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The 2021 Tajogaite eruption in La Palma (Canary Islands, Spain) emitted vast volumes of lava during 85 days, which reached the ocean in several occasions at the western flank of the island. Most of these flows merged to create a primary lava delta, covering an area of 48 ha, with an additional 30 ha underwater. Here we characterize the effects of the lava-seawater interaction on the surrounding marine environment. The area was sampled during two multidisciplinary oceanographic cruises: the first one comprised the days before the lava reached the ocean and after the first contact; and the second took place a month later, when the lava delta was already formed but still receiving lava inputs. Physical-chemical anomalies were found in the whole water column at different depths up to 300 m in all measured parameters, such as turbidity (+9 NTU), dissolved oxygen concentration (-17.17 μmol kg -1 ), pH T25 (-0.1), and chlorophyll-a concentration (-0.33 mg m -3 ). Surface temperature increased up to +2.3 °C (28.5 °C) and surface salinity showed increases and decreases of -1.01 and +0.70, respectively, in a radius of 4 km around the lava delta. In the water column, the heated waters experimented a lava-induced upwelling, bringing deeper, nutrient-rich waters to shallower depths; however, this feature did not trigger any phytoplankton bloom. In fact, integrated chlorophyll-a showed an abrupt decrease of -41 % in just two days and -69 % a month later, compared to prior conditions. The chlorophyll-a depletion reached a distance larger than 2.5 km (not delimited)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Tagoro is one of the few submarine volcanoes in the world that has been monitored since its early eruptive stage in 2011 to present day. After six multidisciplinary oceanographic cruises conducted between 2014 and 2023 to gather a comprehensive dataset of georeferenced video-imagery and in situ measurements of hydrothermal flow velocities and hydrothermal fluid samples, we provide a robust characterization of the ongoing hydrothermal fluid velocity, heat flux, and nutrient release, along with an accurate delimitation of the hydrothermal field area. Our results reveal that Tagoro hydrothermal system extends from the main hydrothermal crater up to the summit, covering an area of 7600 m 2 . This hydrothermal field comprises thousands of small individual vents, displaying diverse morphologies such as crevices and delicate chimney-like structures, irregularly scattered across the dominant diffuse venting surface. Hydrothermal fluid temperatures and velocities at the substratum level reveal a clustered spatial distribution, ranging from 21.0 to 33.3 °C and 1.6-26.8 cm min -1 , respectively. Furthermore, our findings indicate a discernible correlation between hydrothermal fluid temperature and vent density, while significant differences were observed between velocities from diffuse and focused areas. Additionally, heat fluxes exceed 200 MW across the entire active region, with heat flux values ranging from 6.06 to 146.87 kW m -2 and dissolve inorganic nutrient concentrations exhibit significant enrichments, comparable to the magnitude of important nutrient sources in the area as upwelling systems or mesoscale structures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The conformational study of saccharides and glycomimetics in solution is critical for a comprehensive understanding of their interactions with biological receptors and enabling the design of optimized glycomimetics. Here, we report a nuclear magnetic resonance (NMR) study centered on the conformational properties of the hydroxymethyl group and glycosidic bond of four series of aryl S -glucosides. We found that in acetyl-protected and free aryl S -β-glucosides, the rotational equilibrium around the C5-C6 bond (hydroxymethyl group) exhibits a linear dependence on the electronic properties of the aglycone, namely, as the aryl's substituent electron-withdrawing character increases, the dominance of the gg rotamer declines and the gt contribution rises. Likewise, the conformational equilibrium around the glycosidic C1-S bond also depends on the aglycone's electronic properties, where glucosides carrying electron-poor aglycones exhibit stiffer glycosidic bonds in comparison to their electron-rich counterparts. In the case of the α anomers, the aglycone's effect over the glycosidic bond conformation is like that observed on their β isomers; however, we observe no aglycone's influence over the hydroxymethyl group conformation in the α-glucosides.

Tsunamis are triggered by sudden seafloor displacements, and usually originate from seismic activity at faults. Nevertheless, strike-slip faults are usually disregarded as major triggers, as they are thought to be capable of generating only moderate seafloor deformation; accordingly, the tsunamigenic potential of the vertical throw at the tips of strike-slip faults is not thought to be significant. We found the active dextral NW-SE Averroes Fault in the central Alboran Sea (westernmost Mediterranean) has a historical vertical throw of up to 5.4 m at its northwestern tip corresponding to an earthquake of Mw 7.0. We modelled the tsunamigenic potential of this seafloor deformation by Tsunami-HySEA software using the Coulomb 3.3 code. Waves propagating on two main branches reach highly populated sectors of the Iberian coast with maximum arrival heights of 6 m within 21 and 35 min, which is too quick for current early-warning systems to operate successfully. These findings suggest that the tsunamigenic potential of strike-slip faults is more important than previously thought, and should be taken into account for the re-evaluation of tsunami early-warning systems., (© 2021. The Author(s).)

The ability of trans - and cis -1,2-glucopyranosyl and cyclohexyl ditriazoles, synthesized by CuAAC "click" chemistry, to form gels was studied, their physical properties determined, and the self-aggregation behavior investigated by SEM, X-ray, and EDC studies. The results revealed that self-assembly was driven mainly by π-π stacking interactions, in addition to hydrogen bonding, with the aromatic rings adopting a high degree of parallelism, as seen in crystal packings and ECD data. Furthermore, π-bromine interactions between the bromine atom of the aryl substituents and the triazole units might also contribute to an overall stabilization of the supramolecular aggregation of bis(4-bromophenyl)triazoles. The trans or cis spatial disposition of the triazole rings is highly important for gelation, with the cis configuration having higher propensity., (Copyright © 2019, Tejera et al.; licensee Beilstein-Institut.)

Chemoprevention of human cancer appears to be a feasible strategy for cancer control, especially when chemopreventive intervention is involved during early stages of the carcinogenesis process. As a part of our ongoing research program into new chemopreventive agents, herein are reported the isolation, structural elucidation, and biological evaluation of 10 new (1-10) and three known (11-13) sesquiterpenes with a dihydro-β-agarofuran skeleton from the leaves of Maytenus jelskii Zahlbr. Their stereostructures have been elucidated by means of spectroscopic analysis, including 1D and 2D NMR techniques, ECD studies, and biogenetic considerations. The isolated metabolites and eight previously reported sesquiterpenes (14-21) were screened for their antitumor-promoting activity using a short-term in vitro assay for Epstein-Barr virus early antigen (EBV-EA) activation induced by 12-O-tetradecanoylphorbol-13-acetate (TPA). Six compounds from this series (4, 5, 11, and 13-15) were found to exhibit higher efficacies than β-carotene, used as reference inhibitor for EBV-EA activation. In particular, promising antitumor activity was observed for compound 5, exhibiting inhibition even at the lowest concentration assayed (10 mol ratio/TPA). Preliminary structure-activity relationship analysis revealed that the acetate, benzoate, and hydroxy groups are the most desirable substituents on the sesquiterpene scaffold for activity in the EBV-EA activation assay.

A series of alkyl α/β-(1→6)-diglucopyranosides 1-12 were synthesized and assessed for cytotoxicity against HL-60, U937, Molt-3 and MCF-7 cancer cell lines. The menthyl derivatives displayed strong cytotoxic properties showing IC(50) values between 6 and 16 μM. Furthermore, we demonstrated that the selected synthetic (+)-menthyl β-(1→6)-diglucopyranoside 5 induces apoptotic cell death in human leukemia cells through a mechanism that involves activation of multiple caspases. Cell death was completely prevented by the non-specific caspase inhibitor z-VAD-fmk and found to be associated with the release of cytochrome c, an increase in the expression of Bax levels and a decrease in the generation of reactive oxygen species., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

A series of carbasugars were prepared and their conformational properties studied by means of NMR spectroscopy. The results were compared to those previously found for O-, S-, and C-β-glycoside analogs. While the rotational populations of the hydroxymethyl group in O-, S-, and C-glycosides are known to depend on the structural nature of their aglycon, in carbasugars it proved to be independent of the pseudo-aglycon. This result confirms that endocyclic oxygen is necessary for the observed relationship between the structure of the aglycon and the rotational populations of the hydroxymethyl group, and indicates that the stereoelectronic exo-anomeric effect is mainly responsible for such conformational dependence., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

A series of alkyl β-glucosyl sulfoxides were synthesized and characterized in order to study their stereochemical properties. The dependence of the aglycon, solvent and absolute configuration of the sulfinyl group on the conformational properties around the glucosidic and C5-C6 (hydroxymethyl group) bonds were studied. The results for R(S) sulfoxides show linear correlations between the rotamer populations of the hydroxymethyl group and the corresponding Taft's steric parameter (E(S)) of the alkyl group attached to the sulfinyl group in polar and apolar solvents, an increase in the absolute value of E(S) leading to an increase in the gt population. In addition, NOE experiments reveal that as the bulkiness of the alkyl group increases the population of the g- rotamer increases, the latter stabilized by the exo-anomeric effect. These results are in complete agreement with the participation of the exo-anomeric effect in both conformational properties of R(S) sulfoxides. Sulfoxides with the S(S) configuration show different behavior to their R(S) epimers; thus, an increase in the E(S) value of the alkyl group leads to similar or lower gt populations in apolar solvents and to increases in gt in polar solvents. Their NOE studies reveal a conformational equilibrium (in polar and apolar solvents) between g- and g+, dependent on the size of the alkyl group R attached to the sulfinyl group. All these results for both epimers support the general hypothesis that the exo-anomeric effect modifies the conformation of the hydroxymethyl group, fulfills the stereoelectronic requirements, and shows dependence on the solvent.

To examine if the biological activity of the N/OFQ peptide, which is the native ligand of the pain-related and viable drug target NOP receptor, could be modulated by glycosylation and if such effects could be conformationally related, we have synthesized three N/OFQ glycopeptide analogues, namely: [Thr(5)-O-α-D-GalNAc-N/OFQ] (glycopeptide 1), [Ser(10)-O-α-D-GalNAc]-N/OFQ (glycopeptide 2) and [Ser(10)-O-β-D-GlcNAc]-N/OFQ] (glycopeptide 3). They were tested for biological activity in competition binding assays using the zebrafish animal model in which glycopeptide 2 exhibited a slightly improved binding affinity, whereas glycopeptide 1 showed a remarkably reduced binding affinity compared to the parent compound and glycopeptide 3. The structural analysis of these glycopeptides and the parent N/OFQ peptide by NMR and circular dichroism indicated that their aqueous solutions are mainly populated by random coil conformers. However, in membrane mimic environments a certain proportion of the molecules of all these peptides exist as α-helix structures. Interestingly, under these experimental conditions, glycopeptide 1 (glycosylated at Thr-5) exhibited a population of folded hairpin-like geometries. From these facts it is tempting to speculate that nociceptin analogues showing linear helical structures are more complementary and thus interact more efficiently with the native NOP receptor than folded structures, since glycopeptide 1 showed a significantly reduced binding affinity for the NOP receptor.

Seven new withanolides (1-7), along with three known ones (8-10), were isolated from the leaves of Withania aristata. Their structures were elucidated on the basis of spectroscopic analysis, including 2D NMR experiments and spectrometric techniques, and the absolute configuration of 1 and 2 was established by CD analysis. In the search for new cytotoxic compounds from Withania species, the isolated compounds 1-9, along with two derivatives, were assayed for their cytotoxicity against HeLa, MCF-7 and A-549 human tumor cell lines. Derivative (4S,20R,22R)-27-acetoxy-4-p-bromobenzoyloxy-1-oxo-witha-2,5,16,24-tetraenolide (13) showed cytotoxicity against all the cell lines assayed with IC(50) values ranging from 2.8 to 3.6microM, and (4S,20R,22R)-4,27-diacetoxy-4-hydroxy-1-oxo-witha-2,5,16,24-tetraenolide (12) exhibited an IC(50) value of 5.4microM on the MCF-7 cell line., (Copyright 2010 Elsevier Inc. All rights reserved.)

The thyroid hormone and retinol transporter protein known as transthyretin (TTR) is in the origin of one of the 20 or so known amyloid diseases. TTR self assembles as a homotetramer leaving a central hydrophobic channel with two symmetrical binding sites. The aggregation pathway of TTR into amiloid fibrils is not yet well characterized but in vitro binding of thyroid hormones and other small organic molecules to TTR binding channel results in tetramer stabilization which prevents amyloid formation in an extent which is proportional to the binding constant. Up to now, TTR aggregation inhibitors have been designed looking at various structural features of this binding channel others than its ability to host iodine atoms. In the present work, greatly improved inhibitors have been designed and tested by taking into account that thyroid hormones are unique in human biochemistry owing to the presence of multiple iodine atoms in their molecules which are probed to interact with specific halogen binding domains sitting at the TTR binding channel. The new TTR fibrillogenesis inhibitors are based on the diflunisal core structure because diflunisal is a registered salicylate drug with NSAID activity now undergoing clinical trials for TTR amyloid diseases. Biochemical and biophysical evidence confirms that iodine atoms can be an important design feature in the search for candidate drugs for TTR related amyloidosis.

A series of alkyl beta-D-glucopyranosyl-(1-->6)-alpha-D-glucopyranosides were synthesized and analyzed by NMR and CD techniques. As in their beta-anomer series, the rotational populations of the hydroxymethyl group involved in the interglycosidic linkage (torsion angle omega) are shown to depend on the aglycon and the solvent. However, for this alpha-anomer series the rotational dependence arises directly from steric effects. Correlations between rotational populations and molar refractivity (MR) steric parameters, but not Taft's steric parameters (beta-anomers), of the alkyl substituents were observed. The conformational domino effect previously predicted from alkyl beta-(1-->6)-diglucopyranosides is now supported by the conformational properties of their alpha-anomers, the anomeric configuration controlling the domino effect. In addition, the rotational populations around the C5'-C6' bond (torsion angle omega') depend weakly on the structure of the aglycon and the anomeric configuration.

A series of alkyl beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosides, containing nonchiral and chiral aglycons, were synthesized and analyzed by NMR and CD. The results, collected from four sets of disaccharides, demonstrated that the rotational properties of the interglycosidic linkage depend on the structural natures of both the aglycon and the solvent. Stereoelectronic and steric factors explain this rotational dependence, the gauche- trans (gt) rotamer being the most stable. Furthermore, correlations between Taft's steric parameters or between the pKa values of the alkyl substituent (aglycon) versus corresponding rotamer populations were observed. These results point to a natural conformational domino effect in oligosaccharides, where the conformational properties of each (1-->6) interglycosidic linkage will depend on the structure of the previous residue or its aglycon. In addition, a very weak rotational population dependence of the hydroxymethyl group at residue II on the aglycon at residue I was observed. The population of the gauche- gauche (gg) rotamer decreased, and that of gt increased as the Taft's steric parameters of the remote aglycon increased, independently of the disaccharide series and of the solvent.

Fifty-two C-glycosides were synthesized and their in-vitro antiproliferative activity screened against human cervical carcinoma (HeLa) and osteosarcoma (HOS) cell lines. Nine of them had growth inhibitions (GI(50) values) below 10 microM, the C-glucopyranoside 38 being the most active against HeLa (5.4 microM) and the dichlorocyclopropyl derivative 42 against HOS (1.6 microM). Some preliminary structure-activity relationships were established.

A large series of alkyl C-glycosides was synthesized from D-glucal or D-galactal. These compounds were screened against the human promyelocytic leukemia cell line (HL60), showing significant activity and apoptosis. Up to 13 C-glucopyranosides, but no C-galacto- or C-mannopyranosides, exhibited inhibitory concentrations (IC(50) values) below 20 microM, five of them in the range 4-8 microM. Preliminary structure-activity relationships were established.

The tanker Prestige sank off NW Iberia on the 19th November 2002. The stern and bow of the Prestige wreck are located on the southwestern edge of the Galicia Bank, at 3565 m and 3830 m water depths, respectively. This bank is a structural high controlled by major faults with predominant N-S, NNE-SSW, and NNW-SEE trends. It is characterized by moderate to low seismic activity. The faults have controlled the local depositional architecture, deforming, fracturing, relocating and distributing sediments since the Valangian (early Cretaceous). The Prestige sinking area corresponds to an asymmetric half-graben structure with a N-S trend, which conditions the present-day morphology. The faulted flank outcrops and its activity and erosion have favoured the occurrence of mass-movements (slumps, slump debris, mass-flows and turbidity currents), building valleys and depositional lobes. Nearsurface sediments comprise mostly terrigenous and biogenous turbiditic muds and sands with a minor presence of hemipelagic muds, except on the fault scarp where pelagites predominate. Potential geological hazards resulting from tectonic and sedimentary processes affect almost the entire Prestige sinking area.

Sixteen methyl glucopyranosyl glucopyranoside disaccharides (methyl beta-d-Glcp(p-Br-Bz)-(1-->x)-beta/alpha-d-Glcp) containing beta-glycosidic linkages (1-->2, 1-->3, 1-->4, and 1-->6) were synthesized and analyzed by means of CD and NMR spectroscopy in three different solvents. For each of these four types of disaccharides, a correlation was observed between the hydroxymethyl rotational populations around the C5-C6 bond of the glucopyranosyl residue II with the substituents and the anomeric configuration of the methoxyl group in residue I, as well as with the solvent. Nonbonded interactions, the stereoelectronic exo-anomeric effect, and hydrogen bonding were found to be responsible for the observed rotameric differences. Whereas the rotational populations of the (1-->6)-linked disaccharides are mainly dependent on the exo-anomeric effect, the (1-->2)-bonded disaccharides are strongly dependent on the anomeric configuration at C1, and the (1-->3)- and (1-->4)-linked disaccharides are mainly dependent on the substituents and the solvent. The population of the gt rotamer decreases as nonbonded interactions increase but increases as the exo-anomeric effect becomes greater, as well as in the presence of intramolecular hydrogen bonding to the endocyclic oxygen O5'. Comparison of the hydroxymethyl rotational preferences between our model disaccharides revealed a dependence on the glycosidic linkage type. Thus the population of the gg and gt rotamers decreases/increases from (1-->2)- (beta series), to (1-->6)-, to (1-->2)- (alpha series), to (1-->4)-, and to (1-->3)-bonded disaccharides respectively, while the tg rotamer population remains almost constant (around 20%), except for the (1-->3)- and (1-->4)-linked disaccharides with the intramolecular hydrogen bonding to O5', where this population decreases to 10%.

The present report undertakes a challenge of general interest in supramolecular chemistry: the achievement of helical organizations with controlled structure. To achieve this target we considered the possibility of inducing supramolecular chirality using molecules that were designed to organize into columnar mesophases. The use of oxazoline-derived ligands and metal coordination served as tools to prepare molecules with a phasmidic-like structure, which show columnar organization in the liquid crystalline state. To ensure the formation of chiral mesophases, these complexes bear stereogenic centers in the rigid coordination environment of the metal. X-ray and circular dichroism experiments have revealed that chirality transfer does indeed take place from the chiral molecule to the columnar liquid crystal organization. This chiral columnar organization appears as a helix consisting of stacks of molecules that rotate with respect to one another along the column while maintaining their mean planes parallel to each other. In fact, it has been concluded that packing of these polycatenar molecules must be more efficient upon rotation of a molecule with respect to the adjacent one along the column. Furthermore, the same type of helical supraorganization has been found to be present in the mesophase of the racemic mixture and the mixture of diastereomers prepared from the racemic ligand. In this case, segregation of the optical isomers is proposed to occur to give rise to both types of helix (right-handed and left-handed).

From the aerial parts of Laennecia sophiifolia (Kunth) G.L. Nesom, a neo-clerodane and an acyclic furano diterpene were isolated, along with four known compounds, 2beta-hydroxyhardwickiic acid, hawtriwaic acid, apigenin, and beta-sitosterol. Their structures were established as 12-epi-bacchotricuneatin A and (2E,6E)-9-(3-furyl)-6-methyl-2-(4-methylpent-3-enyl)-nona-2,6-dienoic acid, by analysis of spectral evidence. The absolute structure of 12-epi-bacchotricuneatin A was determined by a circular dichroism spectral comparison with that of bacchotricuneatin A.

A study of the applicability of circular dichroism (CD) for the determination of drug levels in human serum is described and a new method for the quantitative determination of optically active absorbing drugs having Cotton effects at wavelengths about 250 nm in human serum and/or plasma is proposed. The principal advantages of this method are speed, economy, and simplicity, no derivatization or chromatographic separation steps being needed. The validity of the CD determination was confirmed by analysis of variance, beta-lactam antibiotics being chosen as model drugs. In addition, the validation studies performed confirm the accuracy and precision of the proposed method. For beta-lactam antibiotics lacking Cotton effects above 250 nm, an alternative method based on the extraction of the drug from serum is considered.

Over 200 urine samples from 61 subjects were analyzed by circular dichroism spectroscopy. The results proved that this technique can be applied to the direct determination of optically active absorbing drugs in urine of subjects under multiple drug administration, independently of the presence of proteins, which can simultaneously be determined. A list of noninterfering drugs is included. The validity of the present method was confirmed by analysis of variance, the beta-lactam antibiotics ampicillin, cefoxitin, and cephalexin being chosen as model drugs and human albumin as the analytical standard for protein determination. The results demonstrated that the proposed method is accurate and precise, the correlation coefficients being higher than 0.9996. A circular dichroism and HPLC data comparison was successfully performed. The principal advantages of this method are simplicity, quickness, and economy, no derivatization or chromatographic separation steps being needed.

The circular dichroism and ultraviolet spectra of 15 commercial cephalosporins in common clinical use are analyzed. Distinguishing between the beta-lactam antibiotics (penicillins, cephalosporins, and cephamycins) on the basis of their CD spectral data has been found to be straightforward. Furthermore, sufficient CD spectral dissimilarities are observed to discriminate among the cephalosporin homologues and to classify these antibiotics in five spectroscopic groups, on the basis of the wavelengths of their Cotton effects. In addition, some chemical structural characteristics for these spectroscopic groups are discussed. Besides molar absorptivity and CD data, the slopes and the intercepts of the equations of the regression line are calculated for each of these antibiotics, the correlation coefficients being higher than 0.9993. The validity of the proposed model is confirmed by analysis of the variance. The results demonstrated that the proposed method is accurate and precise. The method was successfully applied to the direct determination of these drugs in commercial oral suspensions, injections, and capsules. The principal advantages of this method are quickness and simplicity no derivatization or chromatographic separation steps being needed.

The spectroscopic basis for a novel alternative to methylation microanalysis for linkage determination is presented. The complex c.d. spectra of "bichromophoric" D-galactopyranoside derivatives, i.e., containing two types of exciton-coupling chromophore, namely, p-bromobenzoate (lambda max 245 nm) and p-methoxycinnamate (lambda max 311 nm), are highly characteristic at nanomolar levels, indicative of the sugar, the substitution pattern, and the D or L configuration. That these spectra are due to a recently demonstrated pairwise additivity is confirmed. Work directed towards an oligosaccharide derivatization-sequence, resulting in the easily identifiable tetrachromophoric monosaccharide residues, is described. Such an analysis can simultaneously accomplish identification of sugar components, linkage pattern, and determination of absolute configuration at the nanomolar level.