Hydrodynamic radius of dendrimers in solvents

The diffusion properties and hydrodynamic radius, Rh, of macromolecules are important for theoretical studies and practical application. Moreover, comparison of Rh values obtained from simulation and experimental data is used to check the correctness of simulation results. Here, we study the translation mobility of poly(butylcarbosilane) dendrimers in chloroform solution using molecular dynamics simulations and consider simulation details that may influence the accuracy of the result. Different methods to estimate Rh for a dendrimer are discussed with comparison to our experimental data. It was shown that the traditional MD simulation method for extraction of the diffusion coefficient (and calculation of Rh) of dendrimers as a rule faces difficulties and requires simulation resources several times greater than, for example, the same for a linear analogue. In the majority of MD simulation papers, the diffusion coefficient and/or Rh are calculated incorrectly. Also, we establish that correction of Rh according to the simulation box or estimation of Rh by using the gyration radius does not give values close to experimental data. To avoid the mentioned problems, we found an alternative way: to consider rotational diffusion, which gives an Rh similar to that from experiment and is practically independent of the size of the simulation box and other simulation parameters. The calculation of the hydrodynamic radius of a dendrimer from the mean-square displacement requires a huge simulation box and large trajectory. The rotational diffusion method allows the use of smaller boxes to obtain accurate results.

Automated summary

In this study, the translational mobility of poly(butylcarbosilane) dendrimers in chloroform solution was investigated using molecular dynamics simulations. Different methods for estimating the hydrodynamic radius (Rh) of dendrimers were discussed, and it was found that considering rotational diffusion provides accurate results independent of simulation box size and other parameters.