Comparative studies of various run buffers for chiral capillary electrophoresis using chiral crown ether as a chiral selector

In the capillary electrophoretic separation of primary amine enantiomers using (+)-(18-crown-6)-tetracarboxylic acid (18C6H4) as a chiral selector, the presence of run buffer constituents such as tris(hydroxymethyl)aminomethane (Tris) or Na+ competing with analytes for 18C6H4, diminishes the effectiveness of 18C6H4. In order to determine appropriate buffer systems for 18C6H4, various run buffer cationic components including Tris, 1,3-bis[tris(hydroxymethyl)methylamino]propane, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, triethanolamine, tetramethylammonium, and Na+ were compared. Quantitative studies of the effects of the competitive constituents were carried out by measuring the electrophoretic mobilities of histidine as a function of the 18C6H4 concentration. We also derived a simple equation to estimate the optimal chiral selector concentration for a maximum mobility difference in the presence of a competitive inhibitor.     

Catalytic degradation of polystyrene using HUSY catalysts

Summary The addition of carbon dioxide to phenyl glycidyl ether (PGE) was investigated in a semi-batch reactor using immobilized quaternary ammonium chloride catalysts. Five different catalysts were prepared with the following supports : (1) soluble poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC) [C1], (2) insoluble poly(ST-DVB-VBC) [C2], (3) macroporous poly(ST-DVB-VBC) [C3], (4) poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC)-MMT [C4] (5) modified MCM-41 [C5]. The addition of carbon dioxide to PGE can be considered as a pseudo-first order process with respect to the concentration of PGE. The pseudo-first order rate constant for the catalysts decreased in the series C1&gt;C3&gt;C2&gt;C4&gt;C5. The activation energy for C1 to C5 catalysts was 8.6, 20.9, 19.9, 23.9, and 26.8 kJ/mol, respectively. The immobilized catalysts can be reused in least 4 successive runs without any considerable loss of their initial reactivities.     

Supramolecular reactor from self-assembly of rod-coil molecule in aqueous environment

We synthesized an amphiphilic coil-rod-coil triblock molecule consisting of hexa-p-phenylene as a rod block and poly(ethylene oxide) with the number of repeating units of 17 as coil blocks and investigated aggregation behavior in aqueous environment. The rod-coil molecule was observed to aggregate into discrete micelles consisting of hydrophobic disklike rod bundles encapsulated by hydrophilic poly(ethylene oxide) coils. The aromatic bundles of the micelles were demonstrated to be used as an efficient supramolecular reactor for the room temperature Suzuki cross-coupling reaction of a wide range of aryl halides, including even aryl chlorides with phenylboronic acids in aqueous environment. These results demonstrate that self-assembly of amphiphilic rod-coil molecules can provide a useful strategy to construct an efficient supramolecular reactor for aromatic coupling reaction.     

Cancer cells undergoing epigenetic transition show short-term resistance and are transformed into cells with medium-term resistance by drug treatment

To elucidate the epigenetic mechanisms of drug resistance, epigenetically reprogrammed H460 cancer cells (R-H460) were established by the transient introduction of reprogramming factors. Then, the R-H460 cells were induced to differentiate by the withdrawal of stem cell media for various durations, which resulted in differentiated R-H460 cells (dR-H460). Notably, dR-H460 cells differentiated for 13 days (13dR-H460 cells) formed a significantly greater number of colonies showing drug resistance to both cisplatin and paclitaxel, whereas the dR-H460 cells differentiated for 40 days (40dR-H460 cells) lost drug resistance; this suggests that 13dR-cancer cells present short-term resistance (less than a month). Similarly, increased drug resistance to both cisplatin and paclitaxel was observed in another R-cancer cell model prepared from N87 cells. The resistant phenotype of the cisplatin-resistant (CR) colonies obtained through cisplatin treatment was maintained for 2–3 months after drug treatment, suggesting that drug treatment transforms cells with short-term resistance into cells with medium-term resistance. In single-cell analyses, heterogeneity was not found to increase in 13dR-H460 cells, suggesting that cancer cells with short-term resistance, rather than heterogeneous cells, may confer epigenetically driven drug resistance in our reprogrammed cancer model. The epigenetically driven short-term and medium-term drug resistance mechanisms could provide new cancer-fighting strategies involving the control of cancer cells during epigenetic transition.Subject terms: Tumour heterogeneity, Epigenetics     

Formation mechanism of conducting polypyrrole nanotubes in reverse micelle systems

Polypyrrole (PPy) nanotubes were readily fabricated through chemical oxidation polymerization in sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse (water-in-oil) emulsions. The reverse cylindrical micelle phase was characterized, and the key factors affecting the formation of PPy nanotubes were systematically inspected. AOT reverse cylindrical micelles were prepared via a cooperative interaction between an aqueous FeCl3 solution and AOT in an apolar solvent. In the H2O/FeCl3/AOT/apolar solvent system, the aqueous FeCl3 solution played a role in increasing the ionic strength and decreasing the second critical micelle concentration of AOT. As a result, AOT reverse cylindrical micelles could be spontaneously formed in an apolar solvent. In addition, iron cations were adsorbed to the anionic AOT headgroups that were capable of extracting metal cations from the aqueous core. Under these conditions, the addition of pyrrole monomer resulted in the chemical oxidation polymerization of the corresponding monomer at the surface of AOT reverse cylindrical micelles, followed by the formation of tubular PPy nanostructures. In a typical composition (74.0 wt % hexane, 22.4 wt % AOT, and 3.6 wt % aqueous FeCl3 solution at 15 degrees C), the average diameter of PPy nanotubes was approximately 94 nm and their length was more than 2 mum. The PPy nanotube dimensions were affected by synthetic variables such as the weight ratio of aqueous FeCl3 solution/AOT, type of apolar solvent, and reaction temperature. Moreover, the relationship between the diameter and the conductivity of the nanotubes was investigated.     

2,3,7‐Triazabicyclo[3.3.0]octenes Prepared by Tandem Cascade Reaction of Allyl Azides and Olefinic Dipolarophiles

Tandem cascade reactions of allylazides and olefinic dipolarophiles to give cis‐fused 2,3,7‐triazabicyclo [3.3.0]octenes ( 5, 6 or 7 ) are reported. Therein, an intermolecular dipolar cycloaddition of azide and alkene gave a triazoline which was followed by isomerization of the triazoline to a diazoester ( 4 ) and then an intramolecular dipolar cycloaddition from the diazo functional group and the double bond in 4 to give 5 . Compound 5 may further more undergo a Michael addition to give 7‐substituted‐ 2,3,7‐ triazabicyclo [3.3.0]oct‐2‐ene ( 6 ) or a tautomerization to give 2,3,7‐triazabicyclo[3.3.0]oct‐3‐ene ( 7 ). The reaction may be manipulated to stop at a particular stage by adopting a suit able solvent or an appropriate temperature.     

Lyotropic effect in surface charge,electrokinetics, and coagulation of a rutile dispersion

Potentiometric, electrokinetic, and coagulation experiments with a rutile dispersion in the pH region above the point of zero charge exhibit an inverse lyotropic sequence for counterions: Li⁺>K⁺>Cs⁺. The potentiometric and electrokinetic data were interpreted by a surface complexation model assuming the Stern-Gouy-Chapman structure of the interfacial layer, which yielded the values of inner layer capacitances,C, and the intrinsic equilibrium constants,K _ass ⁰ , characterizing the specificity of each counterion. These parameters were used to explain the order of lyotropic sequences in the adsorption, coagulation, and electrokinetic phenomena.     

Phosphorylation of phospholipase D1 and the modulation of its interaction with RhoA by cAMP-dependent protein kinase

Agents that elevate cellular cAMP are known to inhibit the activation of phospholipase D (PLD). We investigated whether PLD can be phosphorylated by cAMP-dependent protein kinase (PKA) and PKA-mediated phosphorylation affects the interaction between PLD and RhoA, a membrane regulator of PLD. PLD1, but not PLD2 was found to be phosphorylated in vivo by the treatment of dibutyryl cAMP (dbcAMP) and in vitro by PKA. PKA inhibitor (KT5720) abolished the dbcAMP-induced phosphorylation of PLD1, but dibutyryl cGMP (dbcGMP) failed to phosphorylate PLD1. The association between PLD1 and Val14RhoA in an immunoprecipitation assay was abolished by both dbcAMP and dbcGMP. Moreover, RhoA but not PLD1 was dissociated from the membrane to the cytosolic fraction in dbcAMP-treated cells. These results suggest that both PLD1 and RhoA are phosphorylated by PKA and the interaction between PLD1 and RhoA is inhibited by the phosphorylation of RhoA rather than by the phosphorylation of PLD1.     

Synthesis of highly enantioenriched all-carbon quaternary centers: conjugate additions of chiral organolithium nucleophiles to alpha,alpha-dinitrile beta,beta-disubstituted olefins

[reaction: see text]. Highly enantioenriched quaternary centers are obtained by the reaction of chiral lithiated intermediates complexed to (-)-sparteine with tetrasubstituted, alpha,alpha-dinitrile activated olefins. Lithiated N-Boc-N-Aryl benzylamine furnishes products with drs from 78:22 to 95:5, with ers exceeding 94:6. Lithiated N-Boc-N-Aryl allylamine reactants provide enecarbamate products with drs from 55:45 to 99:1, with ers ranging from 87:13 to 97:3.