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.

Lateral and rotational mobility of some drug molecules in a poly(ethylene glycol) diacrylate hydrogel and the effect of drug-cyclodextrin complexation.

In relation to drug release properties the lateral and rotational mobility of two drugs and one drug mimic in photopolymerized poly(ethylene glycol) diacrylate (PEGDA) networks were investigated by nuclear magnetic resonance as a function of the network cross-link density and temperature. The network mesh size affects the lateral diffusivity for all drugs, even if the mesh size is an order of magnitude larger than the drug molecular size. The rotational diffusional motion is only appreciably affected when the drug size and network mesh size are of the same order of magnitude. By complexing the drug to cyclodextrin (CD) it is found that in some cases, depending on network mesh size and complex size, the complex is absorbed by the PEGDA gel, but that the diffusion of the drug in the gel is not necessarily slower than in the absence of the CD. This is explained by a theoretical model.

Environmentally friendly flame retardants. A detailed solid-state NMR study of melamine orthophosphate.

We used solid-state NMR spectroscopy to gain detailed information about the proton positions, proximities and the hydrogen-bonding network in the environmentally friendly flame retardant melamine orthophosphate (MP). High-resolution proton one- and two-dimensional solid-state NMR spectra were obtained at high external magnetic field in combination with fast magic angle spinning of the sample. Furthermore, we recorded homo- and heteronuclear correlation spectra of types (15)N­(15)N, (1)H­(13)C, (1)H­(15)N and (1)H­(31)P. In addition, we determined the geometry of the NH and NH(2) groups in MP by (15)N­(1)H heteronuclear recoupling experiments.We were able to completely assign the different isotropic chemical shifts in MP. Furthermore, we could identify the protonation of the melamine and orthophosphate moieties. The experimental results are discussed in connection with the structural model obtained by powder X-ray diffraction together with a combined molecular modeling-Rietveld refinement approach (De Ridder et al. Helv. Chim. Acta 2004; 87: 1894). We show that the geometry of the NH2 groups can only be successfully estimated by solid-state NMR.

Partitioning of main and side-chain units between different phases: a solid-state 13C NMR inversion-recovery cross-polarization study on a homogeneous, metallocene-based, ethylene-1-octene copolymer.

13C NMR inversion-recovery cross-polarization experiments are used to study the phase structure and partitioning of main and side-chain groups in a homogeneous, metallocene-based, ethylene-1-octene copolymer. The results provide strong evidence for a three-phase model, i.e. a rigid, (imperfect) crystalline phase, which is mainly composed of long sequences of methylene carbon atoms of the main chain, a semi-rigid, amorphous interphase (also denoted as 'rigid amorphous'), which is enriched by chain segments bearing methylene and methine carbon atoms of the main chain, and a soft fraction of the amorphous phase (also denoted as 'mobile amorphous'), which is largely composed of side chains and short methylene sequences of the main chain.