal structures and magnetic properties of seven kinds of [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 1,1-dioxide (tdapO2) radical-anion salts, namely, K·tdapO2, K·tdapO2·0.5MeCN, K·(tdapO2)2, Rb·(tdapO2)2, Cs7·(tdapO2)6·ClO4, (NH4)2·tdapO2·I, and Hppda·tdapO2·MeCN, were investigated. Single-crystal X-ray analyses of these radical-anion salts revealed formation of π-stacking columns and the presence of intercolumnar coordination bonding or hydrogen bonding. The intermolecular magnetic coupling constants in these salts range from strong antiferromagnetic (J/kB = -310 K) to ferromagnetic (J/kB = 24 K). Ab initio calculations performed on the nearest-neighbor radical pairs in the π-stacking columns suggested that the magnetic interactions are strongly governed by the overlap between the two anionic radical species and well explain the observed ferromagnetic and antiferromagnetic interactions. In addition, calculations of a hypothetical oxygen-less tdap analogue suggested that the presence of oxygen in tdapO2 significantly reduces the hopping integral and enhances the probability of ferromagnetic interaction.

Informe: análisis de las publicaciones de socios de la Sociedad Española de Geriatría y Gerontología del año 2006 al 2011 / Report: An analysis of publications by members of the Spanish Geriatrics and Gerontology Society from 2006 to 2011

Se presentan los datos de una encuesta que la Sociedad Española de Geriatría y Gerontología (SEGG) hizo en el año 2011 a sus socios con el fin de conocer la producción científica entre los años 2006 y 2011, referida a la publicación de artículos en revistas científicas indexadas en la base de datos Science Citation Index de Web of Science. La calidad científica de las publicaciones se cuantificó mediante el número de citaciones recibidas por publicación y el factor de impacto de la revista. De los 2.450 socios totales respondieron a la encuesta 162 (6,6%), identificándose 903 artículos diferentes, 335 (37%) en revistas específicamente de geriatría y 568 (63%) en revistas de otras especialidades. El número de publicaciones se ha incrementado anualmente desde los 128 en 2006 hasta los 201 en 2010. Las medidas de impacto se pudieron calcular para 530 trabajos. Las publicaciones han sido citadas una media de 8,2 veces, con una mediana de 2, variando entre 0 y 242 citas. El factor de impacto medio ha sido de 3,1 (mediana: 2,4) y un rango entre 0 y 53,5, habiéndose publicado artículos en las revistas de mayor impacto, tanto generales o específicamente de geriatría como de ciencia básica(AU)

Impact of short and long-range effects on the magnetic interactions in neutral organic radical-based materials.

The mutual influence of electronic structure and environment of the constituent units of neutral organic radical-based materials (radical dimers) is analysed by means of wave function calculations (Difference Dedicated Configuration Interaction, DDCI). Focus is put on the magnetic property modulations of two classes of neutral organic materials by inspecting both short- and long-range effects. The exchange coupling constant J for the high-temperature phase of the 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) material is calculated to be J= -95 cm(-1) at the DDCI level. The environmental electronic polarization is taken into account self-consistently using the individual polarizabilities of the atoms in a finite block of the crystal lattice (Discrete Reaction Field, DRF) and accounts for less than 5% of the calculated J value in TTTA. Furthermore, taking advantage of the chemical flexibility of the verdazyl radical family, the contribution of strong electron-withdrawing groups is analysed by extracting the J, U, t and K parameters from pairs of substituted verdazyl-based radicals. Our ab initio calculations of verdazyl radical pairs suggest that the addition of NO2 groups cause (i) the variations of the ferromagnetic and antiferromagnetic contributions to cancel out, leaving an almost constant exchange coupling constant, ca. J≈ 20 cm(-1), and that (ii) enhanced conduction properties can be anticipated. In contrast to inorganic analogues, one may conclude that the magnetic behaviour of neutral organic radical-based materials is mostly governed by the supramolecular arrangement, whereas environmental effects have a lesser impact.

[Report: an analysis of publications by members of the Spanish Geriatrics and Gerontology Society from 2006 to 2011]. / Informe: análisis de las publicaciones de socios de la Sociedad Española de Geriatría y Gerontología del año 2006 al 2011.

Data is presented from the survey conducted by the Sociedad Española de Geriatría y Gerontología (SEGG) (Spanish Society of Geriatrics and Gerontology) among its members in order to assess their scientific production between 2006 and 2011, specifically articles in journals that are indexed in the Science Citation Index. The scientific quality of the publications was quantified using the number of times every article was cited and the journal's impact factor. A total of 162 out of the 2450 members responded (6.6%), reporting a total of 903 individual articles, 335 (37%) of them in geriatrics-specific journals, and 568 (63%) in other journals of other specialties. The number of publications increased yearly from 128 in 2006 to 201 in 2010. The scientific quality could be calculated for 530 articles. On average, publications have been cited 8.2 times (median: 2), with the range of citations being from 0 to 242. The average impact factor was 3.1 (median 2.4), ranging from 0 to 53.5. A number of articles have been published in some of the largest impact factor journals, in those of general-interest, as well as geriatrics-specific and basic science journals.

The Absorption Spectrum of Cytosine Tautomers: Beyond the Static Approach.

The absorption spectrum of cytosine in water has been studied by combining Car-Parrinello molecular dynamics (MD) with a multiconfigurational perturbation theory treatment of the electronic structure. The MD simulations were performed for four different tautomeric forms of cytosine in a unit cell with 60 water molecules. The relative energies and transition dipole moments of a large number of excited states have been calculated on a representative sample of conformations along the MD trajectories. In this way, the broad experimental peaks can be decomposed, and the effect of the distortions on the nature of the excited states can be assessed. The loss of planarity of the molecule is significant, and hence, the excited states can no longer be defined as pure n → π* or π → π* excitations. We propose an analysis to assign the different transitions according to the main contribution. The keto N1H form turns out to be the most stable one, and the calculated spectra of this tautomer show good agreement with experimental measurements. The mixed nπ*/ππ* character of some states leads to a significant increase of intensity in spectral regions dominated by the dark nπ* transitions considering a planar structure.

Nutritional assessment of residents in long-term care facilities (LTCFs): recommendations of the task force on nutrition and ageing of the IAGG European region and the IANA.

Unintentional weight loss and Undernutrition are major problems among older people living in Long-Term Care Facilities (LTCF). Undernutrition manifests in LTCF particularly as weight loss and low Body Mass Index (BMI) and is associated with increased morbidity and mortality as well as with functional decline. There are many factors associated with poor nutritional status and affecting protein-energy intake and/or energy expenditure. These include age of 85 years or older, low nutrient intake, loss of ability to eat independently, swallowing and chewing difficulties, becoming bed-ridden, pressure ulcers, history of hip fracture, dementia, depressive symptoms and suffering from two or more chronic illnesses. Nutritional evaluation is an essential part of the Comprehensive Geriatric Assessment (CGA). This evaluation ranges from methods such as BMI to several validated tools such as Mini-Nutritional Assessment (MNA). After diagnosis, the management of undernutrition in LTCF requires a multidisciplinary approach which may involve dietary and environmental improvements and managing multiple co-morbidities, while avoiding polypharmacy as far as possible. Finally, the need for supplementation or artificial (tube) feeding may be considered taking into account the CGA and individual needs. This document presents a succinct review and recommendations of evaluation and treatment of undernutrition.

Dosificación de Glifosato en diferentes estados vegetativos del Cyperus rotundus / Glyphosphate dosification in differente vegetatives stagies of cyperus rotundus

Este estudio inicia una revisión de la literatura acerca de la distribución, descripción botánica y estudios relacionados con el herbicida para el control del Cyperus rotundus. El objetivo fue determinar la dosis óptima, en el estado vegetativo más adecuado, en el que se obtiene el control más efectivo del agente. El ensayo se llevó a cabo en el CEIAT de la Facultad de Agronomía en Tocumen. Cada experimento se realizó dos veces a lo largo del año 1983. La concentración de glifosato fue 480 gramos de ingrediente activo/litro. Los estados vegetativos en estudio fueron: 2-4 hojas, 4-7 hojas floración temprana y floración tardía. El suelo utilizado fue franco arcillosa y la tierra procedente de un riachuelo seco. En base a lo anteriormente expuesto los autores realizaron la experiencia y llegaron a las respectivas conclusiones y recomendaciones. Entre las conclusiones tenemos que el estado vegetativo que presentó mayor susceptibilidad a las diferentes dosis de glifosato fue el de 4-7 hojas.