Kinetically labile equilibrium shifts induced by the electrospray process

The complexation reactions between the alkaline earth metal ions and EDTA were studied by electrospray mass spectrometry to measure the change in concentration of the metal ion-EDTA complex (MY(2)(-)) in the gas phase relative to the solution-phase equilibrium concentration. This work focused on the solution pH range from 4 to 7 where there exists free metal ions in solution at equilibrium. The equilibrium shift, measured through quantitation of the increased abundance of the MY(2)(-) species in the gas phase, was largest for barium and smallest for magnesium. The cause of the net equilibrium shift of the MY(2)(-) species is the combined effect of an electrolytic increase in pH within the capillary plus an additional shift within the evaporating droplets. In a thin diffusion-limited layer created by the products of electrolysis mixing with the bulk solution at the ES capillary tip, the labile species reequilibrate at a new, higher pH. In the evaporating droplets, the formation of new labile species due to increased solute concentrations is kinetically controlled because the ion residence time in the droplet prior to desorption is only ～5 μs. These results are briefly discussed with respect to the potential for utilizing electrospray mass spectrometry for kinetically labile equilibrium studies.     

Effect of preparation method on the glycaemic index of novel potato clones

The purpose of this study was to investigate whether the effects of cooling and reheating on the glycaemic index (GI) of novel potato clones (selections) differed depending on selection and whether cooling altered starch absorption in vivo. We conducted 3 experiments using 4 novel potato clones in healthy subjects. Experiment 1: the GI of 4 selections each prepared in 3 ways (freshly boiled, cooled, or cooled and reheated) was measured in 2 groups of 10 subjects (each group tested 2 selections). Experiment 2 (n=10): two selections from Experiment 1 were re-tested one year later, by a different subject group. Experiment 3 (n=10): two selections from Experiment 1 were tested by subjects from Experiment 2 to assess the rate and extent of starch absorption using the second-meal effect and the breath hydrogen method, respectively. Experiment 1 demonstrated a selection×treatment interaction for GI (p=0.024); cooling reduced the GI of two selections by 40-50% (p<0.05) but reduced GI of the other 2 by only 8-10% (ns). Experiment 2 confirmed the selection×treatment interaction (p=0.018) seen in Experiment 1. Experiment 3: cooling reduced the GI by an average of 37% (p<0.05) but only increased starch malabsorption in vivo from 3% to 5% (p=0.021); there was no significant second-meal effect. It is concluded that the effect of cooling on the GI of potatoes may vary from 0-50% depending on selection. However, the mechanism for the effect is not clear: the 2% increase in starch malabsorption seen upon cooling potatoes was not nearly enough to account for the 37% reduction in GI.     

Cell entry of one-dimensional nanomaterials occurs by tip recognition and rotation

Materials with high aspect ratio, such as carbon nanotubes and asbestos fibres, have been shown to cause length-dependent toxicity in certain cells because these long materials prevent complete ingestion and this frustrates the cell. Biophysical models have been proposed to explain how spheres and elliptical nanostructures enter cells, but one-dimensional nanomaterials have not been examined. Here, we show experimentally and theoretically that cylindrical one-dimensional nanomaterials such as carbon nanotubes enter cells through the tip first. For nanotubes with end caps or carbon shells at their tips, uptake involves tip recognition through receptor binding, rotation that is driven by asymmetric elastic strain at the tube-bilayer interface, and near-vertical entry. The precise angle of entry is governed by the relative timescales for tube rotation and receptor diffusion. Nanotubes without caps or shells on their tips show a different mode of membrane interaction, posing an interesting question as to whether modifying the tips of tubes may help avoid frustrated uptake by cells.     

The AtCRK5 Protein Kinase Is Required to Maintain the ROS NO Balance Affecting the PIN2-Mediated Root Gravitropic Response in Arabidopsis

The Arabidopsis AtCRK5 protein kinase is involved in the establishment of the proper auxin gradient in many developmental processes. Among others, the Atcrk5-1 mutant was reported to exhibit a delayed gravitropic response via compromised PIN2-mediated auxin transport at the root tip. Here, we report that this phenotype correlates with lower superoxide anion (O₂^•−) and hydrogen peroxide (H₂O₂) levels but a higher nitric oxide (NO) content in the mutant root tips in comparison to the wild type (AtCol-0). The oxidative stress inducer paraquat (PQ) triggering formation of O₂^•− (and consequently, H₂O₂) was able to rescue the gravitropic response of Atcrk5-1 roots. The direct application of H₂O₂ had the same effect. Under gravistimulation, correct auxin distribution was restored (at least partially) by PQ or H₂O₂ treatment in the mutant root tips. In agreement, the redistribution of the PIN2 auxin efflux carrier was similar in the gravistimulated PQ-treated mutant and untreated wild type roots. It was also found that PQ-treatment decreased the endogenous NO level at the root tip to normal levels. Furthermore, the mutant phenotype could be reverted by direct manipulation of the endogenous NO level using an NO scavenger (cPTIO). The potential involvement of AtCRK5 protein kinase in the control of auxin-ROS-NO-PIN2-auxin regulatory loop is discussed.     

Nonlinear absorption of laser light in Bi12GeO20 single crystals

Two-photon absorption (TPA) at 532 nm was investigated in BGO (Bi₁₂GeO₂₀) single crystals using a 16 ps pulse width Nd: YAG laser. The TPA coefficient was measured to be 2.2–2.6 cm/GW for undoped BGO. This suggests that nonlinear absorption plays a significant role in the carrier generation processes induced by short laser pulses. The TPA coefficient for heavily Al-doped BGO is only slightly smaller (1.9–2.3 cm/GW) than that of the undoped BGO. This result has specific importance since linear absorption in the visible wavelength region is strongly suppressed by Al doping.     

Antioxidant deactivation on graphenic nanocarbon surfaces

This article reports a direct chemical pathway for antioxidant deactivation on the surfaces of carbon nanomaterials. In the absence of cells, carbon nanotubes are shown to deplete the key physiological antioxidant glutathione (GSH) in a reaction involving dissolved dioxygen that yields the oxidized dimer, GSSG, as the primary product. In both chemical and electrochemical experiments, oxygen is only consumed at a significant steady-state rate in the presence of both nanotubes and GSH. GSH deactivation occurs for single- and multi-walled nanotubes, graphene oxide, nanohorns, and carbon black at varying rates that are characteristic of the material. The GSH depletion rates can be partially unified by surface area normalization, are accelerated by nitrogen doping, and suppressed by defect annealing or addition of proteins or surfactants. It is proposed that dioxygen reacts with active sites on graphenic carbon surfaces to produce surface-bound oxygen intermediates that react heterogeneously with glutathione to restore the carbon surface and complete a catalytic cycle. The direct catalytic reaction between nanomaterial surfaces and antioxidants may contribute to oxidative stress pathways in nanotoxicity, and the dependence on surface area and structural defects suggest strategies for safe material design.     

Ferulic acid‐loaded collagen hydrolysate and polycaprolactone nanofibres for tissue engineering applications

There is a great need for the progress of composite biomaterials, which are effective for tissue engineering applications. In this work, the development of composite electrospun nanofibres based on polycaprolactone (PCL) and collagen hydrolysate (CH) loaded with ferulic acid (FA) for the treatment of chronic wounds. Response Surface Methodology (RSM) has been applied to nanofibres factor manufacturing assisted by electrospinning. For wound healing applications, the authors have created the efficacy of CH, and PCL membranes can act as a stable, protective cover for wound, enabling continuous FA release. The findings of the RSM showed a reasonably good fit with a polynomial equation of the second order which was statistically acceptable at P  < 0.05. The optimised parameters include the quantity of hydrolysate collagen, the voltage applied and the distance from tip‐to‐collector. Based on the Box–Behnken design, the RSM was used to create a mathematical model and optimise nanofibres with minimum diameter production conditions. Using FTIR, TGA and SEM, optimised nanofibres were defined. In vitro, cytocompatibility trials showed that there was an important cytocompatibility of the optimised nanofibres, which was proved by cell proliferation and cell morphology. In this research, the mixed nanofibres of PCL and CH with ferulic could be a potential biomaterial for wound healing.Inspec keywords: tissue engineering, polymer fibres, wounds, electrospinning, nanofibres, response surface methodology, cellular biophysics, proteins, molecular biophysics, scanning electron microscopy, biomedical materials, nanomedicine, nanocomposites, nanofabrication, Fourier transform infrared spectraOther keywords: wound healing applications, PCL membranes, stable cover, protective cover, continuous FA release, RSM, optimised parameters, hydrolysate collagen, mathematical model, optimised nanofibres, polycaprolactone nanofibres, tissue engineering applications, composite biomaterials, composite electrospun nanofibres, collagen hydrolysate, ferulic acid, chronic wounds, Response Surface Methodology, nanofibres factor     

Improving the thermal stability of 1-3 piezoelectric composite transducers

The effect of temperature on the behavior of 1-3 piezoelectric composites manufactured using various polymeric materials was assessed experimentally through electrical impedance analysis and laser vibrometry. Device behavior varied with temperature irrespective of the polymer filler. Most significant changes in the piezoelectric composites were recorded around the glass transition temperature (Tg) of the polymer; movement to lower fundamental resonant frequencies and higher values of electrical impedance minima were observed at higher temperatures. Decoupling of the pillars from the polymer matrix was observed by laser vibrometry at high temperatures. The use of high Tg polymer extended the operational temperature range of a piezoelectric composite, and a high Tg polymer with improved thermal conductivity also proved beneficial. For all devices, at temperatures very close to room temperature, subtle changes in device performance, linked to polymer softening, were observed. Particulate filled materials have been investigated, and it is recognized that the high viscosities and low mechanical damping of such materials could be problematic for piezoelectric composite manufacture. The thermal solver of the PZFlex finite element code has been used to predict the temporal and spatial temperature response of a selection of the devices presented. The simulated and experimental data compare favorably.