J-aggregation of a water-soluble tetracationic porphyrin in mixed LB films with a calix[8]arene carboxylic acid derivative

The molecular organization of a mixed film, containing a water-soluble tetracationic porphyrin (TMPyP) and a p-tert-butyl calix[8]arene octacarboxylic acid derivative (C8A), at the air-water interface and on a solid support (LB film), has been investigated. Although the TMPyP aggregation was not detected at the air-water interface, TMPyP J-aggregates have been found in the LB films (Y-type). Unlike tetraanionic porphyrins, for example TSPP, the TMPyP J-aggregates are not induced by a zwitterion formation. The TMPyP J-aggregation is a result of a "double comb" configuration, where porphyrins from opposite layers are interwoven in a linear infinite J-aggregate. Our results confirm that TMPyP molecules tend to self-aggregate strongly, provided the electrostatic repulsions of their peripheral groups are cancelled by the anionic groups of the C8A matrix.     

Stable cellulose nanospheres for cellular uptake

Pure, perfectly spherical cellulose nanoparticles with sizes of ≈80-260 nm can be prepared by dialysis starting from trimethylsilylcellulose (TMSC). The aqueous suspensions obtained are storable for several months. Subsequent covalent labeling of the cellulose nanoparticles with FITC has no influence on particle size, shape, and stability. The particles can be sterilized and suspended in biological media without structural changes. Incorporation of FITC-labeled cellulose nanoparticles into living human fibroblasts is studied using confocal LSM. In contrast to cellulose nanocrystals, fast cellular uptake is found for the nanospheres without transfection reagents or attachment of a receptor molecule. This suggests an influence of the geometry of biocompatible nanomaterials on endocytosis.     

Syntheses, structures and intermolecular interactions of tetraorganoammonium, -phosphonium and -stibonium dimethyl- and diphenyltetrahaloantimonates

The syntheses and spectroscopic (NMR, MS) investigations of the antimonates [Ph₄P]⁺[Me₂SbCl₄]⁻ (1), [Me₄Sb]⁺[Me₂SbCl₄]⁻ (2), [Et₄N]⁺[Ph₂SbCl₄]⁻ (3), [Bu₄N]⁺[Ph₂SbCl₄]⁻ (4), [Me₄Sb]⁺[Ph₂SbCl₄]⁻ (5), [Et₃MeSb]⁺[Ph₂SbCl₄]⁻ (6), [Et₄N]⁺[Ph₂SbF₄]⁻ (7) and [Et₄N]⁺[Ph₂SbBr₄]⁻ (8) are reported. Halogen scrambling reactions of Et₄NBr or Ph₄EBr (E = P, Sb) with R₂SbCl₃ (R = Me, Ph) produce mixtures of compounds from which crystals of [Et₄N]⁺[Ph₂SbBr_1.24Cl_2.76]⁻ (9), [Et₄N]⁺[Ph₂SbBr_2.92Cl_1.08]⁻ (10) or [Ph₄Sb]⁺[Me₂SbCl₄]⁻ (11) were isolated. The crystal and molecular structures of 1 and 3-11 are reported.     

161Dy Time‐Domain Synchrotron Mössbauer Spectroscopy for Investigating Single‐Molecule Magnets Incorporating Dy Ions

Time‐domain synchrotron Mössbauer spectroscopy (SMS) based on the Mössbauer effect of ¹⁶¹Dy has been used to investigate the magnetic properties of a Dy^III‐based single‐molecule magnet (SMM). The magnetic hyperfine field of [Dy(Cy₃PO)₂(H₂O)₅]Br₃?2 (Cy₃PO)?2 H₂O?2 EtOH is with B₀=582.3(5) T significantly larger than that of the free‐ion Dy^III with a ⁶H_15/2 ground state. This difference is attributed to the influence of the coordinating ligands on the Fermi contact interaction between the s and 4f electrons of the Dy^III ion. This study demonstrates that ¹⁶¹Dy SMS is an effective local probe of the influence of the coordinating ligands on the magnetic structure of Dy‐containing compounds.     

XUV free-electron laser desorption of NO from graphite (0001)

We report results of femtosecond laser induced desorption of NO from highly oriented pyrolytic graphite using XUV photon energies of hν = 38 eV and hν = 57 eV. Femtosecond pulses with a pulse energy of up to 40 μJ and about 30 fs duration generated at FLASH are applied. The desorbed molecules are detected with rovibrational state selectivity by (1 + 1) REMPI in the A(2)Σ(+) ← X(2)Π γ-bands around λ = 226 nm. A nonlinear desorption yield of neutral NO is observed with an exponent of m = 1.4 ± 0.2. At a fluence of about 4 mJ/cm(2) a desorption cross section of σ(1) = (1.1 ± 0.4) × 10(-17) cm(2) is observed, accompanied with a lower one of σ(2) = (2.6 ± 0.3) × 10(-19) cm(2) observable at higher total fluence. A nonthermal rovibrational population distribution is observed with an average rotational energy of = 38.6 meV (311 cm(-1)), a vibrational energy of = 136 meV (1097 cm(-1)) and an electronic energy of = 3.9 meV (31 cm(-1)).     

Mixed electrolytes in hydrophobic interaction chromatography†

An essential part of the modulation of protein‐binding capacity in hydrophobic interaction chromatography is the buffer‐salt system. Besides using “single” electrolytes, multicomponent electrolyte mixtures may be used as an additional tool. Both the protein solubility and the binding capacity depend on the position of a salt in the so‐called Hofmeister series. Specific interactions are observed for an individual protein‐salt combination. For salt mixtures, selectivity, recovery, and binding capacity do not behave like for the single salts that are positioned in between the two mixed components in the Hofmeister series, as the continuous correlation would suggest. Thus, finding strategies for mixed salts could potentially lead to improved capacities in hydrophobic interaction chromatography. Mixtures of ammonium sulfate, sodium citrate, sodium sulfate, sodium chloride, sodium acetate, and glycine were used to investigate the binding capacities for lysozyme and a monoclonal antibody on various hydrophobic resins. Resin capacity for two investigated proteins increases when mixtures consisting of a chaotropic and a kosmotropic salt are applied. It seems to be related to the rather basic isoelectric points of the proteins.     

Homogenous synthesis of 3-allyloxy-2-hydroxypropyl-cellulose in NaOH/urea aqueous system

3-Allyloxy-2-hydroxypropylcelluloses (AHP-celluloses), reactive unsaturated cellulose derivatives, were homogeneously synthesized by the reaction of cellulose with allyl glycidyl ether (AGE) in NaOH/urea aqueous solution. Water-soluble AHP-celluloses with DS_NMR = 0.32–0.67 were prepared from microcrystalline cellulose. The degree of substitution (DS) of AHP-celluloses could be controlled by varying the molar ratio of AGE and NaOH to AGU and the reaction conditions. The structure of AHP-cellulose samples were characterized by means of FT-IR, NMR spectroscopy and size exclusion chromatography. The cellulose ether shows thermoreversible flocculation. Bromination reactions were carried out as subsequent functionalization both to illustrate the reactivity of the allyl function and to determine the DS values.     

Evaluation of various fire retardants for use in wood flour-polyethylene composites

Wood-plastic composites represent a growing class of materials used by the residential construction industry and the furniture industry. For some applications in these industries, the fire performance of the material must be known, and in some cases improved. However, the fire performance of wood-plastic composites is not well understood, and there is little information regarding the effectiveness of various fire retardants in the public domain. We used oxygen index and cone calorimeter tests to characterize the fire performance of wood flour-polyethylene composites, and compared the results with unfilled polyethylene and solid wood. We then evaluated the effect of five additive-type fire retardants on fire performance. Generally, magnesium hydroxide and ammonium polyphosphate improved the fire performance of WPCs the most while a bromine-based fire retardant and zinc borate improved fire performance the least.