Frank Polzer

Interaction of gold nanoparticles with thermoresponsive microgels: influence of the cross-linker density on optical properties

The interaction of spherical gold nanoparticles (Au-NPs) with microgels composed of chemically cross-linked poly-(N-isopropylacrylamide) is reported. Simple mixing of the two components leads to adsorption of the gold particles onto the microgels. Different loading densities can be achieved by varying the ratio of gold particles to microgel particles. The adsorption of gold nanoparticles is analysed by TEM, UV-Vis absorption spectroscopy and SAXS. The influence of the microgel mesh size on the adsorption of gold nanoparticles is investigated by using microgels with three different cross-linker densities. The results suggest a strong relationship between the nanoparticle penetration depth and the cross-linker density. This, in turn, directly influences the optical properties of the colloids due to plasmon resonance coupling. In addition, information about the mesh size distribution of the microgels is obtained. For the first time the change in optical properties by varying cross-linker density and temperature is directly related to the formation of dimers of gold particles, proven by SAXS.

Poly(ionic liquid)-derived nitrogen-doped hollow carbon spheres: synthesis and loading with Fe₂O₃ for high-performance lithium ion batteries

Porous nitrogen-doped hollow carbon spheres (NHCSs) with tailored particle size, nitrogen content and wall thickness were prepared by grafting a thin layer of poly(ionic liquid) as carbon precursor onto silica particle surface followed by carbonization and template removal. In the next step, Fe2O3 nanoparticles were anchored onto the NHCSs via an impregnation-thermal decomposition route using Fe(NO3)3 as iron source. The as-synthesized Fe2O3–NHCS composite was utilized as the anode material for a lithium-ion battery, which exhibited a high reversible capacity of 1120 mAh g−1 at a rate of 100 mA g−1, and a coulombic efficiency of ∼98% at a rate of 500 mA g−1 after 65 cycles.

Polyelectrolyte as Solvent and Reaction Medium

A poly(ionic liquid) with a rather low glass transition temperature of -57°C was synthesized via free radical polymerization of an acrylate-type ionic liquid monomer. It exhibits fluidic behavior in a wide temperature range from room temperature to the threshold of the thermal decomposition. We demonstrate that it could act as a unique type of macromolecular solvent to dissolve various compounds and polymers and separate substances. In addition, this polyelectrolyte could serve successfully as reaction medium for catalysis and colloid particle synthesis. The synergy in the solvation and stabilization properties is a striking character of this polymer to downsize the in situ generated particles.

Nanotubular J-Aggregates and Quantum Dots Coupled for Efficient Resonance Excitation Energy Transfer

Resonant coupling between distinct excitons in organic supramolecular assemblies and inorganic semiconductors is supposed to offer an approach to optoelectronic devices. Here, we report on colloidal nanohybrids consisting of self-assembled tubular J-aggregates decorated with semiconductor quantum dots (QDs) via electrostatic self-assembly. The role of QDs in the energy transfer process can be switched from a donor to an acceptor by tuning its size and thereby the excitonic transition energy while keeping the chemistry unaltered. QDs are located within a close distance (<4 nm) to the J-aggregate surface, without harming the tubular structures and optical properties of J-aggregates. The close proximity of J-aggregates and QDs allows the strong excitation energy transfer coupling, which is around 92% in the case of energy transfer from the QD donor to the J-aggregate acceptor and approximately 20% in the reverse case. This system provides a model of an organic-inorganic light-harvesting complex using methods of self-assembly in aqueous solution, and it highlights a route toward hierarchical synthesis of structurally well-defined supramolecular objects with advanced functionality.

Asymmetric self-assembly of oppositely charged composite microgels and gold nanoparticles

The electrostatically driven self-assembly of oppositely charged gold nanoparticles (Au NPs) and polystyrene/poly(N-isopropylacrylamide) (PS/PNIPAm) core-shell microgels (CSMs) has been investigated. The co-assembly was accomplished by addition of smaller Au NPs to CSMs in dilute conditions up to a number ratio of about 1 : 1, when the suspension is destabilized. A combination of different techniques (i.e. turbidimetric titration, electrophoretic mobility, UV-visible spectroscopy, dynamic light scattering and microscopy techniques) were used to investigate the association between the two particles and the stability of the different mixtures. Hereby we demonstrate that the size ratio between the two particles (about 4 to 1) and the asymmetric character of the association result in the formation of electrostatic hybrid complexes, analogous to dipolar colloidal molecules, which further rearrange into finite sized clusters for number ratios NAuNPs/NCSMs < 1.

Computationally designed peptides for self-assembly of nanostructured lattices

Peptide lattices were designed using computational methods and controlled by tuning self-assembly solution conditions. Folded peptides present complex exterior surfaces specified by their amino acid sequences, and the control of these surfaces offers high-precision routes to self-assembling materials. The complexity of peptide structure and the subtlety of noncovalent interactions make the design of predetermined nanostructures difficult. Computational methods can facilitate this design and are used here to determine 29-residue peptides that form tetrahelical bundles that, in turn, serve as building blocks for lattice-forming materials. Four distinct assemblies were engineered. Peptide bundle exterior amino acids were designed in the context of three different interbundle lattices in addition to one design to produce bundles isolated in solution. Solution assembly produced three different types of lattice-forming materials that exhibited varying degrees of agreement with the chosen lattices used in the design of each sequence. Transmission electron microscopy revealed the nanostructure of the sheetlike nanomaterials. In contrast, the peptide sequence designed to form isolated, soluble, tetrameric bundles remained dispersed and did not form any higher-order assembled nanostructure. Small-angle neutron scattering confirmed the formation of soluble bundles with the designed size. In the lattice-forming nanostructures, the solution assembly process is robust with respect to variation of solution conditions (pH and temperature) and covalent modification of the computationally designed peptides. Solution conditions can be used to control micrometer-scale morphology of the assemblies. The findings illustrate that, with careful control of molecular structure and solution conditions, a single peptide motif can be versatile enough to yield a wide range of self-assembled lattice morphologies across many length scales (1 to 1000 nm).

Electronic structure of individual hybrid colloid particles studied by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the X-ray microscope.

The electronic structure of individual hybrid particles was studied by nanoscale near-edge X-ray absorption spectromicroscopy. The colloidal particles consist of a solid polystyrene core and a cross-linked poly-N-(isopropylacrylamide) shell with embedded crystalline titanium dioxide (TiO(2)) nanoparticles (d = 6 ± 3 nm). The TiO(2) particles are generated in the carrier network by a sol-gel process at room temperature. The hybrid particles were imaged with photon energy steps of 0.1 eV in their hydrated environment with a cryo transmission X-ray microscope (TXM) at the Ti L(2,3)-edge. By analyzing the image stacks, the obtained near-edge X-ray absorption fine structure (NEXAFS) spectra of our individual hybrid particles show clearly that our synthesis generates TiO(2) in the anastase phase. Additionally, our spectromicroscopy method permits the determination of the density distribution of TiO(2) in single carrier particles. Therefore, NEXAFS spectroscopy combined with TXM presents a unique method to get in-depth insight into the electronic structure of hybrid materials.

Silica-coated Au/Ag nanorods with tunable surface plasmon bands for nanoplasmonics with single particles

We present the synthesis and analysis of silica-coated Au/Ag bimetallic nanorods with controlled surface plasmon bands. Depending on the thickness of Ag shell deposited on the Au nanorod surface, there is a blue-shift on the longitudinal surface plasmon band of Au nanorods, which can be expressed by an approximate formula derived from the absorption profile of light in Ag films using finite difference time domain simulations. The subsequent coating of silica shell not only enhances the stability of the Au/Ag bimetallic nanorods but also provides a mesoporous host for optically active species. Minute red-shifts of the longitudinal resonance mode, induced by stepwise increased silica shell volumes, are shown. Application as carrier for fluorescent rhodamine B molecules is demonstrated by photoluminescence analysis. On the single-particle level, dark field microscopy of Au/Ag-silica nanorods was finally employed. This introduces a route towards revealing the relation between structure, shape, and optical (plasmonic) properties of complex composite metal particles as well as fabrication strategies for nanoassemblies of tailored structures in the field of nanoplasmonics.

Synthesis and Characterization of Monodisperse Thermosensitive Dumbbell-Shaped Microgels

Monodisperse thermosensitive dumbbell-shaped core-shell microgels are fabricated, which consist of a polystyrene core with a cross-linked poly (N-isopropylacrylamide) shell. The morphology of the microgels was investigated through cryogenic transmission electron microscopy and depolarized dynamic light scattering. The effective volume fraction and aspect ratio of the system could be adjusted through the swelling of the thermosensitive shell. We observe a phase transition of the microgels to an ordered, crystal-like state, which is apparent through Bragg-reflections in the visible range. These observations are further supported by rheological measurements where the shear-melting of the crystal phase is clearly detected.

Thermosensitive hollow Janus dumbbells

Thermosensitive hollow Janus dumbbells, consisting of two partially fused hollow poly (N-isopropylacrylamide) (PNIPAM) spheres, were prepared using dumbbell-shaped microgels as templates. One sphere has a shell completely made of PNIPAM while the other one has a hybrid shell, which is a poly(styrene-co-3-(trimethoxysilyl)propyl methacrylate) layer covered by PNIPAM. The morphology of hollow Janus dumbbells is fully characterized by cryo- and transmission electron microscopy, scanning force microscopy, and dynamic light scattering. Transmission electron microscopy demonstrates that the particles have a very narrow size distribution. The analysis by depolarized dynamic light scattering showed that the hollow Janus dumbbells exhibit a thermosensitive behavior comparable to the dumbbell-shaped microgels before the removal of the core.