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.     

Inertial subgradient extragradient algorithms with line-search process for solving variational inequality problems and fixed point problems

Numerical Algorithms - In this paper, basing on the subgradient extragradient method and inertial method with line-search process, we introduce two new algorithms for finding a common element of...     

Luminescent Graphene-Based Materials via Europium Complexation on Dipyridylpyridazine-Functionalized Graphene Sheets

Graphene-based materials exhibit outstanding physical properties and so are potentially applicable in a great variety of fields. Unlike their corresponding oxides, graphite and graphene are not prone to functionalization. Diels–Alder reactions are among the scarce reactions that they can occur without disrupting their conjugated sp² systems. Herein, the reaction between graphite and 3,6-di(2-pyridyl)-1,2,4,5-tetrazine under different conditions affords several graphene-based materials consisting of dipyridylpyridazine-functionalized few-layer graphene, multilayer graphene and graphite, the sheets of which act as ligands for the grafting of a europium complex. These three materials show strong red emission under 365 nm UV radiation. Their emitting particles can be visualized by confocal microscopy. The rich coordination chemistry of dipyridylpyridazine ligands has potential novel properties for similarly functionalized graphene-based materials grafted with other metal complexes.     

Water and oil signal assignment in low-moisture mozzarella as determined by time-domain NMR T2 relaxometry

A time-domain ¹H nuclear magnetic resonance relaxometry method was elaborated for the rapid microstructural characterization of mozzarella cheese. For this purpose, there is a strong need to know how the experimentally determined T₂ relaxation time distribution can be related to specific constituents in mozzarella. In this study, a detailed investigation is offered for fresh and aged low-moisture mozzarella cheese, often applied as a pizza cheese, by application of both a conventional Carr–Purcell–Meiboom–Gill (CPMG) sequence and a free-induction decay CPMG (FID-CPMG) sequence. The relaxation behavior was further elucidated by addition of deuterium oxide and by mild heat treatment of samples. The relaxation times of water protons in mozzarella were found to range from a few microseconds to some tens of milliseconds (in aged mozzarella) or to about hundred milliseconds (in fresh mozzarella). The upper limit of the T₂ distribution can even be extended to the seconds range upon releasing water protons from the mozzarella matrix using a mild heat treatment or upon addition of deuterated water. Both stimuli also provided evidence for the absorption of water into the cheese matrix. The potential release and uptake of water demonstrated that mozzarella acts as a very dynamic system during production and storage. The detected differences in the behavior of the water fraction between fresh and aged low-moisture mozzarella might be utilized to study the influence of either production and/or storage conditions on the cheese ripening process.     

Closed‐form approximations for spread options in Lévy markets

We provide new closed‐form approximations for the pricing of spread options in three specific instances of exponential Lévy markets, ie, when log‐returns are modeled as Brownian motions (Black‐Scholes model), variance gamma processes (VG model), or normal inverse Gaussian processes (NIG model). For the specific case of exchange options (spread options with zero strike), we generalize the well‐known Margrabe formula (1978) that is valid in a Black‐Scholes model to the VG model under a homogeneity assumption.     

Spectral,crystallographic, theoretical and antibacterial studies of palladium(II)/platinum(II) complexes with unsymmetric diphosphine ylides

The reaction of α‐keto‐stabilized diphosphine ylides [Ph₂P(CH₂)_nPPh₂═C(H)C(O)C₆H₄‐p‐CN] (n = 1 (Y¹); n = 2 (Y²)) with dibromo(1,5‐cyclooctadiene) palladium(II)/platinum(II) complexes, [Pd/PtBr₂(cod)], in equimolar ratio gave the new cyclometalated Pd(II) and Pt(II) complexes [Br₂Pd(κ²‐Y¹)] ( 1 ), [Br₂Pt(κ²‐Y¹)] ( 2 ), [Br₂Pd(κ²‐Y²)] ( 3 ) and [Br₂Pt(κ²‐Y²)] ( 4 ). These compounds were screened in a search for novel antibacterial agents and characterized successfully using Fourier transfer infrared and NMR (¹H, ¹³C and ³¹P) spectroscopic methods. Also, the structures of complexes 1 and 2 were characterized using X‐ray crystallography. The results showed that the P,C‐chelated complexes 1 and 2 have structures consisting of five‐membered rings, while 3 and 4 have six‐membered rings, formed by coordination of the ligand through the phosphine group and the ylidic carbon atom to the metal centre. Also, a theoretical study of the structures of complexes 1 – 4 was conducted at the BP86/def2‐SVP level of theory. The nature of metal–ligand bonds in the complexes was investigated using energy decomposition analyses (EDA) and extended transition state combined with natural orbitals for chemical valence analyses. The results of EDA confirmed that the main portions of ΔE_int, about 57–58%, in the complexes are allocated to ΔE_elstat.     

Predicting Low-Pressure O2 Adsorption in Nanoporous Framework Materials for Sensing Applications

A set of 98 nanoporous framework material (NFM) structures was investigated by classical Grand canonical Monte Carlo simulations for low-pressure O₂ adsorption properties (Henry’s constant and isosteric heat of adsorption). The set of materials includes those that have shown high O₂ uptake experimentally as well as a subset of more than 2000 structures previously screened for noble-gas uptake. While use of the general force field UFF is fruitful for noble-gas adsorption studies, its use is shown to be limited for the case of O₂ adsorption—one distinct limitation is a lack of sufficient O₂–metal interactions to be able to describe O₂ interaction with open metal sites. Nonetheless, those structures without open metal sites that have very small pores (<2.5 Å) show increased O₂/N₂ selectivity. Additionally, O₂/N₂ mixture simulations show that in some cases, H₂O or N₂ can hinder O₂ uptake for NFMs with small pores due to competitive adsorption.