The concept of hierarchical bottom-up structuring commonly encountered in natural materials provides inspiration for the design of complex artificial materials with advanced functionalities. Natural ...processes have achieved the orchestration of multicomponent systems across many length scales with very high precision, but man-made self-assemblies still face obstacles in realizing well-defined hierarchical structures. In particle-based self-assembly, the challenge is to program symmetries and periodicities of superstructures by providing monodisperse building blocks with suitable shape anisotropy or anisotropic interaction patterns ('patches'). Irregularities in particle architecture are intolerable because they generate defects that amplify throughout the hierarchical levels. For patchy microscopic hard colloids, this challenge has been approached by using top-down methods (such as metal shading or microcontact printing), enabling molecule-like directionality during aggregation. However, both top-down procedures and particulate systems based on molecular assembly struggle to fabricate patchy particles controllably in the desired size regime (10-100 nm). Here we introduce the co-assembly of dynamic patchy nanoparticles--that is, soft patchy nanoparticles that are intrinsically self-assembled and monodisperse--as a modular approach for producing well-ordered binary and ternary supracolloidal hierarchical assemblies. We bridge up to three hierarchical levels by guiding triblock terpolymers (length scale ∼10 nm) to form soft patchy nanoparticles (20-50 nm) of different symmetries that, in combination, co-assemble into substructured, compartmentalized materials (>10 μm) with predictable and tunable nanoscale periodicities. We establish how molecular control over polymer composition programs the building block symmetries and regulates particle positioning, offering a route to well-ordered mixed mesostructures of high complexity.
We investigate the self-assembly behavior of Janus particles with different geometries at a liquid-liquid interface. The Janus particles we focus on are characterized by a phase separation along ...their major axis into two hemicylinders of different wettability. We present a combination of experimental and simulation data together with detailed studies elucidating the mechanisms governing the adsorption process of Janus spheres, Janus cylinders, and Janus discs. Using the pendant drop technique, we monitor the assembly kinetics following changes in the interfacial tension of nanoparticle adsorption. According to the evolution of the interfacial tension and simulation data, we will specify the characteristics of early to late stages of the Janus particle adsorption and discuss the effect of Janus particle shape and geometry. The adsorption is characterized by three adsorption stages which are based on the different assembly kinetics and different adsorption mechanisms depending on the particle shape.
Well-defined hybrid polymers based on polyhedral oligomeric silsequioxane (POSS) with a variety of architectures have been developed, including telechelic polymers, block copolymers and star-shaped ...polymers. The synthesis, self-assembly and properties of this kind of materials are reviewed. Well-defined POSS-containing hybrid polymers can be constructed by living polymerization techniques, such as ring-opening polymerization and living free-radical polymerization or the combination of living polymerization and coupling reactions, such as click chemistry and hydrosilylation. The self-assembly behavior of well-defined POSS-containing hybrid polymers is also described in detail. The POSS-containing hybrid polymers can self-assemble into nano-scaled aggregates in selective solvents, and form nanostructures in bulk. Some of the interesting self-assembly morphologies are remarkably different from those formed from the conventional purely organic amphiphilic polymers. Well-defined POSS-containing hybrid polymers have shown the unexpected properties, which lead to unlimited possibilities for promising applications, such as biomedicine, electronic, optical, magnetic nanodevices, sensors and stimulated catalysts. We highlight several recent examples of these applications.
Nonviral gene delivery with the help of polycations has raised considerable interest in the scientific community over the past decades. Herein, we present a systematic study on the influence of the ...molecular weight and architecture of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) on the transfection efficiency and the cytotoxicity in CHO-K1 cells. A library of well-defined homopolymers with a linear and star-shaped topology (3- and 5-arm stars) was synthesized via atom transfer radical polymerization (ATRP). The molecular weights of the polycations ranged from 16 to 158 kDa. We found that the cytotoxicity at a given molecular weight decreased with increasing number of arms. For a successful transfection a minimum molecular weight was necessary, since the polymers with a number-average molecular weight, M(n), below 20 kDa showed negligible transfection efficiency at any of the tested polyelectrolyte complex compositions. From the combined analysis of cytotoxicity and transfection data, we propose that polymers with a branched architecture and an intermediate molecular weight are the most promising candidates for efficient gene delivery, since they combine low cytotoxicity with acceptable transfection results.
This paper reports on the highly ordered and tunable inner structure of poly(ionic liquid) nanoparticles, which formed spontaneously by precipitation polymerization from water. Without added ...stabilizer, these "latexes" are much smaller (20-40 nm in diameter) than usual polymer latexes and exhibit either multilamellar or unilamellar vesicular morphology, depending on the tail length of the quaternizing alkyl chains. The simplicity in the synthesis and composition and the high complexity of the ordered structures that resemble liposomes expand the classical profile of homopolymer self-assembly. In addition, unidirectional superassembly to a nanoworm mesostructure is found at elevated concentrations, indicating that the ionic liquid liposomes are apt to integrate into further hierarchical assembly schemes.
Colorful clusters: Silver nanoclusters consisting of only a few atoms exhibit large chemical-environment-responsive shifts of their optical absorption and emission bands, that is, large ...solvatochromism (see picture). The photophysical characteristics and electrochemiluminescence of the Ag clusters give them remarkable advantages over larger nanoparticles in applications such as molecular sensing.
Hierarchical self-assembly offers elegant and energy-efficient bottom-up strategies for the structuring of complex materials. For block copolymers, the last decade witnessed great progress in ...diversifying the structural complexity of solution-based assemblies into multicompartment micelles. However, a general understanding of what governs multicompartment micelle morphologies and polydispersity, and how to manipulate their hierarchical superstructures using straightforward concepts and readily accessible polymers remains unreached. Here we demonstrate how to create homogeneous multicompartment micelles with unprecedented structural control via the intermediate pre-assembly of subunits. This directed self-assembly leads to a step-wise reduction of the degree of conformational freedom and dynamics and avoids undesirable kinetic obstacles during the structure build-up. It yields a general concept for homogeneous populations of well-defined multicompartment micelles with precisely tunable patchiness, while using simple linear ABC triblock terpolymers. We further demonstrate control over the hierarchical step-growth polymerization of multicompartment micelles into micron-scale segmented supracolloidal polymers as an example of programmable mesoscale colloidal hierarchies via well-defined patchy nanoobjects.
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