The major ampullate glands of the spider Nephila clavipes contain approximately 0.2 microliter each of a highly concentrated (approximately 50%) solution of silk fibroin. Therefore, the reservoir of silk in these glands presents an ideal opportunity to observe prefolded conformations of a protein in its native state. To this end, the structure and conformation of major ampullate gland silk fibroin within the glands of the spider N. clavipes were examined by 13C NMR spectroscopy. These results were compared to those from silk protein first drawn from the spinneret and then denatured. The 13C NMR chemical shifts, along with infrared and circular dichroism data, suggest that the silk fibroin in the glands exists in dynamically averaged helical conformations. Furthermore, there is no evidence of proline residues in U-(13)C-D-glucose-labeled silk. This transient prefolded "molten fibril" state may correspond to the silk I form found in Bombyx mori silk. There is no evidence of the final beta-sheet structure in the ampullate gland silk fibroin before final silk processing. However, the conformation of silk in the glands appears to be in a highly metastable state, as plasticization with water produces the beta-sheet structure. Therefore, the ducts connecting the ampullate glands to the spinnerets play a larger role in silk processing than previously thought.
Spider dragline silk is Nature's high-performance protein fiber. This biomaterial has attracted much interest from scientists in various disciplines since it has become feasible to produce spider silk proteins by means of biotechnology. This article reports on research directed toward the regeneration of spider silk. A procedure is describedsincluding spinning and postspinning processings that produces fibers with promising mechanical properties from dissolved natural spider dragline silk. Tensile tests and structural characterization of the regenerated fibers illustrate correlations between the macroscopic and microscopic properties of the final material and between these properties and the fiber's processing history. Results point to the importance of an aqueous environment in the annealing of structure. The revealed structure-property relationships are expected to be of fundamental importance for the future design of man-made protein products.
Fluids in nanoscopic confinements possess a variety of unusual properties, and in particular, remarkable dynamical heterogeneities which vary on length scales as short as a fraction of a nanometer. While the surface forces apparatus provides an experimental probe of macroscopic properties of fluids in contact with atomically smooth solid surfaces, few experimental probes are available which test the microscopic origins of these heterogeneities. In this article we describe our recent efforts to apply nuclear magnetic resonance spectroscopy to nanoscopically confined poly͑styrene͒ ͑PS͒ created by intercalation into a surface-modified fluorohectorite. A comparison between surface-sensitive cross polarization experiments with spin-echo experiments which probe the entire organic layer suggests that PS in the center of the nanopores is more mobile than the bulk at comparable temperatures, while chain segments which interact with the surface are dynamically inhibited.
In polycrystalline samples, NMR "powder spectra" are broad and much structural informa ion is ost as a result of the orientational disorder In th' Lett F n zs er Fourier-transform R m zero magnetic field is described. With no f d d no pre erre irection in space, all direct in ter crystallites contribute equivalently and resolved d 1 1'tt' ve zpo ar sp ettings can be interpreted irect y in terms of internuclear distances. This open th 'bl'-f s e posse ray-o molecular strucure etermination without the need for single crystals or oriented samples
Characterization of dynamics of the charge-carrying species in polymer electrolytes has proven difficult. In this work we focus on a nanocomposite polymer electrolyte created when poly(ethylene oxide) (PEO) is intercalated into a layered silicate, Li–montmorillonite. We characterize both the Li+–silicate distance and the cation dynamics by analysis of the changes in Li7 nuclear magnetic resonance (NMR) line shape observed as the temperature is changed and cation diffusion is enabled. The observed spectra are compared to spectral simulations which emphasize the role of dipolar fields, associated with the static paramagnetic Fe3+ ions randomly distributed at the Al3+ lattice sites, interacting with the mobile cations. Low temperature line shapes are asymmetric, and not simply related to line shapes of more typical NMR interactions. Simulation of Li7 NMR spectra and comparison to experimental spectra shows that the Li+ interacts most strongly with the silicate surface layer, and all our evidence indicates that the cation diffusion is restricted to the surface. Line shape narrowing is observed over the temperature range 270⩽T⩽420 K reflecting diffusion along the silicate surface. At higher temperatures motional narrowing leads to a limiting linewidth which depends on the spacing between silicate planes and not on the spacing between Li+ and those planes. The high temperature line shape has the same orientation dependence as chemical shift anisotropies. Li+ diffusion rates appear consistent with values reported previously for this system and with a simplified line shape analysis.
Articles you may be interested inInvestigation of molecular structure in solids by twodimensional NMR exchange spectroscopy with magic angle spinning A field theory of random heteropolymers near solid surfaces: Analysis of interfacial organization and adsorption-desorption phase diagram Determination of hyperfine interactions from the magnetic field dependence of nuclear modulation frequencies: An electron spin echo envelope modulation study of protons in γirrradiated potassium dihydrogen arsenate Methods are described and demonstrated for detecting the coherent evolution of nuclear spin observables in zero magnetic field with the full sensitivity of high field NMR. The principle motivation is to provide a means of obtaining solid state spectra of the magnetic dipole and electric quadrupole interactions of disordered systems without the line broadening associated with random orientation with respect to the applied magnetic field. Comparison is made to previous frequency domain and high field methods. A general density operator formalism is given for the experiments where the evolution period is initiated by a sudden switching to zero field and is terminated by a sudden restoration of the field. Analytical expressions for the signals are given for a variety of simple dipolar and quadrupolar systems and numerical simulations are reported for up to six coupled spin-l/2 nuclei. Experimental results are reported or reviewed for 1H, 20, 7Li, i3C, and 27 AI nuclei in a variety of polycrystalline materials. The effects of molecular motion and bodily sample rotation are described. Various extensions of the method are discussed, including demagnetized initial conditions and correlation by two-dimensional Fourier transformation of zero field spectra with themselves or with high field spectra.
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