Scaling and mesostructure of Carbopol dispersions

Rheological measurements were performed on aqueous dispersions of two commercial crosslinked polymer microgels, Carbopol Ultrez 10 and Carbopol ETD 2050, prepared over a wide range of concentration and pH. For all concentrations studied, both the yield stress and the elastic modulus initially increased dramatically with pH and displayed broad peaks at intermediate pH. This is consistent with the onset of jamming of the Carbopol particles due to a rapid increase in particle size caused by osmotic swelling in the presence of NaOH. Scaling of both yield stress and elasticity with concentration was observed only at higher concentrations, which we believe indicates a change from a percolated structure at low volume fractions to a space filling network of compressed particles at high volume fractions. This model is supported by confocal microscopy of fluorescently dyed Carbopol dispersions.     

TITAN: an ion trap for accurate mass measurements of ms-half-life nuclides

The introduction of Paul traps, in particular linear radio-frequency quadrupoles in the early 2000s, has revolutionized the use of ion traps for probing the properties of radioactive nuclides. It opened the path to trapping all available nuclides, independent of their chemical properties. We present an overview of direct mass measurements of short-lived nuclides using TITAN, a Penning trap mass spectrometer facility particularly suitable for precision measurements of ms-half-life nuclides.     

Aggregation Pathways of the Amyloid β(1-42) Peptide Depend on Its Colloidal Stability and Ordered β-Sheet Stacking

Amyloid β (Aβ) fibrils are present as a major component in senile plaques, the hallmark of Alzheimer's disease (AD). Diffuse plaques (nonfibrous, loosely packed Aβ aggregates) containing amorphous Aβ aggregates are also formed in brain. This work examines the influence of Cu(2+) complexation by Aβ on the aggregation process in the context of charge and structural variations. Changes in the surface charges of Aβ molecules due to Cu(2+) binding, measured with a ζ-potential measurement device, were correlated with the aggregate morphologies examined by atomic force microscopy. As a result of the charge variation, the "colloid-like" stability of the aggregation intermediates, which is essential to the fibrillation process, is affected. Consequently, Cu(2+) enhances the amorphous aggregate formation. By monitoring variations in the secondary structures with circular dichroism spectroscopy, a direct transformation from the unstructured conformation to the β-sheet structure was observed for all types of aggregates observed (oligomers, fibrils, and/or amorphous aggregates). Compared to the Aβ aggregation pathway in the absence of Cu(2+) and taking other factors affecting Aβ aggregation (i.e., pH and temperature) into account, our investigation indicates that formations of amorphous and fibrous aggregates diverge from the same β-sheet-containing partially folded intermediate. This study suggests that the hydrophilic domain of Aβ also plays a role in the Aβ aggregation process. A kinetic model was proposed to account for the effects of the Cu(2+) binding on these two aggregation pathways in terms of charge and structural variations.     

Triplex-directed covalent cross-linking of a DNA nanostructure

The triplex approach to DNA recognition is exploited to direct covalent inter-strand cross-links to unique locations within a pre-assembled DNA nanostructure. This approach can be used to improve the stability of DNA nanostructures and demonstrates the feasibility of directing other reactive groups to unique locations within these complexes.     

Monomers for Adhesive Polymers, 6

Summary: 1,3‐Bis(methacrylamido)propane‐2‐yl dihydrogen phosphate ( 1 ) was synthesised by phosphorylation of 1,3‐bis(methacrylamido)‐2‐hydroxypropane ( 2 ) with phosphorus oxychloride in tetrahydrofuran (THF) in the presence of triethylamine (TEA). The structure of the new monomer 1 was characterised by IR, ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopies, elemental analysis and mass spectrometry. The monomer dissolves well in water, ethanol or aqueous THF and shows an improved hydrolytic stability compared to the corresponding methacrylate‐based dihydrogen phosphates. 1 was homopolymerised in ethanol with 2,2′‐azoisobutyronitrile (AIBN) as the initiator at 55–75 °C under the formation of an insoluble, cross‐linked product. Aqueous solutions of 1 are strongly acidic and enable to etch enamel and dentin. Nevertheless, 1 did not show any cytotoxic effect. Furthermore, the adhesive properties of 1 were measured.

1,3‐Bis(methacrylamido)propane‐2‐yl dihydrogen phosphate.     

Success or Failure of Chiral Crystallization of Similar Heterocyclic Compounds

Single crystals of two achiral and planar heterocyclic compounds, C₉H₈H₃O(CA1) and C₈H₅NO₂ (CA4), recrystallized from ethanol, were characterized by single crystal X-ray analysis, respectively, and chiral crystallization was observed only for CA1 as P2₁2₁2₁ (# 19), whereas it was not observed for CA4 P2₁/c (# 14). In CA1, as a monohydrate, the hydrogen bonds were pronounced around the water of crystallization (O4), and the planar cyclic sites were arranged in parallel to slightly tilted positions. On the other hand, an anhydride CA4 formed a dimer by hydrogen bonds between adjacent molecules in the crystal, which were aggregated by van der Waals forces and placed in parallel planar cyclic sites.     

Shedding Light on the Interactions of Hydrocarbon Ester Substituents upon Formation of Dimeric Titanium(IV) Triscatecholates in DMSO Solution

The dissociation of hierarchically formed dimeric triple lithium bridged triscatecholate titanium(IV) helicates with hydrocarbyl esters as side groups is systematically investigated in DMSO. Primary alkyl, alkenyl, alkynyl as well as benzyl esters are studied in order to minimize steric effects close to the helicate core. The ¹H NMR dimerization constants for the monomer–dimer equilibrium show some solvent dependent influence of the side chains on the dimer stability. In the dimer, the ability of the hydrocarbyl ester groups to aggregate minimizes their contacts with the solvent molecules. Due to this, most solvophobic alkyl groups show the highest dimerization tendency followed by alkenyls, alkynyls and finally benzyls. Furthermore, trends within the different groups of compounds can be observed. For example, the dimer is destabilized by internal double or triple bonds due to π–π repulsion. A strong indication for solvent supported London dispersion interaction between the ester side groups is found by observation of an even/odd alternation of dimerization constants within the series of n-alkyls, n-Ω-alkenyls or n-Ω-alkynyls. This corresponds to the interaction of the parent hydrocarbons, as documented by an even/odd melting point alternation.