Solution-based Supramolecular Hierarchical Assembly of Frenkel Excitonic Nanotubes Driven by Gold Nanoparticle Formation and Temperature.

Translating nature's successful design principle of solution-based supramolecular self-assembling to broad applications─ranging from renewable energy and information technology to nanomedicine─requires a fundamental understanding of supramolecular hierarchical assembly. Though the forces behind self-assembly (e.g., hydrophobicity) are known, the specific mechanism by which monomers form the hierarchical assembly still remains an open question. A crucial step toward formulating a complete mechanism is understanding not only how the monomer's specific molecular structure but also how manifold environmental conditions impact the self-assembling process. Here, we elucidate the complex correlation between the environmental self-assembling conditions and the resulting structural properties by utilizing a well-characterized model system: well-defined supramolecular Frenkel excitonic nanotubes (NTs), self-assembled from cyanine dye molecules in aqueous solution, which further self-assemble into bundled nanotubes (b-NTs). The NTs and b-NTs inhabit distinct spectroscopic signatures, which allows the use of steady-state absorption spectroscopy to monitor the transition from NTs to b-NTs directly. Specifically, we investigate the impact of temperature (ranging from 23 °C, 55 °C, 70 °C, 85 °C, up to 100 °C) during in situ formation of gold nanoparticles to determine their role in the formation of b-NTs. The considered time regime for the self-assembling process ranges from 1 min to 8 days. With our work, we contribute to a basic understanding of how environmental conditions impact solution-based hierarchical supramolecular self-assembly in both the thermodynamic and the kinetic regime.

Frenkel excitons in heat-stressed supramolecular nanocomposites enabled by tunable cage-like scaffolding.

Delocalized Frenkel excitons-coherently shared excitations among chromophores-are responsible for the remarkable efficiency of supramolecular light-harvesting assemblies within photosynthetic organisms. The translation of nature's design principles to applications in optoelectronic devices has been limited by the fragility of the supramolecular structures used and the delicate nature of Frenkel excitons, particularly under mildly changing solvent conditions and elevated temperatures and upon deposition onto solid substrates. Here, we overcome those functionalization barriers through composition of stable supramolecular light-harvesting nanotubes enabled by tunable (~4.3-4.9 nm), uniform (±0.3 nm) cage-like scaffolds. High-resolution cryogenic electron microscopy, combined with scanning electron microscopy, broadband femtosecond transient absorption spectroscopy and near-field scanning optical microscopy revealed that excitons within the cage-like scaffolds are robust, even under extreme heat stress, and control over nanocomposite dimensions is maintained on solid substrates. Our bio-inspired nanocomposites provide a general framework for the development of next-generation organic devices made from stable supramolecular materials.

Emerging Structural and Interfacial Features of Particulate Polymers at the Nanoscale.

Particulate polymers at the nanoscale are exceedingly promising for diversified functional applications ranging from biomedical and energy to sensing, labeling, and catalysis. Tailored structural features (i.e., size, shape, morphology, internal softness, interior cross-linking, etc.) determine polymer nanoparticles' impact on the cargo loading capacity and controlled/sustained release, possibility of endocytosis, degradability, and photostability. The designed interfacial features, however (i.e., stimuli-responsive surfaces, wrinkling, surface porosity, shell-layer swellability, layer-by-layer surface functionalization, surface charge, etc.), regulate nanoparticles' interfacial interactions, controlled assembly, movement and collision, and compatibility with the surroundings (e.g., solvent and biological environments). These features define nanoparticles' overall properties/functions on the basis of homogeneity, stability, interfacial tension, and minimization of the surface energy barrier. Lowering of the resultant outcomes is directly influenced by inhomogeneity in the structural and interfacial design through the structure-function relationship. Therefore, a key requirement is to produce well-defined polymer nanoparticles with controlled characteristics. Polymers are amorphous, flexible, and soft, and hence controlling their structural/interfacial features through the single-step process is a challenge. The microfluidics reaction strategy is very promising because of its wide range of advantages such as efficient reactant mixing and fast phase transfer. Overall, this feature article highlights the state-of-the-art synthetic features of polymer nanoparticles with perspectives on their advanced applications.

Preparation and Deep Characterization of Composite/Hybrid Multi-Scale and Multi-Domain Polymeric Microparticles.

Polymeric microparticles were produced following a three-step procedure involving (i) the production of an aqueous nanoemulsion of tri and monofunctional acrylate-based monomers droplets by an elongational-flow microemulsifier, (ii) the production of a nanosuspension upon the continuous-flow UV-initiated miniemulsion polymerization of the above nanoemulsion and (iii) the production of core-shell polymeric microparticles by means of a microfluidic capillaries-based double droplets generator; the core phase was composed of the above nanosuspension admixed with a water-soluble monomer and gold salt, the shell phase comprised a trifunctional monomer, diethylene glycol and a silver salt; both phases were photopolymerized on-the-fly upon droplet formation. Resulting microparticles were extensively analyzed by energy dispersive X-rays spectrometry and scanning electron microscopy to reveal the core-shell morphology, the presence of silver nanoparticles in the shell, organic nanoparticles in the core but failed to reveal the presence of the gold nanoparticles in the core presumably due to their too small size (c.a. 2.5 nm). Nevertheless, the reddish appearance of the as such prepared polymer microparticles emphasized that this three-step procedure allowed the easy elaboration of composite/hybrid multi-scale and multi-domain polymeric microparticles.

Single-Step In Situ Assembling Routes for the Shape Control of Polymer Nanoparticles.

Controlling shapes of polymer nanoparticles via single-step process is a challenge due to their amorphous chemical nature. Precise regulation of interfacial interactions, electrical charging and reaction dynamics during ongoing polymerization process provides an environment where uniform nucleation, growth and in situ assembling can be realized, and hence nanoparticles of complex shapes can be obtained. In this work, it is investigated how in situ assembling of the growing nanoparticles succeeds and specifically in different manners by using cationic, anionic, polyionic, and nonionic surface-active agents in a time-dependent blended form. Micelle of molecular surfactants leads the spheres, but long chained polyelectrolytes support in situ assembling of growing spheres to form the nonspherical polymer nanoparticles in order to minimize the surface energy of a system. Similarly, a nonionic polymer promotes the movement of growing species in solution and allows tunable aggregation-based growth which produces more complexed nanoparticles. Furthermore, the application of acid, base and salt solution also contribute specific effect where unexpected size and shape of nanoparticles can be obtained. Overall, the roles of limited polarizability, solvation power, mobility, ionic strength, pH, and microfluidics for the synthesis of various shape-controlled polymer nanoparticles are presented here.

Microfluidic Assisted Synthesis of Multipurpose Polymer Nanoassembly Particles for Fluorescence, LSPR, and SERS Activities.

Potential biomedical applications such as controlled delivery with sustained drug release profile demand for multifunctional polymeric particles of precise chemical composition and with welldefined physicochemical properties. The real challenge is to obtain the reproducible and homogeneous nanoparticles in a minimum number of preparation steps. Here, single-step nanoarchitectures of soft surface layered copolymer nanoparticles with a regular tuning in the size via micro flow-through assisted synthesis are reported. Interfacial copolymerization induces the controlled compartmentalization where a hydrophobic core adopts spherical shape in order to minimize the surface energy and simultaneously shelter in the hydrophilic shelllike surface layer. Surface layer can swell in the aqueous medium and allow controlled entrapping of functional hydrophobic nanoparticles in the hydrophilic interior via electrostatic interaction which can be particularly interesting for combined fluorescence activity. Furthermore, the nanoarchitecture of size and concentration controlled polymer-metal nanoassembly particles can be implemented as an ideal surface-enhanced Raman scattering substrate for detection of the trace amounts of various analytes.

Composite Sensor Particles for Tuned SERS Sensing: Microfluidic Synthesis, Properties and Applications.

Surface-enhanced Raman scattering (SERS) is a promising platform for particle-based sensor signaling, and droplet-based microfluidic systems are particularly advantageous for control of the size and composition of micro- and nanoparticles. For controlled sensing application, a high homogeneity of the sensor particles is a key requirement, and the particles with functional properties demand for the preparation in a minimum number of synthesis steps. Frequently used coflow and flow focusing arrangements, however, produce the microparticles of only larger size. To address such concern for downscaling of particle size, which is crucial for strong sensing outcome, we have used a peculiar micro cross-flow arrangement here for generating the polymer microparticles of broad size range between 30 and 600 µm along with in situ embedded silver nanoparticles. Embedded silver acts as nuclei for additional silver enforcement via silver-catalyzed silver deposition in order to realize the composite microparticles for SERS sensing. The homogeneous size and spatial distribution of silver nanoparticles inside the matrix and enforcement over the surface together with controlled pore size provides a high and homogeneous loading of polymer composite sensor. Moreover, different parameters such as analytes concentration and particles size have been studied here for SERS sensing application of biochemical molecules (amino acids and vitamins). Overall, the platform for size-tuned droplets generation, synthesis of composite microparticles, mechanism for synchronized photopolymerization-photoreduction, tuned silver enforcement, and the impacts of different analytes on differently composed microparticles are systematically investigated in this paper.

Control of shape and size of polymer nanoparticles aggregates in a single-step microcontinuous flow process: a case of flower and spherical shapes.

Controlled aggregation of polymer nanoparticles for building anisotropic nano- and microstructures via a self-assembling bottom-up process is an important strategy. Therefore, in this work, the formation of structured poly(methyl methacrylate) (PMMA) particles with diameters between lower micrometer and submicrometer range by use of a microcontinuous flow arrangement was investigated in the presence of nonionic water-soluble polymer polyvinylpyrrolidone (PVP). The investigations show that the microreaction strategy is well applicable and allows a tuning of size and shape of nanoparticles in dependence on reactant concentrations and flow rate ratios. Larger and complex structured polymer particles have been found at lower PVP concentration, whereas more compact submicron-sized particles were formed at higher PVP concentrations. The addition of ionic surfactants modulates the generation of characteristic particle shapes. The observation of intermediate states between complex flowerlike particles and simple spheres in dependence on the applied concentration of low molecular weight surfactants supports the explanation of particle formation by a mechanism with superposition of particle growth and assembling. When mixed surfactants (PVP-SDS or PVP-CTAB) are used, the final particles shape depends on the concentration of individual concentrations of surfactants and on the competition between mobility, solvation, and micelle formations.

Single-step microfluidic synthesis of various nonspherical polymer nanoparticles via in situ assembling: dominating role of polyelectrolytes molecules.

In this paper, a microfluidic approach has been used for the synthesis of ellipsoidal, dumbbell, rodlike, and necklacelike polymer nanoparticles. High yields of special types of nonspherical nanoparticles have been achieved by the implementation of an emulsion polymerization into microfluidic arrangement with a micro hole-plate reactor for the formation of monomer droplets. Here, in particular, the formation of nonspherical polymer nanoparticles is dependent on the presence of polyelectrolyte surface active molecules such as poly(4-styrenesulfonic acid-co-maleic acid) sodium salt (PSS-co-PM), poly(sodium-p-styrenesulfonate) (PSSS), and polyanetholesulfonic acid sodium salt (PAES). The shapes and sizes of the interparticle nanoassemblies are precisely controlled by adjusting the concentration of polyelectrolytes in the aqueous phase, and by choosing suitable flow rate ratios (aqueous to monomer phase), respectively. The formation of polymer nanoparticles with different morphologies can be explained by a spontaneous in situ assembling under partial electrostatic repulsive control in the single step synthesis. The effect of particle charge and the competition between thermal motion of particles and electrostatic repulsion on the spontaneous assembling under the condition of a limited polarizability are discussed here as an important factor for the formation process of nonspherical polymer nanoparticles.

Vesicle structures from bolaamphiphilic biosurfactants: experimental and molecular dynamics simulation studies on the effect of unsaturation on sophorolipid self-assemblies.

The formation of giant-vesicle-like structures by self-assembling linolenic acid sophorolipid (LNSL) molecules is revealed. Sophorolipids belong to the class of bolaamphiphilic glycolipid biosurfactants. Interestingly, the number of double bonds present in the hydrophobic core of sophorolipids is seen to have a great influence on the type of self-assembled structures formed. Dye encapsulation results establish the presence of an aqueous compartment inside the LNSL vesicles. Molecular dynamics simulation (MD) studies suggest the existence of two possible conformations of LNSLs inside the self-assembled structures and that LNSL molecules arrange in layered structures.

A self-seeding synthesis of Ag microrods of tuned aspect ratio: ascorbic acid plays a key role.

Control of the shape and size of nanoparticles is crucial for using them as labels or as building blocks in nanotechnology. In fact, silver has so far been considered as having the widest variety of different morphologies at the nano-scale and micro-scale levels. To make progress in these criteria, in our paper we have synthesized highly reproducible silver (Ag) microrods of controlled aspect ratios through a rapid self-seeding method. The Ag nano seeds are formed via the reduction of Ag ions in hot ethylene glycol by ascorbic acid, and the subsequent growth of microrods is controlled by further deposition of Ag atoms in the presence of poly(vinylpyrrolidone). Moreover, ascorbic acid is exclusively responsible for the rod morphology, as we describe here in detail. A very low concentration of ascorbic acid forms very few Ag microrods along with a majority of Ag colloidal particles, while random overgrowth on the surfaces is observed for higher concentrations. The critical reaction condition has been found in that the aspect ratio of the Ag microrods can be systematically tuned between 4 and 90. Also, the method in which ascorbic acid is added to the reaction medium plays a key role in controlling the aspect ratio of the Ag microrods. The non-monotonic dependence of the length and the diameter of the Ag microrods has been described by an empirical equation. The function can be interpreted by means of concentration-dependent competition between the adsorption of ligands and metal deposition.

Spontaneous transformation of polyelectrolyte-stabilized silver nanoprisms by interaction with thiocyanate.

The reaction of KSCN with colloidal solutions of triangular silver nanoprisms results in a shape transformation. The reaction cannot be explained by a simple etching of the corners of the triangles, as it is described in earlier reports on the interaction of silver nanoprisms with halide anions leading to the formation of nanodisks. The reaction products after KSCN addition are spherical silver nanoparticles with a homogeneous size distribution, which display the typical short-wavelength plasmon absorption at about 410 nm. The spectral online monitoring of the reaction reflects a rather homogeneous conversion process. In some cases, isosbestic points have been observed, indicating a reaction of the initial particle type directly to the final particle type. The kinetics of the conversion process are better described by a molecular conversion, than by a process with a step-wise transport of material leading to a continuous change in the particle shape. The experimental findings suggest a two-step mechanism for the conversion: In a first (slow) step the particle is destabilized by desorption of the anionic polyelectrolyte ligand. Then the destabilized particles relax quickly in a (fast) second step to a spherical shape. This interpretation seems to have a serious impact on the understanding of non-spherical nanoparticles in general: The comparatively large triangular shaped prismatic particles in aqueous solution are stabilized by their specific electronic properties due to the interaction with one or several ligand molecules and must be understood as a molecular-analog dynamic system than as a small solid-state body.