Choosing between Ti(II) and Ti(III): selective reduction of titanocene dichloride by elemental lanthanides.

The reduction of titanocene dichloride Cp2TiCl2 with lanthanide metals has led to the discovery of a surprising lanthanide effect: while with most lanthanides, a divalent [Cp2Ti] equivalent was obtained, the use of samarium or ytterbium only led to the reduction to trivalent [Cp2TiCl]-type complexes, including the structurally characterized heterobimetallic complex [Cp2Ti(µ-Cl)2SmCl2(THF)3]. These results were corroborated by reactivity studies (alkyne coupling and radical reactions), EPR spectroscopy and electrospray mass spectrometry, providing new insights into the reduction chemistry of lanthanide metals.

Effects of dual tasking on postural and gait performances in children with cerebral palsy and healthy children.

Simultaneous execution of motor and cognitive tasks is embedded in the daily life of children. 53 children of 7-12 years and 22 adults (study 1), 20 healthy children and 20 children of 7-12 years with cerebral palsy (study 2) performed a Stroop-animal task simultaneously with a standing or a walking task in order to determine the attentional demand of postural control and locomotion. Dual-task cost decreased with advancing age in healthy children during balance. CP and healthy children were similarly affected by dual-task constraints during standing and walking. Children with diplegia were more affected by the DT during the postural task than children with hemiplegia. We found that adults could benefit from dual-tasking for standing. The integrated model of task prioritization might explain our results regarding postural reserve of each population.

Study of Iron Piperazine-Based Chelators as Potential Siderophore Mimetics.

Gram-negative bacteria's resistance such as Pseudomonas aeruginosa and the Burkholderia group to conventional antibiotics leads to therapeutic failure. Use of siderophores as Trojan horses to internalize antibacterial agents or toxic metals within bacteria is a promising strategy to overcome resistance phenomenon. To combat the Pseudomonas sp, we have synthesized and studied two piperazine-based siderophore mimetics carrying either catecholate moieties (1) or hydroxypyridinone groups (2) as iron chelators. These siderophore-like molecules were prepared in no more than four steps with good global yields. The physicochemical study has highlighted a strong iron affinity since their pFe values were higher than 20. 1 possesses even a pFe value superior than those of pyoverdine, the P. aeruginosa endogenous siderophore, suggesting its potential ability to compete with it. At physiological pH, 1 forms mainly a 2:3 complex with iron, whereas two species are observed for 2. Unfortunately, the corresponding Ga(III)-1 and 2 complexes showed no antibacterial activity against P. aeruginosa DSM 1117 strain. The evaluation of their siderophore-like activity showed that 1 and 2 could be internalized by the bacteria.

Attentional load of walking in children aged 7-12 and in adults.

The amount of attentional resources necessary to walk in children, and how they evolve during childhood remains unclear. This study examined children's gait parameters in different dual-task conditions. 53 children, divided into two age groups (7-9 and 10-12 years old), and 18 adults walked on a mat in three different cognitive conditions: watching a video (video condition), listening its soundtrack (audio condition), and without any additional task (control condition). Questions were asked at the end of the video and audio conditions to make sure that participants were paying attention to the stimuli. A GAITRite® system was used for recording the gait data. Results showed an increase of velocity and step duration, and a decrease of cadence and percentage of double limb support duration from 7 years of age to adulthood during dual-task walking compared with single-task walking. This improvement seemed to be linear from 7 years to adults' age. The interference of dual-task on gait was larger for the video than for the auditory task and decreased with age. We concluded that walking requires a significant amount of attentional resources in children and that children rely more than adults on visual processes for walking.

Effects of emotional videos on postural control in children.

The link between emotions and postural control has been rather unexplored in children. The objective of the present study was to establish whether the projection of pleasant and unpleasant videos with similar arousal would lead to specific postural responses such as postural freezing, aversive or appetitive behaviours as a function of age. We hypothesized that postural sway would similarly increase with the viewing of high arousal videos in children and adults, whatever the emotional context. 40 children participated in the study and were divided into two groups of age: group 7-9 years (n=23; mean age=8 years ± 0.7) and group 10-12 years (n=17; mean age=11 years ± 0.7). 19 adults (mean age=25.8 years ± 4.4) also took part in the experiment. They viewed emotional videos while standing still on a force platform. Centre of foot pressure (CoP) displacements were analysed. Antero-posterior, medio-lateral mean speed and sway path length increased similarly with the viewing of high arousal movies in the younger, older children, and adults. Our findings suggest that the development of postural control is not influenced by the maturation of the emotional processing.

Interference between oculomotor and postural tasks in 7-8-year-old children and adults.

Several studies in adults having observed the effect of eye movements on postural control provided contradictory results. In the present study, we explored the effect of various oculomotor tasks on postural control and the effect of different postural tasks on eye movements in eleven children (7.8 ± 0.5 years) and nine adults (30.4 ± 6.3 years). To vary the difficulty of the oculomotor task, three conditions were tested: fixation, prosaccades (reactive saccades made toward the target) and antisaccades (voluntary saccades made in the direction opposite to the visual target). To vary the difficulty of postural control, two postural tasks were tested: Standard Romberg (SR) and Tandem Romberg (TR). Postural difficulty did not affect oculomotor behavior, except by lengthening adults' latencies in the prosaccade task. For both groups, postural control was altered in the antisaccade task as compared to fixation and prosaccade tasks. Moreover, a ceiling effect was found in the more complex postural task. This study highlighted a cortical interference between oculomotor and postural control systems.

Thermodynamic stability and kinetic inertness of a Gd-DTPA bisamide complex grafted onto gold nanoparticles.

Gold nanoparticles coated by gadolinium (III) chelates (Au@DTDTPA) where DTDTPA is a dithiolated bisamide derivative of diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA), constituted contrast agents for both X-ray computed tomography and magnetic resonance imaging. In an MRI context, highly stable Gd(3+) complexes are needed for in vivo applications. Thus, knowledge of the thermodynamic stability and kinetic inertness of these chelates, when grafted onto gold nanoparticles, is crucial since bisamide DTPA chelates are usually less suited for Gd(3+) coordination than DTPA. Therefore, these parameters were evaluated by means of potentiometric titrations and relaxivity measurements. The results showed that, when the chelates were grafted onto the nanoparticle, not only their thermodynamic stability but also their kinetic inertness were improved. These positive effects were correlated to the chelate packing at the nanoparticle surface that stabilized the corresponding Gd(3+) complexes and greatly enhanced their kinetic inertness.

A benzimidazole functionalised DO3A chelator showing pH switchable coordination modes with lanthanide ions.

The synthesis of a new macrocyclic chelator incorporating a benzimidazole heterocycle is reported. Lanthanide complexes with macrocyclic chelators based on 1,4,7,10-tetra(carboxymethyl)-1,4,7,10-tetraazacyclododecane (DOTA) and 1,4,7-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecane (DO3A) are of interest in luminescent, radiopharmaceutical and magnetic resonance (MR) biomedical imaging applications. The benzimidazole DO3A chelator allows for sensitisation of europium(iii), terbium(iii) and ytterbium(iii) luminescence by the heterocycle and also shows a pH dependent coordination change due to protonation of the chelator (pKa = 4.1 for the europium(iii) complex). The thermodynamic stability of the complexes has been investigated by potentiometric titration with the gadolinium(iii) complex showing significantly higher stability than the zinc(ii) complex, where log ßZnLH = 28.1 and log ßGdLH = 32.1.

Tetraphosphonated thiophene ligand: mixing the soft and the hard.

The synthesis of ligand L(T)H8, based on a thiophene framework containing two bis(aminomethyldiphosphonate) functions in the ortho position to the central sulfur atom, is described, together with the characterization of the intermediate compounds. The physico-chemical properties of the ligand were first studied by means of potentiometry and UV-Vis absorption spectrophotometric titrations to determine its pK values. Six successive equilibrium constants were determined in aqueous solutions. The same means were then used to quantify the interactions of the ligand with Ni(II), Cu(II) and Zn(II). Following the conventional Irving-Williams trend, L(T) was shown to have the highest affinity towards Cu(II) (log K(CuL(T)) = 16.11(3)), while Zn(II) and Ni(II) showed similar values (log K(ML(T)) = 10.81(8) and 10.9(1), respectively), revealing a large selectivity of L(T) toward Cu(II). Based on a combination of UV-Vis absorption spectroscopy and EPR measurements as a function of pH, along with DFT calculations, the coordination behavior of the hard phosphonate, medium amino and soft thiophene entities are questioned regarding their coordination to the Cu atom.

The effects of clothes on independent walking in toddlers.

The spatiotemporal features of walking in toddlers are known to be related to the level of maturation of the central nervous system. However, previous studies did not assess whether there could be an effect of clothes on the acquisition of walking. In this study, it was hypothesized that clothes modify the toddlers' walking. To test this hypothesis, 22 healthy toddlers divided into 3 groups of walking experience were assessed in four clothing conditions (Diaper+Trousers; Diaper+Pants of tracksuit; Diaper; Underwear). Results revealed significant effects of clothing on velocity and step length of toddlers from 6 to 18 months of walking experience. These results suggested that biomechanical constraints induced by the textile features alter the walking of toddlers. Therefore, in studies of toddler's gait, the clothing worn should be carefully mentioned and controlled.

Modifications of mesenteric adipose tissue during moderate experimental colitis in mice.

AIMS: Adipose tissue secretes various proteins referred to as adipokines, being involved in inflammation. It was recognized that mesenteric adipose tissue (MAT) is altered by inflammation, and pathologies such as inflammatory bowel disease (IBD). The aim of this study was to investigate the alterations of the mesenteric adipose tissue in two experimental colitis models in mice adapted to obtain moderate colonic inflammation. MAIN METHODS: Colonic inflammation was obtained using two models, either DSS dissolved in drinking water or intra-colonic instillation of DNBS. The expression of adipokines (leptin and adiponectin) and inflammatory markers (IL-6, MCP-1, F4/80) was studied by qRT-PCR in the MAT of treated and control mice. KEY FINDINGS: Observations of the colon and IL-6 plasma level determination demonstrated that DNBS treatment led to stronger inflammation. Colitis induced a decrease of mRNA encoding to leptin and adiponectin in MAT. In contrast, colonic inflammation led to an increase of mRNA encoding to IL-6, MCP-1 and F4/80, a specific marker of macrophages. SIGNIFICANCE: The mesenteric adipose tissue, in two models of moderate colitis, shows a loss of adipose profile and a strong increase of inflammatory pattern, close to the observations made in MAT of IBD patients. These data suggest that these pro-inflammatory modifications of MAT have to be taken into account in the pathophysiology of IBD.

Faecalibacterium prausnitzii supernatant improves intestinal barrier function in mice DSS colitis.

OBJECTIVE. The intestinal microbiota plays a substantial role in the pathogenesis of inflammatory bowel disease (IBD). Faecalibacterium prausnitzii (FP) is underrepresented in IBD patients and have been suggested to have anti-inflammatory effects in mice. Increased intestinal permeability is common in IBD but the relationship between FP and intestinal barrier function has not been investigated. Our aim was to study treatment with FP supernatant on intestinal barrier function in a dextran sodium sulfate (DSS) colitis mice model. MATERIAL AND METHODS. C57BL/6 mice received 3% DSS in tap water ad libitum during five days to induce colitis. From day 3 the mice received a daily gavage with FP supernatant or broth during seven days. Ileum and colon were mounted in Ussing chambers for permeability studies with (51)Cr-EDTA and Escherichia coli K-12. Colon was saved for Western blot analyses of tight junction proteins. RESULTS. DSS-treated mice showed significant weight loss and colon shortening. Gavage with FP supernatant resulted in a quicker recovery after DSS treatment and less extensive colonic shortening. Ileal mucosa of DSS mice showed a significant increase in (51)Cr-EDTA-passage compared to controls. (51)Cr-EDTA passage was significantly decreased in mice receiving FP supernatant. No significant differences were observed in passage of E. coli K12. Western blots showed a trend to increased claudin-1 and claudin-2 expressions in DSS mice. CONCLUSIONS. Supernatant of FP enhances the intestinal barrier function by affecting paracellular permeability, and may thereby attenuate the severity of DSS-induced colitis in mice. These findings suggest a potential role of FP in the treatment of IBD.

A modified cyclen azaxanthone ligand as a new fluorescent probe for Zn2+.

A new cyclen derivative L, bearing a methyl-chromeno-pyridinylidene hydrazone moiety, was synthesized and studied in MeOH, as potential fluorescent "OFF-on-ON" sensors for Zn(ii). Photophysical properties of this ligand being PET regulated, L was only weakly emissive in the absence of metal ions (OFF). L fluorescence was increased modestly upon addition of one equivalent of Zn(II), and further increased upon addition of a second equivalent. Therefore, Zn : L behaved as a highly sensitive ON sensor for zinc. This efficiency was correlated to Zn(II) coordination via the hydrazone moiety of the fluorophore, producing an efficient CHelation-Enhanced Fluorescence (CHEF) effect. A complementary theoretical study carried out with DFT calculations further elucidated the optical properties.

Differing effects of prosaccades and antisaccades on postural stability.

The goal of the study was to examine the effect of different types of eye movements on postural stability. Ten healthy young adults (25 ± 3 years) participated in the study. Postural control was measured by the TechnoConcept© platform and recorded in Standard Romberg and Tandem Romberg conditions while participants performed five oculomotor tasks: two fixation tasks (central fixation cross, without and with distractors), two prosaccade tasks toward peripheral targets displayed 4° to the left or to the right of the fixation cross (reactive saccades induced by a gap 0 ms paradigm and voluntary saccades induced by an overlap 600 ms paradigm) and one antisaccade task (voluntary saccade made in the opposite direction of the visual target). The surface, the length, and the mean speed of the center of pressure were analyzed. We found that saccadic eye movements improved postural stability with respect to the fixation tasks. Furthermore, antisaccades were found to decrease postural stability compared to prosaccades (reactive as well as voluntary saccades). This result is in line with the U-shaped nonlinear model described by Lacour et al. (Neurophysiol Clin 38:411-421, 2008), showing that a secondary task performed during a postural task could increase (prosaccade task) or decrease (antisacade task) postural stability depending on its complexity. We suggest that the different degree of attentional resources needed for performing prosaccade or antisaccade tasks are, most likely, responsible for the different effect on postural control.

Origins of balance disorders during a daily living movement in obese: can biomechanical factors explain everything?

Obese people suffer from postural deficits and are more subject to falls than their lean counterpart. To improve prevention and post-fall rehabilitation programs, it seems important to better understand the posturo-kinetic disorders in daily life situations by determining the contribution of some key factors, mainly morphological characteristics and physical activity level, in the apparition of these disorders. Twelve severe android obese and eight healthy non obese adults performed a reaching task mobilizing the whole body. To further determine the origin of the postural and motor behavior differences, non obese individuals also performed an experimental session with additional constraints which simulated some of the obese morphological characteristics. Impact of the sedentary lifestyle was also studied by dissociation of the obese in two subgroups: physically « active ¼ and physically « inactive ¼. Movement kinetics and kinematics were characterized with an optoelectronic system synchronized to a force platform. The mechanical equilibrium pattern was evaluated through the displacements of the Centre of Mass (CoM) and the centre of foot pressure within the Base of Support (BoS). Results showed that obesity decreased movement speed (≈-23%, p<0.01), strongly increased CoM displacement (≈+30%, p<0.05) and induced an important spatio-temporal desynchronization (≈+40%, p<0.05) of the focal and postural components of the movement during the transition between the descending and ascending movements. The role of some morphological characteristics and of physical activity on obese patients' postural control disorder is discussed and set back in the more general context of overall factors contributing to postural deficits with obesity.

A top-down synthesis route to ultrasmall multifunctional Gd-based silica nanoparticles for theranostic applications.

New, ultrasmall nanoparticles with sizes below 5 nm have been obtained. These small rigid platforms (SRP) are composed of a polysiloxane matrix with DOTAGA (1,4,7,10-tetraazacyclododecane-1-glutaric anhydride-4,7,10-triacetic acid)-Gd(3+) chelates on their surface. They have been synthesised by an original top-down process: 1) formation of a gadolinium oxide Gd2O3 core, 2) encapsulation in a polysiloxane shell grafted with DOTAGA ligands, 3) dissolution of the gadolinium oxide core due to chelation of Gd(3+) by DOTAGA ligands and 4) polysiloxane fragmentation. These nanoparticles have been fully characterised using photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), a superconducting quantum interference device (SQUID) and electron paramagnetic resonance (EPR) to demonstrate the dissolution of the oxide core and by inductively coupled plasma mass spectrometry (ICP-MS), mass spectrometry, fluorescence spectroscopy, (29)Si solid-state NMR, (1)H NMR and diffusion ordered spectroscopy (DOSY) to determine the nanoparticle composition. Relaxivity measurements gave a longitudinal relaxivity r1 of 11.9 s(-1) mM(-1) per Gd at 60 MHz. Finally, potentiometric titrations showed that Gd(3+) is strongly chelated to DOTAGA (complexation constant logß110 =24.78) and cellular tests confirmed the that nanoconstructs had a very low toxicity. Moreover, SRPs are excreted from the body by renal clearance. Their efficiency as contrast agents for MRI has been proved and they are promising candidates as sensitising agents for image-guided radiotherapy.

Multiple representations and mechanisms for visuomotor adaptation in young children.

In this study, we utilized transformed spatial mappings to perturb visuomotor integration in 5-yr-old children and adults. The participants were asked to perform pointing movements under five different conditions of visuomotor rotation (from 0° to 180°), which were designed to reveal explicit vs. implicit representations as well as the mechanisms underlying the visual-motor mapping. Several tests allowed us to separately evaluate sensorimotor (i.e., the dynamic dimension of movement) and cognitive (i.e., the explicit representations of target position and the strategies used by the participants) representations of visuo-proprioceptive distortion. Our results indicate that children do not establish representations in the same manner as adults and that children exhibit multiple visuomotor representations. Sensorimotor representations were relatively precise, presumably due to the recovery of proprioceptive information and efferent copy. Furthermore, a bidirectional mechanism was used to re-map visual and motor spaces. In contrast, cognitive representations were supplied with visual information and followed a unidirectional visual-motor mapping. Therefore, it appears that sensorimotor mechanisms develop before the use of explicit strategies during development, and young children showed impaired visuomotor adaptation when confronted with large distortions.

Presbypropria: the effects of physiological ageing on proprioceptive control.

Several changes in the human sensory systems, like presbycusis or presbyopia, are well-known to occur with physiological ageing. A similar change is likely to occur in proprioception, too, but there are strong and unexplained discrepancies in the literature. It was proposed that assessment of the attentional cost of proprioceptive control could provide information able to unify these previous studies. To this aim, 15 young adults and 15 older adults performed a position matching task in single and dual-task paradigms with different difficulty levels of the secondary task (congruent and incongruent Stroop-type tasks) to assess presumed age-related deficits in proprioceptive control. Results showed that proprioceptive control was as accurate and as consistent in older as in young adults for a single proprioceptive task. However, performing a secondary cognitive task and increasing the difficulty of this secondary task evidenced both a decreased matching performance and/or an increased attentional cost of proprioceptive control in older adults as compared to young ones. These results advocated for an impaired proprioception in physiological ageing.

Reweighting of sensory inputs to control quiet standing in children from 7 to 11 and in adults.

How sensory organization for postural control matures in children is not clear at this time. The present study examined, in children aged 7 to 11 and in adults, the postural control modifications in quiet standing when somatosensory inputs from the ankle were disturbed. Since the reweighting of sensory inputs is not mature before 10, we hypothesized that postural stability was more affected in children than in adults when somatosensory inputs were altered and that this postural instability decreased as age increased during childhood. 37 children aged 7 to 11 years and 9 adults participated in the experiments. The postural task was a semi-tandem position with the right foot in front of the left one. Postural performance was measured by means of a force platform. Two experimental conditions were presented to the participants to maintain quiet standing: With or without altered somatosensory inputs (i.e., with or without ankles vibration). Results showed that postural stability--and thus how the reweighting process of the visual/somatosensory inputs matured--increased non-monotonically between 7 years of age and adult age: There was a linear improvement of postural stability from 7 to 10, followed by a more steady behaviour between 10 and 11 and then postural stability increased to reach the adults' level of performance.