Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl

Grignard reagents RMgCl and their so‐called turbo variant, the highly reactive RMgCl?LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity‐enhancing effect. A combination of electrospray‐ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion‐ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl?LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron‐rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents.     

Voltage-dependent anion channel transports calcium ions through biomimetic membranes

The mitochondrial outer membrane channel (VDAC), a central player in mitochondria and cell death, was reconstituted in polymer-supported phospholipid bilayers. Highly purified VDAC was first reconstituted in vesicles; channel properties and NADH-ferricyanide reductase activity were ascertained before deposition onto solid substrates. 1-Palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine/1,2-distearoyl-sn-glycero-3-phosphoethanolamine-poly(ethylene glycol)-N-hydroxysuccinimide mixed vesicles containing VDAC were linked onto amine-grafted surfaces (glass and gold) and disrupted to form a VDAC-containing polymer-tethered planar bilayer. Surface plasmon spectroscopy, fluorescence microscopy, and atomic force microscopy measurements ascertained the membrane thickness, fluidity, and continuity. VDAC reconstituted in bilayers efficiently transported calcium ions and was modulable by two channel blockers, 4,4'-diisothiocyanatostilbene-2,2'-disulfonic acid and l-glutamate. The novel setup may allow the study of the assembly of a polyprotein complex centered on VDAC and its role in mitochondrial biology, calcium fluxes, and apoptosis.     

Responsive thin hydrogel layers from photo-cross-linkable poly(N-isopropylacrylamide) terpolymers

The structural features and swelling properties of responsive hydrogel films based on poly(N-isopropylacrylamide) copolymers with a photo-cross-linkable benzophenone unit were investigated by surface plasmon resonance, optical waveguide mode spectroscopy, and atomic force microscopy. The temperature-dependent swelling behavior was studied with respect to the chemical composition of the hydrogel polymers containing either sodium methacrylate or methacrylic acid moieties. In the sodium methacrylate system, a refractive index gradient was found that was not present in the free acid gel. This refractive index gradient, perpendicular to the swollen hydrogel film surface, could be analyzed in detail by application of the reversed Wentzel-Kramers-Brillouin (WKB) approximation to the optical data. This novel approach to analyzing thin-film gradients with the WKB method presents a powerful tool for the characterization of inhomogeneous hydrogels, which would otherwise be very difficult to capture experimentally. In AFM images of the hydrogel layers, a macroscopic pore structure was observed that depended on the polymer composition as well as on the swelling history. This pore structure apparently prevents the often-observed skin barrier effect and leads to a quickly responding hydrogel.     

A novel 3D mammalian cell perfusion-culture system in microfluidic channels

Mammalian cells cultured on 2D surfaces in microfluidic channels are increasingly used in drug development and biological research applications. These systems would have more biological or clinical relevance if the cells exhibit 3D phenotypes similar to the cells in vivo. We have developed a microfluidic channel based system that allows cells to be perfusion-cultured in 3D by supporting them with adequate 3D cell-cell and cell-matrix interactions. The maximal cell-cell interaction was achieved by perfusion-seeding cells through an array of micropillars; and 3D cell-matrix interactions were achieved by a polyelectrolyte complex coacervation process to form a thin layer of matrix conforming to the 3D cell shapes. Carcinoma cell lines (HepG2, MCF7), primary differentiated (hepatocytes) and primary progenitor cells (bone marrow mesenchymal stem cells) were perfusion-cultured for 72 hours to 1 week in the microfluidic channel, which preserved their 3D cyto-architecture and cell-specific functions or differentiation competence. This transparent 3D microfluidic channel-based cell culture system also allows direct optical monitoring of cellular events for a wide range of applications.     

Oligosaccharide-modified poly(propyleneimine) dendrimers: synthesis, structure determination, and Cu(II) complexation

The multiple application of reductive amination on primary amino groups of first and second generation poly(propyleneimine) dendrimers is used as a one-pot approach to introduce twice the amount of the oligosaccharide units as surface groups, compared to initially present amino groups in the first and second generation dendrimers. This was proven by (1)H NMR, MALDI-TOF-MS, and LILBID-MS analysis. The size of these dendrimers was determined by the hydrodynamic radius using pulsed field gradient NMR and dynamic light scattering. Molecular modeling confirmed the presence of dense-shell dendrimers. These dendrimers exhibit a generation dependent Cu(II)/dendrimer ratio in an aqueous environment, highlighting these materials as possible metal-carrier systems with a well-defined oligosaccharide protection shell for application in a biological environment.     

Nanoparticle-based immunosensors and immunoassays for aflatoxins

Aflatoxins are naturally existing mycotoxins produced mainly by Aspergillus flavus and Aspergillus parasiticus, present in a wide range of food and feed products. Because of their extremely high toxicity and carcinogenicity, strict control of maximum residue levels of aflatoxins in foodstuff is set by many countries. In daily routine, different chromatographic methods are used almost exclusively. As supplement, in several companies enzyme immunoassay-based sample testing as primary screening is performed. Recently, nanomaterials such as noble metal nanoparticles, magnetic particles, carbon nanomaterials, quantum dots, and silica nanomaterials are increasingly utilized for aflatoxin determination to improve the sensitivity and simplify the detection. They are employed either as supports for the immobilization of biomolecules or as electroactive or optical labels for signal transduction and amplification. Several nanoparticle-based electrochemical, piezoelectric, optical, and immunodipstick assays for aflatoxins have been developed. In this review, we summarize these recent advances and illustrate novel concepts and promising applications in the field of food safety.     

The First Bismuth Phosphide Complex: [Li(thf)4]+[{(tBuP)3}2Bi]−

Thermally unstable crystals of the title compound—the first bismuth phosphide complex to be structurally characterized (see picture)—are obtained by the reaction of [Bi(NMe₂)₃] with [tBuPHLi] (1:3) in THF/hexane. Berry pseudorotation of the pseudo-trigonal-bipyramidal [{(tBuP)₃}₂Bi]⁻ ion is prevented for steric reasons.     

Azobenzene-containing polyamic acid with excellent Langmuir-Blodgett-Kuhn film formation behavior suitable for all-optical switching

To generate command surfaces for all-optical switching, highly ordered polymeric Langmuir-Blodgett-Kuhn (LBK) multilayers were fabricated onto silicon substrates and gold-coated optical glass slides from novel azobenzene-bearing polyamic acid systems. Pronounced Bragg peaks and well-defined Kiessig fringes observed in the X-ray reflectivity measurement for samples on silicon substrates indicate that these films possess a regularly repeated Y-type LBK multilayer structure and ultrasmooth surfaces. Fourier transform infrared (FT-IR) spectra taken by grazing incidence reflection suggest specific orientations of the functional groups in the layers. The excellent film-forming properties of the polyamic acid allow for a smooth buildup of several hundreds of layers of the LBK films onto gold-coated glass slides, which in turn allows for determining the geometrical thickness and the anisotropic refractive indices of the films by using optical waveguide spectroscopy. Interestingly, the probe laser beam induced a distinct fluorescence signal from the films, which remained even after the film underwent a thermal imidization process at 160 degrees C for 8 h in vacuo. LBK films fabricated from these compounds can be successfully applied for all-optically switching the alignment of liquid crystals by irradiation with light of different wavelengths.