The effect of hydrogen bonding on diffusion and permeability in UV-cured Polyacrylate-based networks for controlled release.

Polyacrylates are important polymers widely used in pharmaceutical industry such as drug coatings due to their low cost, processability and ease of functionalisation. Chemical functionalities (e.g. H-bonding) can be easily included to modulate the transport of low molecular weight drug-like entities through the network. Understanding how such microscopic structural modifications determine macroscopic diffusion is critical for designing next generation responsive polymers. In this study pulsed field gradient (PFG) 1H NMR measurements of the self-diffusion of a dye molecule (Eosin Y) in a series of polyacrylate networks with differing H-bonding strength were undertaken; it was found that the diffusion of Eosin Y is significantly reduced in networks with H-bonding. Detailed analyses by 1H NMR relaxometry and double quantum (DQ) NMR show that H-bonding can also reduce polymer chain mobility. Furthermore, DSC thermoporometry showed a significant increase in the average network mesh size potentially due to the pre-organization of H-bonding containing monomer during network curing. By introducing the H-bonding disrupter, LiClO4, it was found that the diffusivity of solute becomes positively correlated to the average mesh size across the series of networks. Hence, a modified diffusion model based on hydrodynamic theory is proposed to separate the direct (solute-network) H-bonding contribution to solute diffusion from the indirect contribution arising from monomer pre-ordering induced mesh size reduction. Finally, it is shown that the same direct and indirect contributions to microscopic diffusivity, arising from the H-bond strength of the co-monomers, also contribute significantly to the macroscopic membrane permeability which is similarly subject to H-bond disruption.

Crystallinity of polyolefins with large side groups by low-field 1H NMR T2 relaxometry: Isotactic Polybutene-1 with form II and I crystals.

Phase composition and molecular mobility were studied using 1H NMR T2 relaxometry in isotactic polybutene-1 (iPB-1) with two polymorphs - form I and II crystals. Several types of NMR relaxation methods and data analysis were evaluated for determining the most reliable way for studying physical phases in iPB-1. Three-phase model provided the most appropriate description of the phase composition in iPB-1, i.e., a crystal-amorphous interface separates the crystalline and the amorphous phases. Due to complex molecular mobility in iPB-1, the amount of rigid fraction should be considered as NMR crystallinity number. Two types of chain segments are present in the amorphous phase: (1) chain segments with anisotropic mobility due to chain anchoring to crystals and chain entanglements; and (2) highly mobile chain end segments. The polymorphic phase II to I transition causes significant immobilization of polymer chains in the crystalline and the amorphous phases. Molecular weight of iPB-1 largely influences phase composition and molecular mobility in crystalline and amorphous phases.

Outer-Sphere Control of Catalysis on Surfaces: A Comparative Study of Ti(IV) Single-Sites Grafted on Amorphous versus Crystalline Silicates for Alkene Epoxidation.

The effect of outer-sphere environment on alkene epoxidation catalysis using an organic hydroperoxide oxidant is demonstrated for calix[4]arene-TiIV single-sites grafted on amorphous vs crystalline delaminated zeotype (UCB-4) silicates as supports. A chelating calix[4]arene macrocyclic ligand helps enforce a constant TiIV inner-sphere, as characterized by UV-visible and X-ray absorption spectroscopies, thus enabling the rigorous comparison of outer-sphere environments across different siliceous supports. These outer-sphere environments are characterized by solid-state 1H NMR spectroscopy to comprise proximally organized silanols confined within 12 membered-ring cups in crystalline UCB-4, and are responsible for up to 5-fold enhancements in rates of epoxidation by TiIV centers.

Real-time observation of polymer network formation by liquid- and solid-state NMR revealing multistage reaction kinetics.

The reaction rate for the end-cross-linking process of vinyl-terminated poly(dimethylsiloxane) by a cross-linker with four Si-H functionalities in the presence of solvent was studied by (1)H liquid-state NMR in dependence of the reaction temperature. The properties of the resulting polymer networks, i.e., the gel-point and the formation of the elastically effective network, were monitored in situ during the reaction by single-evolution-time (1)H double-quantum (SET-DQ) low-field NMR. It was found that the cross-linking kinetics shows no uniform reaction order for the conversions of the functional groups before the topological gelation threshold of the polymer network. The two NMR methods are combined to investigate the formation of the elastically effective network in dependence of the conversion of the functional groups of the precursor polymers and the cross-linker. The high chemical and time resolution of the experiments enabled an in-depth analysis of the reaction kinetics, allowing us to conclude on a multistage model for PDMS network formation by hydrosilylation-based end-linking in the presence of solvent. We found that the nonuniform network formation kinetics originates from a dependence of the apparent reaction rate on the number of the Si-H groups of the cross-linker that have already reacted during the progress of the reaction. The fastest overall reaction rate is observed in a range until each cross-linker has reacted once on average, and a uniform apparent overall reaction order of unity with respect to cross-linker concentration is only found at a later stage, when multiply reacted cross-linker molecules with similar reactivity dominate.

Precise dipolar coupling constant distribution analysis in proton multiple-quantum NMR of elastomers.

In this work we present an improved approach for the analysis of (1)H double-quantum nuclear magnetic resonance build-up data, mainly for the determination of residual dipolar coupling constants and distributions thereof in polymer gels and elastomers, yielding information on crosslink density and potential spatial inhomogeneities. We introduce a new generic build-up function, for use as component fitting function in linear superpositions, or as kernel function in fast Tikhonov regularization (ftikreg). As opposed to the previously used inverted Gaussian build-up function based on a second-moment approximation, this method yields faithful coupling constant distributions, as limitations on the fitting limit are now lifted. A robust method for the proper estimation of the error parameter used for the regularization is established, and the approach is demonstrated for different inhomogeneous elastomers with coupling constant distributions.

MQ NMR and SPME analysis of nonlinearity in the degradation of a filled silicone elastomer.

Radiation-induced degradation of polymeric materials occurs through numerous, simultaneous, competing chemical reactions. Although degradation is typically found to be linear in adsorbed dose, some silicone materials exhibit nonlinear dose dependence due to dose-dependent dominant degradation pathways. We have characterized the effects of radiative and thermal degradation on a model filled-PDMS system, Sylgard 184 (commonly used in electronic encapsulation and in biomedical applications), using traditional mechanical testing, NMR spectroscopy, and sample headspace analysis using solid-phase microextraction (SPME) followed by gas chromatography/mass spectrometry (GC/MS). The mechanical data and (1)H spin-echo NMR spectra indicated that radiation exposure leads to predominantly cross-linking over the cumulative dose range studied (0-250 kGy) with a rate roughly linear with dose. (1)H multiple-quantum NMR spectroscopy detected a bimodal distribution in the network structure, as expected from the proposed structure of Sylgard 184. The MQ NMR spectra further indicated that the radiation-induced structural changes were not linear in adsorbed dose and that competing chain scission mechanisms made a greater contribution to the overall degradation process in the range of 50-100 kGy (although cross-linking still dominated). The SPME-GC/MS data were analyzed using principal component analysis (PCA), which identified subtle changes in the distributions of degradation products (the cyclic siloxanes and other components of the material) as a function of age that provide insight into the dominant degradation pathways at low and high adsorbed dose.

Effect of excluded volume on segmental orientation correlations in polymer chains.

We study the impact of excluded volume interactions on the orientation statistics of chain segments in polymer gels, and show that nuclear magnetic resonance (NMR) experiments provide a direct and unique measure of excluded-volume effects on the chain statistics. In particular we consider the tensor order parameter, which can be expressed as the second Legendre polynomial of the segment orientation with respect to a fixed end-to-end distance vector and which is directly related to the residual coupling constant obtained in NMR experiments. We provide analytical results for the case of single chains in a good solvent and for semidilute solutions. Computer simulations using the bond fluctuation model are applied to compare with the analytical predictions. Considering polymer gels at the equilibrium state of swelling we predict a unique relation between the tensor order parameter and the correlation length (blob size) of the gel. Experiments applying multiple-quantum NMR methods to both end-linked and randomly cross-linked polymer networks are in excellent agreement with this prediction. The initial decay of the tensor order parameter as observed in experiments at low and intermediate degrees of swelling can be explained as a solvent effect without making additional assumptions about constraint release processes during swelling.