Pro-oxidative synergic bactericidal effect of NO: kinetics and inhibition by nitroxides

NO plays diverse roles in physiological and pathological processes, occasionally resulting in opposing effects, particularly in cells subjected to oxidative stress. NO mostly protects eukaryotes against oxidative injury, but was demonstrated to kill prokaryotes synergistically with H2O2. This could be a promising therapeutic avenue. However, recent conflicting findings were reported describing dramatic protective activity of NO. The previous studies of NO effects on prokaryotes applied a transient oxidative stress while arbitrarily checking the residual bacterial viability after 30 or 60min and ignoring the process kinetics. If NO-induced synergy and the oxidative stress are time-dependent, the elucidation of the cell killing kinetics is essential, particularly for survival curves exhibiting a "shoulder" sometimes reflecting sublethal damage as in the linear-quadratic survival models. We studied the kinetics of NO synergic effects on H2O2-induced killing of microbial pathogens. A synergic pro-oxidative activity toward gram-negative and gram-positive cells is demonstrated even at sub-μM/min flux of NO. For certain strains, the synergic effect progressively increased with the duration of cell exposure, and the linear-quadratic survival model best fit the observed survival data. In contrast to the failure of SOD to affect the bactericidal process, nitroxide SOD mimics abrogated the pro-oxidative synergy of NO/H2O2. These cell-permeative antioxidants, which hardly react with diamagnetic species and react neither with NO nor with H2O2, can detoxify redox-active transition metals and catalytically remove intracellular superoxide and nitrogen-derived reactive species such as (•)NO2 or peroxynitrite. The possible mechanism underlying the bactericidal NO synergy under oxidative stress and the potential therapeutic gain are discussed.

Kinetics of γ-Mg17Al12 phase dissolution and its effect on room temperature tensile properties in as-cast AZ80 magnesium alloy

As-cast AZ80 magnesium alloy consists of α-Mg, eutectic product of α-Mg and γ-Mg17Al12, with the latter present in the form of partially and fully divorce eutectic. There occurs dissolution of harder γ-Mg17Al12 phase during homogenization treatment at 400 ° and 439 °C. The proportion of the α-Mg and γ-Mg17Al12 phase was varied by solutionizing the alloy for various lengths of time at these temperatures, in order to investigate the kinetics of phase transformation and to evaluate the effect of phase proportion, size and morphology on room temperature tensile properties. It was found that the yield strength decreases with the increase in solutionizing temperature from 400° to 439 °C and at the same time, ductility in general increases with the increasing solutionizing temperature. The variation in tensile properties and the nature of fractographs were analyzed in terms of the effects of microstructure. © (2014) Trans Tech Publications, Switzerland.

Distinct kinetics of molecular gelation in a confined space and its relation to the structure and property of thin gel films

Thin films of molecular gels formed in a confined space have potential applications in transdermal delivery, artificial skin, molecular electronics, etc. The microstructures and properties of thin gel films can be significantly different from those of their bulk counterparts. However, so far a comprehensive understanding of the effects of spatial confinement on the molecular gelation kinetics, fiber network structure and related mechanical properties is still lacking. In this work, using rheological techniques, we investigated the effect of one-dimensional confinement on the formation kinetics of fiber networks in the molecular gelation process. Fractal analyses of the kinetic information in terms of an extended Dickinson model enabled us to describe quantitatively the distinct kinetic signature of molecular gelation. The structural features derived from gelation kinetics support well the fractal patterns of the fiber networks acquired by optical and electron microscopy. With the kinetics-structure correlation, we can gain an in-depth understanding of the confinement-induced differences in the structure and consequently the mechanical properties of a model molecular gelling system. Particularly, the confinement induced structural transition, from a three-dimensional, dense and compact spherulitic network composed of highly branched fibers to a quasi-two-dimensional sparse spherulitic network composed of less branched fibers and entangled fibrils at the boundary areas, renders a gel film to become less stiff but more ductile. Our study suggests here a new strategy of engineering the fiber network microstructure to achieve functional gel films with unusual but useful properties.

Adsorption kinetics and optimum conditions for Cr(VI) removal by activated carbon prepared from luffa sponge

Activated carbon (AC) prepared from luffa sponge was firstly used as an adsorbent to remove Cr(VI) from aqueous solution. The Cr(VI) adsorption behaviors of AC under different conditions, including initial Cr(VI) concentration, quantity of AC, solution pH, and temperature were investigated. The optimal conditions for adsorption of Cr(VI) by AC were pH = 1, initial Cr(VI) concentration = 80 mg/L, T = 303 K, and AC content = 1.6 g/L. The adsorption kinetics could be described by the pseudo-second-order model. Fourier transform infrared spectroscopy was used to investigate the sorption mechanism. Some functional groups such as C–O and O–H were formed on the carbon surface, which could then react with Cr(VI). The surface structure of AC before and after adsorption was analyzed by scanning electronic microscopy. Adsorbed ions choked some of the pores in AC after adsorption. The Brunauer–Emmett–Teller surface area and average pore size of the AC were 834.13 m2/g and 5.17 nm, respectively. The maximum adsorption of Cr(VI) by AC was 149.06 mg/g, which makes AC prepared from luffa sponge promising for removing Cr(VI) from wastewater.

A new insight into growth mechanism and kinetics of mesoporous silica nanoparticles by in situ small angle x-ray scattering

The growth mechanism and kinetics of mesoporous silica nanoparticles (MSNs) were investigated for the first time by using a synchrotron time-resolved small-angle X-ray scattering (SAXS) analysis. The synchrotron SAXS offers unsurpassed time resolution and the ability to detect structural changes of nanometer sized objects, which are beneficial for the understanding of the growth mechanism of small MSNs (∼20 nm). The Porod invariant was used to quantify the conversion of tetraethyl orthosilicate (TEOS) in silica during MSN formation, and the growth kinetics were investigated at different solution pH and temperature through calculating the scattering invariant as a function of reaction time. The growth of MSNs was found to be accelerated at high temperature and high pH, resulting in a higher rate of silica formation. Modeling SAXS data of micelles, where a well-defined electrostatic interaction is assumed, determines the size and shape of hexadecyltrimethylammonium bromide (CTAB) micelles before and after the addition of TEOS. The results suggested that the micelle size increases and the micelle shape changes from ellipsoid to spherical, which might be attributed to the solubilization of TEOS in the hydrophobic core of CTAB micelles. A new "swelling-shrinking" mechanism is proposed. The mechanism provides new insights into understanding MSN growth for the formation of functional mesoporous materials exhibiting controlled morphologies. The SAXS analyses were correlated to the structure of CTAB micelles and chemical reaction of TEOS. This study has provided critical information to an understanding of the growth kinetics and mechanism of MSNs.