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1.
Public Health Nutr ; 27(1): e82, 2024 Feb 08.
Artículo en Inglés | MEDLINE | ID: mdl-38326937

RESUMEN

OBJECTIVES: Consideration of future consequences (CFC) distinguishes individuals who adopt behaviours based on immediate needs and concerns from individuals who consider the future consequences of their behaviours. We aimed to assess the association between CFC and diet, and testing the mediating role of food choice motives on this relationship. DESIGN: Individuals (aged ≥ 18 years) completed the CFC-12 questionnaire in 2014, at least three 24-h dietary records, and a food choice motive questionnaire. A multiple mediator analysis allowed to assess the mediating effect of food choice motives on the cross-sectional association between CFC and diet, adjusted for socio-demographic factors. SETTING: Data from the NutriNet-Santé cohort study. PARTICIPANTS: 27 330 participants. RESULTS: CFC was associated with all food choice motives (P < 0·001), with the strongest positive associations for avoidance for environmental reasons, absence of contaminants and health motives and the strongest negative associations for innovation and convenience. Positive total effects were found between CFC and the consumption of healthy food groups (fruits and vegetables, whole-grain foods, legumes), and negative total effects for alcohol, meat and poultry and processed meat (P < 0·001). CFC was positively associated with diet quality (P < 0·001). Across food groups, major mediators of these relationships were higher health (8·4-32·6%), higher environmental (13·7-22·1 %) and lower innovation (7·3-25·1 %) concerns. CONCLUSIONS: CFC was associated with healthier dietary intake, essentially mediated by a greater motivation of future-oriented participants for self-centred and altruistic outcomes, including health and environment. Focusing on the awareness of future benefits in public health interventions might lead to healthier dietary behaviours.


Asunto(s)
Preferencias Alimentarias , Motivación , Adulto , Humanos , Estudios de Cohortes , Estudios Transversales , Dieta , Encuestas y Cuestionarios , Ingestión de Alimentos , Verduras
2.
J Clin Hypertens (Greenwich) ; 25(10): 895-904, 2023 10.
Artículo en Inglés | MEDLINE | ID: mdl-37740433

RESUMEN

Uncontrolled blood pressure (BP) and therapeutic inertia pose significant challenges in effectively managing hypertension. This study objective was to quantify levels of uncontrolled BP and therapeutic inertia among patients treated for hypertension in primary care. This retrospective cohort study used data recorded by general practitioners from the UK Clinical Practice Research Datalink database. Adults with primary hypertension who received a recorded prescription for any antihypertensive drug between January 2015 and June 2017 (index date) were included, with a follow-up of 18 months. Primary outcomes included the percentage of patients with uncontrolled BP (defined as systolic BP ≥140 mmHg or diastolic BP ≥90 mmHg) and of apparent therapeutic inertia (defined as two consecutive uncontrolled BP records without treatment change) during follow-up. Finally, of 581 260 patients receiving antihypertensive drug(s), 37.2% (n = 216 014) had uncontrolled BP at the index date and 30.3% (n = 175 955) had no record of BP at this date. During follow-up, 59.2% had ≥1 record of uncontrolled BP, in 22% all records showed uncontrolled BP, and 12.8% had no record of BP. Among those with uncontrolled BP at the index date, 72.9% had ≥1 record of uncontrolled BP during follow-up, and in 28.3% all records showed uncontrolled BP. Therapeutic inertia was observed in 33.1% of patients overall, and in 55.7% of those with uncontrolled BP at the index date. In conclusion, BP recording was infrequent, possibly reflecting both a low frequency of measurement and potential under-recording. Uncontrolled BP and therapeutic inertia appear to be widespread in UK general practice.


Asunto(s)
Medicina General , Hipertensión , Adulto , Humanos , Hipertensión/tratamiento farmacológico , Hipertensión/epidemiología , Hipertensión/inducido químicamente , Presión Sanguínea , Antihipertensivos/farmacología , Estudios Retrospectivos , Reino Unido/epidemiología
3.
Clin Pharmacol Ther ; 114(4): 795-801, 2023 10.
Artículo en Inglés | MEDLINE | ID: mdl-37441734

RESUMEN

Regulators are faced with many challenges surrounding health data usage, including privacy, fragmentation, validity, and generalizability, especially in the European Union, for which synthetic data may provide innovative solutions. Synthetic data, defined as data artificially generated rather than captured in the real world, are increasingly being used for healthcare research purposes as a proxy to real-world data (RWD). Currently, there are barriers particularly challenging in Europe, where sharing patient's data is strictly regulated, costly, and time-consuming, causing delays in evidence generation and regulatory approvals. Recent initiatives are encouraging the use of synthetic data in regulatory decision making and health technology assessment to overcome these challenges, but synthetic data have still to overcome realistic obstacles before their adoption by researchers and regulators in Europe. Thus, the emerging use of RWD and synthetic data by pharmaceutical and medical device industries calls regulatory bodies to provide a framework for proper evidence generation and informed regulatory decision making. As the provision of data becomes more ubiquitous in scientific research, so will innovations in artificial intelligence, machine learning, and generation of synthetic data, making the exploration and intricacies of this topic all the more important and timely. In this review, we discuss the potential merits and challenges of synthetic data in the context of decision making in the European regulatory environment. We explore the current uses of synthetic data and ongoing initiatives, the value of synthetic data for regulatory purposes, and realistic barriers to the adoption of synthetic data in healthcare.


Asunto(s)
Inteligencia Artificial , Evaluación de la Tecnología Biomédica , Humanos , Europa (Continente) , Unión Europea
4.
Artículo en Inglés | MEDLINE | ID: mdl-36231817

RESUMEN

Distinguishing between flexible and rigid cognitive restraint (CR) may be useful for understanding the role of CR in dietary behavior and weight status. This study aimed to translate and adapt the flexible and rigid CR scales to the French context and test their psychometric properties. Construct validity, internal consistency, and test-retest reliability were examined in a sample of 620 individuals. Confirmatory factor analysis of the scales found a two-factor structure (flexible CR: 12 items; rigid CR: 15 items) that provided a good fit and supported the initial solution (χ2 = 584.7, df = 322, CFI = 0.96, RMSEA = 0.052 [0.045, 0.059], TLI = 0.95). Higher flexible and rigid CR were associated with higher CR overall, emotional eating (TFEQ-R21) and eating disorders (SCOFF), and lower intuitive eating (IES-2). In addition, higher flexible CR was associated with lower impulsivity (BIS-11) while higher rigid CR was associated with higher uncontrolled eating (TFEQ-R21) and lower self-esteem (RSES), satisfaction with life (SWLS), and optimism (LOT-R). Flexible and rigid CR internal consistency was satisfactory (McDonald ω = 0.77 and 0.74, respectively) and test-retest reliability was good (ICC = 0.81 and 0.79, respectively). This study validated a flexible and rigid CR tool in a French population and confirmed that these two types of CR represent distinct eating behaviors.


Asunto(s)
Cognición , Conducta Alimentaria , Índice de Masa Corporal , Conducta Alimentaria/psicología , Humanos , Psicometría , Reproducibilidad de los Resultados , Encuestas y Cuestionarios
5.
Nutr J ; 19(1): 6, 2020 01 20.
Artículo en Inglés | MEDLINE | ID: mdl-31959166

RESUMEN

BACKGROUND: Dispositional optimism is a psychological trait that has been associated with positive health outcomes such as reduced risk of cardiovascular diseases. However, there is little knowledge on the relationship between optimism and dietary intake in the population. The objective of this cross-sectional study was to assess whether optimism was associated with overall diet quality, food group consumption and snacking. METHODS: In 2016, 32,806 adult participants from the NutriNet-Santé study completed the Life-Orientation Test Revised (LOT-R) which assesses dispositional optimism. Overall diet quality (assessed by the mPNNS-Guideline Score) and consumption of 22 food groups were evaluated using at least three self-reported 24-h dietary records. Snacking behavior was evaluated by an ad-hoc question. Logistic and linear regressions were used to analyze the associations between optimism and these dietary behaviors, taking into account socio-demographic, lifestyle and depressive symptomatology characteristics. RESULTS: Optimism was associated with greater overall diet quality (ß (95% CI) = 0.07 (0.004-0.11), P < 0.0001) and higher consumption of fruit and vegetables, seafood, whole grains, fats, dairy and meat substitutes, legumes, non-salted oleaginous fruits, and negatively associated with consumption of meat and poultry, dairy products, milk-based desserts, sugar and confectionery. In addition, optimism was associated with less snacking (OR (95% CI) = 0.89 (0.84, 0.95)). In contrast, optimism was associated with higher consumption of alcoholic beverage (ß (95% CI) = 5.71 (2.54-8.88), P = 0.0004) and appetizers (OR (95% CI) = 1.09 (1.04, 1.14)). Finally, no association was observed between optimism and energy intake. CONCLUSIONS: Optimism was associated with better overall diet quality and less snacking. It was also associated with consumption of healthy food groups as well as unhealthy food groups typically consumed in social eating occasions. These findings suggest that optimism could be taken into account in the promotion of a healthy eating behavior.


Asunto(s)
Dieta/métodos , Dieta/psicología , Conducta Alimentaria/psicología , Calidad de los Alimentos , Optimismo/psicología , Bocadillos/psicología , Estudios Transversales , Encuestas sobre Dietas/métodos , Encuestas sobre Dietas/estadística & datos numéricos , Femenino , Francia , Humanos , Masculino , Persona de Mediana Edad
6.
Clin Podiatr Med Surg ; 37(1): 125-150, 2020 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-31735264

RESUMEN

The article discusses the nuances required to effectively perform the biomechanical examination in children and assess the findings. The author covers several factors in children that make the examination different in certain respects than in that of adults, including growth, osseous maturation, gait development, and interpretation of symptoms as conveyed by the child. Further delineation is made for prewalkers, foot-flat to foot-flat walkers, and heel-to-toe walkers. Segmental review of the lower extremity is covered by age bracket, with clinical pearls inserted where relevant to assist the clinician. A brief discussion of shoe wear and orthoses is made as well.


Asunto(s)
Deformidades del Pie/terapia , Adolescente , Factores de Edad , Fenómenos Biomecánicos , Niño , Preescolar , Deformidades del Pie/diagnóstico , Deformidades del Pie/fisiopatología , Marcha , Humanos , Lactante , Aparatos Ortopédicos , Selección de Paciente , Examen Físico , Zapatos
7.
Nutrients ; 11(10)2019 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-31618887

RESUMEN

Organic food consumption has risen in many countries during the past decades, but individual motives leading to these choices remain unclear. This study aimed to evaluate the associations between cognitive restraint (CR), history of dieting and organic food intake. This cross-sectional analysis included 20,085 organic food consumers from the NutriNet-Santé cohort. CR (range score 1-4) was evaluated by the Three-Factor-Eating-Questionnaire and practice of dieting (never vs. past/current) was assessed by an ad hoc questionnaire. Frequencies of organic food intake overall and in 16 food groups were assessed by the Organic Food Frequency Questionnaire. Linear regression and analysis of covariance (ANCOVA) were performed to investigate the association between CR score, history of dieting and contribution of organic food intake to the total food intake. A lower overall contribution of organic options in the diet was observed in women with higher levels of CR (ß = -3.61%, 95% CI: -4.32; -2.91 for 1 point of CR, p < 0.001) and with a history of dieting (31.1 ± 0.4% in past/current vs. 32.6 ± 0.3% in never dieters; p = 0.001). Consistent associations were observed in men with a history of dieting (26.4 ± 0.8% in past/current vs. 28.7 ± 0.4% in never dieters; p = 0.012). Overall, individuals-in particular women-with higher CR scores or with a history of dieting selected fewer organic food options. Our findings illustrate the complexity of potentially concurrent motives to food choices, in a context of increasing interest in organic food consumption.


Asunto(s)
Restricción Calórica , Conducta de Elección , Cognición , Comportamiento del Consumidor , Dieta Saludable , Dieta Reductora , Conducta Alimentaria , Alimentos Orgánicos , Adulto , Anciano , Índice de Masa Corporal , Estudios Transversales , Femenino , Francia , Humanos , Masculino , Persona de Mediana Edad , Motivación , Factores Sexuales , Encuestas y Cuestionarios , Pérdida de Peso
8.
Am J Clin Nutr ; 109(1): 117-126, 2019 01 01.
Artículo en Inglés | MEDLINE | ID: mdl-30596882

RESUMEN

Background: Impulsivity is a psychological trait linked to health issues such as obesity. However, few studies have explored the relation between impulsivity, dietary intake, and eating disorders (EDs) in a general population. Objective: The aim of this cross-sectional study was to assess whether impulsivity was associated with energy intake, food-group consumption, snacking, and risk of EDs. Design: In 2014, 51,368 adult participants from the NutriNet-Santé Study completed the 11th version of the Barratt Impulsiveness Scale (BIS-11), which assesses impulsivity. Food-group consumption and diet quality were evaluated by using ≥3 self-reported 24-h dietary records (n = 35,830), whereas snacking behavior was evaluated by an ad hoc question (n = 48,562). Risk of EDs was assessed with the Sick-Control-One-Fat-Food Questionnaire (SCOFF), and categories of ED (restrictive, bulimic, hyperphagic, and other types of EDs) were determined with the Expali algorithm (n = 48,824). Logistic and linear regressions were used to analyze the associations between impulsivity and energy intake, food-group consumption, diet quality, snacking, and risk of EDs, taking into account sociodemographic and lifestyle factors. Results: Positive associations were found between impulsivity and consumption of alcoholic beverages and appetizers, whereas negative associations were found for fruit and vegetables, meat and poultry, processed meat, dairy products, milk-based desserts, and starchy foods. Impulsivity was positively associated with energy intake and negatively associated with diet quality. Impulsivity was also positively associated with snacking (OR: 3.32; 95% CI: 2.99, 3.68) and risk of EDs (OR: 3.02; 95% CI: 2.74, 3.33). The strongest associations were found for bulimic disorders (OR: 4.38; 95% CI: 3.66, 5.23) and hyperphagic disorders (OR: 2.91; 95% CI: 2.56, 3.31). Conclusion: Impulsivity was associated with food intakes, snacking, and risk of EDs and could be taken into account in the promotion of healthy eating behavior. This study was registered at clinicaltrials.gov as NCT03335644.


Asunto(s)
Ingestión de Alimentos/psicología , Trastornos de Alimentación y de la Ingestión de Alimentos/psicología , Conducta Impulsiva/fisiología , Bocadillos/psicología , Adulto , Anciano , Bebidas Alcohólicas , Estudios Transversales , Dieta , Registros de Dieta , Dieta Saludable , Ingestión de Energía , Conducta Alimentaria , Trastornos de Alimentación y de la Ingestión de Alimentos/epidemiología , Femenino , Preferencias Alimentarias/psicología , Francia/epidemiología , Frutas , Conductas Relacionadas con la Salud , Humanos , Estilo de Vida , Masculino , Persona de Mediana Edad , Encuestas y Cuestionarios , Verduras
9.
Int J Behav Nutr Phys Act ; 15(1): 84, 2018 09 06.
Artículo en Inglés | MEDLINE | ID: mdl-30189878

RESUMEN

BACKGROUND: Emotional eating (EmE) is characterized by an over consumption of food in response to negative emotions and is associated with an increased weight status. Consideration of Future Consequences (CFC) or a low level of impulsivity could influence the association between EmE and weight status. The objective was to analyze the moderating influence of CFC and impulsivity on the relationship between EmE and BMI. METHODS: A total of 9974 men and 39,797 women from the NutriNet-Santé cohort study completed the revised 21-item Three-Factor Eating Questionnaire to assess their EmE, the CFC questionnaire (CFC-12) to assess their level of time perspective, and the Barratt Impulsiveness Scale (BIS-11) to assess their impulsivity. Weight and height were self-reported each year over a median follow-up of 5.3 years. The associations between EmE and repeated measures of BMI were estimated by multiple linear mixed-effects regression models stratified by gender, tertiles of the CFC, or tertiles of the BIS-11, taking into account sociodemographic and lifestyle factors. RESULTS: Overall, EmE was positively associated with BMI. CFC and impulsivity did not moderate the effect of EmE on changes of BMI per year, but quantitatively moderated the effect of EmE on overall BMI. In women, the strength of the association between EmE and weight status increased with CFC level. Difference of BMI slopes between a low and a high level of CFC was - 0.43 kg/m2 (95% CI: -0.55, - 0.30) (p < .0001). In addition, the strength of the association between emotional eating and weight status increased with impulsivity level. Difference of BMI slopes between a low and a high level of impulsivity was + 0.37 kg/m2 (95% CI: 0.24, 0.51) (p < .0001). In men, only individuals with a low CFC presented a stronger association of EmE with BMI. CONCLUSIONS: Impulsivity and consideration of future consequences moderated the association between emotional eating and body weight status. This study emphasizes the importance of taking into account psychological traits in obesity prevention.


Asunto(s)
Índice de Masa Corporal , Peso Corporal , Ingestión de Alimentos/psicología , Emociones , Conducta Alimentaria/psicología , Conducta Impulsiva , Obesidad/psicología , Adulto , Anciano , Estudios de Cohortes , Femenino , Humanos , Estilo de Vida , Masculino , Persona de Mediana Edad , Autoinforme , Encuestas y Cuestionarios , Aumento de Peso
10.
Nutr J ; 17(1): 1, 2018 01 05.
Artículo en Inglés | MEDLINE | ID: mdl-29304811

RESUMEN

BACKGROUND: Organic food intake has risen in many countries during the past decades. Even though motivations associated with such choice have been studied, psychological traits preceding these motivations have rarely been explored. Consideration of future consequences (CFC) represents the extent to which individuals consider future versus immediate consequences of their current behaviors. Consequently, a future oriented personality may be an important characteristic of organic food consumers. The objective was to analyze the association between CFC and organic food consumption in a large sample of the adult general population. METHODS: In 2014, a sample of 27,634 participants from the NutriNet-Santé cohort study completed the CFC questionnaire and an Organic-Food Frequency questionnaire. For each food group (17 groups), non-organic food consumers were compared to organic food consumers across quartiles of the CFC using multiple logistic regressions. Moreover, adjusted means of proportions of organic food intakes out of total food intakes were compared between quartiles of the CFC. Analyses were adjusted for socio-demographic, lifestyle and dietary characteristics. RESULTS: Participants with higher CFC were more likely to consume organic food (OR quartile 4 (Q4) vs. Q1 = 1.88, 95% CI: 1.62, 2.20). Overall, future oriented participants were more likely to consume 14 food groups. The strongest associations were observed for starchy refined foods (OR = 1.78, 95% CI: 1.63, 1.94), and fruits and vegetables (OR = 1.74, 95% CI: 1.58, 1.92). The contribution of organic food intake out of total food intake was 33% higher in the Q4 compared to Q1. More precisely, the contribution of organic food consumed was higher in the Q4 for 16 food groups. The highest relative differences between Q4 and Q1 were observed for starchy refined foods (22%) and non-alcoholic beverages (21%). Seafood was the only food group without a significant difference. CONCLUSIONS: This study provides information on the personality of organic food consumers in a large sample of adult participants. Consideration of future consequences could represent a significant psychological determinant of organic food consumption.


Asunto(s)
Conducta de Elección , Dieta/estadística & datos numéricos , Conducta Alimentaria/psicología , Alimentos Orgánicos/estadística & datos numéricos , Conocimientos, Actitudes y Práctica en Salud , Personalidad , Estudios de Cohortes , Femenino , Preferencias Alimentarias , Francia , Humanos , Masculino , Persona de Mediana Edad , Estudios Prospectivos , Encuestas y Cuestionarios , Tiempo
11.
Nutrients ; 9(3)2017 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-28257032

RESUMEN

The objective of this study is to examine the association between impulsivity and weight status in a large sample of the adult general population in France, and the influence of gender on this relationship. A total of 11,929 men and 39,114 women participating in the NutriNet-Santé cohort were selected in this cross-sectional analysis. The Barratt Impulsiveness Scale (BIS-11) was used to assess impulsivity. Weight and height were self-reported. The association between impulsivity and BMI was estimated using logistic regressions adjusted for socio-demographic and lifestyle factors. Individuals with high impulsivity levels (BIS-11 total score >71) were more likely to be obese (Odds Ratio (OR) = 1.80, 95% Confidence Interval (CI): 1.39, 2.33 in men; OR = 1.30, 95% CI: 1.15, 1.48 in women) compared to individuals in the average range of impulsivity. The strongest associations between impulsivity and obesity were observed in men, where highly impulsive participants were more likely to be class III obese (BMI > 40 kg/m²) (OR = 3.57, 95% CI: 1.86, 6.85). This large sample analysis supports the existence of a relationship between impulsivity and weight status and the importance of psychological factors in the prevention of obesity.


Asunto(s)
Dieta/efectos adversos , Conducta Impulsiva , Estado Nutricional , Obesidad Mórbida/etiología , Obesidad/etiología , Sobrepeso/etiología , Delgadez/etiología , Adulto , Índice de Masa Corporal , Estudios de Cohortes , Factores de Confusión Epidemiológicos , Estudios Transversales , Dieta/etnología , Dieta/psicología , Femenino , Estudios de Seguimiento , Francia/epidemiología , Transición de la Salud , Humanos , Internet , Masculino , Estado Nutricional/etnología , Obesidad/epidemiología , Obesidad/etnología , Obesidad/psicología , Obesidad Mórbida/epidemiología , Obesidad Mórbida/etnología , Obesidad Mórbida/psicología , Sobrepeso/epidemiología , Sobrepeso/etnología , Sobrepeso/psicología , Estudios Prospectivos , Escalas de Valoración Psiquiátrica , Autoinforme , Factores Sexuales , Delgadez/epidemiología , Delgadez/etnología , Delgadez/psicología
12.
Prev Med Rep ; 8: 190-196, 2017 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-29881668

RESUMEN

Well-being is often mentioned as an important motive for organic food consumption. Little is known about the relationship between organic food consumption and life satisfaction (a component of well-being). The aim of this study was to investigate the cross-sectional relationship between organic food consumption and life satisfaction. A total of 17,446 volunteers aged 45 or above, from the NutriNet-Santé cohort filled in an organic food semi-quantitative frequency questionnaire and completed the French validated satisfaction with life scale (range score 5-35). Adjusted means (95% confidence intervals) of the satisfaction with life score across quintiles of contribution of organic food to the diet (total and by food group) were estimated using ANCOVA models. In multivariable model, life satisfaction among lowest and highest consumers of organic food reached 24.98 (95%CI: 24.78-25.17) and 25.52 (95%CI: 25.33-25.71) respectively (P trend < 0.0001). Life satisfaction was slightly and positively associated with higher contribution of organic food to the diet (overall and in most food groups). Our findings suggest that high organic food consumption may play a role in life satisfaction of participants over 45 years old through hedonist or eudemonic approaches.

13.
Stud Health Technol Inform ; 210: 364-8, 2015.
Artículo en Inglés | MEDLINE | ID: mdl-25991167

RESUMEN

Diagnostic imaging requisition (DIR) content is legally constrained for care quality and patient safety concerns. A French national indicator, based on administrative and clinical data, has been introduced to monitor nationwide the conformity of such documents (CDIR). The purpose of this study was to assess the effect on CDIR of the deployment of the ORBIS™ electronic medical record at the Tenon hospital (Paris, France). A before-after study has been carried out. A significant increase of CDIR, from 37.0% (n=676) to 49.1% (n=800), was observed (p < 10⁻5). Conformity of administrative criteria improved, but there was no statistical difference of clinical criteria conformity, despite the improvement of clinical history documentation (100%). Up to five different paper-based requisition forms were used by clinical departments in the before period. In the after period, only 27.1% of requisitions were ORBIS-edited with a CDIR of 66.8% (n=217). In both periods, CDIR was correlated to the level of standardization of the forms.


Asunto(s)
Exactitud de los Datos , Diagnóstico por Imagen/estadística & datos numéricos , Registros Electrónicos de Salud/estadística & datos numéricos , Control de Formularios y Registros/estadística & datos numéricos , Mejoramiento de la Calidad/estadística & datos numéricos , Diagnóstico por Imagen/normas , Registros Electrónicos de Salud/normas , Control de Formularios y Registros/normas , Francia , Humanos , Reproducibilidad de los Resultados , Sensibilidad y Especificidad
15.
J Phys Chem A ; 114(46): 12291-8, 2010 Nov 25.
Artículo en Inglés | MEDLINE | ID: mdl-21028769

RESUMEN

Isotropic deviations to the standard Heisenberg Hamiltonian have been extracted for a series of trinuclear extended metal atom chain complexes, namely, [Ni(3)(dpa)(4)Cl(2)], and the hypothetical [NiPdNi(dpa)(4)Cl(2)] and [Pd(3)(dpa)(4)Cl(2)], following a scheme recently proposed by Labéguerie and co-workers (J. Chem. Phys 2008, 129, 154110) within the density functional theory framework. Energy calculations of broken symmetry monodeterminantal solutions of intermediate M(s,tot.) values can provide an estimate of the magnitude of the biquadratic exchange interaction (λ) that accounts for these deviations in systems with S = 1 magnetic sites. With the B3LYP functional, we obtain λ = 1.37, 13.8, and 498 cm(-1) for the three molecules, respectively, meaning that a simple Heisenberg Hamiltonian is enough for describing the magnetic behavior of the Ni(3) complex but definitely not for Pd(3). In the latter case, the origin of such extreme deviation arises from (i) an energetically affordable local non-Hund state (small intrasite exchange integral, K ∼ 1960 cm(-1)) and (ii) a very effective overlap between Pd-4d orbitals and a large J. Furthermore, this procedure enables us to determine the relative weights of the two types of magnetic interactions, σ- and δ-like, that contribute to the total magnetic exchange (J = J(σ) + J(δ)). In all of the systems, J is governed by the σ interaction by 95-98%.

17.
J Phys Chem A ; 113(32): 9075-9, 2009 Aug 13.
Artículo en Inglés | MEDLINE | ID: mdl-19610660

RESUMEN

The dynamical behavior of the [Mo12O12S12(OH)12{O2C-(CH2)N-CO2}]2- complexes is analyzed via first-principles molecular dynamics simulations. Experimental X-ray data play the role of initial configurations for our search in the configuration space. We show that different stable and metastable conformers are possible, and these are thermally accessible at relatively low temperatures. This is the main outcome of our first-principles molecular dynamics approach in which the temperature allowing for thermal activation has been set to T = 500 K, which is consistent with the variable temperature 1H NMR spectra of these complexes in solution taken at comparable, although moderately lower, temperature. This implies that a relatively large manifold of folding configurations is available to the encapsulated guest species. Moreover, the high flexibility of both the host cage and the inserted guests allows for the accommodation of a rather wide variety of functional groups with potential applications in several fields.


Asunto(s)
Ácidos Dicarboxílicos/química , Conformación Molecular , Modelos Moleculares , Teoría Cuántica , Termodinámica
18.
Inorg Chem ; 48(14): 6852-9, 2009 Jul 20.
Artículo en Inglés | MEDLINE | ID: mdl-19534511

RESUMEN

Variable temperature (1)H NMR studies of the host-guest complex [Mo(16)O(16)S(16)(OH)(16)(H(2)O)(4)(PDA)(2)](4-) (1 ; PDA(2-) = phenylenediacetate) previously carried out in D(2)O have revealed a complex behavior in solution, involving a gliding motion of both parallel phenyl rings of the PDA(2-) ligands. In the present work, we present new NMR spectra carried out in the aprotic solvent CD(3)CN, which allow the observation of the proton signals associated with the bridging hydroxo groups of the inorganic host. The new spectra provide detailed information about the concerted reorganization of the guest components, that is, PDA(2-) and water molecules. The existence of an equilibrium between two distinct isomers differing in the linking mode between the inorganic host and the two equivalent PDA(2-) ligands is evidenced. This equilibrium appears strongly dependent upon the temperature, leading to a complete inversion of the distribution between 300 and 226 K. The thermodynamic data related to the isomerization reaction have been determined (Delta(r)H = -50.5 kJ mol(-1) and Delta(r)S = -215 J mol(-1) K(-1)). Furthermore, at low temperature, one of the isomers exists in two conformations, only differing in the H-bond network involving the inner water molecules. Density functional theory calculations were carried out to push ahead the interpretations obtained from experiment, identify the isomers of 1, and specify the role and the positions of the guest water molecules. Among the various structures that have been calculated for 1, three fall in a narrow energy range and should correspond to the species characterized by variable-temperature (1)H NMR experiments in CD(3)CN. Finally, this study shows how the internal disposition of the ligands affects the ellipticity of the Mo(16) ring which varies from one isomer to the other in the 0.73-1 range and highlights solvation of the ring as one of the key parameters for the conformational design of these flexible host-guest systems.

19.
Dalton Trans ; (34): 4565-74, 2008 Sep 14.
Artículo en Inglés | MEDLINE | ID: mdl-19024355

RESUMEN

The complexes [Mo12O12S12(OH)12(Muco)]2- (Muco2- = muconate, C6H4O4(2-)) and [Mo12,O12S12(OH)12(TMT)]2 (TMT2- = tetramethylterephthalate, C12H12O4(2-)) have been obtained from the condensation of the [Mo2O2S2]2+ building block in the presence of Muco2- and TMT2-, respectively. Both compounds were structurally characterized, revealing host-guest architectures with one or two encapsulated water molecules. 1H NMR spectra in DMSO and D2O showed that both complexes had an average symmetry higher than that in the solid state, due to changes in the distribution of encapsulated water molecules. The relative stabilities in water of the seven complexes encapsulating various di- or tricarboxylate guests, either rigid or non-rigid, have been determined. The stability scale obtained for the dianionic complexes is interpreted in relation with the rigidity or flexibility of the guests. A DFT study demonstrates that additional stabilization arises from the presence of inner hydrogen bonds involving 1, 2 or 3 water molecules, which even permit the extension of the H-bonds network to the first solvation sphere of the anion. DFT calculations were carried out on all investigated complexes as isolated or solvated anions and provide the sequence of the bond energies between the host and the guests, which is compared to the experimental data.

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