Single molecule force spectroscopy of smart poly(ferrocenylsilane) macromolecules: Towards highly controlled redox-driven single chain motors

Polymer

Volumn 47, Issue 7, 2006, Pages 2483-2492

  Zou, Shan ^a   Korczagin, Igor ^a   Hempenius, Mark A ^a   Schönherr, Holger ^a   Vancso, G Julius ^a  

^a UNIVERSITY OF TWENTE   (Netherlands)

Author keywords

Atomic force microscopy; Electrochemistry; Stimuli responsive polymer

Indexed keywords

ATOMIC FORCE MICROSCOPY; COPOLYMERS; ELECTROCHEMISTRY; OXIDATION; POLYMERS; REDOX REACTIONS; SPECTROSCOPIC ANALYSIS;

MODEL SYSTEMS; SINGLE CHAIN MOTORS; SINGLE MOLECULE FORCE SPECTROSCOPY; STIMULI-RESPONSIVE POLYMERS;

MACROMOLECULES;

COPOLYMER; ELECTROCHEMISTRY; OXIDATION; SPECTROSCOPY;

EID: 33644981142     PISSN: 00323861     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.polymer.2005.12.091     Document Type: Article

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52. The FJC model, which is applicable for small extensions, solely considers entropic effects. For large extensions, before the chain may rupture (chemical bonds break), the deformation of bond angles and the stretching of covalent bonds will result in an effective increase in the segment length. For larger extensions (for x=L), the simple FJC model thus fails to describe the stretching of the macromolecules. Therefore, enthalpic contributions to the restoring force of the polymer chain must be considered. The simplest way to solve this problem is to separate the restoring force into an entropic and an enthalpic contribution such that the extensibility of the segments can be considered as an additional Hookean term (modified FJC model).
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56. segment of 27 nN/nm. This procedure yielded the result of x=27%.
57. One can also define the cycle with constant piezo extension during the oxidation or reduction processes, if the contraction ratio (before and after oxidation) of the polymer chain against the external force is known. In our experiments, it was not possible to measure the change of the contour length of a particular chain before and after oxidation. These data are also not reported in the literature. It is important to note that the elasticity (in terms of Kuhn length and segment elasticity) of the single polymer chain does not depend on the extension or contour lengths of the polymer, but only reflects the intrinsic properties of the polymer itself. In our experiments, it was not possible to hold the neutral polymer chain between the AFM tip and the substrate and reversibly oxidize/reduce it during force-extension measurements. However, by recording force-extension data at the very same x-, y-position both in neutral and oxidized states, it may be possible to stretch the 'same' PFS chain before and after electrochemical oxidization.
58. 100 chain of ∼58 nm can be calculated by 0.63×92 (DP). So for a PFS chain with 50 nm contour length, the DP can be calculated as 50/0.63=80.