Publication detail

Local Segmental Dynamics of Poly(2-hydroxyethyl methacrylate) in Methanolic Solution Label X-band ESR

Year: 2004

Type of publication: článek v odborném periodiku

Name of source: Journal of Physical Chemistry A

Publisher name: American Chemical Society

Place: Washington

Page from-to: 9482-9490

Titles:

Language	Name	Abstract	Keywords
cze	Místní segmentové dynamiky poly(2-hydroxyethyl metakrylátu) v methanolovém roztoku určené ESR	Kopolymer 2-hydroxyethylmetakrylátu (HEMA) s jednotkami kyseliny metakrylové distribuované nepravidelně podél hlavního řetězce (odpovídající 3 % mol.) byl syntetizován. ESR spektra methanolových roztoků kopolymeru v rozsahu koncentrací od 2 do 50% hm. byly měřeny pro X-band (9GHz) přes široký teplotní rozsah.	2-hydroxyethyl methacrylate;copolymer;spin label;ESR
eng	Local Segmental Dynamics of Poly(2-hydroxyethyl methacrylate) in Methanolic Solution Label X-band ESR	A copolymer of 2-hydroxyethyl methacrylate (HEMA) with spin-labeled methacrylic acid units distributed randomly along the main chain (similar to3 mol %) was synthesized. ESR spectra of methanolic solutions of the copolymer at concentrations ranging from 2 to 50 wt % were measured at X-band (9 GHz) over a broad temperature range. Temperature dependence of the parameter R-S, characterizing the local segmental dynamics in PHEMA chain, and of the other parameters characterizing local dynamics and conformation of the copolymer were determined by fitting experimental ESR spectra to the theoretical spectra calculated using the MOMD model. Arrhenius plots of the rotational parameters exhibit atypical nonlinear behavior characterized by two breaks at particular temperatures in the R-S plot. It is concluded that, similarly to PMMA in a number of solvents, PHEMA in methanol undergoes a conformational transition from a less compact to more compact conformation of the polymer chain when the temperature increases in a particular temperature range. Results of dynamic light scattering and X-ray scattering experiments support this conclusion. Analysis of the shape of the ordering potential, which constrains the preferred orientation of the effective axis of internal rotation of the tethered nitroxide, revealed the occurrence of two different conformations of the nitroxide moiety. Based on the results of quantum chemical calculations, two conformations of the model system (nitroxide plus tether) are proposed, which are in a good agreement with the geometry required by the ordering potentials.	2-hydroxyethyl methacrylate;copolymer;spin label;ESR

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