Conventional and Fast Field Cycling Relaxometry Study of the Molecular Dynamics in Polymer Nanocomposites for Use as Drug Delivery Systems

Abstract

This article presents a molecular dynamics study performed by combining conventional and fast-field cycling NMR relaxation techniques in nanocomposite systems for the optimization of drug delivery systems. The biodegradable polymers polycaprolactone, polylactide, polyvinyl alcohol and maize starch were used as base polymers and they were modified by incorporation of nanoparticles and/or cross-linking reactions, in order to understand the interaction between the bioactive molecules and the supporting matrix for a controlled drug release. Nevirapine was used as a testing bioactive drug. H spin-lattice relaxation times were measured for Larmor frequencies between 10 kHz and 300 MHz to obtain information about molecular motions in different time scales for comprehensive analysis of the possible interactions of the polymer matrices, modified nanoparticles and bioactive molecules. All systems presented some degree of crystallinity and poly-exponential decay of magnetization in the spin-lattice relaxation. The shortest spin-lattice relaxation times were assigned to the more amorphous regions and the relaxation dispersion was similar to that found in polymer melts. The effects of both nanoparticles and bioactive molecules on the molecular dynamics of the polymer matrices were clearly detected. The results show that NMR relaxometry study covers a broad range of frequencies and it is a powerful and suitable method to characterize nanocomposite systems at the molecular scale, provides information about the mobility of polymer chains and the strength of the interaction between polymers/nanoparticles. This information helps to make inferences about drug confinement level inside the systems, which can have a direct influence on the drug release. It is extremely important to know the exact drug release mechanism of bioactive molecules in a medical treatment. The main results indicated that the NMR techniques used were able to evaluate the molecular dynamics of the nanocomposites studied. It can be pointed out that PCL/clay nanocomposites containing nevirapine drug, caused a compensating effect regarding to the distribution of correlation times for the molecular segment motions and the drugs interferes in the nanomaterial molecular dynamics.

The Development and Characterization of Polycaprolactone and Titanium Dioxide Hybrids

“…NMR relaxometry technique has been used by several researchers to measure the nuclear relaxation times, such as: spin-lattice relaxation time in the laboratory frame, spin-lattice relaxation time in the rotating frame and spin-pin relaxation time in the laboratory frame, which gives insight into the molecular dynamics of the nanostructured systems [5] [6] [7]. The spin-lattice relaxation time in the laboratory frame promotes evaluation of the samples in the MHz scale.…”

“…The spin-lattice relaxation parameters involve changes in thermal equilibrium of spin systems and the responses of them are intrinsically related to the system's molecular dynamics that is derived from the morphology of the system [5] [6] [7].…”

Solid State NMR

“…In the low-field NMR, the relaxation parameters T 1 and T 2 for the hydrogen nuclei that constitute the samples can be measured directly, using the pulse sequences for such experiments and are widely used to characterize the types of molecular segments present in the samples and the interactions between them [15][16][17][18][19][20]. The time T 1 is associated with the return of the nucleus excited by the absorption of radiation to the equilibrium.…”

“…Thus, T 1 parameter measures the relaxation of the magnetization component parallel to the external magnetic field, being sensible to fast movements that are sensible to the movements of first order (MHz). The T 1ρ relaxation parameter is measured in low frequencies in the range of tens of kilohertz [1,7,[17][18][19][20][21][22][23].…”

Matéria Evaluation of zinc oxide nanoparticles influence on hydrophilic polymer matrix systems

“…The penetration of water through the matrix promotes transition of the polymer from a glassy state to swollen state as the intermolecular interactions between chains change. This reduces the polymer-polymer attraction forces, leading to more freedom conformational, allowing the drug to diffuse gradually making a tortoise way due to the presence of layers in the system [3], [7]- [10]. The swelling of hydrophilic matrixes due to the relaxation of the polymer chains when in contact with an aqueous medium is described as the formation of "fronts", which delineate the different phases of the matrix [11].…”