Hydrolytic Stability of Crosslinked, Highly Alkaline Diallyldimethylammonium Hydroxide Hydrogels.

The aim of this study was to evaluate the persistence of alkaline hydrogels based on a common (N,N'-methylenebisacrylamide, BIS) and three recently published tetraallyl crosslinkers. Such hydrogels have been shown to be suitable materials for the rehabilitation of cementitious materials. Of the four crosslinkers under investigation, N,N,N',N'-tetraallylpiperazinium dibromide decomposed quickly in 1 m KOH solution and was not considered further. BIS showed the first signs of a decomposition after several days, while tetraallylammonium bromide and N,N,N',N'-tetraallyltrimethylene dipiperidine dibromide remained unaffected. In contrast to BIS, which suffers from low solubility in water, the two tetraallyl crosslinkers show unlimited miscibility with diallyldimethylammonium hydroxide solutions. For the study, gels with up to 50 wt % crosslinker were prepared. Of these, gels containing tetraallylammonium bromide always show the highest degrees of swelling, with a peak value of 397 g/g at a content of 2 wt %. Under accelerated ageing at 60 °C for 28 d, gels crosslinked with BIS ultimately turned liquid, while the storage modulus and the degree of swelling of the two tetraallyl-crosslinked gels remained unchanged. This indicates that alkaline gels can be suitable for long application periods, which are common for rehabilitation measures in the construction industry.

Multivalent Allylammonium-Based Cross-Linkers for the Synthesis of Homogeneous, Highly Swelling Diallyldimethylammonium Chloride Hydrogels.

N,N'-methylenebisacrylamide (BIS) is a very popular cross-linker for the radical polymerisation in water. It is highly reactive but prone to alkaline hydrolysis and suffers from a low solubility. This study shows that with slow polymerising systems such as N,N-diallyldimethylammonium chloride, only inhomogeneous networks are formed. As a consequence, gels with very low cross-linking densities, i.e., high swelling capacities, disintegrate during the swelling test and firm, coherent gels are not accessible due to the solubility limit. A promising alternative are multivalent tetraallyl-based compounds, of which tetraallylammonium bromide (TAAB), N,N,N',N'-tetraallylpiperazinium dibromide (TAPB) and N,N,N',N'-tetraallyltrimethylene dipiperidine dibromide (TAMPB) are the subject of this study. With these, the cross-linking polymerisation appears to be statistical, as gels formed at low monomer conversion have essentially the same swelling properties as those formed at high conversions. This is not observed with BIS. However, gelation with the tetraallyl cross-linkers is much slower than with BIS and follows the order TAPB < TAMPB < TAAB, but the differences become significantly smaller with increasing content. At low contents, all three allow the preparation of gels with high swelling capacities of up to 360 g/g.

Poultry Feather Waste as Bio-Based Cross-Linking Additive for Ethylene Propylene Diene Rubber.

Most rubbers used today rely on sulphur as a cross-linking agent and carbon black from fossil resources to modify the mechanical properties. A very promising substitute can be found in natural keratins such as feathers. These are not only tough, but also contain a relevant amount of sulphur in the form of disulphide bridges. The present study shows that these can be activated under vulcanisation conditions and then bind covalently to EPDM rubber to form a cross-linked network. Feathers were cut into lengths of 0.08, 0.2, and 1 mm and incorporated at 38, 69, or 100 phr into EPDM mixtures containing either no carbon black or no carbon black nor sulphur. The presence of feather cuttings increases the tensile and compressive strength as well as the hardness, and reduces the rebound resilience. Due to their high (approximately 17%) nitrogen content, the feathers also improve the thermal stability of the composite, as the main degradation step is shifted from 400 °C to 470 °C and the decomposition is significantly slowed down. Since elastomers are a large market and feathers in particular are a high-volume waste, the combination of these two offers enormous ecological and economic prospects.

Autogenous Cross-Linking of Recycled Keratin from Poultry-Feather Waste to Hydrogels for Plant-Growth Media.

The global rise in atmospheric temperature is leading to an increasing spread of semi-arid and arid regions and is accompanied by a deterioration of arable land. Polymers can help in a number of ways, but they must not be a burden to the environment. In this context, we present herein a method by which goose feathers, representative of keratin waste in general, can be transformed into hydrogels for use as a plant growth medium. The treatment of shredded feathers in Na2S solution at ambient conditions dissolves approx. 80% of the keratin within 30 min. During evaporation, the thiol groups of cysteine reoxidise to disulphide bridges. Additionally, the protein chains form ß-sheets. Both act as cross-links that enables the formation of gels. The drying conditions were found to be crucial as slower evaporation affords gels with higher degrees of swelling at the cost of reduced gel yields. The cress germination test indicated the absence of toxic substances in the gel, which strongly adheres to the roots. Thereby, the plants are protected from drought stress as long as the gel still contains moisture.

Protein Hydrolysates from Biogenic Waste as an Ecological Flame Retarder and Binder for Fiberboards.

The increasing demand for sustainable building materials requires alternative flame retarders, which have superior sustainability to those previously used. In this respect, we present our initial results with protein hydrolysates made from poultry-feather waste for the preparation of flame-retardant fiberboards. Impregnated wood fibers show a significantly decreased decomposition rate in the region between 300 and 450 °C, as measured by thermogravimetric analysis. Final combustion of the impregnated fibers is shifted up by 50 °C to the interval 450-500 °C and occurs stepwise rather than instantaneously as for untreated wood. At a total protein content of approx. 10 wt %, plates produced in the "wet" process are self-extinguishing and show very little subsequent smouldering. In three-point bending tests, these fiberboard prototypes were able to withstand stresses of up to 15 N/mm2, the threshold required by DIN EN 622 for commercial, formaldehyde-bound MBH fiberboards. This indicates that the upcycled protein hydrolysates not only have an impressive flame-retarding effect but also can be used as a fully sustainable binder for a new generation of ecological fiberboards. As these boards are based solely on natural materials, they can be shredded and composted at the end of their life cycle.

CT texture analysis compared to Positron Emission Tomography (PET) and mutational status in resected melanoma metastases.

PURPOSE: To evaluate the potential of CT texture analysis parameters and metabolic characteristics of melanoma metastases in 18F- FDG PET/CT to predict relevant mutations of tumour cells for targeted therapy in metastatic melanoma patients in correlation with histopathologic specimen. MATERIAL AND METHODS: 66 melanoma patients, examined with contrast-enhanced 18F-FDG PET/CT before scheduled metastasectomy without any prior systemic therapy, were included in this single-centre retrospective analysis under IRB waiver. The largest, resected metastasis in each patient was assessed with CT texture analysis and semiquantitative 18F-FDG PET parameters. Correlation between imaging parameters and histopathological mutations (BRAF- and NRAS- genes) were calculated. RESULTS: Attenuation standard deviation (SD) within target lesion indicated a weak correlation with its SUVpeak (rho -0.292, p 0.017). However, no correlation between CT texture analysis, metabolic 18F-FDG PET parameters and tumour cell mutation could be established. CONCLUSION: CT texture parameters cannot replace the diagnostic value of 18F- FDG PET/CT for metabolic information in melanoma patients. Discrimination between BRAF- and NRAS mutation status was not feasible with CT texture analysis in this exploratory study.

Influence of Environmental Factors on the Swelling Capacities of Superabsorbent Polymers Used in Concrete.

Superabsorbent polymers (SAP) are of major interest as materials to control the cement hydration process. The swelling behavior of the SAPs significantly influences the performance of the resulting concrete by slowly releasing polymer-bound water in order to maintain a consistent w/c value. A round-robin test conducted by the RILEM Technical Committee 260-RSC showed that the same batch of polymer can lead to large deviations in concrete performance and this was assumed to originate in different storage conditions of the SAP. In this contribution the change in the performance of two SAPs, a crosslinked poly(acrylate) and a crosslinked poly(acrylate-co-acrylamide), was assessed after ageing in standard climate, at 50 °C, and under UV irradiation. During storage in standard climate or 50 °C, ageing led to dehydration of the SAP, and this subsequently led to a higher water uptake during swelling. By contrast, UV irradiation reduced the water uptake, most likely as a result of photo-crosslinking. Dynamic water vapor sorption experiments indicated a strong dependence of the water uptake on both the ambient humidity and the temperature. As a result, cement mixtures containing SAP must be calculated on the dry mass of the SAP rather than the actual weight on site. A standard procedure of how to pack and handle SAP to be used in concrete is also provided.

Sorption-active transparent films based on chitosan.

In this paper we describe the preparation of alkanoic acid-based aqueous chitosan solutions, which show no sign of acid-catalysed depolymerisation over time - something commonly accompanying other preparation methods. Longer chitosan chains have previously been shown to exhibit more advantageous biological activities, and constant viscosities are essential for consistent quality in biomedical applications. Avoiding acid-catalysed depolymerisation requires careful control of the stoichiometry between the free amino groups of chitosan and the appropriate solubilising acid. Acetic and butyric acid are both suitable solubilising agents, but chitosan butyrate exhibits lower solution viscosities due to a combined electric and steric shielding of the chains. These solutions dry into clear transparent films that remain fully water soluble and absorb up to 70 wt% of water from 90%-RH vapour phase at 25 °C. The absorption follows simple first-order kinetics and the rate constants increase with increasing humidity up to approx. 71%-RH, where a metastable chitosan trihydrate salt appears to be formed. Desorption is slightly faster, but more complex, as it exhibits two distinct first-order processes. In addition, films prepared in this way are thermally more stable than the usual chitosan hydrochloride.

Preparation and characterisation of highly alkaline hydrogels for the re-alkalisation of carbonated cementitious materials.

Highly alkaline hydrogels that allow the restoration of alkaline buffer in cementitious materials can be obtained from diallyldimethylammonium hydroxide. The latter must be prepared in dilute solutions and polymerised at ambient temperatures in order to avoid decomposition. Using methacrylamide as a neutral co-monomer capable of forming hydrogen bonds, the rheological properties of the gels can be adjusted over a wide range; e.g. the viscosity increases a thousandfold from 0.35 Pa s to >350 Pa s by using 10 mol% methacrylamide. For the proof of principle experiments, gels with 9 mol% methacrylamide were used, which contain approx. 1.6 mol hydroxide ions per kg gel. Ion exchange between this and a neutral chloride containing gel provided an apparent diffusion coefficient of 4.12 × 10-7 m2 s-1 for the hydroxide ions and confirmed the transport of chloride ions into the alkaline gel. The re-alkalisation was tested on fully carbonated mortar prisms made from Portland cement. Re-alkalisation of the mortar was confirmed by the phenolphthalein test according to DIN EN 14630:2007-01 and by a control experiment with pure calcium carbonate using IR spectroscopy.

Interfacial properties of emulsions stabilized with surfactant and nonsurfactant coated boehmite nanoparticles.

The properties of emulsions stabilized with surface-modified boehmite particles of 26 and 8 nm in diameter have been investigated. The surface-modified particles were prepared by mixing aqueous dispersions of cationic boehmite particles with aqueous solutions of the surfactant p-dodecylbenzenesulfonic acid (DBSA) or the nonsurfactant p-toluenesulfonic acid (TSA). For the 26 nm particles, interfacial tension measurements indicate that p-dodecylbenzenesulfonic acid partitions between the particle surface and the oil-water interface, while p-toluenesulfonic acid remains on the particle surface. The partitioning of p-dodecylbenzenesulfonic acid supports the formation of emulsions, although in the absence of the particles the same surfactant concentration is not sufficient for emulsion stabilization. Due to the fast exchange kinetics, p-dodecylbenzenesulfonic acid is gradually replaced by particles. At equilibrium, the interfacial tension in the presence of the surface-modified particles is between the values for the pure particles and the pure surfactant solutions. However, the interfacial tension is independent of the surfactant concentration used in the preparation of the particles. Reducing the particle size to 8 nm leads to increased emulsion stability, and thus, the minimum particle concentration required to prepare stable emulsions was reduced to 0.1 g/L. However, above approximately 3.5 mmol/L of the sulfonic acids, the small particles dissolve slowly, and the emulsion stability is lost. This mechanism can be used to trigger the collapse of the emulsions.

Current-dependent anisotropic conductivity of locally assembled silver nanoparticles in hybrid polymer films.

The electrical behaviour of hybrid poly(ethylene terephthalate) films containing localised, percolating networks of silver nanoparticles separated by pure polymer is studied. The films resemble an array of parallel wires in the submicron range and, thus, exhibit anisotropic conductivity. In the high-conductivity direction at low amplitudes, the films show Ohmic behaviour, while at moderate voltage, non-linearity and a decreasing resistance is observed. The samples were found to heat up during the measurements and the deviation from Ohm's law coincides with the Tg of the polymer. Microstructural analysis of the samples revealed an irreversible agglomeration of the particles at moderate voltages leading to the formation of filaments with higher metallic character than the random particle network.

ZnO nanoparticle-containing emulsions for transparent, hydrophobic UV-absorbent films.

A simple method for the preparation of thin, zinc oxide nanoparticle-containing films showing high UV absorption, high transmittance in the visible range (>88%), and water repellence with contact angles of 120 degrees is presented. The films are coated from an emulsion containing the hydrophobic polymer and the nanoparticles. This emulsion was prepared by mixing commercial o/w emulsions used for hydrophobic coatings on textiles with ZnO nanoparticle-containing o/w emulsions. The latter were designed so that the mixed coating formulation could be prepared without breaking. Preparation and properties of the o/w emulsions as well as the final films are elaborated. The performance of hydrophobic and hydrophilic ZnO nanoparticles during preparation and in the final film is evaluated.

Temperature-dependent colloidal stability of hydrophobic nanoparticles caused by surfactant adsorption/desorption and depletion flocculation.

Nanoparticles coated with self-assembled dodecyltrimethylammonium bromide shells are shown to undergo colloidal destabilization at higher temperatures. This is caused by two different mechanisms depending on the surfactant concentration. Up to a surfactant concentration of 55 mM, the surfactant micelles dissolve before the breakdown of the dispersion. In this case, the breakdown is triggered by desorption of surfactant molecules from the particle surface causing flocculation via hydrophobic interactions. Since the surfactant concentration influences the adsorption-desorption equilibrium, the breakdown temperature increases with increasing surfactant concentration from approximately 100 to 160 degrees C. Beyond 55 mM, surfactant micelles are still present when the dispersion breaks down and destabilization is caused by high temperature depletion flocculation. Since higher surfactant concentrations result in a larger number of micelles in solution, the breakdown temperature for concentrations above 55 mM decreases with increasing surfactant concentration.

Colloidal stability of hydrophobic nanoparticles in ionic surfactant solutions: definition of the critical dispersion concentration.

The dispersion stability diagrams of hydrophobic boehmite nanoparticles in aqueous n-alkyltrimethylammonium bromide solutions (alkyl chain lengths 10-16) were studied over a wide range of particle and surfactant concentrations. The surfactant molecules adsorb tail-on on the particle surface, which provides the colloidal stability through electrostatic repulsion. In the stable region of each diagram, bimodal particle size distributions (50 and 500 nm) are found at lower surfactant concentration, which give way to monomodal distributions (50 nm) at higher concentration. This deagglomeration is connected with the cmc of the surfactants and can be explained by a desorption of counterions from the self-assembled surfactant layer. The desorption is caused by changes in the counterion concentration upon micellization. At low particle concentrations, the transition from the intermediate to the stable region, that is, the disappearance of the precipitate, occurs at a constant surfactant concentration. This concentration is introduced as the "critical dispersion concentration" (cdc), this being the lowest required concentration of a surfactant that is necessary to disperse the hydrophobic particles. The logarithm of the cdc shows a linear dependence on the surfactant chain length, thus a cmc-analogous behavior. The ratio cdc/cmc decreases with increasing surfactant chain length, indicating that long-chain surfactants are more efficient in dispersing nanoparticles than are their lower homologues. The existence of a system-specific critical cdc/cmc ratio, beyond which stable dispersions cannot be obtained, is proposed, which explains the disability of short-chain surfactants to disperse colloids.

A comparative study on the dispersion stability of aminofunctionalised silica nanoparticles made from sodium silicate.

A method to prevent the irreversible agglomeration of silica nanoparticles prepared from sodium silicate, which occurs upon treatment with trialkoxy silanes, is presented. Electrostatic stabilisation is maintained by using mixtures of 3-aminopropyltrimethoxysilane and the cationic derivative N-trimethoxysilylpropyl-N,N,N-trimethylammoniumchloride (TMAPS), which gives rise to stable dispersions of aminofunctionalised particles with unusually high amine content. The particles can be isolated and redispersed without significant increase in particle size. However, an increase in the dispersed particle-size was observed on increasing the APS content in the reaction mixture. This was least pronounced for the 9 nm particles prepared from sodium silicate and more pronounced for the 30 nm particles, for which gel and/or precipitate formation occurred at high APS contents.

The dispersion-stability diagram of boehmite nanoparticles in aqueous AOT solutions.

The dispersion stability of hydrophilic boehmite nanoparticles in aqueous sodium bis(2-ethylhexyl) sulfosuccinate (AOT) solutions was studied in a wide range of particle and surfactant concentrations. The two experimental parameters significantly influence the dispersion stability and span a stability diagram. With increasing surfactant concentration and decreasing particle concentration, the system changes from stable via moderately stable to unstable and back. In concentrated AOT solutions, fully redispersed particles are present, stabilized by a surfactant bilayer or admicelles on the surface. The redispersion can be reversibly induced by dilution or concentration of the samples. The positions of two transitions, namely for complete precipitation and for beginning redispersion, can be fitted accurately using a simple model based on H-type adsorption and including the specific surface area of the particle and the molar area of the surfactant. The transitions are controlled by the concentration of free surfactant molecules in solution as well as the saturation surface coverage and were corroborated by turbidity measurements.

Synthesis, structural analysis, and visualization of a library of dendronized polyphenylacetylenes.

A library of eleven high cis-content cis-transoidal polyphenylacetylenes (PPAs) dendronized with self-assembling dendrons was prepared from a library of fifteen convergently synthesized macromonomers. Using [Rh(C triple bond CPh)(nbd)(PPh(3))(2)] (nbd=2,5-norbornadiene) in the presence of 10 equiv of N,N-dimethylaminopyridine, predictive control over molecular weight and narrow molecular weight distribution are obtained. The PPA backbone serves as a helical scaffold for the self-assembling dendrons. The dendron primary structure dictates the diameter of the cylindrical PPAs in bulk, both in the self-organized hexagonal columnar (Phi(h)) lattice determined by X-ray diffraction (XRD) and in monolayers on highly ordered pyrolytic graphite (HOPG) and mica visualized by atomic force microscopy (AFM). Thermal and bulk phase characteristics of the cylindrical PPAs reinforces the generality that flexible polymer backbones adopt a helical conformation within the cylindrical macromolecules generated by polymers jacketed with self-assembling dendrons.

NiCl(2)(dppe)-catalyzed cross-coupling of aryl mesylates, arenesulfonates, and halides with arylboronic acids.

An investigation of the NiCl(2)(dppe)-, NiCl(2)(dppb)-, NiCl(2)(dppf)-, NiCl(2)(PCy(3))(2)-, and NiCl(2)(PPh(3))(2)-catalyzed cross-coupling of the previously unreported aryl mesylates, and of aryl arenesulfonates, chlorides, bromides, and iodides containing electron-withdrawing and electron-donating substituents with aryl boronic acids, in the absence of a reducing agent, is reported. NiCl(2)(dppe) was the only catalyst that exhibited high and solvent-independent activity in the two solvents investigated, toluene and dioxane. NiCl(2)(dppe) with an excess of dppe, NiCl(2)(dppe)/dppe, was reactive in the cross-coupling of electron-poor aryl mesylates, tosylates, chlorides, bromides, and iodides. This catalyst was also efficient in the cross-coupling of aryl bromides and iodides containing electron-donating substituents. Most surprisingly, the replacement of the excess dppe from NiCl(2)(dppe)/dppe with excess PPh(3) generated NiCl(2)(dppe)/PPh(3), which was found to be reactive for the cross-coupling of both electron-rich and electron-poor aryl mesylates and chlorides. Therefore, the solvent-independent reactivity of NiCl(2)(dppe) provides an inexpensive and general nickel catalyst for the cross-coupling of aryl mesylates, tosylates, chlorides, bromides, and iodides with aryl boronic acids.

Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride.

This paper describes the room-temperature living radical polymerization (LRP) of vinyl chloride in H2O/THF in the presence of Cu0 or CuI salts as catalysts, tren or PEI as ligands, and iodoform as initiator. The disproportionation reaction 2CuI + L --> Cu0 + CuII(L) is the crucial step, as it continuously provides the active species for both the initiation (Cu0) and the reversible termination step (CuII). Mn was found to increase linearly with conversion and is in good agreement with Mth, with the Mw/Mn being approximately 1.5.