Detailed experimental and kinetic modeling study of 3-carene pyrolysis

3-Carene is an important potential biofuel with properties similar to the jet-propellant JP-10. Its thermal decomposition and combustion behavior is to date unknown, which is essential to assess its quality as a fuel. A combined experimental and kinetic modeling study has been conducted to understand the initial decomposition of 3-carene. The pyrolysis of 3-carene was investigated in a jet-stirred quartz reactor at atmospheric pressure, at temperatures varying from 650 to 1050 K, covering the complete conversion range. The decomposition of 3-carene was observed to start around 800 K, and it is almost complete at 970 K. Online gas chromatography shows that primarily aromatics are generated which suggests that 3-carene is not a good fuel candidate. The potential energy surface for the initial decomposition pathways determined by KinBot shows that a hydrogen elimination reaction dominates, giving primarily cara-2,4-diene. Next to this molecular pathway, radical pathways lead to aromatics via ring opening. The kinetic model was automatically generated with Genesys and consists of 2565 species and 9331 reactions. New quantum chemical calculations at the CBS-QB3 level of theory were needed to calculate rate coefficients and thermodynamic properties relevant for the primary decomposition of 3-carene. Both the conversion of 3-carene and the yields of the primary products (ie, benzene and hydrogen gas) are well predicted with this kinetic model. Rate of production analyses shows that the dominant pathways to convert 3-carene are hydrogen elimination reaction and radical chemistry.     

QUANTIS: Data quality assessment tool by clustering analysis

Automatically generated kinetic networks are ideally validated against a large set of accurate, reproducible, and easy-to-model experimental data. However, although this might seem simple, it proves to be quite challenging. QUANTIS, a publicly available Python package, is specifically developed to evaluate both the precision and accuracy of experimental data and to ensure a uniform, quick processing, and storage strategy that enables automated comparison of developed kinetic models. The precision is investigated with two clustering techniques, PCA and t-SNE, whereas the accuracy is probed with checks for the conservation laws. First, the developed tool processes, evaluates, and stores experimental yield data automatically. All data belonging to a given experiment, both unprocessed and processed, are stored in the form of an HDF5 container. The demonstration of QUANTIS on three different pyrolysis cases showed that it can help in identifying and overcoming instabilities in experimental datasets, reduce mass and molar balance closure discrepancies, and, by evaluating the visualized correlation matrices, increase understanding in the underlying reaction pathways. Inclusion of all experimental data in the HDF5 file makes it possible to automate simulating the experiment with CHEMKIN. Because of the employed InChI string identifiers for molecules, it is possible to automate the comparison experiment/simulation. QUANTIS and the concepts demonstrated therein is a potentially useful tool for data quality assessment, kinetic model validation, and refinement.     

Immobilization of Zn(II) in Portland cement pastes

The aim of this paper is to study the solidification/stabilization potential of cementitious matrices on the immobilization of Zn(II) before its disposal into the environment by determining the mechanisms of interaction between the Zn(II) ions and the binder. The results of structural and mineralogical characterization of cement pastes formed with different amounts of immobilized Zn(II) ions are presented and the study includes results from thermogravimetric analysis (TG), scanning electron microscopy, X-ray diffraction, and leaching performance. Zn(II) ions delay the hydration reaction of Portland cement due to the formation of mainly CaZn₂(OH)₆·2H₂O , as well as Zn₅(CO₃)₂(OH)₆, Zn(OH)₂, and ZnCO₃ in minor proportion. Correlations between total mass loss in TG analysis and leached Zn(II) ions in long-term curing pastes have been obtained. This result is important because in a preliminary approach from a TG on an early-aged cement paste containing Zn(II), it could be possible to perform an estimation of the amount of Zn(II) ions that could be leached, thus avoiding costly and time-consuming tests.     

Synthesis of azafluorenones and related compounds using deprotocupration–aroylation followed by intramolecular direct arylation

The efficiency of the deprotocupration–aroylation of 2-chloropyridine using lithiocuprates prepared from CuX (X=Cl, Br) and LiTMP (TMP=2,2,6,6-tetramethylpiperidido, 2 equiv) was investigated. CuCl was identified as a more suitable copper source than CuBr for this purpose. Different diaryl ketones bearing a halogen at the 2 position of one of the aryl groups were synthesized in this way from azines and thiophenes. These were then involved in palladium-catalyzed ring closure: substrates underwent expected CH-activation-type arylation to afford fluorenone-type compounds, and were also subjected to cyclization reactions leading to xanthones, notably in the presence of oxygen-containing substituents or reagents.     

Characterization of uranium isotopic abundances in depleted uranium metal assay standard 115

Certified reference material (CRM) 115, Uranium (Depleted) Metal (Uranium Assay Standard), was analyzed using a TRITON Thermal Ionization Mass Spectrometer to characterize the uranium isotope-amount ratios. The certified ²³⁵U/²³⁸U “major” isotope-amount ratio of 0.0020337 (12) in CRM 115 was determined using the total evaporation (TE) and the modified total evaporation (MTE) analytical techniques. In the MTE method, the total evaporation process is interrupted on a regular basis to allow correction of background from peak tailing, internal calibration of the secondary electron multiplier detector versus the Faraday cups, peak-centering, and ion source re-focusing. For the “minor” ²³⁴U/²³⁸U and ²³⁶U/²³⁸U isotope-amount ratio measurements using MTE, precision and accuracy comparable to conventional analyses are achieved, without compromising the quality of the ²³⁵U/²³⁸U isotope-amount ratios. Characterized values of the ²³⁴U/²³⁸U and ²³⁶U/²³⁸U isotope-amount ratios in CRM 115 are 0.000007545 (10) and 0.000032213 (84), respectively. The ²³³U/²³⁸U isotope-amount ratio in CRM 115 is estimated to be <5 × 10^?9. The homogeneity of the CRM 115 materials is established through the absence of any statistically significant unit-to-unit variation in the uranium isotope-amount ratios. The measurements leading to the certification of uranium isotope-amount ratios are discussed.     

Miniaturised enzymatic conductometric biosensor with Nafion membrane for the direct determination of formaldehyde in water samples

A new conductometric enzyme-based biosensor was developed for the determination of formaldehyde (FA) in aqueous solutions. The biosensor was prepared by cross-linking formaldehyde dehydrogenase from Pseudomonas putida with bovine serum albumin in saturated glutaraldehyde vapours (GA) at the surface of interdigitated gold microelectrodes. Nicotinamide adenine dinucleotide cofactor (NAD⁺) was added in solution at each measurement to maintain enzyme activity. Addition of a Nafion layer over the enzyme modified electrode resulted in a significant increase of biosensor signal due to enhanced accumulation of protons generated by enzymatic reaction at the electrode surface. Different parameters affecting enzyme activity or playing a role in ionic transfer through the Nafion membrane were optimised. In optimal conditions (0.045 mg enzyme, 30 min exposure to GA, 0.3 μL of a 1 % (v/v) Nafion solution deposit, measurement in 5 mM phosphate buffer pH 7 containing 20 μM NAD⁺), the biosensor signal was linear up to 10 mM FA, and the detection limit was 18 μM. Relative standard deviations calculated from five consecutive replicates of FA solutions were lower than 5 % in the 1–10 mM range. The biosensor was successfully applied to the determination of FA in spiked water samples (tap water and Rhone river water), with recoveries in the 95–110 % range.

Screening of Wood/Forest and Vine By-Products as Sources of New Drugs for Sustainable Strategies to Control Fusarium graminearum and the Production of Mycotoxins

Fusarium graminearum is a fungal pathogen that can colonize small-grain cereals and maize and secrete type B trichothecene (TCTB) mycotoxins. The development of environmental-friendly strategies guaranteeing the safety of food and feed is a key challenge facing agriculture today. One of these strategies lies on the promising capacity of products issued from natural sources to counteract crop pests. In this work, the in vitro efficiency of sixteen extracts obtained from eight natural sources using subcritical water extraction at two temperatures was assessed against fungal growth and TCTB production by F. graminearum. Maritime pine sawdust extract was shown to be extremely efficient, leading to a significant inhibition of up to 89% of the fungal growth and up to 65% reduction of the mycotoxin production by F. graminearum. Liquid chromatography/mass spectrometry analysis of this active extract revealed the presence of three families of phenolics with a predominance of methylated compounds and suggested that the abundance of methylated structures, and therefore of hydrophobic compounds, could be a primary factor underpinning the activity of the maritime pine sawdust extract. Altogether, our data support that wood/forest by-products could be promising sources of bioactive compounds for controlling F. graminearum and its production of mycotoxins.