Spherulitic growth of hen egg-white lysozyme crystals

In protein crystallography, spherulites are considered the result of a failed crystallization experiment. Understanding the formation of these structures may contribute to finding methods to prevent their formation. Here, we present an in situ study on lysozyme spherulites grown from sodium nitrate and sodium thiocyanate solutions, investigating their morphology and growth kinetics using optical microscopy. In a morphodrom, we indicate the conditions at which spherulites form for the lysozyme-nitrate system, showing that liquid-liquid phase separation is not a prerequisite to form sheaflike spherulites and that supersaturation is not the only factor determining their creation. Despite their sheaflike morphology, the spherulites all appear to be formed through heterogeneous nucleation. The spherulites are of a new polymorphic form and are less stable than the monoclinic form. For a single needle, growth kinetics indicate surface processes to be the rate-limiting step during growth, but for an entire spherulite volume, diffusion still plays a role. Spherulites simulated by using a time-dependent, tip-splitting model are found to compare well to experimentally observed spherulites.     

Imaging surface plasmon resonance for multiplex microassay sensing of mycotoxins

A prototype imaging surface plasmon resonance-based multiplex microimmunoassay for mycotoxins is described. A microarray of mycotoxin–protein conjugates was fabricated using a continuous flow microspotter device. A competitive inhibition immunoassay format was developed for the simultaneous detection of deoxynivalenol (DON) and zearalenone (ZEN), using a single sensor chip. Initial in-house validation showed limits of detection of 21 and 17 ng/mL for DON and 16 and 10 ng/mL for ZEN in extracts, which corresponds to 84 and 68 μg/kg for DON and 64 and 40 μg/kg for ZEN in maize and wheat samples, respectively. Finally, the results were critically compared with data obtained from liquid chromatography-mass spectrometry confirmatory analysis method and found to be in good agreement. The described multiplex immunoassay for the rapid screening of several mycotoxins meets European Union regulatory limits and represents a robust platform for mycotoxin analysis in food and feed samples.     

In-situ synthesis of a palladium-polyaniline hybrid catalyst for a Suzuki coupling reaction

Palladium-catalyzed cross-coupling reactions are one of the most frequently used synthetic tools for the construction of new carbon-carbon bonds in organic synthesis. The present study describes the use of palladium-polyaniline composite material as a catalyst for the Suzuki coupling of aryl halides. Palladium-polyaniline nanocomposite material was synthesized using an in-situ technique in which palladium acetate and aniline hydrochloride were used as the precursors of the composite. Electron microscopy imaging showed that the palladium particles were well-dispersed within the polymer matrix and were typically 3-5 nm in diameter. The metal-polymer composite material was used as a catalyst for the coupling of phenylboronic acid with aryl halides in the presence of an inorganic base and showed excellent yield with high TOF values.     

Influence of cationic composition and pH on the formation of metal stearates at oil-water interfaces

We study the formation of layers of metal stearates at the interface between a decane solution of stearic acid and aqueous salt solutions of variable composition and pH by monitoring the evolution of their mechanical, optical, and chemical properties as a function of time after formation of the interface. For values of the pH below the pK(a) of stearic acid hardly any interfacial activity is observed. For pH > pK(a), stearic acid deprotonates at the interface and forms metal stearates, eventually leading to the formation of macroscopic solid layers. Dynamic interfacial tension measurements reveal that the process takes place in several stages, which we attribute to the successive formation of dilute and dense monolayers followed by three-dimensional growth. In the presence of divalent ions, the solid layers display a significant increase in the dilatational storage modulus. Experiments performed with an aqueous phase containing multiple cation species (artificial seawater) give rise to particularly pronounced growth of solid layers, which preferentially incorporate Ca(2+) as revealed by X-ray photoelectron and infrared spectroscopy. Our results highlight in particular the importance of the complex synergistic effects of simultaneously present monovalent and divalent cation species on the interfacial adsorption.     

Effect of broadband-noise masking on the behavioral response of a harbor porpoise (Phocoena phocoena) to 1-s duration 6-7 kHz sonar up-sweeps

Naval sonar systems produce signals which may affect the behavior of harbor porpoises, though their effect may be reduced by ambient noise. To show how natural ambient noise influences the effect of sonar sweeps on porpoises, a porpoise in a pool was exposed to 1-s duration up-sweeps, similar in frequency range (6-7 kHz) to those of existing naval sonar systems. The sweep signals had randomly generated sweep intervals of 3-7 s (duty cycle: 19%). Behavioral parameters during exposure to signals were compared to those during baseline periods. The sessions were conducted under five background noise conditions: the local normal ambient noise and four conditions mimicking the spectra for wind-generated noise at Sea States 2-8. In all conditions, the sweeps caused the porpoise to swim further away from the transducer, surface more often, swim faster, and breathe more forcefully than during the baseline periods. However, the higher the background noise level, the smaller the effects of the sweeps on the surfacing behavior of the porpoise. Therefore, the effects of naval sonar systems on harbor porpoises are determined not only by the received level of the signals and the hearing sensitivity of the animals but also by the background noise.     

Colour-encoded paramagnetic microbead-based direct inhibition triplex flow cytometric immunoassay for ochratoxin A, fumonisins and zearalenone in cereals and cereal-based feed

A combined (triplex) immunoassay for the simultaneous detection of three mycotoxins in grains was developed with superparamagnetic colour-encoded microbeads, in combination with two bead-dedicated flow cytometers. Monoclonal antibodies were coupled to the beads, and the amounts of bound mycotoxins were inversely related to the amounts of bound fluorescent labelled mycotoxins (inhibition immunoassay format). The selected monoclonal antibodies were tested for their target mycotoxins and for cross-reactivity with relevant metabolites and masked mycotoxins. In the triplex format, low levels of cross-interactions between the assays occurred at irrelevant high levels only. All three assays were influenced by the sample matrix of cereal extracts to some extent, and matrix-matched calibrations are recommended for quantitative screening purposes. In a preliminary in-house validation, the triplex assay was found to be reproducible, sensitive and sufficiently accurate for the quantitative screening at ML level. The triplex assay was critically compared to liquid chromatography–tandem mass spectrometry using reference materials and fortified blank material. Results for the quantification of ochratoxin A and zearalenone were in good agreement. However, the fumonisin assay was, due to overestimation, only suitable for qualitative judgements. Both flow cytometer platforms (Luminex 100 and FLEXMAP 3D) performed similar with respect to sensitivity with the advantages of a higher sample throughput and response range of the FLEXMAP 3D and lower cost of the Luminex 100.

Calix[4]arenes as molecules for second order nonlinear optics

Abstract

The synthesis of a novel class of molecules for second order nonlinear optics, i.e. calix[4]arenes with extended π-systems, is described. These compounds are obtained via Wittig-Horner reactions of the formylated calix[4]arenes 5 and 6 to give the stilbene derivatives 7–9, or by diazotization of calix[4]arene, 1, followed by alkylation to give the phenylazocalix[4]arenes 11 and 12. The molecular second order nonlinear optical properties (β_z) of these calix[4]arenes have been measured by electric field-induced second harmonic generation. The influence of different acceptors as well as the influence of the different conformations of the calix[4]arenes on β_z values were determined. Surprisingly, the wavelength of the charge-transfer band λ_max is lower when β_z increases upon increasing the number of acceptors.     

Enantiopure Isoindolinones through Viedma Ripening

Here we demonstrate that deracemization of isoindolinones using Viedma ripening is possible starting from a racemic mixture of conglomerate crystals. Crystals of the enantiopure isoindolinones lose their chiral identity upon dissolution even without the need for a catalyst. This enabled complete deracemization of the reported isoindolinones without a catalyst.     

Hydrolysis of Tetraglycine by a Zr(IV)-Substituted Wells–Dawson Polyoxotungstate Studied by Diffusion Ordered NMR Spectroscopy

The use of diffusion ordered NMR spectroscopy (DOSY) for the analysis of complex reaction mixtures involving polyoxometalates (POMs) was demonstrated for the hydrolysis of the peptide tetraglycine by the K₁₅H[Zr(α₂-P₂W₁₇O₆₁)₂]·25H₂O Wells–Dawson type cluster. ¹H DOSY NMR studies have shown that severe signal overlap observed in the one-dimensional ¹H NMR spectrum of reaction mixtures containing a POM and peptides could be overcome by the two-dimensional character of a DOSY NMR measurement. A clear distinction between the ¹H NMR signals of the products formed during the hydrolysis of 5.0 mM of tetraglycine catalyzed by 1.0 mM of K₁₅H[Zr(α₂-P₂W₁₇O₆₁)₂]·25H₂O was observed based on the extra dimension containing information about diffusion coefficients that distinguishes a typical DOSY measurement from conventionally used 1D ¹H NMR. The spectrum clearly shows the presence of 5 species with diffusion coefficients of 3.71 × 10^?10 m²/s (3.91; 3.84; 3.82 and 3.62 ppm), 4.39 × 10^?10 m²/s (3.87; 3.76 and 3.61 ppm), 5.26 × 10^?10 m²/s (3.67 and 3.63 ppm), and 7.46 × 10^?10 m²/s (3.37 ppm) that are assigned to the non-hydrolyzed tetraglycine, the hydrolysis intermediate products triglycine and glycylglycine, and the end product of hydrolysis glycine, respectively. In addition, a signal assigned to cyclic glycylglycine, with a diffusion coefficient practically identical to the diffusion coefficient of glycylglycine was observed at 3.86 ppm. In addition, ¹H and ³¹P NMR spectroscopy were further used to study the binding of tetraglycine to K₁₅H[Zr(α₂-P₂W₁₇O₆₁)₂]·25H₂O and the solution speciation of K₁₅H[Zr(α₂-P₂W₁₇O₆₁)₂]·25H₂O.     

Recipe for new diorganostannates, [R2Sn(OS(O)2R1)4]2-, bearing alkanesulfonate groups using dialkyl sulfite as the reagent

A one-pot reaction between di-n-propyl/di-n-butyltin oxide, dialkyl sulfite, and triethylamine or tetra-n-alkylammonium iodide proceeds under ambient conditions (110-120 degrees C, 20 h) via sulfur-centered Arbuzov rearrangement to afford the corresponding dianionic tetraalkanesulfonato diorganostannates [R2Sn(OSO2Me)4].2Et3NMe [R = n-Pr (1), n-Bu (2)] as well as [n-Bu(2)Sn(OSO(2)R(1))(4)].(2)R(2)(4)N [R(1) = Me, Et, n-Pr; R(2) = Et (3, 5, and 7), n-Bu (4, 6, and 8)]. X-ray crystal structures of 2 and 3 reveal a monomeric motif of the dianion, with methanesulfonate groups acting as unidentate ligands. The (119)Sn NMR spectral studies suggest the existence of pentacoordinated tin species in solution.