Quantitative measurement of the polydispersity in the extent of functionalization of glass-forming calix[4]resorcinarenes.

The polydispersity in the degree of functionalization for two calix[4]resorcinarenes was determined by measuring quantitatively their molecular mass distribution with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. A mathematical method for polydisperse materials is described that creates a calibration curve to correct the ion signal intensities in the mass spectrum to give a more reliable molecular mass distribution. Correction is required due to various sample preparation and instrumental effects that may produce a systematic mass bias in the number of oligomers measured. This method employs gravimetric mixtures of analytes with different degrees of functionalization. One calix[4]resorcinarene was found to give accurate molecular mass distributions with little correction, while another, having a very similar molecular structure, was found to exhibit strong over-counting of the oligomers having a high degree of functionalization.

Structure and mechanical properties of poly(D,L-lactic acid)/poly(epsilon -caprolactone) blends.

A series of blends of the biodegradable polymers poly(D,L-lactic acid) and poly( epsilon -caprolactone) were prepared by varying mass fraction across the range of compositions. Tensile testing was performed at room temperature using an extensometer and the elastic modulus was calculated for each blend. The blends were also tested to failure, and the strain-at-failure and yield stress recorded. While the blend has been shown to have a lower critical solution temperature, the mechanical properties were insensitive to the annealing conditions. Scanning electron microscopy was used to characterize the blend microstructure and poor adhesion was observed at the interface between blend components. Differential scanning calorimetry was performed but the results were somewhat variable, indicating this blend may have complex phase behavior that depends sensitively on the method of preparation. However, nuclear magnetic resonance data indicate the two components are phase separated. A percolation model is used to explain the observed mechanical data and the results are consistent with the predictions of the Kerner-Uemura-Takayangi model. The results of these experiments demonstrate the utility of polymer blending in tuning material properties.

The role of solid state 13C NMR spectroscopy in studies of the nature of native celluloses.

Published spectroscopic observations pertaining to the crystal structure of native celluloses are reviewed for the purpose of defining our current level of understanding about crystalline polymorphism in these materials. Emphasis is placed on observations from solid state 13C nuclear magnetic resonance (NMR), which first led to the postulate that most native, semicrystalline celluloses are composites of two crystalline allomorphs, labeled Ialpha and Ibeta. Historical background is presented, highlighting the structural controversies which mainly arose because different native celluloses were used, each one representing a different mixture of allomorphs. Input from Raman, infrared (IR) and electron diffraction data is included in the discussion of our current understanding of polymorphism in native celluloses. Also noted is the input from more recently studied celluloses (e.g., Halocynthia) as well as from newer processes that convert the Ialpha to the Ibeta form. On the basis of Raman and IR observations, it is argued that the Ialpha and Ibeta allomorphs differ in hydrogen bonding patterns only and that backbone conformations are nearly identical. Also, the point is made that the absence of correlation field splittings in the Raman spectra calls into question (although it does not disprove) whether the normal two-chain-per-unit-cell, monoclinic Ibeta allomorph really possesses two equivalent chains. Considerable discussion is devoted to the allomorphic composition of cellulose crystallites in higher plants. Published methods of NMR lineshape analysis for the higher plant celluloses are reviewed and critiqued, both from the point of view of lineshape theory and from the point of view of self-consistency of inferences that are based on lineshape analyses for different carbons (particularly C1 and C4). It is concluded that higher plant celluloses most likely possess a minor amount of the Ialpha allomorph where the Ialpha/Ibeta ratio is probably less than 0.25.

Some perspectives on the interpretation of proton NMR spin diffusion data in terms of polymer morphologies.

Proton spin diffusion data yield morphological information over dimensions covering approximately the 2-50 nm range. In this article, the interpretation of such data for polymers is emphasized, recognizing that the mathematical framework for much of this interpretation already exists in the literature. Practical issues are considered, for example, a useful scaling of plotted data is suggested, key attributes of the data are identified and ambiguities in the mapping of data into morphological models are spelled out. Discussion is limited to two-phase systems, where it is assumed that, by employing multiple-pulse methods polarization gradients can be generated, whose spunal sharpness is limited solety by the morphological definition of the interfaces. Interpretation of data in terms of morphology and stoichiometry is emphasized, where stoichiometric issues pertain only to chemically heterogeneous systems. Extraction of stoichiometric information from spin diffusion data is not commonly attempted; the discussion included herein allows for the possibility that the composition of phases may be chemically mixed. Methods for generating gradients are discussed only briefly. A standardized spin diffusion plot is proposed and the initial slope of this plot is tocussed on for providing information about morphology and stoichiometry. Ambiguities of interpretation considered include the dimensionality of the deduced morphology and, for systems with chemical heterogeneity the uniqueness of the compositional characterization of each phase. In addition, funite difference methods are used to simulate entire spin diffusion curves for idealized lamellar and hexagonal rod/matrix morphologies. Comparisons of these curves show that distinguishing 1-D and 2-D morphologies on the basis of experimental data is unlikely to be successful over the range of stoichiometrics where such morphologies are expected. Several examples of spin diffusion data are presented. Brief treatments of the following topics are included: finite interface width, estimation of spin diffusion constants, and incorporation of longitudinal relaxation effects. Finally, a short experimental discussion on the preparation of polarization gradients is given including those preparations which make use of differences in the multiple-pulse relaxation time, T1xz. It is noted that T1xz decays may be strongly perturbed in the presence of magic angle spinning, therefore, strategies are also outlined for minimizing these effects.

Modification of crystallinity and crystalline structure of Acetobacter xylinum cellulose in the presence of water-soluble beta-1,4-linked polysaccharides: 13C-NMR evidence.

Cellulose produced by Acetobacter xylinum in medium containing 0.5% xyloglucan or glucomannan showed altered crystallinities and shifted I alpha/I beta ratios when analysed by solid-state 13C-NMR. By estimating the spectra of cellulose components in each composite, a decreased I alpha content was shown to be countered by increased I beta content in cellulose aggregated in the presence of xyloglucan, causing minimal loss of crystallinity. However, the I alpha decrease was linked primarily to increased disordered content in cellulose produced in medium containing glucomannan. These results are considered in the light of two models for the morphological disposition of the I alpha phase: (i) a series model, proposed on the basis of electron diffraction measurements for an algal cellulose, in which regions of I alpha and I beta alternate along the length of a microfibril, and (ii) a superlattice model, in which the I alpha and I beta domains co-exist throughout the cross-section of each microfibril and form as a result of hierarchical aggregation. The latter model offers clearer insight into the role of the polysaccharides in inhibiting the formation of I alpha crystalline regions. In this superlattice model, polysaccharides adsorbed on surfaces of the most elementary aggregates are displaced to varying degrees during subsequent aggregation, with the presence of these polysaccharides altering the extent of I alpha production at interfaces.

Native cellulose: a composite of two distinct crystalline forms.

Multiplicities in the resonances of chemically equivalent carbons, which appear in the solid-state carbon-13 nuclear magnetic resonance spectra of native celluloses, have been examined at high resolution. The patterns of variation are consistent with the existence of two distinct crystalline forms. One form is dominant in bacterial and algal celluloses, whereas the other is dominant in celluloses from higher plants.