Multidimensional 2H NMR study of dynamical heterogeneity in polymer nanocomposites.

Nanoconfined polymer chains-as can be formed when polymers intercalate into layered inorganic materials-show remarkable bulk properties, many of which are connected to dynamical heterogeneity in the polymeric phase. Microscopically, it appears that slow dynamical modes are associated with the species in direct contact with the surface, with substantially more mobile species only a fraction of a nm away. In the more distant phase, larger angle and moderately fast dynamics (typically, ns-micros) grows in over a broad temperature range not well correlated to bulk phase transitions. In this work, we probe the slowest dynamical modes and apply one- and two-dimensional (2)H exchange NMR experiments to study thin polymer layers intercalated between the flat inorganic faces of fluorohectorite (FH). One sample is created by intercalation of perdeuterated poly(ethylene oxide) into FH, and the second by intercalation of d(3)-poly(styrene) into a surface-modified FH. Large-amplitude reorientation of the PEO backbone is substantially hindered in the narrow two-dimensional layers, and reorientation is limited to small-amplitude steps at rates that are largely independent of temperature. Simulations of the two-dimensional exchange experiments suggest that dynamics in nanoconfined polymers is associated with small-angle rotational diffusion.

Bandwidth extension in noise spectroscopy.

Noise spectroscopy has previously been demonstrated to provide broad-bandwidth excitation with minimal applied RF field strengths. Nonetheless, its application to broadline solid-state NMR spectroscopy has appeared limited by the need to have unrealistically short probe- and receiver-recovery times after pulses. In this Communication, we explain theoretically and demonstrate experimentally that accurate lineshapes can be observed in 2H solid-state NMR spectroscopy even where the probe ringdown time greatly exceeds the required time between sampled data points. Moreover, accurate lineshapes can be observed to +/-125 kHz using RF fields as weak as a few hundred hertz.

Presence of phosphorus in Nephila clavipes dragline silk.

Solid-state 31P-NMR of Nephila clavipes dragline silk indicates the presence of phosphorus in at least two chemically distinct environments. Amino acid analyses of acid-hydrolyzed silk confirm the presence of phosphotyrosine as one of the phosphorus-containing components. The unusual chemical shift (18.9 ppm downfield from 85% H3PO4), proton chemical shift, and acid lability of a second component suggest that it is part of a strained five-membered cyclic phosphate that might be found on a beta-D-ribose. The five-membered cyclic phosphate is not removed from the silk fibers by exhaustive aqueous extraction. It is absent in nascent silk fibroin from the glands, suggesting that its formation is part of the fiber processing that occurs in the ducts leading to the spinnerets. High-resolution NMR spectra of silk dissolved in propionic acid/12 N HCl (50:50 v/v) show five phosphorus sites assigned to phosphorylated tyrosine residues, phosphorylated serine residues, inorganic phosphate, and two hydrolysis products of the cyclic phosphate compound. The observed posttranslational phosphorylation may be important in the processing and modulation of the physical properties of dragline silk.