Solvent effects in the interaction of methyl-beta-cyclodextrin with solvatochromic merocyanine dyes

The UV-vis spectroscopic behavior of dyes: 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (1) and 4-[(1-methyl-4(1H)-pyridinylidene)-ethylidene]-2,5-cyclohexadien-1-one (2) was investigated in solutions of methyl- beta-cyclodextrin (methyl-beta-CyD), using water, methanol, ethanol, propan-2-ol, butan-1-ol, acetone, acetonitrile, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), chloroform and dichloromethane as solvents. In aqueous solutions of dye (2) the addition of M-beta-CD leads to a bathochromic shift (of the maximum absorption), showing that the probe was transferred to a microenvironment of lower polarity and suggesting the formation of a 1 : 1 dye (2) : CyD inclusion complex, with a binding constant of 128.5 +/- 3.5 dm(3) mol(-1). Data for dye 2 in alcohols showed hypsochromic shifts, which increased in the following order: methanol < ethanol < propan-2-ol < butan-1-ol. These observations appear to reflect dye-solvent interactions through hydrogen bonding. If dye-solvent interactions are strong, the CyD-dye interactions are consequently weak, but the latter increase in importance when the dye-solvent interaction becomes weaker. With hydrogen-bond accepting solvents, data for both dyes showed clearly increasing hypsochromic shifts following the order: DMSO < DMA < DMF < acetone < acetonitrile. This order is exactly the inverse of the increasing order of basicity of the medium. This indicates that the dominant factor for the observed effects in these solvents is the solvent-CyD interaction through hydrogen bonding involving the hydroxyl groups of the CyD and the basic groups of the solvents. These interactions diminish in intensity if the basic character of the medium is reduced, increasing the capability of the dye to interact with the CyD using its phenoxide donor moiety. The largest hypsochromic shifts were obtained in chloroform (66.0 nm) and dichloromethane (67.5 nm) with dye after addition of methyl-beta-CyD. In these specific situations, solvents display weak basic and acid properties, that enhanced CyD-dye interactions to such an extent that association complexes formed through hydrogen bonding could be detected (K11) values of 24.8 +/- 4.9 dm3 mol(-1) in dichloromethane and 66.1 +/- 8.0 dm3 mol(-1) in chloroform).     

Non-linear dynamics of a cracked cantilever beam under harmonic excitation

The presence of cracks in a structure is usually detected by adopting a linear approach through the monitoring of changes in its dynamic response features, such as natural frequencies and mode shapes. But these linear vibration procedures do not always come up to practical results because of their inherently low sensitivity to defects. Since a crack introduces non-linearities in the system, their use in damage detection merits to be investigated. With this aim the present paper is devoted to analysing the peculiar features of the non-linear response of a cracked beam.The problem of a cantilever beam with an asymmetric edge crack subjected to a harmonic forcing at the tip is considered as a plane problem and is solved by using two-dimensional finite elements; the behaviour of the breathing crack is simulated as a frictionless contact problem. The modification of the response with respect to the linear one is outlined: in particular, excitation of sub- and super-harmonics, period doubling, and quasi-impulsive behaviour at crack interfaces are the main achievements. These response characteristics, strictly due to the presence of a crack, can be used in non-linear techniques of crack identification.     

A review of the problem of the shear centre(s)

The problem of defining and determinating the shear centre is present in the literature since the first decades of this century. It soon interlaced with the definition of the twist centre and their ways became unextricable in the following decades. A number of researchers dealt with this subject meeting with variable issues, yet in the authors' opinion it seems of some interest to run through it again. In this paper a general survey of the literature is performed and the two definitions of the shear centre (here named kinematic and energetic) are compared. It is remarked how the energetic definition for the shear centre makes it coincide with a suitably chosen twist centre. An example is given to show that the two definitions generally fail to provide the same place even for simple cross sections. It is shown that the two definitions provide the same place, using standard approximate formul?, in the case of thin-walled mono-connected sections with regularly varying thickness and two-connected sections with constant thickness. As a new result, it will be shown that the two definitions of shear centre do not provide the same place for thin-walled sections with connection higher than two even in the trivial case of uniform thickness; an example is given. Received November 25, 1997     

Scenarios in the experimental response of a vibro-impact single-degree-of-freedom system and numerical simulations

Nonlinear Dynamics - In this paper, possible scenarios within the experimental dynamic response of a vibro-impact single-degree-of-freedom system, symmetrically constrained by deformable and...     

Kinetic modeling of CO(ad) monolayer oxidation on carbon-supported platinum nanoparticles

We present a theoretical study of CO(ad) electrooxidation on Pt nanoparticles. Effects of size and surface texture of nanoparticles on the interplay of relevant kinetic processes are investigated. Thereby, strong impacts of particle size on electrocatalytic activities, observed in experiments, are rationalized. Our theoretical approach employs the active site concept to account for the heterogeneous surface of nanoparticles. It, moreover, incorporates finite rates of surface mobility of adsorbed CO. As demonstrated, the model generalizes established mean field or nucleation and growth models. We find very good agreement of our model with chronoamperometric current transients at various particle sizes and electrode potentials (Maillard, F.; Savinova, E. R.; Stimming, U. J. Electroanal. Chem., in press, doi:10.1016/j.jelechem.2006.02.024). The full interplay of on-site reactivity at active sites and low surface mobility of CO(ad) unfolds on the smallest nanoparticles ( approximately 2 nm). In this case, the solution of the model requires kinetic Monte Carlo simulations specifically developed for this problem. For larger nanoparticles (>4 nm) the surface mobility of CO(ad) is high compared to the reaction rate constants, and the kinetic equations can be solved in the limiting case of infinite surface mobility. The analysis provides an insight into the prevailing reaction mechanisms and allows for the estimation of relevant kinetic parameters.     

Identification of multiple open and fatigue cracks in beam-like structures using wavelets on deflection signals

A novel method for damage detection of multi-cracked beam-like structures by analyzing the static deflection is presented. The damage incurred produces a change in the stiffness of the beam. This causes a localized singularity which can be identified by a wavelet analysis of the displacement response. The existence and location of the cracks can be revealed by positions of the peaks in the continuous wavelet transform (CWT). To achieve this, the static profile of beams is analyzed with Gauss2 wavelet to identify the cracks. Beams under some ideal boundary and prescribed load conditions are considered. The deflected shape of the beam with open and fatigue cracks has been simulated under static loading using lumped crack models adopted from fracture mechanics and involving various degrees of complexity. The deflection of cracked beam in closed form for several cases of loads, crack sizes, and crack locations is calculated, and an explicit expression for the damage index (DI), based on CWT, is developed; it is demonstrated that the proposed damage index does not depend on mechanical properties of a homogeneous beam, and that the DI of one crack does not depend on the size and location of other cracks in a multiple cracked beam. Hence, the obtained expression for the DI can be used to find the size of each crack independently. Numerical results show that the method can detect cracks of small depth and is also applicable under the presence of measurement noise.