Benzoylureas as removable cis amide inducers: synthesis of cyclic amides via ring closing metathesis (RCM)

Rapid and high yielding synthesis of medium ring lactams was made possible through the use of a benzoylurea auxiliary that serves to stabilize a cisoid amide conformation, facilitating cyclization. The auxiliary is released after activation under the mild conditions required to deprotect a primary amine, such as acidolysis of a Boc group in the examples given here. This methodology is a promising tool for the synthesis of medium ring lactams, macrocyclic natural products and peptides.     

Janus droplets: liquid marbles coated with dielectric/semiconductor particles

The manufacturing of water droplets wrapped with two different powders, carbon black (semiconductor) and polytetrafluoroethylene (dielectric), is presented. Droplets composed of two hemispheres (Janus droplets) characterized by various physical and chemical properties are reported first. Watermelon-like striped liquid marbles are reported. Janus droplets remained stable on solid and liquid supports and could be activated with an electric field.     

Waves in an inhomogeneous plasma with Hall dispersion

The evolution of steady-state periodic solutions of the Korteweg-de Vries equation (the socalled cnoidal waves), propagating along the direction of the gravitational force with an arbitrary orientation of the magnetic field, is studied for plasma characterized by Hall dispersion and Joule dissipation, using the magnetohydrodynamic approximation. The wavelength is regarded as much shorter than the characteristic scale of the inhomogeneity. The dependence of the wave amplitude on the distance to the source of the wave is considered for various limiting cases. The behavior of the wave depends on the temperature distribution in the medium. In the particular case of an isothermal atmosphere, the problem is solved analytically for a cold plasma in the absence of dissipation. The amplitude of both fast and slow waves increases when the wave travels upward and diminishes when the wave travels downward. The nonlinearity of the wave (i.e., the parameter characterizing the deviation of the wave from sinusoidal form) diminishes in the case of fast magnetoacoustic waves when the wave travels upward and increases when the wave travels downward. The situation is reversed for slow magnetoacoustic waves.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 5, pp. 139–144, September–October, 1976.The author is grateful to V. B. Baranov for constant interest in the work and valuable comments.     

Structural correlations in comb heteropolymers in good and backbone-selective solvents

Molecular dynamics (MD) simulations of coarse-grained regular comb heteropolymers have been performed to explore structural correlations at equilibrium in a nonselective solvent and during the transition from coil to micelle in a backbone-selective solvent. We primarily consider the static structure factor measured directly from the simulations. In the good solvent, we consider cases ranging from short to long side chains, with respect to the spacer length. Reasonable agreement with a previously published theoretical structure factor is observed for a limited subset of the comb architectures in a small wavevector range. When the side chains are much longer than the spacers, the side-chain structure factor approaches that of starlike polymers. Additionally, plateau values of the structure factor scale with the side-chain length to the power of 0.736 when the side chains are shorter than the spacers. The transition from an open coil to a collapsed micelle is examined in MD simulations with explicit-solvent particles. Upon a sudden quench the from nonselective solvent to the backbone-selective solvent, the coil-to-micelle transition occurs via a side-chain clusterization mechanism. The time-dependent structure factors measured during the collapse process have plateau values that scale with the average cluster size to the power of 0.9. The origin of these two scaling exponents is still unknown. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 983-993, 2005     

Naphthenic acids as indicators of crude oil biodegradation in soil,based on semi‐quantitative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Crude oil contaminated soil cores were collected from a basin that contained oily solids left from three decades of oil production. Hydrocarbon biomarker analyses revealed that the soil extracts were moderately biodegraded compared with the non‐degraded source oil. The degree of biodegradation also decreased with core depth (7 cm to 1 m). These data were correlated to compositional changes observed in acidic NSO‐compounds that were selectively ionized and mass resolved by negative ion electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT‐ICR MS). Among the NSO‐compounds ionized, the increase in naphthenic acid concentration (e.g., acyclic and alicyclic carboxylic acids) best correlated with the increase in biodegradation (e.g., from non‐degraded to moderately degraded) as determined by the hydrocarbon biomarker analyses. The most biodegraded surface extracts (7 cm) exhibited an 80% increase in the abundance of acids relative to the source oil. Use of an internal standard allowed the semi‐quantitative determination of the total naphthenic acid concentration, which decreased significantly (P < 0.05) with soil depth. Furthermore, the shift to higher double bond equivalents (DBEs), from acyclic to alicyclic acids, indicated that the increase in acids in the soil extracts was predominately due to biotic processes. This work demonstrates the potential of ESI FT‐ICR MS as a semi‐quantitative tool to monitor the production of naphthenic acids during crude oil biotransformation in the environment. Copyright © 2008 John Wiley & Sons, Ltd.     

Self-assembly in evaporated polymer solutions: influence of the solution concentration

Amorphous polymers were dissolved in chlorinated organic solvents and deposited on thin horizontal substrates. The solutions with various concentrations of polymers were deposited and evaporated under ambient conditions in a slow air current. Self-assembled oriented mesoscopically scaled patterns were observed. The patterns were studied with optical and atomic force microscopy. The concentration of the solution exerts a decisive influence on the mesoscopic cell characteristic dimension. Cell dimensions grow linearly with the polymer solution concentration for all kinds of tested polymers, chlorinated solvents and substrates. The dependence could be explained by a physical mechanism, based on the mass transport instability occurring under the intensive evaporation of the solvent. In situ FTIR study of the process was performed first. It was established with FTIR spectroscopy that film porosity is not due to water droplet condensation under evaporation.     

Activation of Erk and JNK MAPK pathways by acute swim stress in rat brain regions

Background

The mitogen-activated protein kinases (MAPKs) have been shown to participate in a wide array of cellular functions. A role for some MAPKs (e.g., extracellular signal-regulated kinase, Erk1/2) has been documented in response to certain physiological stimuli, such as ischemia, visceral pain and electroconvulsive shock. We recently demonstrated that restraint stress activates the Erk MAPK pathway, but not c-Jun-N-terminal kinase/stress-activated protein kinase (JNK/SAPK) or p38MAPK, in several rat brain regions. In the present study, we investigated the effects of a different stressor, acute forced swim stress, on the phosphorylation (P) state of these MAPKs in the hippocampus, neocortex, prefrontal cortex, amygdala and striatum. In addition, effects on the phosphorylation state of the upstream activators of the MAPKs, their respective MAPK kinases (MAPKKs; P-MEK1/2, P-MKK4 and P-MKK3/6), were determined. Finally, because the Erk pathway can activate c-AMP response element (CRE) binding (CREB) protein, and swim stress has recently been reported to enhance CREB phosphorylation, changes in P-CREB were also examined.

Results

A single 15 min session of forced swimming increased P-Erk2 levels 2–3-fold in the neocortex, prefrontal cortex and striatum, but not in the hippocampus or amygdala. P-JNK levels (P-JNK1 and/or P-JNK2/3) were increased in all brain regions about 2–5-fold, whereas P-p38MAPK levels remained essentially unchanged. Surprisingly, levels of the phosphorylated MAPKKs, P-MEK1/2 and P-MKK4 (activators of the Erk and JNK pathways, respectively) were increased in all five brain regions, and much more dramatically (P-MEK1/2, 4.5 to > 100-fold; P-MKK4, 12 to ~300-fold). Consistent with the lack of forced swim on phosphorylation of p38MAPK, there appeared to be no change in levels of its activator, P-MKK3/6. P-CREB was increased in all but cortical (prefrontal, neocortex) areas.

Conclusions

Swim stress specifically and markedly enhanced the phosphorylation of the MAPKKs P-MEK1/2 and P-MKK4 in all brain regions tested without apparent alteration in the phosphorylation of P-MKK3/6. Curiously, phosphorylation of their cognate substrates (Erk and JNK) was increased to a much more modest extent, and in some brain regions was not altered. Similarly, there was a region-specific discrepancy between Erk and CREB phosphorylation. Possible explanations for these findings and comparison with the effects of restraint stress will be discussed.

     

Evaluation of a new carbon/zirconia‐based sorbent for the cleanup of food extracts in multiclass analysis of pesticides and environmental contaminants

A novel carbon/zirconia‐based material, Supel^TM QuE Verde, was evaluated in a filter‐vial dispersive solid‐phase extraction cleanup of pork, salmon, kale, and avocado extracts for the residual analysis of 65 pesticides and 52 environmental contaminants (flame retardants, polychlorinated biphenyls, polybrominated diphenyl ethers, and polycyclic aromatic hydrocarbons) using low‐pressure gas chromatography with tandem mass spectrometry. An amount of 180 mg sorbent per 0.6 mL extract in filter‐vial dispersive solid‐phase extraction cleanup was found the optimum in terms of achieving satisfactory removal of co‐extractives and recoveries of analytes, especially for structurally planar compounds. For analytes partially retained by Verde, normalization to an internal standard resulted in 62–107% recoveries. Addition of Verde to primary secondary amine and C₁₈ in cleanup resulted in 38% more removal of gas‐chromatography‐amenable co‐extractives in avocado, 30% in kale, 39% in salmon, and 50% in pork. The removal efficiency of co‐extracted chlorophyll was 93% for kale and 64% for avocado based on ultraviolet‐visible absorbance. The developed method was validated at three spiking levels (10, 25, and 100 ng/g), and 70–120% recoveries with ≤20% relative standard deviation were achieved for 96 (83%) out of 117 analytes in pork, 79 (69%) in salmon, 71 (62%) in kale, and 75 (65%) in avocado.