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Despite the dif culty in device fabrication and microscopic force measurement, rigorous studies of single-molecule optomechanical transduction using an individual polymer chain containing photoresponsive azobenzene ligands in the backbone were reported Gaub and coworkers demonstrated for the rst time the optomechanical conversion in a single-molecule device using atomic force microscope (AFM) techniques (Hugel et al, 2002) One end of a single polyazopeptide molecule with elasticity of E = 20000 pN was attached to the cantilever of the AFM and the other end to a total internal re ection surface UV (365-nm) pulses shortened the molecule by 28 nm and 420-nm light pulses lengthened the molecule by 14 nm Alternating UV (365 nm) and 420-nm pulses caused reversible contraction and extension of the molecule As shown in Fig 13.

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solvent molecules do not move together with the ions These methods have, understandably, been applied most often to aqueous solutions The ionic mobility and diffusion coefficient are also affected by the ion hydration The particle dimensions calculated from these values by using Stokes' law (Eq 262) do not correspond to the ionic dimensions found, for example, from the crystal structure, and hydration numbers can be calculated from them In the absence of further assumptions, diffusion measurements again yield only the sum of the hydration numbers of the cation and the anion Similarly, concepts of solvation must be employed in the measurement of equilibrium quantities to explain some anomalies, primarily the salting-out effect.

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24a, at the rst step, 420-nm pulses lengthened the polymer with a force of 80 pN (I), then expanded mechanically to a restoring force of 200pN (II) UV pulses caused a contraction of the polymer chain (III) and the force on the polymer was reduced to 85 pN (IV) Finally, 420-nm pulses changed the system back to its original state From point II to III, the contraction of the polymer chain lifted the weight and thereby did mechanical work Fig 1324b describes the corresponding force extension The slope of the optical branches of the cycle are determined by the stiffness of the cantilever The work output of the system (shadow area in Fig 1324b) is the mechanical energy related to the contraction of the polymer The energy input needed to perform this mechanical work is light energy However, the ef ciency of energy conversion.

Addition of an electrolyte to an aqueous solution of a non-electrolyte results in transfer of part of the water to the hydration sheath of the ion, decreasing the amount of 'free' solvent, and the solubility of the nonelectrolyte decreases This effect depends, however, on the electrolyte selected In addition, the activity coefficient values (obtained, for example, by measuring the freezing point) can indicate the magnitude of hydration numbers Exchange of the open structure of pure water for the more compact structure of the hydration sheath is the cause of lower compressibility of the electrolyte solution compared to pure water and of lower apparent volumes of the ions in solution in comparison with their effective volumes in the crystals Again, this method yields the overall hydration number The fact that the water molecules forming the hydration sheath have limited mobility, ie.

F0 Extension (b)

that the solution is to certain degree ordered, results in lower values of the ionic entropies In special cases, the ionic entropy can be measured (eg from the dependence of the standard potential on the temperature for electrodes of the second kind) Otherwise, the heat of solution is the measurable quantity Knowledge of the lattice energy then permits calculation of the heat of hydration For a saturated solution, the heat of solution is equal to the product of the temperature and the entropy of solution, from which the entropy of the salt in the solution can be found However, the absolute value of the entropy of the crystal must be obtained from the dependence of its thermal capacity on the temperature down to very low temperatures The value of the entropy of the salt can then yield the overall hydration number.

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