An LDQBD process under degradation,inspection, and two types of repair

A warm standby n-system with operational and repair times following phase-type distributions is considered. The online unit goes through degradating levels, determined by inspections. Two types of repairs are performed, preventive and corrective, depending on the degradation level. The standby units undergo corrective repair. This systems is governed by a level-dependent-quasi-birth-and-death proces (LDQBD process), whose generator is constructed. The availability, rate of occurrence of failures, and other quantities of interest are calculated. A numerical example including an optimization problem and illustrating the calculations is presented. This system extend other previously studied in the literature.     

A maintenance model with failures and inspection following Markovian arrival processes and two repair modes

We consider a deteriorating system submitted to external and internal failures, whose deterioration level is known by means of inspections. There are two types of repairs: minimal and perfect, depending on the deterioration level, each one following a different phase-type distribution. The failures and the inspections follow different Markovian arrival processes (MAP). Under these assumptions, the system is governed by a generalized Markov process, whose state space and generator are constructed. This general model includes the phase-type renewal process as a special case. The distribution of the number of minimal and perfect repairs between two inspections are determined. A numerical application optimizing costs is performed, and different particular cases of the model are compared.     

Numerical modelling and simulation of Laviron treatment for poly-phenothiazine derivative-modified glassy carbon electrodes

Electropolymerization of a new phenothiazine derivative (bis-phenothiazin-3-yl methane, BPhM) on glassy carbon electrodes leads to electroactive and conducting layers of poly-BPhM. Based on the Laviron method, the kinetic parameters (the heterogeneous electron transfer rate constants k _s and transfer coefficients α) were calculated out of the experimental and theoretical data. The theoretical data have been obtained by using the analogical modelling and numerical simulating method. The modified electrodes present high values of k _s(~50s⁻¹) in phosphate buffer solutions of different pH values. A good correlation of mathematical and numerical simulated kinetic parameters has been obtained, with the experimental values and the norm of residuals being very close to zero.     

Reactivity of ortho‐Substituted Aryl–Palladium Complexes towards Carbodiimides,Isothiocyanates, Nitriles,and Cyanamides

Complexes [Pd(C₆H₃XH‐2‐R′‐5)Y(N^N)] (X=O, NH; Y=Br, I; R′=H, NO₂; N^N=N,N,N′,N′‐tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine (dtbbpy)) react with RN?C?E (E=NR, S) or RC≡N (R=alkyl, aryl, NR′′₂) and TlOTf (OTf=CF₃SO₃) to give, respectively, 1) products of the insertion of the C?E group into the C? Pd bond, protonation of the N atom, and coordination of X to Pd, [Pd{κ²‐X,E‐(XC₆H₃{EC(NHR)}‐2‐R′‐4)}(N^N)]OTf or [Pd(κ²‐X,N‐{ZC₆H₃(NH?CR)‐2‐R′‐4})(N^N)]OTf, or products of the coordination of carbodiimides and OH addition, [Pd{κ²‐C,N‐(C₆H₄{OC(NR)}NHR‐2)}(bpy)]OTf; or 2) products of the insertion of the C≡N group to Pd and N‐protonation, [Pd(κ²‐X,N‐{XC₆H₃(NH?CR)‐2‐R′‐4})(N^N)]OTf.     

Predicting the bioactivity of glasses using the network connectivity or split network models

Bioactive glasses (BG) are used as bone substitutes and re-mineralising additives in toothpastes. They work by precipitating apatite on their surface, and the network connectivity (NC) and split network models can be used to predict their bioactivity, i.e. their ability to form apatite.While NC predicts glass degradation and has been used successfully to predict the bioactivity of BG, it does not take into account their phosphate content. Our experimental data confirm predictions using the split network model by Edén [Journal of Non-Crystalline Solids 357 (2011) 1595–1602], that “as long as P remains predominantly as Q_P⁰ tetrahedra and the average silicate network-polymerisation is ‘favourable’, the bioactivity enhances monotonically for increasing phosphorus content of the BG”. Results show that phosphate plays a key role in bioactivity and apatite formation of BG. This can be explained by the fact that phosphorus does not form part of the silicate network, but instead forms a separate orthophosphate phase. However, NC and split network models are still useful approaches for predicting BG bioactivity and apatite formation, if care is exercised when applying the models to glasses that contain more components than simple SiO₂–P₂O₅–CaO–Na₂O systems.     

Bioinspired terpene synthesis: a radical approach

This tutorial review highlights the development of radical-based bioinspired synthesis of terpenes from the initial proposal to the development of modern catalytic methods for performing such processes. The power of the radical approach is demonstrated by the straightforward syntheses of many natural products from readily available starting materials. The efficiency of these processes nicely complements the described cationic polyolefin cyclisations and even suggests that modern radical methods provide means to improve upon nature's synthetic pathways.     

A new and efficient approach to isoxazolines. First synthesis of 3-aryl-5-dichloromethyl-2-isoxazolines

An efficient synthetic method for 3-aryl-5-dichloromethyl-2-isoxazolines has been established. Reactions between anhydrous chloral and acetophenones in hot acetic acid lead to 1-aryl-4,4,4-trichloro-3-hydroxybutan-1-ones (chloralacetophenones), which provided 1-aryl-4,4-dichlorobut-3-en-1-ones (2,2-dichlorovinylacetophenones) by dehydration and subsequent electrochemical reduction. These β,γ-unsaturated enones reacted with hydroxylamine yielding oxime intermediates whose treatment with aqueous sodium hydroxide gave novel 3-aryl-5-dichloromethyl-2-isoxazolines in fair to high yields. The molecular structure of a member of this family of compounds, 5-dichoromethy1-3-(4-methoxyphenyl)-2-isoxazoline, was determined by X-ray crystallography.