Steffi Stumpf

Self-healing metallopolymers based on cadmium bis(terpyridine) complex containing polymer networks

The utilization of metal–ligand interactions within polymers generates materials which are of interest for several applications, including self-healing materials. In this work we use methacrylate copolymers containing terpyridine moieties in the side chain for the formation of self-healing metallopolymer networks. The materials were synthesized using the reversible addition–fragmentation chain transfer (RAFT) polymerization technique and subsequent crosslinking by the addition of a metal salt, here cadmium(II) salts, with different counter-ions. The influence of the counter-ions on the self-healing process within these structures was analyzed. The research resulted in a new polymeric material featuring a high (intrinsic) healing efficiency at relatively low temperatures (<75 °C).

Localized atmospheric plasma sintering of inkjet printed silver nanoparticles

Atmospheric pressure argon plasma sintering of silver nanoparticle inks was investigated to improve the plasma sintering process in terms of sintering speed, substrate friendliness and technical complexity. Sintering times were reduced to several seconds while achieving similar conductivity values of above 10% compared to bulk silver. Sintering can be carried out under ambient conditions at specific locations without exposing the entire substrate. Plasma sintering at atmospheric pressure exhibits the capability to be used in roll-to-roll production processes.

Towards single-pass plasma sintering: temperature influence of atmospheric pressure plasma sintering of silver nanoparticle ink

A combination of atmospheric pressure plasma sintering (APPS) and a mild thermal treatment of less than 110 °C was investigated in order to reduce the sintering time of inkjet-printed silver nanoparticle inks. Cold as well as warm plasma sources revealed a resistivity down to 6 times of bulk silver within a single pass at a movement speed of 20 mm s−1, which equals a reduction of process time by a factor of at least five compared to previously reported plasma sintering techniques. The developed process was used to produce components for flexible electronics, like honeycomb grid structures and UHF RFID antennas on thermo-sensitive substrate materials. This approach represents a significant step towards a roll-to-roll (R2R) compatible technology.

Dual pH and ultrasound responsive nanoparticles with pH triggered surface charge-conversional properties

A series of dual pH- and ultrasound responsive statistical copolymers were synthesized via the reversible addition–fragmentation chain transfer (RAFT) polymerization of 3,4-dihydro-2H-pyran (DHP) protected HEMA 2-((tetrahydro-2H-pyran-2-yl)oxy)ethyl methacrylate (THP-HEMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). The RAFT-controlled nature of the (co)polymerizations was verified by detailed kinetic studies. The chemical structure and the co-monomer composition of the copolymers were confirmed by 1H NMR spectroscopy. The number-average molar mass values (Mn) and dispersities (ĐM = Mw/Mn) of the copolymers were estimated by size exclusion chromatography (SEC). The thermal properties of the (co)polymers were analyzed by means of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Additionally, the DMAEMA moieties of the copolymers were quaternized with an excess of methyl iodide. The synthesized polymers self-assemble into nanoparticles in aqueous media via the nanoprecipitation method and were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Zeta potential measurements revealed that all DMAEMA containing nanoparticles undergo a surface charge conversion from positive to negative at slightly acidic pH values. However, quaternized DMAEMA nanoparticles possess pH independent positive surface charges. At acidic pH values, the nanoparticles disassemble and dissolve in water due to the protonation of the DMAEMA moieties and/or due to the acidic hydrolysis of the THP-HEMA groups. It was found that the surface charge and the stability of the nanoparticles were greatly affected by the DMAEMA content of the polymers, meaning that the isoelectric point (IEP), at which the charge is reversed and the pH value at which the disassembly occurs, increased with the higher DMAEMA content in the copolymer. Moreover, it was proven that the ionization of the carboxyl RAFT end-group of the polymers enhanced the anionic character and the stability of the nanoparticles at neutral pH values. DLS and scanning electron microscopy (SEM) measurements revealed that these nanoparticles can be further disrupted by ultrasound exposure. Nile Red was encapsulated into nanoparticles as a model hydrophobic drug. The release profile of the Nile Red was significantly accelerated in acidic media or under ultrasound exposure. The cytotoxicity assay results showed that negatively charged nanoparticles are non-toxic and biocompatible, whereas positively charged nanoparticles are extremely toxic to L929 cells.

Hierarchical Self-Assembly of Double-Crystalline Poly(ferrocenyldimethylsilane)-block-poly(2-iso-propyl-2-oxazoline) (PFDMS-b-PiPrOx) Block Copolymers

The step-wise solution self-assembly of double crystalline organometallic poly(ferrocenyldimethylsilane)-block-poly(2-iso-propyl-2-oxazoline) (PFDMS-b-PiPrOx) diblock copolymers is demonstrated. Two block copolymers are obtained by copper-catalyzed azide-alkyne cycloaddition (CuAAC), featuring PFDMS/PiPrOx weight fractions of 46/54 (PFDMS30-b-PiPrOx75) and 30/70 (PFDMS30-b-PiPrOx155). Nonsolvent induced crystallization of PFDMS in acetone leads in both cases to cylindrical micelles with a PFDMS core. Afterward, the structures are transferred into water for sequential temperature-induced crystallization of the PiPrOx corona, leading to hierarchical double crystalline superstructures, which are investigated using scanning electron microscopy, wide angle X-ray scattering, and differential scanning calorimetry.

Drugs as matrix to detect their own drug delivery system of PEG-b-PCL block copolymers in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

RATIONALE The fate of drug delivery systems (DDSs) in vivo is a widely discussed question. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is an important tool to localize proteins and small compounds in many different tissues. This basic study was performed as an aid to obtain spatial information on DDSs in the future. METHODS LDI and MALDI-TOF MS was used to investigate five drug molecules, i.e. madurahydroxylactone (MHL), tetrakis(4-hydroxyphenyl)porphyrin (THP), chartreusin (Chart), amphotericin B (AmB) and retinoic acid (RA). The drug molecules were analyzed in terms of their efficiency to act as matrix for different homopolymers and the block copolymer poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-b-PCL). The block copolymer was further utilized as a DDS to encapsulate the drug molecules previously investigated as matrices. The obtained DDSs were investigated by MALDI. RESULTS The spectra obtained with the drugs Chart, MHL, THP and AmB did not reach the quality of the standard matrix RA. Nonetheless, they showed surprisingly good results as matrices for different homopolymers and the block copolymer. However, only the DDSs containing THP as the drug provided spectra where the drug and the block copolymer were detected. CONCLUSIONS These results form the foundation for obtaining mass-related information about the localization of DDSs and drugs in tissues.