Thermal Decomposition Kinetics of Dicyclopentadiene‐1,8‐dione: The Reaction Path through Quantum Chemical Calculation

Thermal decomposition kinetics of dicyclopentadiene‐1,8‐dione 7 implied an intramolecular competition between α,β‐ and β,γ‐double bond to assist the CO elimination. Experimental thermolysis of 7 in dioxane gave 3a,7a‐dihydro‐1H‐inden‐1‐one (cis‐bicyclo[4.3.0]nona‐2,4,7‐triene‐9‐one), CO gas, and a very small amount of indanone. This result suggested β,γ‐double bond favored the extrusion of CO gas. Calculations of several density functional theory (DFT) levels of theory and CBS‐QB3 method were employed. Two mechanisms were considered: a one‐step concerted pathway and a stepwise mechanism involving [1,3] and [1,5] hydrogen sigmatropic migrations. The CAM‐B3LYP/6‐31G(d,p) calculation reasonably agrees with the experimental kinetic parameters. The mechanism appears to be unimolecular in one step concerted through a five‐membered cyclic transition state. Isomerization of product cis‐bicyclo[4.3.0]nona‐2,4,7‐triene‐9‐one yielding 1‐indanone is presented and described. Calculation from substrate 7 may explain in a similar way the mechanism of decomposition of compounds 1‐6 . The present work may well promote to the possibility of carrying out experimental research works on the thermal decarbonylation kinetics in a liquid solution and in the gas phase of β,γ‐unsaturated aliphatic ketones.     

Adhesion of nonmotile Pseudomonas aeruginosa on "soft" polyelectrolyte layer in a radial stagnation point flow system: measurements and model predictions

Prediction of bacterial deposition rates onto substrates in natural aquatic systems is quite challenging because of the inherent complexity of such systems. In this study, we compare experimental deposition kinetics of nonmotile bacteria (Pseudomonas aeruginosa) on an alginate-coated substrate in a radial stagnation point flow (RSPF) system to predictions based on DLVO theory. The "softness" of the surface layer of the bacteria and alginate-coated substrate was considered in the calculations of their electrokinetic surface properties, and the relevance of both the classical zeta potential and the outer surface potential as surrogates for surface potential was investigated. Independent of the used electrical potentials, we showed that significant discrepancies exist between theory and experiments. Analysis of microscopic images in the RSPF system has demonstrated, for the first time, that irreversible deposition of particles or cells entrapped in the secondary energy minimum can occur on the alginate layer, despite the hydrodynamic forces resulting from the radial flow in the RSPF system. It is suggested that polymeric structures associated with the surface of the particle/cell and the alginate-coated substrate are responsible for the transition between the secondary minimum and primary energy well. This mode of deposition is likely to be important in the deposition of microorganisms in complex aquatic systems.     

Generation,Spectroscopic Characterization by EPR,and Decay of a Pyranine‐Derived Radical

The pyraninoxyl radical is readily formed from the MnO₂‐promoted oxidation of pyranine. The free radical can be formed in high concentrations (mM ), and presents a characteristic EPR spectrum that indicates a high spin‐density delocalization. It is relatively stable under nitrogen (half‐life ca. 50 min) but readily decays in presence of O₂. In spite of its high stability, the radical readily reacts with antioxidants (phenols and ascorbic acid) with a partial recovery of the parent pyranine. High concentrations of the pyraninoxyl radical (ca. 9 μM ) are present when pyranine is exposed to a free radical source (10 mM 2,2′‐azobis[2‐amidinopropane], 37°). The fact that these radicals readily react with antioxidants (ascorbic acid and caffeic acid) supports the proposal that protection by antioxidants of peroxyl radical‐promoted pyranine bleaching is mainly due to the occurrence of a repair mechanism.     

An experimental and computational investigation of the Diels-Alder cycloadditions of halogen-substituted 2(H)-pyran-2-ones

[reaction: see text] Diels-Alder reactions of 3- and 5-halo-subsituted 2(H)-pyran-2-ones with both electron-rich and electron-deficient dienophiles afford stable and readily isolable bridged bicyclic lactone cycloadducts. These cycloadditions proceed with excellent regioselectivity and very good stereoselectivity. In contrast, Diels-Alder reactions of 4-halo-subsituted 2(H)-pyran-2-ones afford cycloadducts which are very prone to loss of bridging CO(2) and the subsequent formation of barrelenes ([2.2.2]cyclooctenes). Furthermore, these cycloadditions proceed with only moderate regio- and stereoselectivity. For both series of the 3- and 5-halo-subsituted 2(H)-pyran-2-ones and 4-halo-subsituted 2(H)-pyran-2-ones, the reactivity patterns do not significantly change between the halogens. The regio- and stereochemical preferences of the cycloadditions of halo-substituted 2(H)-pyran-2-ones are investigated computationally. Calculations were carried out on the transition states leading to the four possible regio- and stereoisomeric cycloadducts by using density functional theory (B3LYP/6-31G). These studies allow prediction of the regio- and stereoselectivity in these reactions which are broadly in line with experimental observations.     

Synthesis and Characterization of [Fe(Htrz)2(trz)](BF4)] Nanocubes

Compounds that exhibit spin-crossover (SCO) type behavior have been extensively investigated due to their ability to act as molecular switches. Depending on the coordinating ligand, in this case 1H-1,2,4-triazole, and the crystallite size of the SCO compound produced, the energy requirement for the spin state transition can vary. Here, SCO [Fe(Htrz)₂(trz)](BF₄)] nanoparticles were synthesized using modified reverse micelle methods. Reaction conditions and reagent ratios are strictly controlled to produce nanocubes of 40–50 nm in size. Decreases in energy requirements are seen in both thermal and magnetic transitions for the smaller sized crystallites, where, compared to bulk materials, a decrease of as much as 20 °C can be seen in low to high spin state transitions.     

Highlights from the 55th Bürgenstock Conference on Stereochemistry 2022

In May 2022, the 55th Bürgenstock Conference on Stereochemistry happened in person once again. This summary provides insight into the scientific themes discussed during the most recent meeting of this historic and multi-disciplinary conference.     

Extraction of Acetogenins Using Thermosonication-Assisted Extraction from Annona muricata Seeds and Their Antifungal Activity

The objective of this work was to find the optimal conditions by thermosonication-assisted extraction (TSAE) of the total acetogenin content (TAC) and yield from A. muricata seeds, assessing the effect of the temperature (40, 50, and 60 °C), sonication amplitude (80, 90, and 100%), and pulse-cycle (0.5, 0.7, and 1 s). In addition, optimal TSAE conditions of acetogenins (ACGs) were compared with extraction by ultrasound at 25 °C and the soxhlet method measuring TAC and antioxidant capacity. Moreover, solubility and identification of isolated ACGs were performed. Furthermore, the antifungal activity of ACGs crude extract and isolated ACGs was evaluated. Optimal TSAE conditions to extract the highest TAC (35.89 mg/g) and yield (3.6%) were 50 °C, 100% amplitude, and 0.5 s pulse-cycle. TSAE was 2.17-fold and 15.60-fold more effective than ultrasound at 25 °C and the Soxhlet method to extract ACGs with antioxidant capacity. Isolated ACGs were mostly soluble in acetone and methanol. Seven ACGs were identified, and pseudoannonacin was the most abundant. The inhibition of Candida albicans, Candida krusei, and Candida tropicalis was higher from isolated ACGs than crude extract. TSAE was effective to increase the yield in the ACGs extraction from A. muricata seeds and these ACGs have important antifungal activity.     

On the isomerization of ent-kaurenic acid

Kaurenic acid (1a) is a tetracyclic diterpene that has an exocyclic double bond at delta16. Isokaurenic acid (2a) has an endocyclic delta15double bond. This compound has been isolated from Espeletia tenore (Espeletinae), a resinous plant from the Venezuelan Andes, but its occurrence is rare. In order to obtain a larger amount of 2a, the isomerization of la, which is easily obtained from other Espeletinae, was tried. Kaurenic acid methyl ester (1b) was treated with dil. HCl in CH3Cl/EtOH, after 6 h under reflux a yield of 41.5% isokaurenic acid methyl ester (2b) was obtained but 35.7% 16alpha-ethoxy-kauran-19-oic acid methyl ester (3b) had formed as a byproduct. Treating 1b with CF3COOH in refluxing CH2Cl2 permitted to obtain a yield of 66.6% of 2b in 4 h and only traces of 16alpha-hydroxy-kauran-19-oic acid methyl ester (3a) as a byproduct. Both isomers were separated on a silica gel column impregnated with 20% AgNO3. Treating 2b with KOH in refluxing DMSO yielded pure isokaurenic acid, no back isomerization was observed.     

A Highly Selective Potassium Sensor for the Detection of Potassium in Living Tissues

The development of highly selective sensors for potassium is of great interest in biology. Two new hydrosoluble potassium sensors (Calix‐COU‐Alkyne and Calix‐COU‐Am) based on a calix[4]arene bis(crown‐6) and an extended coumarin were synthesized and characterized. The photophysical properties and complexation studies of these compounds have been investigated and show high molar extinction coefficients and high fluorescence quantum yields. Upon complexation with potassium in the millimolar concentration range, an increase of one‐ and two‐photon fluorescence emission is detected. A twofold fluorescence enhancement is observed upon excitation at λ=405 nm. The ligands present excellent selectivity for potassium in the presence of various competitive cations in water and in a physiological medium. The photophysical properties are not affected by the presence of a large amount of competing cations (Na⁺, Ca²⁺, Mg²⁺, etc.). Ex vivo measurements on mouse hippocampal slices show that Calix‐COU‐Alkyne accumulates extracellularly and does not alter the neuronal activity. Furthermore, the sensor can be utilized to monitor slow extracellular K⁺ increase induced by inhibition of K⁺ entry into the cells.