Synthesis of Marine (-)-Pelorol and Future Perspectives.

Meroterpenoid-type marine natural compounds have attracted an increasing amount of attention due to their peculiar chemical structures and their potential for the development of therapeutically important probes. Within this group of substances pelorol stands out; it is a natural compound isolated from marine organisms with a unique structure and an interesting biological profile. In this article, we summarize and highlight the most interesting aspects of the synthetic procedures towards this compound, which have two common key steps.

Cytotoxicity and Chemotaxonomic Significance of Saponins from Wild and Cultured Shoots.

The shoots of L. are consumed worldwide, although most species belonging to this genus have a restricted range, and several taxa remain unstudied. In this work, a total of four taxa from different locations were scrutinized and compared with cultivated .

Properties of Cosmic Deuterons Measured by the Alpha Magnetic Spectrometer.

Precision measurements by the Alpha Magnetic Spectrometer (AMS) on the International Space Station of the deuteron (D) flux are presented. The measurements are based on 21×10^{6} D nuclei in the rigidity range from 1.9 to 21 GV collected from May 2011 to April 2021.

Outcomes of transvaginal radiofrequency ablation for symptomatic leiomyomas.

Objective: Describe the effect of transvaginal radiofrequency ablation for leiomyoma in symptomatic patients and post procedure follow-up.

Material And Methods: A retrospective forward-looking observational study was performed including 63 patients who underwent transvaginal radiofrequency ablation between January 2016 and December 2022 at San Cecilio University Hospital in Granada, Spain. The variables registered were: age, parity, the clinical features that lead to the medical visit and pre-surgical treatment.

Presumed fluoxetine maculopathy.

To report a unique case of a patient who developed simultaneous bilateral maculopathy presumed from intake of fluoxetine. The optic coherence tomography (OCT) macular showed a subfoveal disruption in the outer retinal layer in both eyes (OU), higher in the left one (OS). Although reported cases of serotonin recapture inhibitors (SSRIs) Maculopathy so far have been caused by sertraline, fluoxetine shares the biological mechanism, and OCT findings and ocular symptoms are the same as published.

Temporal Structures in Positron Spectra and Charge-Sign Effects in Galactic Cosmic Rays.

We present the precision measurements of 11 years of daily cosmic positron fluxes in the rigidity range from 1.00 to 41.9 GV based on 3.

Marine Puupehenone and Puupehedione: Synthesis and Future Perspectives.

Puupehenone and puupehedione are natural products isolated from marine organisms. These compounds display a broad spectrum of biological activities, the in vitro antitubercular activity of puupehenone being a stand out, and are equipped with an interesting structural complexity. These products have served to stimulate the continual interest of the synthetic community.

A Concise Diastereoselective Total Synthesis of α-Ambrinol.

(-)--α-Ambrinol is a natural product present in ambergris, a substance of marine origin that has been highly valued by perfumers. In this paper, we present a new approach to its total synthesis. The starting material is commercially available α-ionone and the key step is an intramolecular Barbier-type cyclization induced by CpTiCl, an organometallic compound prepared in situ by a CpTiCl reduction with Mn.

Unifying the Synthesis of a Whole Family of Marine Meroterpenoids through a Biosynthetically Inspired Sequence of 1,2-Hydride and Methyl Shifts as Key Step.

Marine meroterpenoids have attracted a great deal of attention from synthetic research groups due to their attractive and varied biological activities and their unique and diverse structures. In most cases, however, further biological studies have been severely limited mainly to the scarcity of natural supply and because almost none of the reported syntheses methods has enabled unified access for a large number of marine meroterpenoids with aureane and avarane skeletons. Based on our previous publications and the study of recent manuscripts on marine meroterpenoids, we have conceived a unified strategy for these fascinating marine compounds with aureane or avarane skeletons using available drimane compounds as starting materials.

Fatty acid profiling in the genus Pinus in relation to its chemotaxonomy and nutritional or pharmaceutical properties.

To develop and utilize the oil of Pinus seeds and explore natural resources rich in pinolenic acid (PNLA), twenty-one Pinus taxa were evaluated in a search of Δ5-unsaturated polymethylene-interrupted fatty acids (Δ5-UPIFA)-rich oils. While the fatty acid (FA) composition was determined by GC-FID and GC-MS, NMR of crude oils proved to be a fast method for establishing the ratio between Δ5-UPIFA and total FA. For all analyzed taxa, both the geographical origin and the concentration of total FA in the seeds are provided.

Enantioselective total synthesis of putative dihydrorosefuran, a monoterpene with an unique 2,5-dihydrofuran structure.

An original synthesis of the structure of dihydrorosefuran, a compound allegedly identified in and , has been developed. The key steps in the five-step 36% overall yield synthesis are a CpTiCl mediated Barbier-type allenylation of a linear aldehyde and the formation of a 2,5-dihydrofuran scaffold through a Ag(I)-mediated cyclization. Neither of the reported spectral data for dihydrorosefuran match those of the synthetic product, suggesting that the isolated compound from is in fact the natural product rosiridol, while the real structure of the product from remains unknown.

Buglossoides spp. seeds, a land source of health-promoting n-3 PUFA and phenolic compounds.

Ahiflower oil© is extracted from the seeds of Buglossoides arvensis, which contains high amounts of stearidonic acid (SDA, 18:4n-3), while its phenolic composition still is unreported. Moreover, several Buglossoides taxa remain unstudied and could become natural sources of SDA. In this work, seeds of several Buglossoides taxa and Ahiflower oil© were screened for fatty acids, phenolic compounds, and in vitro antiproliferative activities against colorectal cancer cells.

First Direct Detection Constraints on Planck-Scale Mass Dark Matter with Multiple-Scatter Signatures Using the DEAP-3600 Detector.

Dark matter with Planck-scale mass (≃10^{19}  GeV/c^{2}) arises in well-motivated theories and could be produced by several cosmological mechanisms. A search for multiscatter signals from supermassive dark matter was performed with a blind analysis of data collected over a 813 d live time with DEAP-3600, a 3.3 t single-phase liquid argon-based detector at SNOLAB.

Marine Terpenic Endoperoxides.

Organic extracts of marine invertebrates, mainly sponges, from seas all over the world are well known for their high in vitro anticancer and antibiotic activities which make them promising sources of compounds with potential use as pharmaceutical leads. Most of the structures discovered so far have a peculiar structural feature in common: a 1,2-dioxane ring. This is a highly reactive heterocycle that can be considered as an endoperoxide function.

Initial experience with a homemade "hybrid-tome" for needle-knife precut in patients with difficult biliary cannulation.

Current clinical guidelines recommend needle-knife precut (NKP) as the primary and best method for performing a biliary cannulation (BC) when simple techniques fail and the criteria are met for difficult BC (DBC). However, many endoscopists avoid or defer early NKP in favor of alternative, simpler techniques that have not been shown to be either safer or more effective. Our goal is to test a device that provides the needle-knife papillotome (NKPT) with traction capability and which can facilitate the learning and execution of NKP.

Pulse-shape discrimination against low-energy Ar-39 beta decays in liquid argon with 4.5 tonne-years of DEAP-3600 data.

The DEAP-3600 detector searches for the scintillation signal from dark matter particles scattering on a 3.3 tonne liquid argon target. The largest background comes from beta decays and is suppressed using pulse-shape discrimination (PSD).

Divergent Strategy in Marine Tetracyclic Meroterpenoids Synthesis.

The divergent total synthesis strategy can be successfully applied to the preparation of families of natural products using a common late-stage pluripotent intermediate. This approach is a powerful tool in organic synthesis as it offers opportunities for the efficient preparation of structurally related compounds. This article reviews the synthesis of the marine natural product aureol, as well as its use as a common intermediate in the divergent synthesis of other marine natural and non-natural tetracyclic meroterpenoids.

The Proven Versatility of CpTiCl.

In the last two decades, titanocene monochloride has been postulated as a monoelectronic transfer reagent capable of catalyzing an important variety of chemical transformations. In this Perspective, our contributions to this growing field of research are summarized and analyzed. Especially known have been our contributions in C-C bond formation reactions, hydrogen-atom transfer from water to radicals, and isomerization reactions, as well as the development of a catalytic cycle that has subsequently allowed the preparation of a great variety of natural terpenes.

A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation.

A new concise general methodology for the synthesis of different tetracyclic meroterpenoids is reported: (±)-aureol (), the key intermediate of this general route. The synthesis of (±)-aureol () was achieved in seven steps (28% overall yield) from (±)-albicanol. The key steps of this route include a C-C bond-forming reaction between (±)-albicanal and a lithiated arene unit and a rearrangement involving 1,2-hydride and 1,2-methyl shifts promoted by BF•EtO as activator and water as initiator.

Stereoselective Barbier-Type Allylations and Propargylations Mediated by CpTiCl.

CpTiCl, prepared in situ by manganese reduction of CpTiCl, is an excellent new system for the Barbier-type allylation and propargylation of carbonyl compounds. It can be used in catalytic amounts when combined with EtN·HBr/TMSBr, which acts as a regenerating system. The high regio- and stereoselectivity shown by this system makes it useful for prenylation and crotylation processes in the synthesis of natural products.

Purification process for MUFA- and PUFA-based monoacylglycerols from edible oils.

Important health benefits have been attributed to monoacylglycerols (MAGs) due to their various physiological functions, owing to which they become candidates for use as functional foods in order to prevent the onset of certain diseases such as colon cancer. In this work, six edible oils, namely: olive, linseed, sunflower, evening primrose, DHASCO and ARASCO have been processed to obtain different MUFA- and PUFA- based MAGs. First, the oils were hydrolyzed by means of an enzymatic process using porcine pancreatic lipase and then the reaction products were fractionated by using a liquid chromatography column containing silica gel as stationary phase in order to purify the MAGs-enriched fraction.

Cp2TiCl/D2O/Mn, a formidable reagent for the deuteration of organic compounds.

Cp2TiCl/D2O/Mn is an efficient combination, sustainable and cheap reagent that mediates the D-atom transfer from D2O to different functional groups and can contribute to the synthesis of new deuterated organic compounds under friendly experimental conditions and with great economic advantages.

Flexible endoscopic treatment of Zenker's diverticulum: thirteen years' experience in Spain.

Introduction: Flexible endoscopic treatment is one of the alternative approaches for the management of Zenker's diverticum. The present paper shows our short-term and long-term results with flexible endoscopic cricopharyngeal myotomy/septotomy.

Patients And Methods: A retrospective analysis of our experience in patients with Zenker's diverticulum treated using a flexible endoscope, assisted by a flexible diverticuloscope, between 2002 and 2015.

Unprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes: Electrophilic Quenching of Their Metallotropic Equilibrium.

The synthesis and structural characterization of allenyl titanocene(IV) [TiClCp2 (CH=C=CH2 )] 3 and propargyl titanocene(IV) [TiClCp2 (CH2 -C≡C-(CH2 )4 CH3 )] 9 have been described for the first time. Advanced NMR methods including diffusion NMR methods (diffusion pulsed field gradient stimulated spin echo (PFG-STE) and DOSY) have been applied and established that these organometallics are monomers in THF solution with hydrodynamic radii (from the Stokes-Einstein equation) of 3.5 and 4.