A Selective Sulfide Oxidation Catalyzed by Heterogeneous Artificial Metalloenzymes Iron@NikA

Performing a heterogeneous catalysis with proteins is still a challenge. Herein, we demonstrate the importance of cross-linked crystals for sulfoxide oxidation by an artificial enzyme. The biohybrid consists of the insertion of an iron complex into a NikA protein crystal. The heterogeneous catalysts displays a better efficiency-with higher reaction kinetics, a better stability and expand the substrate scope compared to its solution counterpart. Designing crystalline artificial enzymes represents a good alternative to soluble or supported enzymes for the future of synthetic biology.     

Spectroscopies and Electron Microscopies Unravel the Origin of the First Colour Photographs

The first colour photographs were created by a process introduced by Edmond Becquerel in 1848. The nature of these photochromatic images colours motivated a debate between scientists during the XIX^th century, which is still not settled. We present the results of chemical analysis (EDX, HAXPES and EXAFS) and morphology studies (SEM, STEM) aiming at explaining the optical properties of the photochromatic images (UV-visible spectroscopy and low loss EELS). We rule out the two hypotheses (pigment and interferences) that have prevailed since 1848, respectively based on variations in the oxidation degree of the compound forming the sensitized layer and periodically spaced photolytic silver planes. A study of the silver nanoparticles dispersions contained in the coloured layers showed specific localizations and sizes distributions of the nanoparticles for each colour. These results allow us to formulate a plasmonic hypothesis on the origin of the photochromatic images colours.     

Chemo- and Regioselective Additions of Nucleophiles to Cyclic Carbonates for the Preparation of Self-Blowing Non-Isocyanate Polyurethane Foams

Polyurethane (PU) foams are indisputably daily essential materials found in many applications, notably for comfort (for example, matrasses) or energy saving (for example, thermal insulation). Today, greener routes for their production are intensively searched for to avoid the use of toxic isocyanates. An easily scalable process for the simple construction of self-blown isocyanate-free PU foams by exploiting the organocatalyzed chemo- and regioselective additions of amines and thiols to easily accessible cyclic carbonates is described. These reactions are first validated on model compounds and rationalized by DFT calculations. Various foams are then prepared and characterized in terms of morphology and mechanical properties, and the scope of the process is illustrated by modulating the composition of the reactive formulation. With impressive diversity and accessibility of the main components of the formulations, this new robust and solvent-free process could open avenues for construction of more sustainable PU foams, and offers the first realistic alternative to the traditional isocyanate route.     

DMT1 Inhibitors Kill Cancer Stem Cells by Blocking Lysosomal Iron Translocation

Cancer stem cells (CSC) constitute a cell subpopulation in solid tumors that is responsible for resistance to conventional chemotherapy, metastasis and cancer relapse. The natural product Salinomycin can selectively target this cell niche by directly interacting with lysosomal iron, taking advantage of upregulated iron homeostasis in CSC. Here, inhibitors of the divalent metal transporter 1 (DMT1) have been identified that selectively target CSC by blocking lysosomal iron translocation. This leads to lysosomal iron accumulation, production of reactive oxygen species and cell death with features of ferroptosis. DMT1 inhibitors selectively target CSC in primary cancer cells and circulating tumor cells, demonstrating the physiological relevance of this strategy. Taken together, this opens up opportunities to tackle unmet needs in anti-cancer therapy.     

Stabilizing torsion-free periodic orbits using method of harmonic oscillators

Nonlinear Dynamics - An odd number of real Floquet multipliers greater than unity prevents the classical time delayed feedback control from stabilizing torsion-free orbits of nonautonomous systems....     

Parallel radial basis function methods for the global optimization of expensive functions

We introduce a master–worker framework for parallel global optimization of computationally expensive functions using response surface models. In particular, we parallelize two radial basis function (RBF) methods for global optimization, namely, the RBF method by Gutmann [Gutmann, H.M., 2001a. A radial basis function method for global optimization. Journal of Global Optimization 19(3), 201–227] (Gutmann-RBF) and the RBF method by Regis and Shoemaker [Regis, R.G., Shoemaker, C.A., 2005. Constrained global optimization of expensive black box functions using radial basis functions, Journal of Global Optimization 31, 153–171] (CORS-RBF). We modify these algorithms so that they can generate multiple points for simultaneous evaluation in parallel. We compare the performance of the two parallel RBF methods with a parallel multistart derivative-based algorithm, a parallel multistart derivative-free trust-region algorithm, and a parallel evolutionary algorithm on eleven test problems and on a 6-dimensional groundwater bioremediation application. The results indicate that the two parallel RBF algorithms are generally better than the other three alternatives on most of the test problems. Moreover, the two parallel RBF algorithms have comparable performances on the test problems considered. Finally, we report good speedups for both parallel RBF algorithms when using a small number of processors.     

Linked Primes and Orders in Artinian Rings

It is shown that prime ideals of a Noetherian ring are linked if and only if certain corresponding prime ideals are linked in an associated Artinian ring. Furthermore, it is shown that there is a canonical linking ideal, which can be found by using a construction based on middle annihilator ideals.     

Robust optimization and portfolio selection: The cost of robustness

Robust optimization is a tractable alternative to stochastic programming particularly suited for problems in which parameter values are unknown, variable and their distributions are uncertain. We evaluate the cost of robustness for the robust counterpart to the maximum return portfolio optimization problem. The uncertainty of asset returns is modelled by polyhedral uncertainty sets as opposed to the earlier proposed ellipsoidal sets. We derive the robust model from a min-regret perspective and examine the properties of robust models with respect to portfolio composition. We investigate the effect of different definitions of the bounds on the uncertainty sets and show that robust models yield well diversified portfolios, in terms of the number of assets and asset weights.     

Approximations of open quotient and speed quotient from glottal airflow and egg waveforms : Effects of measurement criteria and sound pressure level

Noninvasive measures of vocal fold activity are useful for describingnormal and disordered voice production. Measures of open and speed quotient from glottal airflow and electroglottographic (EGG) waveforms have been used to describe timing events associated with vocal fold vibration. To date, there has been little consistency in the measurement criteria used to calculate quotient values. In this study, criteria of 20% and 50% were applied to the AC amplitude of glottal airflow and inverted EGG waveforms for measurement of open quotient. Criteria of 20%, 50%, and 80%, and a midslope criterion that segmented the waveform between 20% and 80% of the waveform amplitude, were used for the calculation of speed quotient. Subjects produced waveforms at sound pressure levels (SPL) of 70, 75, 80 and 85 dB. Results indicated that approximations of open quotient obtained from the glottal airflow waveform significantly decreased using both the 20% and 50% criteria as SPL increased from 80 to 85 dB. No significant changes were found in open quotient from the EGG waveform as a function of SPL. Results of speed quotient measures from the glottal airflow and EGG waveforms showed a generally increasing trend as SPL increased, although the differences were not statistically significant. The data suggest that the signal type, measurement criterion and SPL must be considered in interpreting quotient measures.     

Characterization of silicon nanowires grown on silicon, stainless steel and indium tin oxide substrates

Silicon nanowires (SiNWs) have been grown on crystalline silicon (Si), indium tin oxide (ITO) and stainless steel (SS) substrates using a gold catalyst coating with a thickness of 200 nm via pulsed plasma-enhanced chemical vapor deposition (PPECVD). Their morphological, mineralogical and surface characteristics have been investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman analysis. SiNWs growth is accompanied by oxidation, thus yielding partially (SiO _x ) and fully oxidized (SiO₂) Si sheaths. The mean diameters of these SiNWs range from 140 to 185 nm. Si with (111) and (220) planes exists in SiNWs grown on all three substrates while Si with a (311) plane is detected only for Si and ITO substrates. Computational simulation using density functional theory (DFT) has also been conducted to supplement the experimental Raman analyses for crystalline Si and SiO₂. XPS results reveal that ca. 30 % of the SiNWs have been oxidized for all substrates. The results presented in this paper can be used to aid selection of appropriate substrates for SiNW growth, depending on specific applications.