Stemmosides C and D, two novel unusual pregnane glycosides from Solenostemma argel: structural elucidation and configurational study by a combined NMR-quantum mechanical strategy

Stemmosides C and D, two novel pregnane glycosides characterized by an unusual C-17 side chain were isolated from the pericarps of Solenostemma argel. In addition, stemmoside D displays an uncommon 14β proton configuration, apparently being the first pregnane isolated from plants known to have a 15 keto, cis CD ring junction. Their structures have been established by ESIMS and NMR experiments. The relative configuration of the molecules was determined using a strategy based on the simulation of ¹H, ¹³C, and J coupling NMR parameters. DFT calculations of ¹H and ¹³C chemical shifts, and of the ¹H homonuclear spin–spin coupling constants were performed with the mPW1PW91 functional using the 6-31G(d,p) basis set on the fully optimized geometries of all the possible stereoisomers.     

The photoisomerization mechanism of azobenzene: a semiclassical simulation of nonadiabatic dynamics

We have simulated the photoisomerization dynamics of azobenzene, taking into account internal conversion and geometrical relaxation processes, by means of a semiclassical surface hopping approach. Both n-->pi* and pi-->pi* excitations and both cis-->trans and trans-->cis conversions have been considered. We show that in all cases the torsion around the N==N double bond is the preferred mechanism. The quantum yields measured are correctly reproduced and the observed differences are explained as a result of the competition between the inertia of the torsional motion and the premature deactivation of the excited state. Recent time-resolved spectroscopic experiments are interpreted in the light of the simulated dynamics.     

Stereoselective Epoxidation of Cyclic Dienes and Trienes by Dioxiranes

Epoxides are essential building blocks in organic chemistry. The epoxidation of unsubstituted cyclic dienes 2 , 3 , 4 and triene 5 using dimethyldioxirane ( 1a ) and its trifluoro analog 1b methyl(trifluoromethyl)dioxirane has been investigated. The excellent yields obtained (90–98%) are accompanied by outstandingly high diastereoselectivities (90–98%). Interpretation of results based upon the early idea that polar groups can direct the dioxirane attack by dipole–dipole interaction provides a likely rationale, along with a more generalized mechanistic view.     

Lewis Acid Promoted Dearomatization of Naphthols

Two-step dearomative functionalization of naphthols promoted by Lewis acids and copper(I) catalysis was developed. Initially, Lewis acid complexation inverted the electronic properties of the ring and established an equilibrium with the dearomatized counterpart. Subsequent trapping of the dearomatized intermediate with organometallics as well as organophosphines was demonstrated and provided the corresponding dearomatized products.     

From Fish Waste to Value: An Overview of the Sustainable Recovery of Omega-3 for Food Supplements

The disposal of food waste is a current and pressing issue, urging novel solutions to implement sustainable waste management practices. Fish leftovers and their processing byproducts represent a significant portion of the original fish, and their disposal has a high environmental and economic impact. The utilization of waste as raw materials for the production of different classes of biofuels and high-value chemicals, a concept known as “biorefinery”, is gaining interest in a vision of circular economy and zero waste policies. In this context, an interesting route of valorization is the extraction of omega-3 fatty acids (ω-3 FAs) for nutraceutical application. These fatty acids, such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) have received attention over the last decades due to their beneficial effects on human health. Their sustainable production is a key process for matching the increased market demand while reducing the pressure on marine ecosystems and lowering the impact of waste production. The high resale value of the products makes this waste a powerful tool that simultaneously protects the environment and benefits the global economy. This review aims to provide a complete overview of the sustainable exploitation of fish waste to recover ω-3 FAs for food supplement applications, covering composition, storage, and processing of the raw material.     

Curing of a rigid rod epoxy resin with an aliphatic diacid: an example of a lightly crosslinked liquid crystalline thermoset

By reacting a rigid rod epoxy terminated molecule (p-bis(2,3-epoxypropoxy)-α-methylstilbene) with an aliphatic carboxylic acid (decanedioic acid), a lightly crosslinked liquid crystalline network is obtained. This network exhibits a smectic-like phase. While the mesophasic structure resulted “frozen” by the crosslinks in the case of higly crosslinked liquid crystalline epoxy resins, in this case a reversible transition from the liquid crystalline to the isotropic phase is observed. Moreover, while curing the same rigid rod epoxy molecule with amines resulted in a thermoset with a nematic structure, in this case a more ordered mesophase can be obtained. Preliminary results show that it is possible to orient macroscopically the mesogenic chains by stretching thin films above the glass transition temperature (T_g) and then quickly cooling down to the glassy state. This makes this material very attractive in the field of optical applications.     

Permutation Entropy-Based Interpretability of Convolutional Neural Network Models for Interictal EEG Discrimination of Subjects with Epileptic Seizures vs. Psychogenic Non-Epileptic Seizures

The differential diagnosis of epileptic seizures (ES) and psychogenic non-epileptic seizures (PNES) may be difficult, due to the lack of distinctive clinical features. The interictal electroencephalographic (EEG) signal may also be normal in patients with ES. Innovative diagnostic tools that exploit non-linear EEG analysis and deep learning (DL) could provide important support to physicians for clinical diagnosis. In this work, 18 patients with new-onset ES (12 males, 6 females) and 18 patients with video-recorded PNES (2 males, 16 females) with normal interictal EEG at visual inspection were enrolled. None of them was taking psychotropic drugs. A convolutional neural network (CNN) scheme using DL classification was designed to classify the two categories of subjects (ES vs. PNES). The proposed architecture performs an EEG time-frequency transformation and a classification step with a CNN. The CNN was able to classify the EEG recordings of subjects with ES vs. subjects with PNES with 94.4% accuracy. CNN provided high performance in the assigned binary classification when compared to standard learning algorithms (multi-layer perceptron, support vector machine, linear discriminant analysis and quadratic discriminant analysis). In order to interpret how the CNN achieved this performance, information theoretical analysis was carried out. Specifically, the permutation entropy (PE) of the feature maps was evaluated and compared in the two classes. The achieved results, although preliminary, encourage the use of these innovative techniques to support neurologists in early diagnoses.