C NMR Spectroscopic Examination
of Lower Alcohol Vapor Sorption by Cross-Linked
Poly(Methyl Methacrylate) Particles
Yu. E. Moskalenko, N. N. Shevchenko, M. V. Mokeev,
A. Yu. Men’shikova, A. V. Yakimanskii, and A. V. Gribanov
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received July 1, 2009
Abstract—The sensitivity and selectivity of methyl methacrylate–ethylene glycol dimethacrylate copolymers
with respect to lower alcohol (methanol, ethanol, and propanol-2) vapors were examined by solid-state
NMR spectroscopy. A comparative analysis was carried out for the capabilities of various spectral techniques
for studying sorption processes in cross-linked polymer particles.
OF SYSTEMS AND PROCESSES
ISSN 1070-4272, Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 3, pp. 400–405. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © Yu.E. Moskalenko, N.N. Shevchenko, M.V. Mokeev, A.Yu. Men’shikova, A.V. Yakimanskii, A.V. Gribanov, 2010, published in
Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 3, pp. 401–406.
Polymeric materials are widely used as sorbents for
highly selective detection and separation of organic
compounds. Monodispersed cross-linked polymer
particles, capable of self-assembly into three-dimen-
sionally ordered regular structures , hold the
promise of a new generation of sorbents: The size and
the pore structure of these nanoparticles are direc-
tionally controlled by the synthesis conditions.
Molecularly imprinted polymers represent a new
generation of sorbents in which the highly specific
binding sites are complementary in terms of size,
shape, and structure to the target organic molecules
introduced into the reaction mass in the polymer
matrix formation stage. This allows the resulting
particles to selectively bind such molecules and retain
them in a polymer via different interactions . These
easy to prepare polymers exhibit enhanced chemical
and physical resistance and can be regarded as
synthetic receptors [3–6]. The most promising
applications for them include solid-phase extraction of
organic compounds from solutions [7–10] and
capillary electrochromatography and electrophoresis
[11–16], as well as selective binding and detecting
organic substances with different sensors [12, 17–19].
Methyl methacrylate-based polymers have historically
been applied to preparation of various materials, in
particular, sorbents. One of the high-priority tasks for
modern chemical industry is to determine the content
of harmful substances, in particular, lower alcohols, in
occupational air. Development of state-of-the-art air
quality control systems utilizing advanced polymer
systems necessitates detailed study of the limiting
stage of indication, vapor sorption by polymer matrix.
By now, solid-state NMR spectroscopy enabled a
major breakthrough in determining the chemical
structure of insoluble polymers, as well as in studying
the orientation and phase relationships in single- and
multicomponent polymer systems and molecular
motion in solid polymers . Solid-state NMR
spectroscopy is not routinely used in sorption studies,
but this powerful technique can clearly provide deep
insight into sorption mechanisms.
A variety of techniques are employed in solid-state
NMR spectroscopy for averaging the dipole–dipole
interactions and chemical shift anisotropy so as to
decrease the line width and increase the sensitivity.
“Magic angle” spinning (MAS) of the sample is one of
the major techniques applied in solid-state NMR
spectroscopy for averaging the anisotropic interactions.
However, for nuclei with low natural abundances
C) a single spectral measurement with the
use of the MAS technique solely takes much time. The
sensitivity of low-abundance nuclei can be increased