Synthesis of Soluble Quinacridone Photocatalysts for the Homogeneous Oxidation of Thioethers

Evaluation of quinacridone (QA) derivatives as homogeneous metal-free photocatalysts is here presented. QA derivatives were synthetized and systematically characterized, measuring their ground state and excited state redox potentials in dichloromethane (DCM) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), in order to understand how structural modifications influenced their photocatalytic properties. In particular, the effect of dicyanomethylene and nitro EWG groups was investigated, in order to develop a photocatalyst capable of promoting oxidative processes in the presence of molecular oxygen. Among the analyzed derivatives, 2,9-dinitro-N,N′-dibutylquinacridone (DNDBQA) was the one with the highest excited state reduction potential (E_red*=1.60 V in HFIP vs SCE), while N,N’-dibutylquinacridone (DBQA) showed valuable excited state redox potentials (E_red*=1.29 V; E_ox*=−1.28 V in HFIP vs SCE), making it suitable for bimodal applications in oxidative and reductive photocatalytic processes. Afterwards, the synthetized QA derivatives were examined as photocatalysts to promote the selective aerobic oxidation of thioether to sulfoxide. Promising results in thioanisole oxidation were achieved with all the QA derivatives tested as photocatalysts, in terms of yield and selectivity. Remarkably, DBQA showed the best performances, catalyzing the reaction in only 20 minutes, using 0.5 % of the photocatalyst, and showing excellent performances in the oxidation of several thioether derivatives.     

Partitioning study of polycyclic aromatic hydrocarbons between water and some selected water-insoluble phases

An investigation on the partitioning of naphthalene and phenanthrene between water and some water-insoluble phases has been carried out by Uv-vis-NIR spectrophotometry. The analysis of the experimental results emphasized the role of intermolecular interactions and structural features of the hosting phases as driving forces of the partitioning of these polycyclic aromatic hydrocarbons. The critical comparison of the resulting distribution constants allowed to evaluate the potentials of some extracting phases to set up sensitive analytical methods and/or effective environment remediation technologies.     

Visible and near-infrared absorption spectroscopy by an integrating sphere and optical fibers for quantifying and discriminating the adulteration of extra virgin olive oil from Tuscany

Because of its high price, extra virgin olive oil is frequently targeted for adulteration with lower quality oils. This paper presents an innovative optical technique capable of quantifying and discriminating the adulteration of extra virgin olive oil caused by lower-grade olive oils. An original set-up for diffuse-light absorption spectroscopy in the wide 400–1,700 nm spectral range was experimented. It made use of an integrating sphere containing the oil sample and of optical fibers for illumination and detection; it provided intrinsically scattering-free absorption spectroscopy measurements. This set-up was used to collect spectroscopic fingerprints of authentic extra virgin olive oils from the Italian Tuscany region, adulterated by different concentrations of olive-pomace oil, refined olive oil, deodorized olive oil, and refined olive-pomace oil. Then, a straightforward multivariate processing of spectroscopic data based on principal component analysis and linear discriminant analysis was applied which was successfully capable of predicting the fraction of adulterant in the mixture, and of discriminating its type. The results achieved by means of optical spectroscopy were compared with the analysis of fatty acids, which was carried out by standard gas chromatography.     

Vanadium and molybdenum peroxides: synthesis and catalytic activity in oxidation reactions

Catalysis by transition metal ions in oxidation reactions with hydrogen peroxide and alkyl hydroperoxides is a leading topic in the pursuit of more sustainable and selective processes, to obtain compounds with high added value. The most recent achievements concerning the synthesis and characterization, as well as the key aspects of reactivity, of V(V) and Mo(VI) peroxo complexes have been collected here.     

Multi-molecule reaction of serum albumin can occur through thiol-yne coupling

The free-radical hydrothiolation of alkynes (thiol-yne coupling, TYC) unites two thiol fragments across the carbon-carbon triple bond to give a dithioether derivative with exclusive 1,2-addition; this reaction can be used for modification of peptides and proteins allowing glycoconjugation and fluorescent labeling. These results have implications not only as a flexible strategy for attaching two modifications at a single site in proteins but also for unanticipated side-reactions of reagents (such as cycloalkynes) used in other protein coupling reactions.     

DEPNET: How to benefit from social dependence†

In this paper, two different views of sociality, one based upon interferences, and the other based upon complementarity, or interdependence, are confronted. The latter is shown to present a number of theoretical advantages over the former, allowing for an account of different types of social actions— influencing, exchange, cooperation—and of how these emerge from structural social conditions. A formal model of dependence relations is presented, and an algorithm for calculating the dependence networks and situations in a multi‐agent context is briefly shown. A simulator of dependence relations, which edits a set of agents (in terms of their goals, actions, and plans) and applies the algorithm to calculate their dependence relations relative to any given goal, is described, and its applications are discussed. Some elementary simulations are exemplified in order to illustrate the experimental application of the simulator in a two‐agent context. Future expansions of the simulator are finally discussed.     

Supply chain models for an assembly system with preprocessing of raw materials: A simple and better algorithm

Recently, Rahman and Sarker [1] formulated a nonlinear cost function to include the costs of inventories, ordering, shipping and deliveries for a manufacturing system where raw materials enter into the assembly line from two different channels. In order to find the best integer solutions to the variables, they proposed an algorithm that uses the branch and bound concept. The authors claim that their algorithm finds an optimal solution. In this paper, we present a simple and better heuristic algorithm that provides better solutions with a lower number of evaluations than Rahman and Sarker’s algorithm.     

A complement to “A comprehensive note on: An economic order quantity with imperfect quality and quantity discounts”

Chang [1] [H.-C. Chang, A comprehensive note on: an economic order quantity with imperfect quality and quantity discounts, Appl. Math. Model. 35 (10) (2011) 5208-5216] corrects a flaw in Lin’s inventory model [T.Y. Lin, An economic order quantity with imperfect quality and quantity discounts, Appl. Math. Model. 34 (10) (2010) 3158–3165]. Then, he develops an algorithm to find the optimal solution for the corrected Lin’s inventory model and furthermore derives close form expressions to determining the optimal solution to an EOQ inventory model considering items with imperfect quality with different holding costs for good and defective items. In both models there is a discrete variable and he presents some inequalities in order to find the integer value. This paper provides some simple formulas to obtain, in an easy way, the integral value for the discrete variable.