Oxidative electrochemical polymerization of (N,N ′-ethylenebis(salicylideneaminato)) nickel(II), [Ni(salen)], in acetonitrile/TEAP was reinvestigated. The polymers were characterized by in situ FTIR and UV-visible spectroscopies in order to explore film structure and to clarify the electronic states as a function of the electrochemically controlled applied redox potential; oxidized species involved in polymerization and oxidative switching of the polymer were also assessed by ex situ EPR experiments. Integration of data from all techniques revealed that (a) electropolymerization of [Ni(salen)] is ultimately a ligand-based-process that takes place through a mixture of o-and p-linking of the phenyl rings and (b) poly[Ni(salen)] exhibits physical/chemical properties that cannot be attributed to an aggregation of individual complexes, behaving rather like a polyphenylene compound, with the metal ion acting as a bridge between biphenylene moieties.

The nickel(II) complex with H 2 saltMe, a N 2 O 2 Schiff base ligand derived from salicylaldehyde, was oxidatively electropolymerized on Pt electrodes in CH 3 CN/0.1 mol dm -3 tetraethylammonium perchlorate (TEAP) to generate polymer films that exhibit reversible oxidative electrochemical behavior in a wide potential range (0.0-1.3 V), high conductivity, and stability/durability. The films of poly[Ni(saltMe)] can be made to exhibit the three regimes of charge transport behavior by manipulation of the film thickness and the experimental time scale. Films prepared by a small number of potential cycles show thin-layer/surface-type cyclic voltammetry behavior in the scan rate range used. Thicker polymers exhibit a changeover from this thinlayer regime to diffusion control at a critical scan rate that depends on film thickness. In chronoamperometry experiments a transition from semiinfinite diffusion to finite diffusion conditions was observed at longer times following the potential step.Values of D 1/2 C for the second electrochemical stage of film oxidation redox obtained from both techniques were in good agreement. A comparison of the values for oxidative and reductive electrochemical reactions suggests that ingress of counterions and solvent swelling must occur predominantly up to 0.8V in the positive going potential scan.

Poly(sodium styrene sulfonate) (pNaSS) was grafted onto poly(ε-caprolatone) (PCL) surfaces via ozonation and graft polymerization. The effect of ozonation and polymerization time, as well as the Mohr’s salt concentration in the grafting solution, on the degree of grafting was investigated. The degree of grafting was determined through toluidine blue staining. The surface chemical change was characterized by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The result demonstrated that the grafting did not induce any degradation of PCL, and that pNaSS was grafted onto PCL as a thin and covalently stable layer. Furthermore, the modified PCL surface reveals a significant increase in the metabolic activity of fibroblastic cells, as well as a better cell spreading with higher adhesion strength. Consequently, bioactivity of PCL is greatly enhanced by immobilizing a thin layer of pNaSS onto its surface. The grafting of pNaSS is a promising approach to increase the bioactivity of PCL-based materials used in tissue engineering applications, such as ligament reconstruction.

No abstract

No abstract

Human gait analysis provides valuable information regarding the way of walking of a given subject. Low-cost RGB-D cameras, such as the Microsoft Kinect, are able to estimate the 3-D position of several body joints without requiring the use of markers. This 3-D information can be used to perform objective gait analysis in an affordable, portable, and non-intrusive way. In this contribution, we present a system for fully automatic gait analysis using a single RGB-D camera, namely the second version of the Kinect. Our system does not require any manual intervention (except for starting/stopping the data acquisition), since it firstly recognizes whether the subject is walking or not, and identifies the different gait cycles only when walking is detected. For each gait cycle, it then computes several gait parameters, which can provide useful information in various contexts, such as sports, healthcare, and biometric identification. The activity recognition is performed by a predictive model that distinguishes between three activities (walking, standing and marching), and between two postures of the subject (facing the sensor, and facing away from it). The model was built using a multilayer perceptron algorithm and several measures extracted from 3-D joint data, achieving an overall accuracy and F1 score of 98%. For gait cycle detection, we implemented an algorithm that estimates the instants corresponding to left and right heel strikes, relying on the distance between ankles, and the velocity of left and right ankles. The algorithm achieved errors for heel strike instant and stride duration estimation of 15 ± 25 ms and 1 ± 29 ms (walking towards the sensor), and 12 ± 23 ms and 2 ± 24 ms (walking away from the sensor). Our gait cycle detection solution can be used with any other RGB-D camera that provides the 3-D position of the main body joints.

The oxidative polymerisation of the complex2,3-dimethyl-N,N'-bis-(salicylidene)butane-2,3-diaminatonick-el(II), [Ni(saltMe)], was monitored by the electrochemical quartz microbalance (EQCM) and crystal impedance techniques. Polymerisation efficiency was maintained throughout deposition of a film, which behaved rigidly, on the electrode. A combined EQCM-PBD (probe beam deflection) study of the redox process of the film exposed to a monomer-free solution of 0.1 M tetraethylammonium perchlorate (TEAP) in acetonitrile showed an electroneutrality mechanism dominated by anion movement accompanied by co-transfer of solvent above 0.8 V. The individual contributions of all the mobile species involved in the redox switching of the poly[Ni(saltMe)] film were determined quantitatively by temporal convolution analysis; the estimated solution-phase diffusion coefficient of the exchanged species was 1.24 x 10(-5) cm2s-1.

Electrogenerated polymers based on the nickel(II) complex 2,3-dimethyl-N,N'-bis(salicylidene)butane-2,3-diaminatonickel(II), poly[Ni(saltMe)], were characterised by in situ FTIR and UV/Vis spectroscopy and ex-situ EPR spectroscopy in order to gain insights into film structure, electronic states and charge conduction. The role of the nickel ions during film oxidation was probed by using EPR to study naturally abundant Ni and 61Ni-enriched polymers. The data from all the spectroscopic techniques are consistent, and clearly indicate that polymerisation and redox switching are associated with oxidative ligand based processes; coulometry suggests that one positive charge was delocalised through each monomer unit. EPR provided evidence for the non-direct involvement of the metal in polymer oxidation: the polymer is best described as a polyphenylene-type compound (conducting polymer), rather than an aggregation of nickel complexes (redox polymer), and the main charge carriers are identified as polarons. An explanation for the high electrochemical stability and conductivity of poly[Ni(saltMe)] with respect to that of poly[Ni(salen)] is proposed. based on stereochemical repulsion between monomeric units; this can impose a less compact supramolecular structure on polymers with bulkier substituents.