Is the manifestation of the local dynamics in the spin-lattice NMR relaxation in dendrimers sensitive to excluded volume interactions?

The effect of excluded volume (EV) interactions on the manifestation of the local dynamics in the spin-lattice NMR relaxation in dendrimers has been studied by using Brownian dynamics simulations. The study was motivated by the theory developed by Markelov et al., [J. Chem. Phys., 2014, 140, 244904] for a Gaussian dendrimer model without EV interactions. The theory connects the experimentally observed dependence of the spin-lattice relaxation rate 1/T(1)H on the location of NMR active groups with the restricted flexibility (semiflexibility) of dendrimers. Semiflexibility was introduced through the correlations between the orientations of different segments. However, these correlations exist even in flexible dendrimer models with EV interactions. We have simulated coarse-grained flexible and semiflexible dendrimer models with and without EV interactions. Every dendrimer segment consisted of two rigid bonds. Semiflexibility was introduced through a potential which restricts the fluctuations of angles between neighboring bonds but does not change orientational correlations in the EV model as compared to the flexible case. The frequency dependence of the reduced 1/T(1)H(ωH) for segments and bonds belonging to different dendrimer shells was calculated. It was shown that the main effect of EV interactions consists of a much stronger contribution of the overall dendrimer rotation to the dynamics of dendrimer segments as compared to phantom models. After the exclusion of this contribution the manifestation of internal dynamics in spin-lattice NMR relaxation appears to be practically insensitive to EV interactions. For the flexible models, the position ωmax of the peak of the modified 1/T(1)H(ωH) does not depend on the shell number. For semiflexible models, the maximum of 1/T(1)H(ωH) for internal segments or bonds shifts to lower frequencies as compared to outer ones. The dependence of ωmax on the number of dendrimer shells appears to be universal for segments and bonds in dendrimer models with and without EV interactions.

Molecular dynamics simulation of spin-lattice NMR relaxation in poly-L-lysine dendrimers: manifestation of the semiflexibility effect.

NMR relaxation experiments are widely used to investigate the local orientation mobility in dendrimers. In particular, the NMR method allows one to measure the spin-lattice relaxation rate, 1/T1, which is connected with the orientational autocorrelation function (ACF) of NMR active groups. We calculate the temperature (Θ) and frequency (ω) dependences of the spin-lattice NMR relaxation rates for segments and NMR active CH2 groups in poly-L-lysine (PLL) dendrimers in water, on the basis of full-atomic molecular dynamics simulations. It is shown that the position of the maximum of 1/T1(ω) depends on the location of the segments inside the dendrimer. This dependence of the maximum is explained by the restricted flexibility of the dendrimer. Such behavior has been predicted recently by the analytical theory based on the semiflexible viscoelastic model. The simulated temperature dependences of 1/T1 for terminal and inner groups in PLL dendrimers of n = 2 and n = 4 generations dissolved in water are in good agreement with the NMR experimental data, which have been obtained for these systems previously by us. It is shown that in the case of PLL dendrimers, the traditional procedure of the interpretation of NMR experimental data - when smaller values of 1/T1 correspond to higher orientation mobility - is applicable to the whole accessible frequency interval only for the terminal groups. For the inner groups, this procedure is valid only at low frequencies.

Linker formation in an overcharged complex of two dendrimers and linear polyelectrolyte.

The complexes formed by two dendrimers with charged terminal groups and oppositely charged long linear polyelectrolyte (LPE) have been studied using Brownian dynamics simulations. The structural properties of the complexes and their dependence on the LPE chain length were investigated. It was observed that dendrimers in the considered complexes are sufficiently overcharged; i.e., the number of adsorbed LPE monomers is larger than required for the neutralization. The degree of overcharging increases with the increase of the LPE length and is accompanied by the linker appearance until saturation in overcharging is reached. Nonmonotonic dependence of the linker size on the LPE length was observed. To describe the structural properties of the complexes formed by two macroions and a polyelectrolyte chain, the correlation theory has been developed.