Electrochemical control of a non-covalent binding between ferrocene and beta-cyclodextrin

The forces required for the detachment of ferrocene (Fc) from β-cyclodextrin (βCD) in a single host (βCD)–guest (Fc) complex were investigated using force spectroscopy under electrochemical conditions. The redox state of the guest Fc moiety as well as the structure of the supporting matrix was found to decisively affect the nanomechanical properties of the complex.

A sensorless virtual slave control scheme for kinematically dissimilar master-slave teleoperation

The use of telerobotic systems is essential for remote handling (RH) operations in radioactive areas of scientific facilities that generate high doses of radiation. Recent developments in remote handling technology has seen a great deal of effort being directed towards the design of modular remote handling control rooms equipped with a standard master arm which will be used to separately control a range of different slave devices. This application thus requires a kinematically dissimilar master-slave control scheme. In order to avoid drag and other effects such as friction or other non-linear and unmodelled slave arm effects of the common position-position architecture in nonbackdrivable slaves, this research has implemented a force-position control scheme. End-effector force is derived from motor torque values which, to avoid the use of radiation intolerant and costly sensing devices, are inferred from motor current measurement. This has been demonstrated on a 1-DOF test-rig with a permanent magnet synchronous motor teleoperated by a Sensable Phantom Omni® haptic master. This has been shown to allow accurate control while realistically conveying dynamic force information back to the operator.

Realization of Sinusoidal Forces at CEM

This paper describes the procedure implemented at CEM for dynamic force calibration using sinusoidal excitations of force transducers. The method is based on a sinusoidal excitation of force transducers equipped with an additional top mass excited with an electrodynamic shaker system. The acceleration is measured by means of a laser vibrometer.

Highly demanding resistive vibration exercise program is tolerated during 56 days of strict bed-rest

Several studies have tried to find countermeasures against musculoskeletal de-conditioning during bed-rest, but none of them yielded decisive results. We hypothesised that resistive vibration exercise (RVE) might be a suitable training modality. We have therefore carried out a bed-rest study to evaluate its feasibility and efficacy during 56 days of bed-rest. Twenty healthy male volunteers aged 24 to 43 years were recruited and, after medical check-ups, randomised to a non-exercising control (Ctrl) group or a group that performed RVE 11 times per week. Strict bed-rest was controlled by video surveillance. The diet was controlled. RVE was performed in supine position, with a static force component of about twice the body weight and a smaller dynamic force component. RVE comprised four different units (squats, heel raises, toe raises, kicks), each of which lasted 60 - 100 seconds. Pre and post exercise levels of lactate were measured once weekly. Body weight was measured daily on a bed scale. Pain questionnaires were obtained in regular intervals during and after the bed-rest. Vibration frequency was set to 19 Hz at the beginning and progressed to 25.9 Hz (SD 1.9) at the end of the study, suggesting that the dynamic force component increased by 90%. The maximum sustainable exercise time for squat exercise increased from 86 s (SD 21) on day 11 of the BR to 176 s (SD 73) on day 53 (p = 0.006). On the same days, post-exercise lactate levels increased from 6.9 mmol/l (SD2.3) to 9.2 mmol/l (SD 3.5, p = 0.01). On average, body weight was unchanged in both groups during bed-rest, but single individuals in both groups depicted significant weight changes ranging from -10% to + d10% (p < 0.001). Lower limb pain was more frequent during bed-rest in the RVE subjects than in Ctrl (p = 0.035). During early recovery, subjects of both groups suffered from muscle pain to a comparable extent, but foot pain was more common in Ctrl than in RVE (p = 0.013 for plantar pain, p = 0.074 for dorsal foot pain). Our results indicate that RVE is feasible twice daily during bed-rest in young healthy males, provided that one afternoon and one entire day per week are free. Exercise progression, mainly by progression of vibration frequency, yielded increases in maximum sustainable exercise time and blood lactate. In conclusion, RVE as performed in this study, appears to be safe.

Minority influence and innovation:antecedents, processes and consequences

Social groups form an important part of our daily lives. Within these groups pressures exist which encourage the individual to comply with the group’s viewpoint. This influence, which creates social conformity, is known as ‘majority influence’ and is the dominant process of social control. However, there also exists a ‘minority influence’, which emerges from a small subsection of the group and is a dynamic force for social change. Minority Influence and Innovation seeks to identify the conditions under which minority influence can prevail, to change established norms, stimulate original thinking and help us to see the world in new ways. With chapters written by a range of expert contributors, areas of discussion include: •processes and theoretical issues •the factors which affect majority and minority influence •interactions between majority and minority group members This book offers a thorough evaluation of the most important current developments within this field and presents consideration of the issues that will be at the forefront of future research. As such it will be of interest to theorists and practitioners working in social psychology. This book offers a thorough evaluation of the most important current developments within this field and presents consideration of the issues that will be at the forefront of future research. As such it will be of interest to theorists and practitioners working in social psychology.

Música na multideficiência: impacto na qualidade de vida e no comportamento pessoal e social de uma comunidade em particular

A presente investigação reflete um estudo que investiga o impacto da música na melhoria da qualidade de vida de uma população de adultos com deficiência mental e/ou sensorial e/ou motora, ao nível dos comportamentos individuais e sociais, e das capacidades de comunicação e expressão interpessoal. Com ele, tenciona-se trilhar um caminho na aceitação e valorização de cada indivíduo enquanto ser individual e social, encarando os seus aspetos singulares, biológicos e sociais como oportunidades de exploração de capacidades e particularidades, e investigando a concretização destes ideais através da música. Neste sentido, durante o ano letivo de 2014/2015, conduziu-se uma intervenção prática semanal junto de uma comunidade com multideficiência que frequenta um Centro de Atividades Ocupacionais de uma Instituição Particular de Solidariedade Social do concelho de Ílhavo. Após terem sido delineados objetivos específicos para o grupo e objetivos individuais para cada um dos elementos da amostra, realizaram-se dois períodos de experimentação, entre os quais se procedeu à aferição de ferramentas. Os resultados das sessões implementadas foram avaliados através de uma escala de avaliação e de questionários. Provou-se que todos os objetivos foram concretizados e concluiu-se que a música pode proporcionar melhorias significativas na qualidade de vida de uma população com deficiência ou incapacidade. A proposta não é de inclusão, mas sim de não exclusão, sendo o projeto musical um agente dinamizador e consciencializador de princípios éticos de uma cidadania mais participativa.

A Multifaceted Study of Scedosporium boydii Cell Wall Changes during Germination and Identification of GPI-Anchored Proteins

International audience

Caractérisation pharmacocinétique et pharmacodynamique de la lidocaïne avec ou sans adrénaline lors d’un bloc paravertébral du plexus brachial chez le chien

Au cours des vingt dernières années, l’anesthésie régionale est devenue, autant en médecine vétérinaire qu’humaine, un outil essentiel à l’élaboration de protocoles analgésiques péri-opératoires. Parmi l’éventail de techniques mises au point en anesthésie canine, le bloc paravertébral du plexus vertébral (PBPB) et sa version modifiée sont d’un grand intérêt pour toute procédure du membre thoracique, dans sa portion proximale. Toutefois, l’essentiel des données publiées à ce jour provient d’études colorimétriques, sans évaluation clinique, et peu d’information est disponible sur les techniques de localisation nerveuse envisageables à ce site. Notre étude visait à décrire une approche échoguidée du PBPB modifié, puis à caractériser ses paramètres pharmacocinétiques et pharmacodynamiques après administration de lidocaïne (LI) ou lidocaïne adrénalinée (LA). Huit chiens ont été inclus dans un protocole prospectif, randomisé, en aveugle et croisé, réparti sur trois périodes. L’impact pharmacodynamique du bloc effectué avec LI ou LA a été évalué régulièrement pour 180 min suivant son exécution. Le traitement à l’adrénaline n’a pas démontré d’impact significatif (P = 0,845) sur la durée du bloc sensitif, tel qu’évalué par un stimulus douloureux mécanique appliqué aux dermatomes ciblés. À l’opposé, l’atteinte proprioceptive évaluée par la démarche a été trouvée prolongée (P = 0,027) et le bloc moteur mesuré par le pic de force verticale (PVF) au trot sur la plaque de force s’est avéré plus marqué (PVF réduit; P = 0,007) sous LA. À l’arrêt comme au trot, le nadir de la courbe PVF-temps a été trouvé retardé (P < 0,005) et la pente ascendante de retour aux valeurs normales adoucie (P = 0,005). Parallèlement aux évaluations cliniques, des échantillons plasmatiques ont été collectés régulièrement afin de quantifier et décrire le devenir pharmacocinétique de la lidocaïne. Parmi les trois élaborés, un modèle bi-compartimental doté d’une double absorption asynchrone d’ordre zéro a finalement été sélectionné et appliqué aux données expérimentales. Sous LA, la Cmax a été trouvée significativement diminuée (P < 0,001), les phases d’absorption prolongées [P < 0,020 (Dur1) et P < 0,001 (Dur2)] et leurs constantes réduites [P = 0,046(k01) et P < 0,001 (k02)], le tout en concordance avec les effets proprioceptifs et moteurs rapportés. Bien que l’extrapolation du dosage soit maintenant théoriquement envisageable à partir du modèle mis en lumière ici, des études supplémentaires sont encore nécessaires afin d’établir un protocole de PBPB d’intérêt clinique. L’analyse sur plaque de force pourrait alors devenir un outil de choix pour évaluer l’efficacité du bloc dans un cadre expérimental.

Caractérisation pharmacocinétique et pharmacodynamique de la lidocaïne avec ou sans adrénaline lors d’un bloc paravertébral du plexus brachial chez le chien

Au cours des vingt dernières années, l’anesthésie régionale est devenue, autant en médecine vétérinaire qu’humaine, un outil essentiel à l’élaboration de protocoles analgésiques péri-opératoires. Parmi l’éventail de techniques mises au point en anesthésie canine, le bloc paravertébral du plexus vertébral (PBPB) et sa version modifiée sont d’un grand intérêt pour toute procédure du membre thoracique, dans sa portion proximale. Toutefois, l’essentiel des données publiées à ce jour provient d’études colorimétriques, sans évaluation clinique, et peu d’information est disponible sur les techniques de localisation nerveuse envisageables à ce site. Notre étude visait à décrire une approche échoguidée du PBPB modifié, puis à caractériser ses paramètres pharmacocinétiques et pharmacodynamiques après administration de lidocaïne (LI) ou lidocaïne adrénalinée (LA). Huit chiens ont été inclus dans un protocole prospectif, randomisé, en aveugle et croisé, réparti sur trois périodes. L’impact pharmacodynamique du bloc effectué avec LI ou LA a été évalué régulièrement pour 180 min suivant son exécution. Le traitement à l’adrénaline n’a pas démontré d’impact significatif (P = 0,845) sur la durée du bloc sensitif, tel qu’évalué par un stimulus douloureux mécanique appliqué aux dermatomes ciblés. À l’opposé, l’atteinte proprioceptive évaluée par la démarche a été trouvée prolongée (P = 0,027) et le bloc moteur mesuré par le pic de force verticale (PVF) au trot sur la plaque de force s’est avéré plus marqué (PVF réduit; P = 0,007) sous LA. À l’arrêt comme au trot, le nadir de la courbe PVF-temps a été trouvé retardé (P < 0,005) et la pente ascendante de retour aux valeurs normales adoucie (P = 0,005). Parallèlement aux évaluations cliniques, des échantillons plasmatiques ont été collectés régulièrement afin de quantifier et décrire le devenir pharmacocinétique de la lidocaïne. Parmi les trois élaborés, un modèle bi-compartimental doté d’une double absorption asynchrone d’ordre zéro a finalement été sélectionné et appliqué aux données expérimentales. Sous LA, la Cmax a été trouvée significativement diminuée (P < 0,001), les phases d’absorption prolongées [P < 0,020 (Dur1) et P < 0,001 (Dur2)] et leurs constantes réduites [P = 0,046(k01) et P < 0,001 (k02)], le tout en concordance avec les effets proprioceptifs et moteurs rapportés. Bien que l’extrapolation du dosage soit maintenant théoriquement envisageable à partir du modèle mis en lumière ici, des études supplémentaires sont encore nécessaires afin d’établir un protocole de PBPB d’intérêt clinique. L’analyse sur plaque de force pourrait alors devenir un outil de choix pour évaluer l’efficacité du bloc dans un cadre expérimental.

Dynamic covalent chemistry on surfaces employing highly reactive cyclopentadienyl moieties

Silicon substrates coated with a bromide-terminated silane are transformed into highly reactive, cyclopentadiene covered analogues. These surfaces undergo rapid cycloaddition reactions with various dienophile-capped polymers. Mild heating of the substrates causes the retro-Diels-Alder reaction to occur, thus reforming the reactive cyclopentadiene surface, generating an efficiently switchable surface.

Dynamic response of a beam on elastic foundation of finite depth under a moving force

In this paper, dynamic response of an infinitely long beam resting on a foundation of finite depth, under a moving force is studied. The effect of foundation inertia is included in the analysis by modelling the foundation as a series of closely spaced axially vibrating rods of finite depth, fixed at the bottom and connected to the beam at the top. Viscous damping in the beam and foundation is included in the analysis. Steady state response of the beam-foundation system is obtained. Detailed numerical results are presented to study the effect of various parameters such as foundation mass, velocity of the moving load, damping and axial force on the beam. It is shown that foundation inertia can considerably reduce the critical velocity and can also amplify the beam response.

Dynamic structure of charge carrier in polyaniline by near-infrared excited resonance Raman spectroscopy

New vibrational Raman features characteristic to the conductive form of polyaniline have been observed with the near-infrared excitation at 1047 nm. Based on an analogy with the resonance Raman spectrum of Michler's ketone in the lowest excited triplet (T-1) state, we consider these features as due to a dynamic structure of a diimino-1,4-phenylene unit in the polyaniline chain exchanging a positive charge very rapidly. This consideration directly leads to a conducting mechanism in which a positive charge migrates from one nitrogen to the other through the conjugated chain of polyaniline.

Spatio-temporal correlations in aqueous systems: computational studies of static and dynamic heterogeneity by 2D-IR spectroscopy

Local heterogeneity is ubiquitous in natural aqueous systems. It can be caused locally by external biomolecular subsystems like proteins, DNA, micelles and reverse micelles, nanoscopic materials etc., but can also be intrinsic to the thermodynamic nature of the aqueous solution itself (like binary mixtures or at the gas-liquid interface). The altered dynamics of water in the presence of such diverse surfaces has attracted considerable attention in recent years. As these interfaces are quite narrow, only a few molecular layers thick, they are hard to study by conventional methods. The recent development of two dimensional infra-red (2D-IR) spectroscopy allows us to estimate length and time scales of such dynamics fairly accurately. In this work, we present a series of interesting studies employing two dimensional infra-red spectroscopy (2D-IR) to investigate (i) the heterogeneous dynamics of water inside reverse micelles of varying sizes, (ii) supercritical water near the Widom line that is known to exhibit pronounced density fluctuations and also study (iii) the collective and local polarization fluctuation of water molecules in the presence of several different proteins. The spatio-temporal correlation of confined water molecules inside reverse micelles of varying sizes is well captured through the spectral diffusion of corresponding 2D-IR spectra. In the case of supercritical water also, we observe a strong signature of dynamic heterogeneity from the elongated nature of the 2D-IR spectra. In this case the relaxation is ultrafast. We find remarkable agreement between the different tools employed to study the relaxation of density heterogeneity. For aqueous protein solutions, we find that the calculated dielectric constant of the respective systems unanimously shows a noticeable increment compared to that of neat water. However, the `effective' dielectric constant for successive layers shows significant variation, with the layer adjacent to the protein having a much lower value. Relaxation is also slowest at the surface. We find that the dielectric constant achieves the bulk value at distances more than 3 nm from the surface of the protein.

Characterization of self-organized InAs/GaAs quantum dots under strain-induced and temperature-controlled nucleation mechanisms by atomic force microscopy and photoluminescence spectroscopy

Atomic force microscopy and photoluminescence spectroscopy (PL) has been used to study asymmetric bilayer InAs quantum dot (QD) structures grow by molecular-beam epitaxy on GaAs (001) substrates. The two InAs layers were separated by a 7-nm-thick GaAs spacer layer and were grown at different substrate temperature. We took advantage of the intrinsic nonuniformity of the molecular beams to grow the seed layer with an average InAs coverage of 2.0 ML. Then the seed layer thickness could be divided into three areas: below, around and above the critical thickness of the 2D-3D transition along the 11101 direction of the substrate. Correspondingly, the nucleation mechanisms of the upper InAs layer (UIL) could be also divided into three areas: temperature-controlled, competition between temperature-controlled and strain-induced, and strain-induced (template-controlled) nucleation. Small quantum dots (QDs) with a large density around 5 x 10(10) cm(-2) are found in the temperature-controlled nucleation area. The QD size distributions undergo a bimodal to a unimodal transition with decreasing QD densities in the strain-induced nucleation area, where the QD densities vary following that of the seed layer (templating effect). The optimum QD density with the UIL thickness fixed at 2.4 ML is shown to be around 1.5 x 10(10) cm(-2), for which the QD size distribution is unimodal and PL emission peaks at the longest wavelength. The QDs in the in-between area exhibit a broad size distribution with small QDs and strain-induced large QDs coexisting.