•Model simulations characterise and forecast oceanographic conditions during HABs.•Forecast system describes and predicts inflows and outflows to harvesting areas.•Model able to forecast along-shore ...advection and arrival of autumn HABs to Galicia.•Galician pilot HAB bulletins for managers and the aquaculture sector are presented.•Model forecasts and bulletins provide early warning of the risk of Dinophysis events.
The northwestern Iberian coast (Galician Rías and shelf) is frequently affected by toxic harmful algal blooms (HABs) (mainly Dinophysis spp.), leading to lengthy harvesting closures in a region where aquaculture has a strong socioeconomic impact. The project ASIMUTH (http://www.asimuth.eu) aimed to develop forecasting capabilities to warn of impending HABs along the European Atlantic coast. Simulations with the ROMS model (hydrodynamical and ecological simulations complemented with Lagrangian particle tracking simulations) of the Galician coastal circulation have been performed in the framework of the ASIMUTH project to characterize and forecast oceanographic conditions before and during HAB periods. In this work, we present the Galician ASIMUTH forecast system and demonstrate its skill in predicting HAB transport and its usefulness to provide assessment for the management of the areas affected by toxic outbreaks. Experience gained during DSP events in 2005 and 2013 is shown. We also describe the Galician pilot HAB bulletins, aimed at distributing forecasts of HAB events that might induce closures of harvesting areas or, when the areas are already closed, at giving information on forthcoming oceanographic conditions that could favour or hamper the opening of an area. Our results show that the model forecasts and the bulletins can provide early warning of the risk of Dinophysis spp. events and the risk of closures linked to the presence of DSP toxins above regulatory levels in harvesting areas.
State‐of‐the‐art chiroptical spectroscopies are valuable tools for structural elucidation. However, the potential of these spectroscopies for everyday applications has not been exploited to date ...partially due to the lack of sufficiently stable and efficient chiroptical systems. To this end, the development of suitable chiroptical structures is essential. Herein, we present the synthesis of spiro‐compounds (P2)‐1 and (P4)‐2 as well as (M2)‐1 and (M4)‐2 exhibiting remarkable chiroptical responses. Theoretical simulations show that (P2)‐1, constituted by two (P)‐configured spiranic chiral axes, presents an all‐carbon double helix structure with (M)‐helicity. On the other hand, molecular dynamic simulations reveal (P4)‐2 to have a single path for geometry‐modification along its flat conformational space, certifying it as a chiral flexible shape‐persistent macrocycle. Geometric quantification of chirality has been used to compare the spiranic derivatives presented herein.
Revealing chirality′s secrets: Diethynylspiranes have been employed for the construction of all‐carbon double helices as well as chiral flexible shape‐persistent macrocycles. The uncovering of these very diverse chiral scaffolds opens new opportunities for chiroptical applications (see scheme).
Harmful algal blooms of toxin-producing microalgae are recurrent in southern Chile. Paralytic shellfish poisoning (PSP) outbreaks pose the main threat to public health and the fishing industry in the ...Patagonian fjords. This study aims to increase understanding of the individual and spatial variability of PSP toxicity in the foot of Concholepas concholepas, Chile’s most valuable commercial benthic invertebrate species, extracted from the Guaitecas Archipelago in Chilean Patagonia. The objective is to determine the effect of pigment removal and freezing during the detoxification process. A total of 150 specimens (≥90 mm length) were collected from this area. The live specimens were transferred to a processing plant, where they were measured and gutted, the foot was divided into two equal parts, and pigment was manually removed from one of these parts. The PSP toxicity of each foot (edible tissue) was determined by mouse bioassay (MBA) and high-performance liquid chromatography with fluorescence detection and postcolumn oxidation (HPLC-FLD PCOX). The individual toxicity per loco, as the species is known locally, varied from <30 to 146 μg STX diHCL eq 100 g−1 (CV = 43.83%) and from 5.96 to 216.3 μg STX diHCL eq 100 g−1 (CV = 34.63%), using MBA and HPLC, respectively. A generalized linear model showed a negative relation between individual weight and toxicity. The toxicological profile showed a dominance of STX (>95%), neoSTX and GTX2. The removal of pigment produced a reduction in PSP toxicity of up to 90% and could represent a good detoxification tool moving forward. The freezing process in the muscle with pigment did not produce a clear pattern. There is a significant reduction (p < 0.05) of PSP toxicity via PCOX but not MBA. Furthermore, the study discusses possible management and commercialization implications of the findings regarding small-scale fisheries.
Novel studies are helping to consider minimally invasive surgery for treating patients with renal cell carcinoma and venous tumor thrombus. Evidence regarding its feasibility and safety is still ...sparse and does not include a subclassification for level III thrombi. We aim to compare the safety of laparoscopic
open surgery in patients with levels I-IIIa thrombus.
This is a cross-sectional comparative study using single-institutional data on adult patients treated surgically between June 2008 and June 2022. Participants were categorized into open and laparoscopic surgery groups. Primary outcome was difference in the incidence of 30-day major postoperative complications (Clavien-Dindo III-V) between groups. Secondary outcomes were differences in operative time, length of hospital stay, intraoperative blood transfusions, delta hemoglobin level, 30-day minor complications (Clavien-Dindo I-II), estimated overall survival, and progression-free survival between groups. A logistic regression model was performed including adjustment for confounding variables.
Overall, 15 patients in the laparoscopic group and 25 patients in the open group were included. Major complications occurred in 24.0% of patients within the open group and 6.7% of patients were treated laparoscopically (
= 0.120). Minor complications arose in 32.0% of patients treated with open surgery and in 13.3% of patients treated in the laparoscopic group (
= 0.162). Although not significant, there was a higher perioperative death rate within open surgery cases. The laparoscopic approach presented a crude odds ratio for major complications of 0.22 (95% confidence interval 0.02-2.1,
= 0.191) compared with open surgery. No differences were found between groups regarding oncologic outcomes.
Laparoscopic approach for patients with venous thrombus levels I-IIIa seems to be as safe as open surgery.
Renal cell carcinoma (RCC) is the major cause of death among patients with von Hippel-Lindau (VHL) disease. Resistance to therapies targeting tumor angiogenesis opens the question about the ...underlying mechanisms. Previously we have described that RWDD3 or RSUME (RWD domain-containing protein SUMO Enhancer) sumoylates and binds VHL protein and negatively regulates HIF degradation, leading to xenograft RCC tumor growth in mice. In this study, we performed a bioinformatics analysis in a ccRCC dataset showing an association of RSUME levels with VHL mutations and tumor progression, and we demonstrate the molecular mechanism by which RSUME regulates the pathologic angiogenic phenotype of VHL missense mutations. We report that VHL mutants fail to downregulate RSUME protein levels accounting for the increased RSUME expression found in RCC tumors. Furthermore, we prove that targeting RSUME in RCC cell line clones carrying missense VHL mutants results in decreased early tumor angiogenesis. The mechanism we describe is that RSUME sumoylates VHL mutants and beyond its sumoylation capacity, interacts with Type 2 VHL mutants, reduces HIF-2α-VHL mutants binding, and negatively regulates the assembly of the Type 2 VHL, Elongins and Cullins (ECV) complex. Altogether these results show RSUME involvement in VHL mutants deregulation that leads to the angiogenic phenotype of RCC tumors.
Here we report on the identification and applications of an aqueous 29-atom silver cluster stabilized with 12 lipoate ligands, i.e. Ag29(R-α–LA)12 or (29,12), wherein R-α–LA = R-α-lipoic acid, a ...natural dithiolate. Its uniformity is checked by HPLC-ESI-MS and analytical ultracentrifugation, which confirms its small dimension (∼3 nm hydrodynamic diameter). For the first time, this cluster has been detected intact via electrospray ionization mass spectrometry, allowing one to confirm its composition, its 3- charge-state, and the 8-electron shell configuration of its metallic silver core. Its electronic structure and bonding, including T-symmetry and profound chirality in the outer shell, have been analyzed by DFT quantum-chemical calculations, starting from the known structure of a nonaqueous homologue. The cluster is effective against Methicillin-Resistant Staphylococcus aureus bacteria (MRSA) at a minimum inhibitory concentration (MIC) of 0.6 mg-Ag/mL. A preformed Candida albicans fungal biofilm, impermeable to other antifungal agents, was also inhibited by aqueous solutions of this cluster, in a dose–response manner, with a half-maximal inhibitory concentration (IC50) of 0.94 mg-Ag/mL. Scanning electron micrographs showed the post-treatment ultrastructural changes on both MRSA and C. albicans that are characteristic of those displayed after treatment by larger silver nanoparticles.
In the search for solution-processable TADF materials as a light emitting layer for OLED devices, polymers have attracted considerable attention due to their better thermal and morphological ...properties in the film state with respect to small molecules. In this work, a new polymer (
-TPS-DMAC-TRZ) with thermally activated delayed fluorescence (TADF) light-emitting characteristics was prepared from a conjugation-break unit (TPS) and a well-known TADF core (DAMC-TRZ). This material was designed to preserve the photophysical properties of DAMC-TRZ, while improving other properties, such as thermal stability, promoted by its polymerization with a TPS core. Along with excellent solubility in common organic solvents such as toluene, chloroform and THF, the polymer (M
= 9500; M
= 15200) showed high thermal stability (TDT
= 481 °C), and a T
value of 265 °C, parameters higher than the reference small molecule DMAC-TRZ (TDT
= 305 °C; T
= 91 °C). The photoluminescence maximum of the polymer was centered at 508 nm in the solid state, showing a low redshift compared to DMAC-TRZ (500 nm), while also showing a redshift in solution with solvents of increasing polarity. Time-resolved photoluminescence of
-TPS-DMAC-TRZ at 298 K, showed considerable delayed emission in solid state, with two relatively long lifetimes, 0.290 s (0.14) and 2.06 s (0.50), and a short lifetime of 23.6 ns, while at 77 K, the delayed emission was considerably quenched, and two lifetimes in total were observed, 24.6 ns (0.80) and 180 ns (0.20), which was expected from the slower RISC process at lower temperatures, decreasing the efficiency of the delayed emission and demonstrating that
-TPS-DMAC-TRZ has a TADF emission. This is in agreement with room temperature TRPL measurements in solution, where a decrease in both lifetime and delayed contribution to total photoluminescence was observed when oxygen was present. The PLQY of the mCP blend films with 1%
-TPS-DMAC-DMAC-TRZ as a dopant was determined to be equal to 0.62, while in the pure film, it was equal to 0.29, which is lower than that observed for DMAC-TRZ (0.81). Cyclic voltammetry experiments showed similarities between
-TPS-DMAC-TRZ and DAMC-TRZ with HOMO and LUMO energies of -5.14 eV and -2.76 eV, respectively, establishing an electrochemical bandgap value of 2.38 eV. The thin film morphology of
-TPS-DMAC-TRZ and DMAC-TRZ was compared by AFM and FE-SEM, and the results showed that p-TPS-DMAC-TRZ has a smoother surface with fewer defects, such as aggregations. These results show that the design strategy succeeded in improving the thermal and morphological properties in the polymeric material compared to the reference small molecule, while the photophysical properties were mostly maintained, except for the PLQY determined in the pure films. Still, these results show that p-TPS-DMAC-TRZ is a good candidate for use as a light-emitting layer in OLED devices, especially when used as a host-guest mixture in suitable materials such as mCP.
Four new oligo(azine)s were synthesized from dimethyldiphenylsilane and tetraphenylsilane core‐based dialdehydes and hydrazine by high‐temperature polycondesation and proposed as materials for ...optoelectronic applications. The oligo(azine)s were characterized by EA, FT‐IR, and NMR. Although most of samples were poorly soluble, TPS‐containing PAZ‐4 was soluble in aprotic polar solvents. According to SEC and FT‐IR studies, the samples were oligomers with up to five repeating units long. TGA showed highly stable samples with TDT10% over 420°C except for PAZ‐1 that contains a DMS core along with phenyl units, and thus, the lowest carbon content in the series. From DSC analysis, the substitution of phenyl groups in PAZ‐1/3 by biphenyl moieties in PAZ‐2/4 allowed to obtain oligo(azine)s with lower Tg values. PAZ‐4 showed a UV‐A absorption with optical band‐gap values of 2.91 and 2.65 eV from UV–vis (solution) and DRS (films), respectively. PL analysis showed a violet emission. PAZ‐4 showed resistivity of 29.24 Ω cm, similar to wide‐band gap materials. Their contact angle measurements showed a critical surface tension of 42.29 dynes/cm, revealing its hydrophobicity. AFM analysis indicated that the PAZ‐4 films had homogeneous surfaces. Young's modulus close to 4.46 GPa was established by microindentation for the PAZ‐4 thin‐films.
Sea turtles are vulnerable to climate change since their reproductive output is influenced by incubating temperatures, with warmer temperatures causing lower hatching success and increased ...feminization of embryos. Their ability to cope with projected increases in ambient temperatures will depend on their capacity to adapt to shifts in climatic regimes. Here, we assessed the extent to which phenological shifts could mitigate impacts from increases in ambient temperatures (from 1.5 to 3°C in air temperatures and from 1.4 to 2.3°C in sea surface temperatures by 2100 at our sites) on four species of sea turtles, under a “middle of the road” scenario (SSP2‐4.5). Sand temperatures at sea turtle nesting sites are projected to increase from 0.58 to 4.17°C by 2100 and expected shifts in nesting of 26–43 days earlier will not be sufficient to maintain current incubation temperatures at 7 (29%) of our sites, hatching success rates at 10 (42%) of our sites, with current trends in hatchling sex ratio being able to be maintained at half of the sites. We also calculated the phenological shifts that would be required (both backward for an earlier shift in nesting and forward for a later shift) to keep up with present‐day incubation temperatures, hatching success rates, and sex ratios. The required shifts backward in nesting for incubation temperatures ranged from −20 to −191 days, whereas the required shifts forward ranged from +54 to +180 days. However, for half of the sites, no matter the shift the median incubation temperature will always be warmer than the 75th percentile of current ranges. Given that phenological shifts will not be able to ameliorate predicted changes in temperature, hatching success and sex ratio at most sites, turtles may need to use other adaptive responses and/or there is the need to enhance sea turtle resilience to climate warming.
Sea turtles are vulnerable to climate change and their ability to cope with projected increases in temperatures will depend on their capacity to adapt to shifts in climatic regimes. We assessed the extent to which phenological shifts could mitigate impacts from increases in temperatures on four species of sea turtles. Expected shifts in nesting will not be sufficient to maintain current incubation temperatures at 7 (29%) of our sites, hatching success rates at 10 (42%) of our sites, with current trends in hatchling sex ratio being able to be maintained at half of the sites.
Three new silylated-oligo(azomethine)s with TPS and EDOT units in their structure and moderated molecular weights are reported. The materials showed high solubility in DCM, THF, and chloroform, and ...high thermal stability. Electronic experiments evidenced wide-band-gaps materials (2.73–2.83 eV). DFT and TDDFT calculations were performed for pentamers obtaining good agreements with the experiment UV–vis parameters and band-gaps values.
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•New silicon-based oligomaterials with EDOT unit in their structure.•Optical, electronic, and thermal properties.•DFT and TDDFT calculations for pentamers.•Wide-band-gap materials with potential optoelectronic applications.
A series of three new oligo-poly(azomethine)s (o-PAzMs) were successfully synthesized, incorporating tetraphenylsilane (TPS) and 3,4-ethylenedioxythiophene (EDOT) moieties with Mn and Mw between 3.9 and 5.4 kDa and 8.3–11.6 kDa, respectively. The silylated o-PAzMs were highly soluble in low-boiling point solvents such as CHCl3, THF, and CH2Cl2. All three materials are highly thermally stable, with onset temperatures of degradation of at least 250 °C and with TDT10% between 340 and 460 °C. The glass transition temperature values agree with the flexibility of the repetitive units and showed values between 125 and 155 °C. The absorption and emission of the o-PAzMs were observed in the blue-violet UV–vis region (350–550 nm) with moderate Stokes shifts (48–71 nm). The oligomers are π-conjugated wide-band gap materials (2.83–2.73 eV), where the high electronic transitions would be associated with disruption of π-conjugation, which is promoted by the TPS core and (d-p)π orbital interactions. This disruption controls the effect from the EDOT unit rich donor on HOMO (−5.79 eV to −5.71 eV) and LUMO (−2.98 eV to −2.89 eV) energy values. Furthermore, DFT and TDDFT calculations were performed to theoretically characterize the observed UV–Vis transitions and frontier molecular orbitals (MOs) energies.
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