Cerium oxide (CeO(2)) nanoparticles display excellent antioxidant properties by scavenging free radicals. However, some studies have indicated that they can cause an adverse response by generating reactive oxygen species (ROS). Hence, it is important to clarify the factors that affect the oxidant/antioxidant activities of CeO(2) nanoparticles. In this work, we report the effects of different buffer anions on the antioxidant activity of CeO(2) nanoparticles. Considering the main anions present in the body, Tris-HCl, sulfate, and phosphate buffer solutions have been used to evaluate the antioxidant activity of CeO(2) nanoparticles by studying their DNA protective effect. The results show that CeO(2) nanoparticles can protect DNA from damage in Tris-HCl and sulfate systems, but not in phosphate buffer solution (PBS) systems. The mechanism of action has been explored: cerium phosphate is formed on the surface of the nanoparticles, which interferes with the redox cycling between Ce(3+) and Ce(4+). As a result, the antioxidant activity of CeO(2) nanoparticles is greatly affected by the external environment, especially the anions. These results may provide guidance for the further practical application of CeO(2) nanoparticles.

Hyperbranched multiarm copolymers (HMCs) have shown great potential to be excellent precursors in self-assembly to form various supramolecular structures in all scales and dimensions in solution. However, theoretical studies on the self-assembly of HMCs, especially the self-assembly dynamics and mechanisms, have been greatly lagging behind the experimental progress. Herein, we investigate the effect of degree of branching (DB) on the self-assembly structures of HMCs by dissipative particle dynamics (DPD) simulation. Our simulation results demonstrate that the self-assembly morphologies of HMCs can be changed from spherical micelles, wormlike micelles, to vesicles with the increase of DBs, which are qualitatively consistent with the experimental observations. In addition, both the self-assembly mechanisms and the dynamic processes for the formation of these three aggregates have been systematically disclosed through the simulations. These self-assembly details are difficult to be shown by experiments and are very useful to fully understand the self-assembly behaviors of HMCs.

Self-assembly of amphiphilic hyperbranched multiarm copolymers (HMCs) has shown great potential for preparing all kinds of delicate supramolecular structures in all scales and dimensions in solution. However, theoretical studies on the influencing factors for the self-assembly of HMCs have been greatly lagging behind. The phase diagram of HMCs in selective solvents is very necessary but has not been disclosed up to now. Here, the self-assembly of HMCs with different hydrophilic fractions in various solvents was studied systematically by using dissipative particle dynamics (DPD) simulations. Three morphological phase diagrams are constructed and a rich variety of morphologies, ranging from spherical micelles, worm-like micelles, membranes, vesicles, vesosomes, small micellar aggregates (SMAs), and aggregates of spherical and worm-like micelles to helical micelles, are obtained. In addition, both the self-assembly mechanisms and the dynamic processes for the formation of these self-assemblies have been systematically investigated. The simulation results are consistent with available experimental observations. Besides, several novel structures, like aggregates of spherical and worm-like micelles, vesosomes and helical micelles, are firstly discovered for HMC self-assembly. We believe the current work will extend the knowledge on the self-assembly of HMCs, especially on the control of supramolecular structures and on fabricating novel self-assemblies.

The understanding of shape transformations of vesicles is of fundamental importance in biological and clinical sciences. Hyperbranched polymer vesicles (branched polymersomes) are newly emerging polymer vesicles with special structure and property. They have also been regarded as a good model for biomembranes. However, the shape transformations of hyperbranched polymer vesicles have not been studied from either an experimental or theoretical level. Herein, the shape transformations of vesicles self-assembled from amphiphilic hyperbranched multiarm copolymers (HMCs) in response to the interaction parameters between the hydrophobic core and hydrophilic arms and the polymer concentrations are investigated carefully through dissipative particle dynamics (DPD) simulations. In the morphological phase diagram, two types of vesicles are obtained: one type corresponds to vesicles without holes formed at low concentrations including unilamellar vesicles, double-lamellar vesicles, discocyte-shaped vesicles, and tubular vesicles, and the other type corresponds to vesicles with holes formed at high concentrations including stomatocyte-shaped vesicles, toroidal vesicles, genus-3 (G-3) toroidal vesicles with three holes, and genus-4 (G-4) toroidal vesicles with four holes. In addition, both the self-assembly mechanisms and the dynamics for the formation of these vesicles have been systematically studied. The current work will offer theoretical support for fabricating novel vesicles with various shapes from hyperbranched polymers.

Multilayer onion‐like vesicles are valuable in cell mimics and biomedicine fields. However, as an excellent self‐assembly precursor, the formation of multilayer onion‐like vesicles by the self‐assembly of hyperbranched multiarm copolymers (HMCs) were not reported due to the complex self‐assembly dynamics. In this article, the self‐assembly behavior of multilayer onion‐like vesicles from HMCs was systematically investigated using dissipative particle dynamics simulation. The formation conditions for different kinds of vesicles were disclosed through the construction of the morphological phase diagram. Moreover, the formation mechanisms of the onion‐like vesicles with different layers were revealed. We observed that it is the fusion mechanism in low concentrations and the molecular rearrangement mechanism in high concentrations. For low concentration, the law between the number of the membrane layers and the morphology of the aggregates in the fusion process was disclosed. Meanwhile, the membrane of the onion‐like vesicles self‐assembled from HMCs is monolayer structure and the thickness of each layer is decreased in sequence from inside to outside. The current observations have important guiding significance for its application in drug delivery systems.

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Computer simulation has been becoming a versatile tool that can investigate detailed information from the microscopic scale to the mesoscopic scale. However, the crucial first step of molecular simulation is model building, particularly for hyperbranched polymers (HBPs) and hyperbranched multi-arm copolymers (HBMCs) with complex and various topological structures. Unlike well-defined polymers, not only the molar weight of HBPs/HBMCs with polydispersity, but the HBPs/HBMCs with the same degree of polymerization (DP) and degree of branching (DB) also have many possible topological structures, thus making difficulties for user to build model in molecular simulation. In order to build a bridge between model building and molecular simulation of HBPs and HBMCs, we developed HBP Builder, a C language open source HBPs/HBMCs building toolkit. HBP Builder implements an automated protocol to build various coarse-grained and fully atomistic structures of HBPs/HBMCs according to user’s specific requirements. Meanwhile, coarse-grained and fully atomistic output structures can be directly employed in popular simulation packages, including HOOMD, Tinker and Gromacs. Moreover, HBP Builder has an easy-to-use graphical user interface and the modular architecture, making it easy to extend and reuse it as a part of other program.

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