Dynamic covalent hydrazine chemistry as a selective extraction and cleanup technique for the quantification of the Fusarium mycotoxin zearalenone in edible oils

A novel, cost-efficient method for the analytical extraction of the Fusarium mycotoxin zearalenone (ZON) from edible oils by dynamic covalent hydrazine chemistry (DCHC) was developed and validated for its application with high performance liquid chromatography-fluorescence detection (HPLC-FLD). ZON is extracted from the edible oil by hydrazone formation on a polymer resin functionalised with hydrazine groups and subsequently released by hydrolysis. Specifity and precision of this approach are superior to liquid partitioning or gel permeation chromatography (GPC). DCHC also extracts zearalanone (ZAN) but not α-/β-zearalenol or -zearalanol. The hydrodynamic properties of ZON, which were estimated using molecular simulation data, indicate that the compound is unaffected by nanofiltration through the resin pores and thus selectively extracted. The method's levels of detection and quantification are 10 and 30 μg/kg, using 0.2 g of sample. Linearity is given in the range of 10–20,000 μg/kg, the average recovery being 89%. Bias and relative standard deviations do not exceed 7%. In a sample survey of 44 commercial edible oils based on various agricultural commodities (maize, olives, nuts, seeds, etc.) ZON was detected in four maize oil samples, the average content in the positive samples being 99 μg/kg. The HPLC-FLD results were confirmed by HPLC–tandem mass spectrometry and compared to those obtained by a liquid partitioning based sample preparation procedure.     

Synthesis and Intracellular Redox Cycling of Natural Quinones and Their Analogues and Identification of Indoleamine‐2,3‐dioxygenase (IDO) as Potential Target for Anticancer Activity

Natural quinones, often linked with cellular oxidation processes, exhibit pronounced biological activity. In particular, the structurally unique isothiazolonaphthoquinone aulosirazole, isolated from blue‐green alga, possesses selective antitumor cytotoxicity, although its mechanism of action is unknown. The first synthesis of aulosirazole uses a route centered upon a late‐stage regioselective Diels–Alder reaction. The structurally related natural product pronqodine A, an inhibitor of prostaglandin release, and analogues thereof, were also prepared for comparison. Biological evaluation of the compounds identified one potential target as the immunoregulatory enzyme indoleamine‐2,3‐dioxygenase (IDO). The isothiazoloquinones are also efficient substrates for the human quinone reductase NQO1, and undergo intracellular NQO1‐dependent redox cycling resulting in the generation of reactive oxygen species, and at lower doses have the potential to alter the ratio of intracellular oxidized to reduced pyridine nucleotides.     

Phase Behavior of a Designed Cyclopropyl Analogue of Monoolein: Implications for Low‐Temperature Membrane Protein Crystallization

Lipidic cubic phases (LCPs) are used in areas ranging from membrane biology to biodevices. Because some membrane proteins are notoriously unstable at room temperature, and available LCPs undergo transformation to lamellar phases at low temperatures, development of stable low‐temperature LCPs for biophysical studies of membrane proteins is called for. Monodihydrosterculin (MDS) is a designer lipid based on monoolein (MO) with a configurationally restricted cyclopropyl ring replacing the olefin. Small‐angle X‐ray scattering (SAXS) analyses revealed a phase diagram for MDS lacking the high‐temperature, highly curved reverse hexagonal phase typical for MO, and extending the cubic phase boundary to lower temperature, thereby establishing the relationship between lipid molecular structure and mesophase behavior. The use of MDS as a new material for LCP‐based membrane protein crystallization at low temperature was demonstrated by crystallizing bacteriorhodopsin at 20 °C as well as 4 °C.     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Mechanism of copper underpotential deposition at Pt(<Emphasis Type="Italic">hkl</Emphasis>)-electrodes: Quantum-chemical modelling

Mechanism of copper underpotential deposition at stepped faces of platinum single crystals Pt(hkl) is studied using cyclic voltammetry, scanning probe microscopy, and quantum-chemical modelling. It is shown that the first stage of UPD is one-dimensional decoration of the (100)- or (110)-orientated steps, then copper monolayer forms at (111)-terraces. The final stage is the secondary step decoration. Quantum-chemical modelling, with the using of long-distance potentials of the Cu-Pt and Cu-Cu pair interactions, allows estimating the energy of copper adsorption at different structure elements of the substrate (steps, kinks, terraces) and revealing the succession of the adatom monolayer formation; it also provides additional information for the identifying of the nature of voltametric peaks for different stages of the copper adsorption-desorption.     

New rules for the old game of porous micro- and nanoparticle synthesis

The field of research focused on the synthesis of micro- and nanoparticles has not yet conclusively addressed the challenges presented by the hierarchical control of surface topography. An established approach to hierarchical multicomposite nanostructured particles is based on template-directed synthesis, while spectacular advances have been reached in nanoparticle fabrication based on a variety of physicochemical processes. These results exemplify an additive route to hierarchical control, where multiple layers are stacked onto each other or where discretely identifiable particles are assembled into a larger spherical conglomerate. We present here a new strategy for the synthesis of micro- and nanoparticles, which we refer to as "textured isomorphic synthesis", that uses only the toolbox of inorganic chemistry coupled to the physics of cavitation, viscous fingering, and bubble nucleation. The results illustrate a topological route to hierarchical control of particle topography where dimples or holes are deterministically introduced on a planar substrate later transformed into isomorphic hollow spherical micro- and nanostructures.     

C60/corannulene on Cu(110): a surface-supported bistable buckybowl-buckyball host-guest system

Corannulene (COR) buckybowls were proposed as near ideal hosts for fullerene C60, but direct complexation of C60 and COR has remained a challenge in supramolecular chemistry. We report the formation of surface-supported COR-C60 host-guest complexes by deposition of C60 onto a COR lattice on Cu(110). Variable-temperature scanning tunneling microscopy studies reveal two distinctly different states of C60 on the COR host lattice, with different binding energies and bowl-ball separations. The transition from a weakly bound precursor state to a strongly bound host-guest complex is found to be thermally activated. Simple model calculations show that this bistability originates from a subtle interplay between homo- and heteromolecular interactions.     

La3B6O13(OH): The First Acentric High-Pressure Borate Displaying Edge-Sharing BO4 Tetrahedra

La₃B₆O₁₃(OH) was obtained by a high-pressure/high-temperature experiment at 6 GPa and 1673 K. The compound crystallizes in the space group P2₁ (no. 4) with the lattice parameters a=4.785(2), b=12.880(4), c=7.433(3) Å, and β=90.36(10)°, and is built up of corner- as well as edge-sharing BO₄ tetrahedra. It represents the first acentric high-pressure borate containing these B₂O₆ entities. The compound develops borate layers of „sechser“-rings with the La³⁺ cations positioned between the layers. Single-crystal and powder X-ray diffraction, vibrational and MAS NMR spectroscopy, second-harmonic generation (SHG) and thermoanalytical measurements, as well as computational methods were used to affirm the proposed structure and the B₂O₆ entities.     

THE EFFECTS OF THROMBOXANE INHIBITORS ON THE MICROVASCULAR AND TUMOR RESPONSE TO PHOTODYNAMIC THERAPY

Abstract— Vascular stasis and tissue ischemia are known to cause tumor cell death in several experimental models after photodynamic therapy (PDT); however, the mechanisms leading to this damage remain unclear. Because previous studies indicated that thromboxane release is implicated in vessel damage, we further examined the role of throm-boxane in PDT. Rats bearing chondrosarcoma were injected with 25 mg/kg Photofrin® (intravenously) 24 h before treatment. Light (135 J/cm ² , 630 nm) was delivered to thc tumor area after injection of one of the following inhibitors: (1) R68070: a thromboxane synthetase inhibitor; (2) SQ-29548: a thromboxane receptor antagonist; and (3) Flunarizine: an inhibitor of platelet shape change. Systemic thromboxane levels were determined. Vessel constriction and leakage were evaluated by intravital microscopy. Tumor response was assessed after treatment. Thromboxane levels were decreased more than 50% with SQ-29548 as compared to controls. Thromboxane levels in animals given R68070 and Flunarizine remained at baseline levels. SQ-29548 and R68070 reduced vessel constriction compared to controls, while Flunarizine totally prevented vessel constriction. R68070 and SQ-29548 inhibited vessel permeability compared to PDT controls; Flunarizine did not. Animals given these inhibitors showed markedly reduced tumor cure. These results indicate that the release of thromboxane is linked to the vascular response in PDT.     

Rational design of combination enzyme therapy for celiac sprue

Celiac sprue (also known as celiac disease) is an inheritable, gluten-induced enteropathy of the upper small intestine with an estimated prevalence of 0.5%-1% in most parts of the world. The ubiquitous nature of food gluten, coupled with inadequate labeling regulations in most countries, constantly poses a threat of disease exacerbation and relapse for patients. Here, we demonstrate that a two-enzyme cocktail comprised of a glutamine-specific cysteine protease (EP-B2) that functions under gastric conditions and a PEP, which acts in concert with pancreatic proteases under duodenal conditions, is a particularly potent candidate for celiac sprue therapy. At a gluten:EP-B2:PEP weight ratio of 75:3:1, grocery store gluten is fully detoxified within 10 min of simulated duodenal conditions, as judged by chromatographic analysis, biopsy-derived T cell proliferation assays, and a commercial antigluten antibody test.