Mediating Oxidation of Thioethers with Iodine-A Mild and Versatile Pathway to Trigger the Formation of Peptide Hydrogels.

The development of redox-triggerable peptide hydrogels poses fundamental challenges, since the highly specific peptide architectures required inevitably limit the versatility of such materials. A powerful, yet rarely applied approach to bypass those barriers is the application of a mediating redox reaction to gradually decrease the pH during hydrogel formation. We report a versatile strategy to trigger the formation of peptide hydrogels from readily accessible acid-triggerable gelators by generating protons by oxidation of thioethers with triiodide. Adding thiodiglycol as a readily available thioether auxiliary to the basic precursor solution of a peptide gelator efficiently yielded hydrogels after mixing with triiodide, as studied in detail for Nap-FF and demonstrated for other peptides. Furthermore, incorporation of the thioether moiety in the gelator backbone via the amino acid methionine, as shown for the tailormade Nap-FMDM peptide, reduces the number of required additives.

Magneto-responsive hydrogels by self-assembly of low molecular weight peptides and crosslinking with iron oxide nanoparticles.

Hydrogels that respond to non-invasive, external stimuli such as a magnetic field are of exceptional interest for the development of adaptive soft materials. To date magneto tuneable gels are predominantly based on macromolecular building blocks, while comparable low molecular weight systems are rarely found in the literature. Herein, we report a highly efficient peptide-based gelator (Nap GFYE), which can form hydrogels and incorporate Fe3O4 superparamagnetic nanoparticles in the gel matrix. The magnetic nanoparticles act as a physical crosslinker for the self-assembled peptide nanostructures and thus give rise to a fortified hybrid gel with distinctively improved mechanical properties. Furthermore, the particles provide the material with magnetic susceptibility and a gel to sol transition is observed upon application of a weak magnetic field. Magnetization of the inorganic-organic hybrid nanomaterial leads to on-demand release of an incorporated fluorescent dye into the supernatant.

Photoresponsive hybrid hydrogel with a dual network of agarose and a self-assembling peptide.

Responsive hybrid hydrogels composed of a self-assembling low molecular weight gelator and a polymeric network are of particular interest for the development of smart nanomaterials. Key advantages of such hybrid hydrogels are their ease in preparation as well as their unique mechanical properties. Herein we describe a photoresponsive peptide AAP-FGDS, which exhibits excellent photochemical properties and highly reversible changes in the rheological properties. Addition of AAP-FGDS to a covalent, non-responsive agarose network gives rise to a robust hybrid hydrogel with phototunable mechanical properties and shape memory. Upon irradiation with UV light the self-assembled three dimensional structure disaggregates to yield a softer yet self-supporting hydrogel. Irradiation with visible light followed by the reassembly of the peptide allows the fixation of a different shape programmed by mechanical deformation. Upon repeated deactivation of the peptide network the original shape is recovered.

Magneto- and photo-responsive hydrogels from the co-assembly of peptides, cyclodextrins, and superparamagnetic nanoparticles.

Dual response to external non-invasive stimuli, such as light and magnetic field, is a highly desirable property in soft nanomaterials with potential applications in soft robotics, tissue engineering, and life-like materials. Within this class of materials, hydrogels obtained from the self-assembly of low molecular weight gelators (LMWGs) are of special interest due to their ease of preparation and modification. Herein, we report a modular co-assembly strategy for a magneto- and photo-responsive supramolecular hydrogel based on the arylazopyrazole (AAP) modified pentapeptide gelator Nap-GFFYS, and ß-cyclodextrin vesicles (CDVs) with superparamagnetic cobalt ferrite nanoparticles embedded in their membranes. Upon application of a magnetic field, a reversible increase in the storage modulus is observed during rheological measurements. Additionally, a gel rod could be manipulated with a weak permanent magnet, resulting in macroscopic bending of the rod. Furthermore, through irradiation with UV and visible light, respectively, the host-guest interaction between the AAP moiety and the hydrophobic cavity of the ß-CD can be deactivated on demand, thus lowering the stiffness of the hydrogel reversibly.

The influence of hyaluronan on the structure of a DPPC-bilayer under high pressures.

The superior lubrication properties of synovial joints have inspired many studies aiming at uncovering the molecular mechanisms which give rise to low friction and wear. However, the mechanisms are not fully understood yet, and, in particular, it has not been elucidated how the biolubricants present at the interface of cartilage respond to high pressures, which arise during high loads of joints. In this study we utilize a simple model system composed of two biomolecules that have been implied as being important for joint lubrication. It consists of a solid supported dipalmitoylphosphatidylcholin (DPPC) bilayer, which was formed via vesicles fusion on a flat Si wafer, and the anionic polysaccharide hyaluronan (HA). We first characterized the structure of the HA layer that adsorbed to the DPPC bilayers at ambient pressure and different temperatures using X-ray reflectivity (XRR) measurements. Next, XRR was utilized to evaluate the response of the system to high hydrostatic pressures, up to 2kbar (200MPa), at three different temperatures. By means of fluorescence microscopy images the distribution of DPPC and HA on the surface was visualized. Our data suggest that HA adsorbs to the headgroup region that is oriented towards the water side of the supported bilayer. Phase transitions of the bilayer in response to temperature and pressure changes were also observed in presence and absence of HA. Our results reveal a higher stability against high hydrostatic pressures for DPPC/HA composite layers compared to that of the DPPC bilayer in absence of HA.

Solid-Supported Lipid Multilayers under High Hydrostatic Pressure.

In this work, the structure of solid-supported lipid multilayers exposed to increased hydrostatic pressure was studied in situ by X-ray reflectometry at the solid-liquid interface between silicon and an aqueous buffer solution. The layers' vertical structure was analyzed up to a maximum pressure of 4500 bar. The multilayers showed phase transitions from the fluid into different gel phases. With increasing pressure, a gradual filling of the sublayers between the hydrophilic head groups with water was observed. This process was inverted when the pressure was decreased, yielding finally smaller water layers than those in the initial state. As is commonly known, water has an abrasive effect on lipid multilayers by the formation of vesicles. We show that increasing pressure can reverse this process so that a controlled switching between multi- and bilayers is possible.

Sewage sludge ash to phosphate fertilizer by chlorination and thermal treatment: residence time requirements for heavy metal removal.

Heavy metal removal from sewage sludge ash can be performed by mixing the ash with environmentally compatible chlorides (e.g. CaCl2 or MgCl2) and water, pelletizing the mixture and treating the pellets in a rotary reactor at about 1000 degrees C. Thermogravimetry-mass spectroscopy, muffle oven tests (500-1150 degrees C) and investigations in a laboratory-scale rotary reactor (950-1050 degrees C, residence time 1-25 min) were carried out. In the rotary reactor, up to 97% of Cu, 95% Pb and 95% Zn can be removed at 1050 degrees C. As Cl release starts from 400 degrees C (obtained from thermogravimetry-mass spectrometry experiments), heavy metals are already removed partially within the heating period. This heavy metal removal can be described as being similar to a first-order rate law. To meet the limit values specified in the Austrian and German fertilizer ordinances, residence times of the order of minutes are sufficient at 950 degrees C.

Limitations for heavy metal release during thermo-chemical treatment of sewage sludge ash.

Phosphate recycling from sewage sludge can be achieved by heavy metal removal from sewage sludge ash (SSA) producing a fertilizer product: mixing SSA with chloride and treating this mixture (eventually after granulation) in a rotary kiln at 1000 ± 100°C leads to the formation of volatile heavy metal compounds that evaporate and to P-phases with high bio-availability. Due to economical and ecological reasons, it is necessary to reduce the energy consumption of this technology. Generally, fluidized bed reactors are characterized by high heat and mass transfer and thus promise the saving of energy. Therefore, a rotary reactor and a fluidized bed reactor (both laboratory-scale and operated in batch mode) are used for the treatment of granulates containing SSA and CaCl(2). Treatment temperature, residence time and - in case of the fluidized bed reactor - superficial velocity are varied between 800 and 900°C, 10 and 30 min and 3.4 and 4.6 ms(-1). Cd and Pb can be removed well (>95 %) in all experiments. Cu removal ranges from 25% to 84%, for Zn 75-90% are realized. The amount of heavy metals removed increases with increasing temperature and residence time which is most pronounced for Cu. In the pellet, three major reactions occur: formation of HCl and Cl(2) from CaCl(2); diffusion and reaction of these gases with heavy metal compounds; side reactions from heavy metal compounds with matrix material. Although, heat and mass transfer are higher in the fluidized bed reactor, Pb and Zn removal is slightly better in the rotary reactor. This is due the accelerated migration of formed HCl and Cl(2) out of the pellets into the reactor atmosphere. Cu is apparently limited by the diffusion of its chloride thus the removal is higher in the fluidized bed unit.