Surface Analysis of Titanium Cleaning and Activation Processes: Non-thermal Plasma Versus Other Techniques

A medium pressure (5 kPa) dielectric barrier discharge operating in different atmospheres (air and argon) is used to develop a fast and easy way to remove adsorbed carbon contamination. Chemical and physical changes at the sample surface after plasma treatment are studied, making use of contact angle measurements, X-ray photoelectron spectroscopy analysis and atomic force microscopy measurements. The obtained results are compared with other chemical and thermal treatments typically used. This comparison shows that plasma treatment at medium pressure is able to remove up to 20 % more of the adsorbed carbon compared to the classical cleaning methods, while at the same time being less aggressive, leaving the sub-surface chemistry unchanged. Moreover, the analysis techniques give a fundamental insight in the reactions processes at the titanium surface when exposed to a medium pressure plasma.     

Dually fluorescent silica nanoparticles

The cationic dyes 9-aminoacridine (9AA) and safranine (Sf) were entrapped into silica spheres of about 0.2 μm diameter prepared by modified Stöber method. The fluorescent materials are investigated by steady-state and time-resolved emission, in addition of confocal fluorescence microscopy. Silica particles containing 9-aminoacridine (SP9AA) and safranine (SPSf) or both dyes (SPSf9AA) are emissive particles. When both dyes are present in the same particle but loaded in sequential stages 9AA emission is quenched as a consequence of energy transfer from 9AA (donor) to Sf (acceptor). This result suggests that particle growing processes where the acceptor is incorporated first into the core do not prevent donor/acceptor pairs to be close due to an overlay of the concentration gradients of both dyes in a radial core-shell like distribution.     

Multiplexing biochemical signals

In this Letter we show that living cells can multiplex biochemical signals, i.e., transmit multiple signals through the same signaling pathway simultaneously, and yet respond to them very specifically. We demonstrate how two binary input signals can be encoded in the concentration of a common signaling protein, which is then decoded such that each of the two output signals provides reliable information about one corresponding input. Under biologically relevant conditions the network can reach the maximum amount of information that can be transmitted, which is 2 bits.     

Engineered C–N Lyase: Enantioselective Synthesis of Chiral Synthons for Artificial Dipeptide Sweeteners

Aspartic acid derivatives with branched N‐alkyl or N‐arylalkyl substituents are valuable precursors to artificial dipeptide sweeteners such as neotame and advantame. The development of a biocatalyst to synthesize these compounds in a single asymmetric step is an as yet unmet challenge. Reported here is an enantioselective biocatalytic synthesis of various difficult N‐substituted aspartic acids, including N‐(3,3‐dimethylbutyl)‐l ‐aspartic acid and N‐[3‐(3‐hydroxy‐4‐methoxyphenyl)propyl]‐l ‐aspartic acid, precursors to neotame and advantame, respectively, using an engineered variant of ethylenediamine‐N,N′‐disuccinic acid (EDDS) lyase from Chelativorans sp. BNC1. This engineered C–N lyase (mutant D290M/Y320M) displayed a remarkable 1140‐fold increase in activity for the selective hydroamination of fumarate compared to that of the wild‐type enzyme. These results present new opportunities to develop practical multienzymatic processes for the more sustainable and step‐economic synthesis of an important class of food additives.     

Experimental and Computational Evidence for the Mechanism of Intradiol Catechol Dioxygenation by Non‐Heme Iron(III) Complexes

Catechol intradiol dioxygenation is a unique reaction catalyzed by iron‐dependent enzymes and non‐heme iron(III) complexes. The mechanism by which these systems activate dioxygen in this important metabolic process remains controversial. Using a combination of kinetic measurements and computational modelling of multiple iron(III) catecholato complexes, we have elucidated the catechol cleavage mechanism and show that oxygen binds the iron center by partial dissociation of the substrate from the iron complex. The iron(III) superoxide complex that is formed subsequently attacks the carbon atom of the substrate by a rate‐determining C?O bond formation step.     

Pro-Inflammatory Interactions of Dolutegravir with Human Neutrophils in an In Vitro Study

There is increasing awareness of an association between the uptake of the HIV integrase inhibitor, dolutegravir, in first-line antiretroviral regimens with unusual weight gain and development of the metabolic syndrome, particularly in African women. Although seemingly unexplored, the development of systemic inflammation linked to the putative pro-inflammatory activity of dolutegravir represents a plausible pathophysiological mechanism of this unusual weight gain. This possibility was explored in the current study undertaken to investigate the effects of dolutegravir (2.5–20 μg/mL) on several pro-inflammatory activities of neutrophils isolated from the blood of healthy, adult humans. These activities included the generation of reactive oxygen species (ROS), degranulation (elastase release) and alterations in the concentrations of cytosolic Ca²⁺ using chemiluminescence, spectrophotometric and fluorimetric procedures, respectively. Exposure of neutrophils to dolutegravir alone resulted in the abrupt, dose-related, and significant (p < 0.0039–p < 0.0022) generation of ROS that was attenuated by the inclusion of the Ca²⁺-chelating agent, EGTA, or inhibitors of NADPH oxidase (diphenyleneiodonium chloride, DPI), phospholipase C (U733122), myeloperoxidase (sodium azide) and phosphoinositol-3-kinase (wortmannin). In addition, exposure to dolutegravir augmented the release of elastase by stimulus-activated neutrophils. These pro-inflammatory effects of dolutegravir on neutrophils were associated with significant, rapid, and sustained increases in the concentrations of cytosolic Ca²⁺ that appeared to originate from the extracellular compartment, seemingly consistent with an ionophore-like property of dolutegravir. These findings are preliminary and necessitate verification in the clinical setting of HIV infection. Nevertheless, given the complex link between inflammation and obesity, these pro-inflammatory interactions of dolutegravir with neutrophils may contribute to unexplained weight gain, possibly via the development of insulin resistance.     

On the convex hull of the simple integer recourse objective function

We consider the objective function of a simple integer recourse problem with fixed technology matrix.Using properties of the expected value function, we prove a relation between the convex hull of this function and the expected value function of a continuous simple recourse program.We present an algorithm to compute the convex hull of the expected value function in case of discrete right-hand side random variables. Allowing for restrictions on the first stage decision variables, this result is then extended to the convex hull of the objective function.Supported by the National Operations Research Network in the Netherlands (LNMB).