Preparation and evaluation of monolithic poly(N-vinylcarbazole-co-1,4-divinylbenzene) capillary columns for the separation of small molecules

Short-term polymerization or the so-called low-conversion polymerization was applied for the preparation of N-vinylcarbazole (NVC) and 1,4-divinylbenzene (DVB) monolithic capillary columns. The synthesis was carried out by thermally initiated free radical copolymerization under the influence of inert micro- (toluene) and macroporogen (1-decanol) and α,α′-azoisobutyronitrile (AIBN) as radical initiator. The morphological and porous properties were studied by scanning electron microscopy (SEM), nitrogen adsorption, and mercury intrusion porosimetry (MIP). The copolymerization process was studied by monomer conversion measurements. This approach led to increased porosity and specific surface area. A specific surface area above 400 m²/g of the monolith and a distinct bimodal pore size distribution were obtained. The chromatographic performance was determined in terms of theoretical plate heights and number of theoretical plates. The lowest plate height value was found to be 3.9 μm (corresponding to ≈256,000 plates per meter) applying methylparaben utilizing an 80 mm?×?0.2 mm i.d. monolithic capillary. The developed NVC/DVB monolithic supports showed high separation efficiency towards small molecules, which was exemplified applying reversed-phase (RP) separation of alkylbenzenes, beta-blockers, flavanoids, parabens, and phenones. The loading capacity was analyzed for isocratic separation of seven alkylbenzenes and was found to be up to 77 ng total mass of alkylbenzenes. Furthermore, a long-term stability test of 1,000 consecutive runs was performed and resulted in a maximum variance of 0.97, 0.85, and 0.16 % RSD for resolution, peak width at half height, and retention times, respectively. The material was proven to have a high permeability of 1.11E?14 m², applying water as a mobile phase.     

Anticancer Aminoferrocene Derivatives Inducing Production of Mitochondrial Reactive Oxygen Species

Elevated levels of reactive oxygen species (ROS) and deficient mitochondria are two weak points of cancer cells. Their simultaneous targeting is a valid therapeutic strategy to design highly potent anticancer drugs. The remaining challenge is to limit the drug effects to cancer cells without affecting normal ones. We have previously developed three aminoferrocene (AF)-based derivatives, which are activated in the presence of elevated levels of ROS present in cancer cells with formation of electron-rich compounds able to generate ROS and reduce mitochondrial membrane potential (MMP). All of them exhibit important drawbacks including either low efficacy or high unspecific toxicity that prevents their application in vivo up to date. Herein we describe unusual AF-derivatives lacking these drawbacks. These compounds act via an alternative mechanism: they are chemically stable in the presence of ROS, generate mitochondrial ROS in cancer cells, but not normal cells and exhibit anticancer effect in vivo.     

The heterogeneous distribution of the liquid phase in partially filled porous glasses and its effect on self-diffusion

The spatial distribution of the liquid phase in a typical, partially filled, porous glass (VitraPor #5) has been examined with the aid of magnetic resonance microscopy and field gradient nuclear magnetic resonance diffusometry techniques. The correlation length of the material turned out to be long enough to permit the visualization of the microscopic heterogeneity of the material by magnetic resonance imaging. Contrasts are dominated by transverse relaxation depending on local filling degree, which in turn depends on local microstructure. The bimodal heterogeneity of the latter was also visualized by scanning electron microscopy. The effect of heterogeneity on an effective diffusion coefficient has been examined for polar (water) and nonpolar (cyclohexane) molecules.     

Guided Antitumoural Drugs: (Imidazol-2-ylidene)(L)gold(I) Complexes Seeking Cellular Targets Controlled by the Nature of Ligand L

Three [1,3-diethyl-4-(p-methoxyphenyl)-5-(3,4,5-trimethoxyphenyl)imidazol-2-ylidene](L)gold(I) complexes, 4 a (L=Cl), 5 a (L=PPh₃), and 6 a (L=same N-heterocyclic carbene (NHC)), and their fluorescent [4-(anthracen-9-yl)-1,3-diethyl-5-phenylimidazol-2-ylidene](L)gold(I) analogues, 4 b , 5 b , and 6 b , respectively, were studied for their localisation and effects in cancer cells. Despite their identical NHC ligands, the last three accumulated in different compartments of melanoma cells, namely, the nucleus ( 4 b ), mitochondria ( 5 b ), or lysosomes ( 6 b ). Ligand L was also more decisive for the site of accumulation than the NHC ligand because the couples 4 a / 4 b , 5 a / 5 b , and 6 a / 6 b , carrying different NHC ligands, afforded similar results in cytotoxicity tests, and tests on targets typically found at their sites of accumulation, such as DNA in nuclei, reactive oxygen species and thioredoxin reductase in mitochondria, and lysosomal membranes. Regardless of the site of accumulation, cancer cell apoptosis was eventually induced. The concept of guiding a bioactive complex fragment to a particular subcellular target by secondary ligand L could reduce unwanted side effects.     

Azimuthal Dipolar Rotor Arrays on Surfaces

A set of dipolar molecular rotor compounds was designed, synthesized and adsorbed as self-assembled 2D arrays on Ag(111) surfaces. The title molecules are constructed from three building blocks: (a) 4,8,12-trioxatriangulene (TOTA) platforms that are known to physisorb on metal surfaces such as Au(111) and Ag(111), (b) phenyl groups attached to the central carbon atom that function as pivot joints to reduce the barrier to rotation, (c) pyridine and pyridazine units as small dipolar units on top. Theoretical calculations and scanning tunneling microscopy (STM) investigations hint at the fact that the dipoles of neighboring rotors interact through space through pairs of energetically favorable head-to-tail arrangements.     

A Convenient Photocatalytic Fluorination of Unactivated CH Bonds

Fluorination reactions are essential to modern medicinal chemistry, thus providing a means to block site‐selective metabolic degradation of drugs and access radiotracers for positron emission tomography imaging. Despite current sophistication in fluorination reagents and processes, the fluorination of unactivated C? H bonds remains a significant challenge. Reported herein is a convenient and economic process for direct fluorination of unactivated C? H bonds that exploits the hydrogen abstracting ability of a decatungstate photocatalyst in combination with the mild fluorine atom transfer reagent N‐fluorobenzenesulfonimide. This operationally straightforward reaction provides direct access to a wide range of fluorinated organic molecules, including structurally complex natural products, acyl fluorides, and fluorinated amino acid derivatives.     

A Metallic Room‐Temperature Oxide Ion Conductor

Nanoparticles of Bi₃Ir, obtained from a microwave‐assisted polyol process, activate molecular oxygen from air at room temperature and reversibly intercalate it as oxide ions. The closely related structures of Bi₃Ir and Bi₃IrO_x (x≤2) were investigated by X‐ray diffraction, electron microscopy, and quantum‐chemical modeling. In the topochemically formed metallic suboxide, the intermetallic building units are fully preserved. Time‐ and temperature‐dependent monitoring of the oxygen uptake in an oxygen‐filled chamber shows that the activation energy for oxide diffusion (84 meV) is one order of magnitude smaller than that in any known material. Bi₃IrO_x is the first metallic oxide ion conductor and also the first that operates at room temperature.