The correlation of 11B NMR ASIS effects with MO-derived charge densities for closo-C2B5H7 and some chloro derivatives

Aromatic-solvent-induced ¹¹B NMR shifts (¹¹B ASIS effects), observed for closo-2, 4-C₂B₅H₇ and its 5-chloro and 5, 6-dichloro derivatives, are correlated to ab initio STO-3G derived atom charge densities. A near linear relationship is found upon incorporating nearestneighbor charge density contributions.     

Machine Learning Algorithm to Predict Acidemia Using Electronic Fetal Monitoring Recording Parameters

Background: Electronic fetal monitoring (EFM) is the universal method for the surveillance of fetal well-being in intrapartum. Our objective was to predict acidemia from fetal heart signal features using machine learning algorithms. Methods: A case–control 1:2 study was carried out compromising 378 infants, born in the Miguel Servet University Hospital, Spain. Neonatal acidemia was defined as pH < 7.10. Using EFM recording logistic regression, random forest and neural networks models were built to predict acidemia. Validation of models was performed by means of discrimination, calibration, and clinical utility. Results: Best performance was attained using a random forest model built with 100 trees. The discrimination ability was good, with an area under the Receiver Operating Characteristic curve (AUC) of 0.865. The calibration showed a slight overestimation of acidemia occurrence for probabilities above 0.4. The clinical utility showed that for 33% cutoff point, missing 5% of acidotic cases, 46% of unnecessary cesarean sections could be prevented. Logistic regression and neural networks showed similar discrimination ability but with worse calibration and clinical utility. Conclusions: The combination of the variables extracted from EFM recording provided a predictive model of acidemia that showed good accuracy and provides a practical tool to prevent unnecessary cesarean sections.     

Self-similar vortex reconnection

As shown by Crow in 1970, the evolution of two almost parallel vortex filaments with opposite circulation exhibits a long-wave instability. Ultimately, the symmetric mode increases its amplitude reconnecting both filaments and ending into the formation of an almost periodic structure of vortex rings. This is a universal process, which appears in a wide range of scales: from the vortex trails behind an airplane to a microscopic scale of superfluids and Bose–Einstein condensates. In this paper, I will focus on the vortex reconnection for the latter case by employing Gross–Pitaevskii theory. Essentially, I focus on the well-known laws of interaction and motion of vortex filaments. By means of numerical simulations, as well as theoretically, I show that a self-similar finite-time dynamics manifests near the reconnection time. A self-similar profile is selected showing excellent agreement with numerical simulations.     

Simulation of Organic Liquid Product Deoxygenation through Multistage Countercurrent Absorber/Stripping Using CO2 as Solvent with Aspen-HYSYS: Process Modeling and Simulation

In this work, the deoxygenation of organic liquid products (OLP) obtained through the thermal catalytic cracking of palm oil at 450 °C, 1.0 atmosphere, with 10% (wt.) Na₂CO₃ as a catalyst, in multistage countercurrent absorber columns using supercritical carbon dioxide (SC-CO₂) as a solvent, with an Aspen-HYSYS process simulator, was systematically investigated. In a previous study, the thermodynamic data basis and EOS modeling necessary to simulate the deoxygenation of OLP was presented. This work addresses a new flowsheet, consisting of 03 absorber columns, 10 expansions valves, 10 flash drums, 08 heat exchanges, 01 pressure pump, and 02 make-ups of CO₂, aiming to improve the deacidification of OLP. The simulation was performed at 333 K, 140 bar, and (S/F) = 17; 350 K, 140 bar, and (S/F) = 38; 333 K, 140 bar, and (S/F) = 25. The simulation shows that 81.49% of OLP could be recovered and that the concentrations of hydrocarbons in the extracts of absorber-01 and absorber-02 were 96.95 and 92.78% (wt.) on a solvent-free basis, while the bottom stream of absorber-03 was enriched in oxygenated compounds with concentrations of up to 32.66% (wt.) on a solvent-free basis, showing that the organic liquid products (OLP) were deacidified and SC-CO₂ was able to deacidify the OLP and obtain fractions with lower olefin contents. The best deacidifying condition was obtained at 333 K, 140 bar, and (S/F) = 17.     

Ultrasonic and Raman Scattering Spectroscopy of Zinc Thiocyanate Complexes in Water at 25<Superscript>∘</Superscript>C: Kinetics of Complex Formation Determined by Multivariate Analysis

Advances have been made recently in broadening the accessible ultrasonic absorption frequency range and improving the detectability of minor species present in solution using Raman spectroscopy. Development of chemometric techniques in these areas needs to keep pace with the improvement of these experimental methods. Refinements in the analysis of ultrasonic and Raman data based on multivariable least squares and factor analysis, respectively, are examined to investigate the kinetics of zinc thiocyanate complex formation in water. Analysis of ultrasonic absorption relaxation spectra verified that the observed process in aqueous Zn(SCN)₂ involves substitution of water from the first coordination shell of Zn²⁺. Use of a multivariable least-squares error surface is described that enhances the reliability of assigned frequencies of ultrasonic absorption maxima. Factor analysis of Raman scattering data provided direct evidence that at least four complex species, such as Zn(SCN)⁺ and Zn(SCN)₂, are simultaneously present in the aqueous zinc thiocyanate solutions.     

Rhodium catalyzed hydroformylation of 2-phenylsulfonylbicyclo[2.2.1] alkenes: effect of the phenylsulfonyl group

The preliminary results of the hydroformylation of 2-phenylsulfonyl substituted norbornene and norbornadiene derivatives catalyzed by the unmodified Rh(CO)₂acac system are presented. The reaction, occurring under standard oxo conditions, gives polyfunctionalized exo norbornene- and exo norbornanecarboxaldehydes. The effect of the phenylsulfonyl group has been evaluated: it has been found that the steric properties of the sulfonyl substituent, more than the electronic ones, influence the regioselectivity of the process.     

Multicommutation-NIR determination of Hexythiazox in pesticide formulations

A multicommutated flow-system was designed in order to increase analytical throughput and for controlling thermal effects on the NIR spectra for determination of Hexythiazox in pesticide formulations. An on-line standard addition was carried out showing the versatility and repeatability of multicommutation for the on-line mixing and dilution of solutions. Results obtained for commercial samples were statistically comparable with those obtained by an HPLC-reference method. Multicommutation-NIR allows the analysis of 52 samples per hour, in front of the 30 samples per hour analyzed by the NIR-batch procedure and the 7 samples per hour analyzed by HPLC-reference method.     

Electrochemical oxidation of organic pollutants for the wastewater treatment: direct and indirect processes

In recent years, there has been increasing interest in finding innovative solutions for the efficient removal of contaminants from water, soil and air. The present tutorial review summarizes the results of an extensive selection of papers dealing with electrochemical oxidation, which is proposed as an alternative for treating polluted wastes. Both the direct and indirect approaches are considered, and the role of electrode materials is discussed together with that of other experimental parameters. Apart from discussing the possibility of removing selected contaminants from water using different anodes, efficiency rates for pollutant removal have been collected, the dependence of these rates on operational conditions advantages and disadvantages determining the further full-scale commercial application.     

Rhodium-catalyzed intermolecular hydroacylation of 1-alkynes: Effect of phosphines and MK-10 on the reaction selectivity

The use of bulky ligands in the rhodium-catalyzed reaction of aldehydes 7 (R¹ = Ph) and 18 with 1-octyne increased the selectivity for ketones 13 and 20, to the detriment of ketones 12 and 19. Bulky phosphines reduced the hydroacylation reaction rate, leading to competition from the addition of the benzoic acid co-catalyst to the alkynes. This competing reaction can be suppressed by using the clay Montmorillonite K 10 (MK-10) as the co-catalyst instead of benzoic acid.     

Tuning Cellular Biological Functions Through the Controlled Release of NO from a Porous Ti‐MOF

Materials for the controlled release of nitric oxide (NO) are of interest for therapeutic applications. However, to date, many suffer from toxicity and stability issues, as well as poor performance. Herein, we propose a new NO adsorption/release mechanism through the formation of nitrites on the skeleton of a titanium‐based metal–organic framework (MOF) that we named MIP‐177, featuring a suitable set of properties for such an application: (i) high NO storage capacity (3 μmol mg^?1_solid), (ii) excellent biocompatibility at therapeutic relevant concentrations (no cytotoxicity at 90 μg mL^?1 for wound healing) due to its high stability in biological media (<9 % degradation in 72 hours) and (iii) slow NO release in biological media (≈2 hours for 90 % release). The prospective application of MIP‐177 is demonstrated through NO‐driven control of mitochondrial respiration in cells and stimulation of cell migration, paving the way for the design of new NO delivery systems for wound healing therapy.