New investigations on ferrofluidics: ferrofluidic marbles and magnetic-field-driven drops on superhydrophobic surfaces

The motion of ferrofluidic marbles on flat polymer substrates is reported. Nanopowders of polyvinylidene fluoride and gammaFe2O3 were used for the preparation of ferrofluidic marbles. The marbles are activated easily with an external magnetic field. A microfluidic device based on ferrofluidic marbles (the ferrofluidic bearing) is described. Velocities of marbles as high as 25+/-3 cm/s were registered. The sliding of ferrofluidic drops on superhydrophobic surfaces was studied. It was demonstrated that the threshold magnetic force necessary for the drop displacement depends linearly on the drop radius, thus the motion of the drop is defined by the processes occurring in the vicinity of the triple line only.     

Mechanisms of oxidation of guanine in DNA by carbonate radical anion, a decomposition product of nitrosoperoxycarbonate

Peroxynitrite is produced during inflammation and combines rapidly with carbon dioxide to yield the unstable nitrosoperoxycarbonate, which decomposes (in part) to CO(3) (.-) and (.)NO(2) radicals. The CO(3) (.-) radicals oxidize guanine bases in DNA through a one-electron transfer reaction process that ultimately results in the formation of stable guanine oxidation products. Here we have explored these mechanisms, starting with a spectroscopic study of the kinetics of electron transfer from 20-22mer double-stranded oligonucleotides to CO(3) (.-) radicals, together with the effects of base sequence on the formation of the end-products in runs of one, two, or three contiguous guanines. The distributions of these alkali-labile lesions were determined by gel electrophoresis methods. The cascade of events was initiated through the use of 308 nm XeCl excimer laser pulses to generate CO(3) (.-) radicals by an established method based on the photodissociation of persulfate to sulfate radicals and the oxidation of bicarbonate. Although the Saito model (Saito et al., J. Am. Chem. Soc. 1995, 117, 6406-6407) predicts relative ease of one-electron oxidations in DNA, following the trend 5'-GGG > 5'-GG > 5'-G, we found that the rate constants for CO(3) (.-)-mediated oxidation of guanines in these sequence contexts (k(5)) showed only small variation within a narrow range [(1.5-3.0)x10(7) M(-1) s(-1)]. In contrast, the distributions of the end-products are dependent on the base sequence context and are higher at the 5'-G in 5'-GG sequences and at the first two 5'-guanines in the 5'-GGG sequences. These effects are attributed to a combination of initial hole distributions among the contiguous guanines and the subsequent differences in chemical reaction yields at each guanine. The lack of dependence of k(5) on sequence context indicates that the one-electron oxidation of guanine in DNA by CO(3) (.-) radicals occurs by an inner-sphere mechanism.     

Micrometrically scaled textured metallic hydrophobic interfaces validate the Cassie-Baxter wetting hypothesis

The possibility of forming a hydrophobic metallic interface is shown when it is micrometrically textured. On such surface obtained by gold coating the polymer honeycomb template, the apparent contact angle of water was observed to be close to or greater than 90 degrees . The metal hydrophobicity is explained by trapping air inside pores of pattern according to the Cassie-Baxter wetting model. The agreement between calculated and observed values of the apparent contact angle justifies the applicability of this model in the present case. Formation of the acute local (Young) angle on the pore surface is provided by its concave form.     

Determination of protein oxidation by mass spectrometry and method transfer to quality control

Characterization and quantitative analysis of oxidation plays an important role in biopharmaceutical development. This study demonstrates an approach to the assessment of susceptible to oxidation methionine residues in monoclonal antibodies and recombinant proteins. A method for the determination of oxidation levels by peptide mapping with mass spectrometric (MS) detection is described and its advantages compared to the UV detection are presented. Good linearity and reproducibility for determination of oxidation with MS detection are demonstrated (R2 > 0.99; RSDs of 4-9%). Aspects of method transfer to quality control group (QC) are discussed. As well, a quick and easy flow injection/MS method is proposed to substitute for peptide map analysis. Peptide coverage, linearity, reproducibility, robustness, sensitivity and quantitative oxidation results are compared for the flow injection/MS and LC/MS approaches.     

The simplest binary fluorocarbon as a ligand. Synthetic, spectroscopic, crystallographic, and computational studies of a molybdenum complex of terminally ligated carbon monofluoride (fluoromethylidyne)

Cp*Mo(CO)3CF3 undergoes two-electron reduction using potassium graphite or magnesium graphite to give Cp*Mo(CO)2(CF), the first example of a transition metal complex containing a terminal fluoromethylidyne ligand, which has been characterized spectroscopically, crystallographically, and computationally.     

Variations of the antioxidant system during development of the cold-tolerant beetle, Tenebrio molitor

Data relating to the peculiarities of antioxidant enzyme activities, glutathione (GSH) level and lipid peroxidation (LP) intermediates specific to at each ontogenic stage of Tenebrio molitor are presented. Metamorphosis is accompanied by a shift of prooxidant-antioxidant balance towards oxidative processes, since pupae have the highest levels of lipid peroxidation intermediates. Cold acclimation (4 degree C) can promote oxidative stress at the cold sensitive developmental stage--imagoes, which enhance their levels of diene conjugates and ketodienes after a 2-week cold acclimation. This enhancement is accompanied by an increase in catalase (CAT) activity. GSH levels undergo no changes in imagoes after cold acclimation. Neither larval nor pupal T. molitor show significant changes in LP product contents after cold acclimation. Chilling results in a significant increase in CAT activities in pupae, but not in larvae. GSH levels are reduced both in larvae and pupae after cold exposure. However, cold acclimation does not affect superoxide dismutase (SOD) activity in any of the developmental stages of T. molitor.     

Microstructure determination of AOT + phenol organogels utilizing small-angle X-ray scattering and atomic force microscopy.

Dry reverse micelles of the anionic twin-tailed surfactant bis(2-ethylhexyl) sulfosuccinate (AOT) dissolved in nonpolar solvents spontaneously form an organogel when p-chlorophenol is added in a 1:1 AOT:phenol molar ratio. The solvents used were benzene, toluene, m-xylene, 2,2,4-trimethylpentane (isooctane), decane, dodecane, tetradecane, hexadecane, and 2,6,10,14-tetramethylpentadecane (TMPD). The proposed microstructure of the gel is based on strands of stacked phenols linked to AOT through hydrogen bonding. Small-angle X-ray scattering (SAXS) spectra of the organogels suggest a characteristic length scale for these phenol-AOT strands that is independent of concentration but dependent on the chemical nature of the nonpolar solvent used. Correlation lengths determined from the SAXS spectra indicate that the strands self-assemble into fibers. Direct visualization of the gel in its native state is accomplished by using tapping mode atomic force microscopy (AFM). It is shown that these organogels consist of fiber bundle assemblies. The SAXS and AFM data reinforce the theory of a molecular architecture consisting of three length scales-AOT/phenolic strands (ca. 2 nm in diameter) that self-assemble into fibers (ca. 10 nm in diameter), which then aggregate into fiber bundles (ca. 20-100 nm in diameter) and form the organogel.