Trits(Pyrazol-1-YL)methane metal complexes for catalytic mild oxidative functionalizations of alkanes, alkanes and ketones

This work concerns recent advances (since 2005) in the oxidative functionalization of alkanes, alkenes and ketones, under mild conditions, catalyzed by homoscorpionate tris(pyrazol-1-yl)methane metal complexes. The main types of such homogeneous or supported catalysts are classified, and the critical analysis of the most efficient catalytic systems in the different reactions is presented. These reactions include the mild oxidation of alkanes (typically cyclohexane as a model substrate) with hydrogen peroxide (into alkyl hydroperoxides, alcohols, and ketones), the hydrocarboxylation of gaseous alkanes (with carbon monoxide and potassium peroxodisulfate) into the corresponding Cn+1 carboxylic acids, as well as the epoxidation of alkenes and the Baeyer-Villiger oxidation of linear and cyclic ketones with hydrogen peroxide into the corresponding esters and lactones. Effects of various reaction parameters are highlighted and the preferable requirements for a prospective homogeneous or supported C-scorpionate-M-based catalyst in oxidative transformations of those substrates are identified. (C) 2014 Elsevier B.V. All rights reserved.

Machine learning Vasicek model calibration with Gaussian processes

In this article, we calibrate the Vasicek interest rate model under the risk neutral measure by learning the model parameters using Gaussian processes for machine learning regression. The calibration is done by maximizing the likelihood of zero coupon bond log prices, using mean and covariance functions computed analytically, as well as likelihood derivatives with respect to the parameters. The maximization method used is the conjugate gradients. The only prices needed for calibration are zero coupon bond prices and the parameters are directly obtained in the arbitrage free risk neutral measure.

Comparison of deposited surface area of airbone ultrafine particles generated from two welding processes

This article describes work performed on the assessment of the levels of airborne ultrafine particles emitted in two welding processes metal-active gas (MAG) of carbon steel and friction-stir welding (FSW) of aluminium in terms of deposited area in alveolar tract of the lung using a nanoparticle surface area monitor analyser. The obtained results showed the dependence from process parameters on emitted ultrafine particles and clearly demonstrated the presence of ultrafine particles, when compared with background levels. The obtained results showed that the process that results on the lower levels of alveolar-deposited surface area is FSW, unlike MAG. Nevertheless, all the tested processes resulted in important doses of ultrafine particles that are to be deposited in the human lung of exposed workers.

Brownian bridge and other path-dependent Gaussian processes vectorial simulation

The iterative simulation of the Brownian bridge is well known. In this article, we present a vectorial simulation alternative based on Gaussian processes for machine learning regression that is suitable for interpreted programming languages implementations. We extend the vectorial simulation of path-dependent trajectories to other Gaussian processes, namely, sequences of Brownian bridges, geometric Brownian motion, fractional Brownian motion, and Ornstein-Ulenbeck mean reversion process.

Vanadium complexes: recent progress in oxidation catalysis

Oxidovanadium complexes and, to a less extent, some non-oxido ones, are widely used as catalysts or catalyst precursors for various oxidative catalytic reactions by H2O2, (BuOOH)-Bu-t or O-2 under mild conditions. Oxidation reactions (oxidation of alkanes and alcohols, epoxidation of alkenes and allylic alcohols, oxidative bromination, sulfoxidation and oxidative Strecker reactions) of organic compounds are the most relevant ones and are reviewed considering the recent advances in the last five years (2010-2014). The main types of both homogeneous and supported vanadium catalysts and the most efficient catalytic systems in the different reactions are presented and compared. The proposed mechanisms of various catalytic oxidation processes are also outlined. (C) 2015 Elsevier B.V. All rights reserved.

In situ NIR spectroscopy monitoring of plasmid production processes effect of producing strain, medium composition and the cultivation strategy

BACKGROUNDWhile the pharmaceutical industry keeps an eye on plasmid DNA production for new generation gene therapies, real-time monitoring techniques for plasmid bioproduction are as yet unavailable. This work shows the possibility of in situ monitoring of plasmid production in Escherichia coli cultures using a near infrared (NIR) fiber optic probe. RESULTSPartial least squares (PLS) regression models based on the NIR spectra were developed for predicting bioprocess critical variables such as the concentrations of biomass, plasmid, carbon sources (glucose and glycerol) and acetate. In order to achieve robust models able to predict the performance of plasmid production processes, independently of the composition of the cultivation medium, cultivation strategy (batch versus fed-batch) and E. coli strain used, three strategies were adopted, using: (i) E. coliDH5 cultures conducted under different media compositions and culture strategies (batch and fed-batch); (ii) engineered E. coli strains, MG1655endArecApgi and MG1655endArecA, grown on the same medium and culture strategy; (iii) diverse E. coli strains, over batch and fed-batch cultivations and using different media compositions. PLS models showed high accuracy for predicting all variables in the three groups of cultures. CONCLUSIONNIR spectroscopy combined with PLS modeling provides a fast, inexpensive and contamination-free technique to accurately monitoring plasmid bioprocesses in real time, independently of the medium composition, cultivation strategy and the E. coli strain used.