Helicoidal Patterning of Gold Nanorods by Phase Separation in Mixed Polymer Brushes

Tao, Huachen; Chen, Linye; Galati, Elizabeth; Manion, Joseph G.; Seferos, Dwight S.; Zhulina, Ekaterina B.; Kumacheva, Eugenia

doi:10.1021/acs.langmuir.9b02001

Cited by 17 publications

(14 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…39,40 While the mobility of thiol-terminated ligands on planar gold surfaces has attracted significant interest (vide supra), for AuNPs tethered with thiol-terminated high-molecular weight polymer ligands, studies of the dynamic properties of the thiol−gold interface remain scarce. Evidence for the surface mobility of thiol groups was obtained either for low-molecular weight oligomers, 41 or indirectly, in studies of phase separation in mixtures of thiol-terminated poly(ethylene glycol)/polystyrene 42,43 or poly(ethylene glycol)/poly(N-isopropylacrylamide) ligands. 42 The effect of temperature on increasing surface mobility of the ligands and change in solvent quality has not been explored.…”

mentioning

confidence: 99%

Morphological Transitions in Patchy Nanoparticles

et al. 2020

Self Cite

View full text Add to dashboard Cite

Nanoparticles (NPs) decorated with topographically or chemically distinct surface patches are an emerging class of colloidal building blocks of functional hierarchical materials. Surface segregation of polymer ligands into pinned micelles offers a strategy for the generation of patchy NPs with controlled spatial distribution and number of patches. The thermodynamic nature of this approach poses a question about the stability of multiple patches on the NP surface, as the lowest energy state is expected for NPs carrying a single patch. In the present work, for gold NPs end-grafted with thiol-terminated polymer molecules, we show that the patchy surface morphology is preserved under conditions of strong grafting of the thiol groups to the NP surface (i.e., up to a temperature of 40 °C), although the patch shape changes over time. At higher temperatures (e.g., at 80 °C), the number of patches per NP decreases, due to the increased lateral mobility and coalescence of the patches as well as the ultimate loss of the polymer ligands due to desorption at enhanced solvent quality. The experimental results were rationalized theoretically, using a scaling approach. The results of this work offer insight into the surface science of patchy nanocolloids and specify the time and temperature ranges of the applications of patchy NPs.

show abstract

mentioning

confidence: 99%

Morphological Transitions in Patchy Nanoparticles

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…The dimension, spatial distribution, and the number of patches are determined by the grafting density, solvent quality, relative size, and local surface curvature of the core particle (Figure 2f-h) [59]. Similarly, AuNRs with helicoidal PS patches are also achieved [60], by precisely controlling the molar ratio between two immiscible polymer brushes grafted on AuNRs. These polymer patches can be cross-linked to preserve the structure, or can go back to corona shell by increasing the solvent quality.…”

Section: Phase Separation-derived Methodsmentioning

confidence: 98%

Patchy Nanoparticle Synthesis and Self-Assembly

Kim¹,

Yao²,

Kalutantirige³

et al. 2020

Self-Assembly of Nanostructures and Patchy Nanoparticles

View full text Add to dashboard Cite

Biological building blocks (i.e., proteins) are encoded with the information of target structure into the chemical and morphological patches, guiding their assembly into the levels of functional structures that are crucial for living organisms. Learning from nature, researchers have been attracted to the artificial analogues, “patchy particles,” which have controlled geometries of patches that serve as directional bonding sites. However, unlike the abundant studies of micron-scale patchy particles, which demonstrated complex assembly structures and unique behaviors attributed to the patches, research on patchy nanoparticles (NPs) has remained challenging. In the present chapter, we discuss the recent understandings on patchy NP design and synthesis strategies, and physical principles of their assembly behaviors, which are the main factors to program patchy NP self-assembly into target structures that cannot be achieved by conventional non-patched NPs. We further summarize the self-assembly of patchy NPs under external fields, in simulation, and in kinetically controlled assembly pathways, to show the structural richness patchy NPs bring. The patchy NP assembly is novel by their structures as well as the multicomponent features, and thus exhibits unique optical, chemical, and mechanical properties, potentially aiding applications in catalysts, photonic crystals, and metamaterials as well as fundamental nanoscience.

show abstract

“…When ligands are weakly grafted to a core, they can “move” on the nanoparticle surface − through a series of successive desorption–readsorption processes . Quite recently, the experimental studies have confirmed that the surface morphology of patchy nanoparticles in poor solvents can be determined by the mobility of polymer ligands .…”

Section: Introductionmentioning

confidence: 99%

Structural Changes in Hairy Nanoparticles—Insights from Molecular Simulations

Staszewski

2020

J. Phys. Chem. C

View full text Add to dashboard Cite

Coarse-grained molecular dynamics simulations are used to study the reorganization of mobile ligands pinned to isolated nanospheres. Three types of ligands are considered: (i) freely jointed homogeneous attractive chains (H); (ii) flexible diblock copolymers composed of inert linkers and the attractive end-groups (D1); and (iii) diblock copolymers built of inert flexible linkers and end-groups being attractive rigid-rods (D2). The impact of the type of ligands, their number, and the strength of interactions on the structure of hairy nanoparticles are discussed. It is shown that the properties of ligands determine the morphology of polymer corona. For the H-particles, the one-patchy and the core−shell particles are found, while for particles D1 and D2, the ligands aggregate into a few patches. As the number of ligands increases, more patches are formed. Rigidity of attractive groups favors the formation of higher number of patches. The ligands are regularly distributed in patches on the core surface. Two patches are almost symmetrically located on the core, three patches are placed nearly at the vertices of an equilateral triangle, and four patches lie at the vertices of a regular tetrahedron.

show abstract

Helicoidal Patterning of Gold Nanorods by Phase Separation in Mixed Polymer Brushes

Cited by 17 publications

References 56 publications

Morphological Transitions in Patchy Nanoparticles

Morphological Transitions in Patchy Nanoparticles

Patchy Nanoparticle Synthesis and Self-Assembly

Structural Changes in Hairy Nanoparticles—Insights from Molecular Simulations

Contact Info

Product

Resources

About