An Oxidation Study of Phthalimide-Derived Hydroxylactams

A systematic study of the oxidation of 3-hydroxy-2-substituted isoindolin-1-ones (hydroxylactams) and their conversion to the corresponding phthalimides was undertaken using three oxidants. Of special interest was the introduction of nickel peroxide (NiO2) as an oxidation system for hydroxylactams and comparison of its performance with the commonly used pyridinium chlorochromate (PCC) and iodoxybenzoic acid (IBX) reagents. Using a range of hydroxylactams, optimal conversions of these substrates to the corresponding imides was achieved with 50 equivalents of freshly prepared NiO2 in refluxing toluene over 5–32 h reaction times. By comparison, oxidations of the same substrates using PCC/silica gel (three equivalents) and IBX (three equivalents) required oxidation times of 1–3 h for full conversion but required lengthier purification. While nominal amounts (~25 mg) of substrate hydroxylactams were used to ascertain conversion, scale-up procedures using all three methods gave good to excellent isolated yields of imides.

Dicoordinate Au(I)–Ethylene Complexes as Hydroamination Catalysts

A series of gold(I)–ethylene  complexes containing a family of bulky phosphine ligands has been prepared. The use of these sterically congested ligands is crucial to stabilize the gold(I)–ethylene bond and prevent decomposition, boosting up their catalytic performance in the highly underexplored hydroamination of ethylene. The precatalysts bearing the most sterically demanding phosphines showed excellent results reaching full conversion to the hydroaminated products under low ethylene pressure (1 bar). Kinetic analysis together with density functional theory (DFT) calculations revealed that the assistance of a second molecule of the nucleophile as a proton shuttle is preferred even when using an extremely congested cavity-shaped Au(I) complex.

Mathematical Modeling of Urea Reaction with Sulfuric Acid and Phosphoric Acid to Produce Ammonium Sulfate and Ammonium Dihydrogen Phosphate Respectively

Urea is the final product of protein metabolism in mammals and can be found in different biological fluids. Use of mammalian urine in agricultural production as organic fertilizer requires safe handling to avoid the formation of ammonia that will decrease the fertilizer value due to the loss of nitrogen. Safe handling is also required to minimize the decomposition of urea into condensed products such as biuret and cyanuric acid, which will also have a negative impact on the potential sustainable production of crops and sanitation technologies. The study of thermodynamics and reaction kinetics of urea stabilization plays a key role in understanding the conditions under which undesirable compounds and impurities in urea-based fertilizers and urea-based selective catalytic reduction systems are formed. For this reason, we studied the reaction of urea in acid media to achieve urea stabilization by modeling the reaction of urea with sulfuric acid and phosphoric acid, and estimating the reaction enthalpy and adiabatic heat difference for control of the heat released from the neutralization step using Ca(OH)2 or MgO for the safety of the process. Numerical and simulation analyses were performed by studying the effect of the surrounding temperature, the ratio of acid reagent to urea concentration, the rate of addition, and the reaction rate to estimate the required time to achieve an optimum value of urea conversion into ammonium dihydrogen phosphate or ammonium sulfate as potential technological opportunities for by-product valorization. Full conversion of urea was achieved in about 10 h for reaction rates in the order of 1 × 10−5s−1 when the ratio of H2SO4 to CH4N2O was 1.5. When increasing the ratio to 10, the time required for full conversion was considerably reduced to 3 h.

SOME COMMENTS ON THE INTERPRETATION OF THE TRIBOLOGICAL WEAR COEFFICIENT

An original model of tribological wear is presented, an alternative to the commonly used J.F. Archard’s model. The impossibility is established of a full conversion of mechanical work into the heat of dissipation and thereby of avoiding wear in the sliding friction of solids. The assumption is consequently questioned that only some contacts of surface asperities are subject to temporary wear. Material wastage is assumed to occur at each contact of asperities. The volume of worn material is dependent on the volumetric wear coefficient of the “energy dissipation zone” in friction. The dimensions of the zone are determined in both the elements in friction. Linear wear intensities and volumetric wear are described in analytical terms. The thermodynamic analysis of the tribological process indicates some limitations to these intensities. Energetic efficiencies of solid wear and heating as a result of friction are defined. Some new interpretations of the wear coefficient are proposed.

Folate-Targeted Monodisperse PEG-Based Conjugates Made by Chemo-Enzymatic Methods for Cancer Diagnosis and Treatment

This paper focuses on preliminary in vitro and in vivo testing of new bivalent folate-targeted PEGylated doxorubicin (DOX) made by modular chemo-enzymatic processes (FA2-dPEG-DOX2). A unique feature is the use of monodisperse PEG (dPEG). The modular approach with enzyme catalysis ensures exclusive γ-conjugation of folic acid, full conversion and selectivity, and no metal catalyst residues. Flow cytometry analysis showed that at 10 µM concentration, both free DOX and FA2-dPEG-DOX2 would be taken up by 99.9% of triple-negative breast cancer cells in 2 h. Intratumoral injection to mice seemed to delay tumor growth more than intravenous delivery. The mouse health status, food, water consumption, and behavior remained unchanged during the observation.

One-Stage Catalytic Oxidation of Adamantane to Tri-, Tetra-, and Penta-Ols

Tertiary tetraols of adamantane (C10H16, Tricyclo[3.3.1.1(3,7)]decan) have been widely used for the synthesis of highly symmetric compounds with unique physical and chemical properties. The methods for one-stage simultaneously selective, deep, and cheap oxidation of adamantane to tetraols of different structures have not yet been developed. In this research, chemically simple, cheap, and environmentally friendly reagents are used and that is the first step in this direction. The conditions, under which the impact of a hydrogen peroxide water solution on adamantane dissolved in acetonitrile results in full conversion of adamantane and formation of a total 72% mixture of its tri-, tetra-, and penta-oxygenated products, predominantly poliols, have been found. Conversion and adamantane oxidation depth are shown to depend on the ratio of components of the water-acetonitrile solution and the method of oxidizer solution introduction when using the dimer form of 1:1 dimethylglyoxime and copper dichloride complex as a catalyst. Under the conditions of mass-spectrometry ionization by electrons (70 eV), fragmentation across three C–C bonds of the molecular ions framework of adamantane tertiary alcohols Ad(OH)n in the range n = 0–4 increases linearly with the rise of n.

Effect of Milling Parameters on the Development of a Nanostructured FCC–TiNb15Mn Alloy via High-Energy Ball Milling

In this work, a blend of Ti, Nb, and Mn powders, with a nominal composition of 15 wt.% of Mn, and balanced Ti and Nb wt.%, was selected to be mechanically alloyed by the following two alternative high-energy milling devices: a vibratory 8000D mixer/mill® and a PM400 Retsch® planetary ball mill. Two ball-to-powder ratio (BPR) conditions (10:1 and 20:1) were applied, to study the evolution of the synthesized phases under each of the two mechanical alloying conditions. The main findings observed include the following: (1) the sequence conversion evolved from raw elements to a transitory bcc-TiNbMn alloy, and subsequently to an fcc-TiNb15Mn alloy, independent of the milling conditions; (2) the total full conversion to the fcc-TiNb15Mn alloy was only reached by the planetary mill at a minimum of 12 h of milling time, for either of the BPR employed; (3) the planetary mill produced a non-negligible Fe contamination from the milling media, when the highest BPR and milling time were applied; and (4) the final fcc-TiNb15Mn alloy synthesized presents a nanocrystalline nature and a partial degree of amorphization.

Environmental and human health at risk – scenarios to achieve the EU’s 50% pesticide reduction goals.

The recently released Farm to Fork Strategy sets, for the first time ever, pesticide reduction goals at the EU level: 50% reduction in overall use and risk of chemical pesticides and 50% use reduction of more hazardous pesticides. However, little guidance is provided to achieve these targets. In this study, we compiled the characteristics and recommended application rates of 230 EU approved, synthetic, open-field use active substances and explored the potential of eight pesticide reduction scenarios (defined based on application rates, pesticide type, persistence, and hazard) to achieve the reduction goals. Our approach revealed that all 230 substances are potentially harmful to humans or ecosystems, and that only severe pesticide use restrictions such as full conversion to organic farming or allowing only low hazard substances will result in 50% reductions. Our results emphasis the need of an EC action plan on how to achieve and maintain the aimed reduction levels.

Time-resolved secretome analysis of three Colletotrichum species identifies copper radical alcohol oxidases for the production of fatty aldehydes

Copper Radical Alcohol Oxidases (CRO-AlcOx), which have been recently discovered among fungal phytopathogens are attractive for the production of fragrant fatty aldehydes. To investigate the secretion of CRO-AlcOx by natural fungal strains, we undertook time-course analyses of the secretomes of three Colletotrichum species (C. graminicola, C. tabacum and C. destructivum) using proteomics. The addition of a copper-manganese-ethanol mixture to Colletotrichum cultures unexpectedly induced the secretion of up to 400 proteins, 29-52% of which were carbohydrate-active enzymes (CAZymes), including a wide diversity of copper-containing oxidoreductases from the auxiliary activities (AA) class (AA1, AA3, AA5, AA7, AA9, AA11-AA13, AA16). Under these specific conditions, while a CRO-glyoxal oxidase from the AA5_1 subfamily was among the most abundantly secreted proteins, the targeted AA5_2 CRO-AlcOx were secreted at lower levels, suggesting heterologous expression as a more promising strategy for CRO-AlcOx production and utilization. C. tabacum and C. destructivum CRO-AlcOx were expressed in Pichia pastoris and their preference toward both aromatic and aliphatic primary alcohols was assessed. The CRO-AlcOx from C. destructivum was further investigated in applied settings, revealing a full conversion of C6 and C8 alcohols into their corresponding fragrant aldehydes.