RESUMEN

The Argentine shortfin squid Illex argentinus is one of the most important commercial species for the Argentine fisheries. The understanding of its stock structure is therefore necessary to ensure fishery sustainability and, given the relevance of squids in the regional food web, for biodiversity conservation. An overlap between parasitology and fisheries lies in the use of parasites as biological tags to identify the stock composition of exploited resources, however, the efficiency of this methodology has been questioned for stock assessment in cephalopods. In this work, the value of parasite assemblages of I. argentinus to discriminate between the co-occurring summer spawning stock (SSS) and south patagonic stock (SPS) in a mixing area over the Patagonian continental shelf during summer was evaluated for two cohorts. Five shortfin squid samples corresponding to SSS and SPS were examined for metazoan parasites. The squid size affected the parasite assemblage similarities, conversely, no gender effect on the infracommunities was observed. Multivariate analysis evidenced similarity in parasite assemblage composition and structure between both stocks captured in the mixing area on the same date. This similarity was related to the presence of short-lived trophically transmitted parasites, which are associated with their recently consumed food items and, indirectly, to the oceanographic conditions. The same set of host and environmental variables were identified as the most probable causes of the temporal variability observed in parasite assemblages between SPS cohorts and even intra-cohort. Despite the value of parasites as tags for discriminating squid stocks may have little value when cohabiting stocks are analysed, their variability could serve as a valuable indicator of environmental conditions. The use of parasites as biological tags to discriminate stocks needs to be verified at different spatiotemporal scales, including samples from other non-sympatric stocks in the analyses.

RESUMEN

Cranial sutures separate neighboring skull bones and are sites of bone growth. A key question is how osteogenic activity is controlled to promote bone growth while preventing aberrant bone fusions during skull expansion. Using single-cell transcriptomics, lineage tracing, and mutant analysis in zebrafish, we uncover key developmental transitions regulating bone formation at sutures during skull expansion. In particular, we identify a subpopulation of mesenchyme cells in the mid-suture region that upregulate a suite of genes including BMP antagonists (e.g. grem1a) and pro-angiogenic factors. Lineage tracing with grem1a:nlsEOS reveals that this mid-suture subpopulation is largely non-osteogenic. Moreover, combinatorial mutation of BMP antagonists enriched in this mid-suture subpopulation results in increased BMP signaling in the suture, misregulated bone formation, and abnormal suture morphology. These data reveal establishment of a non-osteogenic mesenchyme population in the mid-suture region that restricts bone formation through local BMP antagonism, thus ensuring proper suture morphology.

Asunto(s)

Proteínas Morfogenéticas Óseas , Suturas Craneales , Mesodermo , Osteogénesis , Proteínas de Pez Cebra , Pez Cebra , Animales , Pez Cebra/embriología , Pez Cebra/genética , Suturas Craneales/metabolismo , Suturas Craneales/embriología , Suturas Craneales/crecimiento & desarrollo , Proteínas de Pez Cebra/metabolismo , Proteínas de Pez Cebra/genética , Proteínas Morfogenéticas Óseas/metabolismo , Proteínas Morfogenéticas Óseas/genética , Mesodermo/metabolismo , Mesodermo/embriología , Mesodermo/citología , Regulación del Desarrollo de la Expresión Génica , Transducción de Señal , Cráneo/embriología , Análisis de la Célula Individual , Mutación

RESUMEN

LED spectrophotometry is a robust technique for the indirect characterization of wastewater pollutant load through correlation modeling. To tackle this issue, a dataset with 1300 samples was collected, from both raw and treated wastewater from 45 wastewater treatment plants in Spain and Chile collected over 4 years. The type of regressor, scaling, and dimensionality reduction technique and nature of the data play crucial roles in the performance of the processing pipeline. Eighty-four pipelines were tested through exhaustive experimentation resulting from the combination of 7 regression techniques, 3 scaling methods, and 4 possible dimensional reductions. Those combinations were tested on the prediction of chemical oxygen demand (COD) and total suspended solids (TSS). Each pipeline underwent a tenfold cross-validation on 15 sub-datasets derived from the original dataset, accounting for variations in plants and wastewater types. The results point to the normalization of the data followed by a conversion through the PCA to finally apply a Random Forest Regressor as the combination which stood out These results highlight the importance of modeling strategies in wastewater management using techniques such as LED spectrophotometry.

Asunto(s)

Espectrofotometría , Aguas Residuales , Aguas Residuales/química , España , Eliminación de Residuos Líquidos/métodos , Análisis de la Demanda Biológica de Oxígeno , Chile , Contaminantes Químicos del Agua/análisis

RESUMEN

Hallux amputations have long been performed for the definitive treatment of hallux osteomyelitis resulting from ulcerations. These amputations have been performed at various levels of the hallux. The aim of this study is to assess the long-term outcomes in patients with hallux amputations performed at these various levels and to determine whether there is an ideal anatomic level that would limit post-operative complications and need for revisional surgery. An Institutional Review Board (IRB)-approved retrospective chart review of 148 feet with hallux amputations performed at various levels from July 1, 2013 to July 16, 2020 at an academic medical center was conducted. A 2-year minimum follow up was required for inclusion in the study. Incidence of re-ulceration, need for further amputation, healing of index procedure, and revascularization status were evaluated. Statistical analysis utilizing chi square analysis was performed to calculate p-values where <.05 was statistically significant. In this retrospective study with a minimum of 2-year follow-up, there was a tendency for amputations performed at the level of the head of the proximal phalanx (21%) to have a lower rate of reulceration (24%) followed by amputations performed at the level of the metatarsophalangeal joint and interphalangeal joints (36%). However, neither proved to be statistically significant.

Asunto(s)

Amputación Quirúrgica , Hallux , Humanos , Estudios Retrospectivos , Masculino , Femenino , Persona de Mediana Edad , Hallux/cirugía , Resultado del Tratamiento , Anciano , Osteomielitis/cirugía , Complicaciones Posoperatorias/epidemiología , Estudios de Seguimiento , Reoperación/estadística & datos numéricos , Adulto

RESUMEN

Host phylogeny and ecological convergence are two factors thought to influence the structure of parasite communities. The aims of this study were to determine the diversity of metazoan parasites of 10 sympatric fish species of the family Carangidae from the southeastern Gulf of California, and to analyze their similarity at infracommunity and component community levels, in order to determine if the host species, particularly those congeneric with similar ecological characteristics, exhibit similar assemblages of parasites. In total, 874 fish specimens were examined and 40 parasite species were identified. The component community was composed by 21 parasite species in Caranx caninus, 20 in C. caballus, 11 in C. vinctus, five in Chloroscombrus orqueta, four in Carangoides otrynter, seven in Hemicaranx leucurus, eight in Selene brevoortii, 14 in S. peruviana, and 11 in Trachinotus rhodopus. The metazoan parasite communities of C. vinctus, Ch. orqueta, H. leucurus, and S. brevoortii are reported here for the first time. The parasite communities of the remaining six carangid species have been reported from regions other than the Gulf of California. All fish species differed significantly regarding the diversity of their parasite infracommunities. This possibly is due to different patterns of habitat use among fish species, and because of the differential host specificity among parasite taxa. Nonetheless, when the analysis was restricted to common parasite species, some fish showed similar parasite infracommunities, particularly congeners of the genus Selene as well as C. caballus and C. vinctus. The component communities of species of Selene were highly similar (>65%), but the three species of Caranx were not. This result supports the hypothesis that congeneric fish species with similar ecological filters harbor similar parasite communities. However, the difference observed between C. caninus and C. caballus suggests that these species, despite being evolutionary and ecologically related, have different physiological or immunological characteristics (compatibility filters) that may result in different parasite communities.

Asunto(s)

Enfermedades de los Peces , Animales , Enfermedades de los Peces/parasitología , Enfermedades de los Peces/epidemiología , California/epidemiología , Simpatría , Filogenia , Perciformes/parasitología , Especificidad del Huésped , Interacciones Huésped-Parásitos

RESUMEN

The Argentine shortfin squid, Illex argentinus, inhabits in the southwest Atlantic; it is a semelparous species which grows rapidly along its 1 year lifespan. The identification of its stocks is critical for sustainable fishery exploitation. Parasites have been used as biological indicators in a lower number of studies dealing with squids, therefore a validation of this methodology is necessary. The intra- and inter-cohort variability of parasite assemblages in the summer-spawning stock of I. argentinus was analysed to assess their value as indicators of stock structure. Four squid samples from the continental shelf of central Patagonia, corresponding to 3 consecutive cohorts, were examined for metazoan parasites. Results evidenced heterogeneity in terms of parasite assemblage composition and structure, dominated by short-lived gastrointestinal parasites, with a strong influence of host size, but no effect of squid sex. These changes are related to their recent habitats and diets, which change with ontogeny and migrations, clouding any interpretation of patterns when samples spatially or temporally separated are compared. Many squid species share these characteristics; therefore, it is recommended that the use of parasites as biological tags should be restricted to simultaneous sampling, while size or age must be considered for deriving proper conclusions.

Asunto(s)

Parásitos , Humanos , Animales , Decapodiformes , Ecosistema , Explotaciones Pesqueras

RESUMEN

A family of acylhydrazones have been prepared and characterized with the aim of investigating their potential as information storage systems. Their well-established synthetic methodologies allowed for the preparation of seven chemically stable acylhydrazones in excellent yields that have been photophysically and photochemically characterized. In addition, DFT and TD-DFT calculations have been performed to gain more insights into the structural, energetic and photophysical properties of the E/Z isomers. Our results reveal that E/Z configurational isomerization upon irradiation is highly dependent on the stabilization of the E or Z isomers due to the formation of intramolecular H bonds and the electronic/steric effects intrinsically related to their structures. In addition, Raman spectroscopy is also used to confirm the molecular structural changes after the formation of hydrogen bonds in the isomers.

Asunto(s)

Espectrometría Raman , Modelos Moleculares , Isomerismo , Espectroscopía de Resonancia Magnética , Teoría Funcional de la Densidad

RESUMEN

Organ development involves the sustained production of diverse cell types with spatiotemporal precision. In the vertebrate jaw, neural-crest-derived progenitors produce not only skeletal tissues but also later-forming tendons and salivary glands. Here we identify the pluripotency factor Nr5a2 as essential for cell-fate decisions in the jaw. In zebrafish and mice, we observe transient expression of Nr5a2 in a subset of mandibular postmigratory neural-crest-derived cells. In zebrafish nr5a2 mutants, nr5a2-expressing cells that would normally form tendons generate excess jaw cartilage. In mice, neural-crest-specific Nr5a2 loss results in analogous skeletal and tendon defects in the jaw and middle ear, as well as salivary gland loss. Single-cell profiling shows that Nr5a2, distinct from its roles in pluripotency, promotes jaw-specific chromatin accessibility and gene expression that is essential for tendon and gland fates. Thus, repurposing of Nr5a2 promotes connective tissue fates to generate the full repertoire of derivatives required for jaw and middle ear function.

Asunto(s)

Receptores Citoplasmáticos y Nucleares , Pez Cebra , Ratones , Animales , Pez Cebra/metabolismo , Receptores Citoplasmáticos y Nucleares/metabolismo , Diferenciación Celular/fisiología , Tejido Conectivo/metabolismo , Proteínas de Pez Cebra/genética , Proteínas de Pez Cebra/metabolismo , Cresta Neural/metabolismo , Regulación del Desarrollo de la Expresión Génica

RESUMEN

Adenocephalus pacificus is a tapeworm parasitic of marine mammals and the main agent of human diphylobothriosis caused by consumption of raw or undercooked marine fishes, being considered as a reemerging disease. Despite having a broad distribution in marine mammals in both hemispheres, plerocercoid larvae in fish have only been reported in the Pacific Ocean, in Peruvian waters, from where most human cases are known. In Argentine waters larval stages of Diphyllobothriidae have been recorded in Merluccius hubbsi, a main fish resource mostly exported frozen, headed and gutted (H&G) or as fillets; therefore, the possible presence of A. pacificus in edible products, and the extent of the risk of parasitism for humans becomes of health and commercial relevance. With the aim of detecting and identifying potentially zoonotic diphyllobothriids and quantifying infection levels in viscera and fillets of hakes, 43 entire fish, 471 H&G, and 942 fillets obtained from research cruises in 2019 and 2021 from the southern Argentine Sea (44-53°S; 63-68°W) were examined by transillumination and under stereoscopic microscopy. Plerocercoids were recovered at low prevalence and mean abundance in entire fish (13.95 % and 0.35) and H&G fish (2.76 % and 0.03) but no larval worms were found adhered to musculature or peritoneum, furthermore, no larvae were found in the fillets. Larvae were genetically identified, based on sequences of the large subunit ribosomal RNA nuclear gene (lsrDNA) and the cytochrome c oxidase subunit 1 (cox1) mitochondrial gene, as members of A. pacificus, representing the first report of this species in a fish host outside South American Pacific coasts. No spatial nor bathymetric patterns in parasite burdens were observed across sampling sites, but prevalence increased with fish size. The recorded low parasite burdens, the absence of infective stages in fillets and the fact that most products are commercialized deeply frozen, diminish the risk of parasitism for consumers to a minimum. However, the identification of this zoonotic agent and the assessment of its distribution in fish products are a first indispensable step for the design of efficient and suitable measures, such as freezing or cooking meet, to ensure the prevention of human infections.

Asunto(s)

Diphyllobothrium , Enfermedades de los Peces , Gadiformes , Animales , Humanos , Gadiformes/parasitología , Diphyllobothrium/genética , Peces/parasitología , Larva/genética , Mamíferos , Enfermedades de los Peces/parasitología

RESUMEN

Interest is growing in simple, fast and inexpensive systems to analyze urban wastewater quality in real time. In this research project, a methodology is presented for the characterization of COD, BOD5, TSS, TN, and TP of wastewater samples, without the need to alter the samples or use chemical reagents, from a few wavelengths, belonging to the different color groups that compose the visible spectrum in isolation: (380-700 nm): violet (380-427 nm), blue (427-476 nm), cyan (476-497 nm), green (497-570 nm), yellow (570-581 nm), orange (581-618 nm), and red (618-700 nm). In this study, about 650 raw and treated urban wastewater samples from over 43 WWTPs and a total of 36 estimation models based on genetic algorithms have been calculated. Seven models were calculated for each pollutant parameter; one model for each color group of the visible spectrum, except for TN, which includes an additional model combining the wavelengths of the violet and red region of the spectrum. All the calculated models showed high accuracy, with an R2 between 80 and 85 % for COD, BOD5 and TSS, and 66-74 % for TN and TP. The tests carried out have shown the accuracy of the models of the different color groups to be very close to each other. However, it is noted that the models making use of the wavelengths between 497 and 570 nm (green) were the ones that showed the best performance in all the parameters under study. This research work lays the foundations for the development of cheaper, faster, and simpler wastewater monitoring and characterization equipment.

RESUMEN

Zebrafish (Danio rerio) are aquatic vertebrates with significant homology to their terrestrial counterparts. While zebrafish have a centuries-long track record in developmental and regenerative biology, their utility has grown exponentially with the onset of modern genetics. This is exemplified in studies focused on skeletal development and repair. Herein, the numerous contributions of zebrafish to our understanding of the basic science of cartilage, bone, tendon/ligament, and other skeletal tissues are described, with a particular focus on applications to development and regeneration. We summarize the genetic strengths that have made the zebrafish a powerful model to understand skeletal biology. We also highlight the large body of existing tools and techniques available to understand skeletal development and repair in the zebrafish and introduce emerging methods that will aid in novel discoveries in skeletal biology. Finally, we review the unique contributions of zebrafish to our understanding of regeneration and highlight diverse routes of repair in different contexts of injury. We conclude that zebrafish will continue to fill a niche of increasing breadth and depth in the study of basic cellular mechanisms of skeletal biology.

Asunto(s)

Tendones , Pez Cebra , Animales , Pez Cebra/genética , Huesos , Cartílago

RESUMEN

In this study, a set of 10 positional indolocarbazole (ICz) isomers substituted with dicyanomethylene groups connected via para or meta positions are computationally investigated with the aim of exploring the efficiency of structural isomerism and substitution position in controlling their optical and electronic properties. Unrestricted density functional theory (DFT), a spin-flip time-dependent DFT approach, and the multireference CASSCF/NEVPT2 method have been applied to correlate the diradical character with the energetic trends (i.e., singlet-triplet energy gaps). In addition, the nucleus-independent chemical shift together with ACID plots and Raman intensity calculations were used to strengthen the relationship between the diradical character and (anti)aromaticity. Our study reveals that the substitution pattern and structural isomerism represent a very effective way to tune the diradical properties in ICz-based systems with meta-substituted systems with a V-shaped structure displaying the largest diradical character. Thus, this work contributes to the elucidation of the challenging chemical reactivity and physical properties of diradicaloid systems, guiding experimental chemists to produce new molecules with desirable properties.

RESUMEN

In an urban wastewater treatment plant (WWTP), early knowledge of the pollutant load levels throughout the plant is key to optimize its processes and achieve better purification levels. Molecular spectrophotometry has begun to gain prominence in this wastewater characterization process, as it is a simple, fast, inexpensive and non-invasive technique. In this research work, different mathematical models based on genetic algorithms have been developed for the estimation of chemical oxygen demand (COD) and total suspended solids (TSS) from the spectral response of the samples, measured in the 380-700 nm range by means of a light-emitting diode (LED) spectrophotometer developed by the researchers. A field campaign was carried out in Mapocho-Trebal WWTP (Chile), where 550 samples were obtained in three different parts of the plant: at the inlet (raw wastewater), at the outlet (secondary treated wastewater) and at the outlet of the primary clarifier. A total of 18 estimation models have been calculated by mean of HeuristicLab software, which have presented a high accuracy, with a Pearson's coefficient between 80 and 90% in most cases. In order to achieve the most accurate models possible to characterize each part of the plant, specific models have also been developed, as well as combined models that are valid for all types of wastewater.

Asunto(s)

Aguas Residuales , Purificación del Agua , Análisis de la Demanda Biológica de Oxígeno , Modelos Genéticos , Espectrofotometría , Eliminación de Residuos Líquidos/métodos , Aguas Residuales/análisis , Purificación del Agua/métodos

Asunto(s)

Humanos , Anemia de Células Falciformes/psicología , Familia , Percepción , Adaptación Psicológica , Entrevistas como Asunto , Investigación Cualitativa

RESUMEN

Measuring how the pollution load evolves in real time along sewer networks is key for proper management of water resources and protecting the environment. The technique of molecular spectroscopy for water characterization has increasingly widespread use, as it is a non-invasive technique that leads to the correlation of the physical-chemical conditions of wastewater with spectroscopic surrogates by a series of mathematical estimation models. In the present research work, different symbolic regression models obtained with evolutive genetic algorithms are evaluated for the estimation of chemical oxygen demand (COD); five-day biochemical oxygen demand (BOD5); total suspended solids (TSS); total phosphorus (TP); and total nitrogen (TN), from the spectral response of samples measured between 380 and 700 nm and without the use of chemicals or pre-treatment. Around 650 wastewater samples were used in the campaign, from 43 different wastewater treatment plants (WWTP) in which both, raw/influent and treated/effluent, were examined through 18 models composed of Classical Genetic Algorithm (CGA), the Age-Layered Population Structure (ALPS), and Offspring Selection (OS) by mean of HeuristicLab software, to make a comparison among them and to determine which models and wavelengths are most suitable for the correlation. Models are proposed considering both raw and treated samples together (15) and only with tertiary treated wastewater reclaimed for agriculture irrigation effluent (3). The Pearson correlation coefficients were in the range of 67-91% for the test data in the case of the combined models. The results conform the first steps for a real-time monitoring of WWTP.

Asunto(s)

Purificación del Agua , Algoritmos , Análisis de la Demanda Biológica de Oxígeno , Análisis Costo-Beneficio , Nitrógeno , Análisis Espectral , Eliminación de Residuos Líquidos/métodos , Aguas Residuales/análisis , Purificación del Agua/métodos

RESUMEN

A major feature of Saethre-Chotzen syndrome is coronal craniosynostosis, the fusion of the frontal and parietal bones at the coronal suture. It is caused by heterozygous loss-of-function mutations in either of the bHLH transcription factors TWIST1 and TCF12. Although compound heterozygous Tcf12; Twist1 mice display severe coronal synostosis, the individual role of Tcf12 had remained unexplored. Here, we show that Tcf12 controls several key processes in calvarial development, including the rate of frontal and parietal bone growth, and the boundary between sutural and osteogenic cells. Genetic analysis supports an embryonic requirement for Tcf12 in suture formation, as combined deletion of Tcf12 in embryonic neural crest and mesoderm, but not in postnatal suture mesenchyme, disrupts the coronal suture. We also detected asymmetric distribution of mesenchymal cells on opposing sides of the wild-type frontal and parietal bones, which prefigures later bone overlap at the sutures. In Tcf12 mutants, reduced asymmetry is associated with bones meeting end-on-end, possibly contributing to synostosis. Our results support embryonic requirements of Tcf12 in proper formation of the overlapping coronal suture.

Asunto(s)

Factores de Transcripción con Motivo Hélice-Asa-Hélice Básico/metabolismo , Craneosinostosis/metabolismo , Osteogénesis , Cráneo/embriología , Animales , Factores de Transcripción con Motivo Hélice-Asa-Hélice Básico/genética , Craneosinostosis/embriología , Craneosinostosis/genética , Células Madre Mesenquimatosas/metabolismo , Mesodermo/metabolismo , Ratones , Ratones Endogámicos C57BL , Cresta Neural/metabolismo , Cráneo/metabolismo

RESUMEN

Sutures separate the flat bones of the skull and enable coordinated growth of the brain and overlying cranium. The coronal suture is most commonly fused in monogenic craniosynostosis, yet the unique aspects of its development remain incompletely understood. To uncover the cellular diversity within the murine embryonic coronal suture, we generated single-cell transcriptomes and performed extensive expression validation. We find distinct pre-osteoblast signatures between the bone fronts and periosteum, a ligament-like population above the suture that persists into adulthood, and a chondrogenic-like population in the dura mater underlying the suture. Lineage tracing reveals an embryonic Six2+ osteoprogenitor population that contributes to the postnatal suture mesenchyme, with these progenitors being preferentially affected in a Twist1+/-; Tcf12+/- mouse model of Saethre-Chotzen Syndrome. This single-cell atlas provides a resource for understanding the development of the coronal suture and the mechanisms for its loss in craniosynostosis.

Asunto(s)

Suturas Craneales/metabolismo , Regulación del Desarrollo de la Expresión Génica , Osteogénesis/genética , Análisis de la Célula Individual/métodos , Transcriptoma/genética , Acrocefalosindactilia/embriología , Acrocefalosindactilia/genética , Acrocefalosindactilia/patología , Animales , Factores de Transcripción con Motivo Hélice-Asa-Hélice Básico/genética , Factores de Transcripción con Motivo Hélice-Asa-Hélice Básico/metabolismo , Suturas Craneales/citología , Suturas Craneales/embriología , Duramadre/citología , Duramadre/embriología , Duramadre/metabolismo , Mesodermo/citología , Mesodermo/embriología , Mesodermo/metabolismo , Ratones Noqueados , Ratones Transgénicos , Osteoblastos/citología , Osteoblastos/metabolismo , RNA-Seq/métodos , Cráneo/citología , Cráneo/embriología , Cráneo/metabolismo , Proteína 1 Relacionada con Twist/genética , Proteína 1 Relacionada con Twist/metabolismo

RESUMEN

Proper function of the vertebrate skeleton requires the development of distinct articulating embryonic cartilages. Irx transcription factors are arranged in co-regulated clusters that are expressed in the developing skeletons of the face and appendages. IrxB cluster genes are required for the separation of toes in mice and formation of the hyoid joint in zebrafish, yet whether Irx genes have broader roles in skeletal development remains unclear. Here, we perform a comprehensive loss-of-function analysis of all 11 Irx genes in zebrafish. We uncover conserved requirements for IrxB genes in formation of the fish and mouse scapula. In the face, we find a requirement for IrxAb genes and irx7 in formation of anterior neural crest precursors of the jaw, and for IrxBa genes in formation of endodermal pouches and gill cartilages. We also observe extensive joint loss and cartilage fusions in animals with combinatorial losses of Irx clusters, with in vivo imaging revealing that at least some of these fusions arise through inappropriate chondrogenesis. Our analysis reveals diverse roles for Irx genes in the formation and later segmentation of the facial skeleton.

Asunto(s)

Cartílago/embriología , Condrogénesis/genética , Proteínas de Homeodominio/metabolismo , Familia de Multigenes , Proteínas Mutantes/metabolismo , Cráneo/embriología , Factores de Transcripción/metabolismo , Proteínas de Pez Cebra/metabolismo , Pez Cebra/embriología , Pez Cebra/genética , Alelos , Animales , Animales Modificados Genéticamente , Tipificación del Cuerpo/genética , Expresión Génica , Regulación del Desarrollo de la Expresión Génica , Proteínas de Homeodominio/genética , Mutación , Cresta Neural/metabolismo , Factores de Transcripción/genética , Proteínas de Pez Cebra/genética

RESUMEN

This work describes the synthesis and properties of a dicyanomethylene-substituted indolo[3,2-b]carbazole diradical ICz-CN. This quinoidal system dimerises almost completely to (ICz-CN)2 , which contains two long C(sp3 )-C(sp3 ) σ-bonds between the dicyanomethylene units. The minor open-shell ICz-CN component in the solid-state mixture was identified by EPR spectroscopy. Cyclic voltammetry and UV-visible spectroelectrochemical data, as well as comparison with reference monomer ICz-Br reveal that the nature of the one-electron oxidation of (ICz-CN)2 at ambient temperature and ICz-CN at elevated temperature is very similar in all these compounds due to the prevailing localization of their HOMO on the ICz backbone. The peculiar cathodic behaviour reflects the co-existence of (ICz-CN)2 and ICz-CN. The involvement of the dicyanomethylene groups stabilizes the close-lying LUMO and LUMO+1 of (ICz-CN)2 and especially ICz-CN compared to ICz-Br, resulting in a distinctive cathodic response at low overpotentials. Differently from neutral ICz-CN, its radical anion and dianion are remarkably stable under ambient conditions. The UV/Vis(-NIR) electronic transitions in parent (ICz-CN)2 and ICz-CN and their different redox forms have been assigned convincingly with the aid of TD-DFT calculations. The σ-bond in neutral (ICz-CN)2 is cleaved in solution and in the solid-state upon soft external stimuli (temperature, pressure), showing a strong chromism from light yellow to blue-green. Notably, in the solid state, the monomeric diradical species is predominantly formed under high hydrostatic pressure (>1 GPa).

RESUMEN

Local administrations are increasingly demanding real-time continuous monitoring of pollution in the sanitation system to improve and optimize its operation, to comply with EU environmental policies and to reach European Green Deal targets. The present work shows a full-scale Wastewater Treatment Plant field-sampling campaign to estimate COD, BOD5, TSS, P, TN and NO3-N in both influent and effluent, in the absence of pre-treatment or chemicals addition to the samples, resulting in a reduction of the duration and cost of analysis. Different regression models were developed to estimate the pollution load of sewage systems from the spectral response of wastewater samples measured at 380-700 nm through multivariate linear regressions and machine learning genetic algorithms. The tests carried out concluded that the models calculated by means of genetic algorithms can estimate the levels of five of the pollutants under study (COD, BOD5, TSS, TN and NO3-N), including both raw and treated wastewater, with an error rate below 4%. In the case of the multilinear regression models, these are limited to raw water and the estimate is limited to COD and TSS, with less than a 0.5% error rate.