Estimating blue mussel (Mytilus edulis) connectivity and settlement capacity in mid-latitude fjord regions.

The mussel industry faces challenges such as low and inconsistent levels of larvae settlement and poor-quality spat, leading to variable production. However, mussel farming remains a vital sustainable and environmentally responsible method for producing protein, fostering ecological responsibility in the aquaculture sector. We investigate the population connectivity and larval dispersion of blue mussels (Mytilus edulis) in Scottish waters, as a case study, using a multidisciplinary approach that combined genetic data and particle modelling. This research allows us to develop a thorough understanding of blue mussel population dynamics in mid-latitude fjord regions, to infer gene-flow patterns, and to estimate population divergence. Our findings reveal a primary south-to-north particle transport direction and the presence of five genetic clusters. We discover a significant and continuous genetic material exchange among populations within the study area, with our biophysical model's outcomes aligning with our genetic observations. Additionally, our model reveals a robust connection between the southwest coast and the rest of the west coast. This study will guide the preservation of mussel farming regions, ensuring sustainable populations that contribute to marine ecosystem health and resilience.

Sexual dimorphism in the gonad lipidome of blue mussels (Mytilus sp.): New insights from a global lipidomics approach.

Blue mussels (Mytilus sp.) are an economically important species for European aquaculture. Their importance as a food source is expected to increase in the coming net-zero society due to their low environmental footprint; however, their production is affected by anthropogenic stressors and climate change. During reproduction, lipids are key molecules for mussels as they are the main source of energy on which newly hatched embryos depend in the first days of their development. In this work, blue mussels of different origins are analysed, focusing on the differences in lipid composition between the ovary (BMO) and the testis (BMT). The lipidome of blue mussel gonads (BMG) is studied here by combining traditional lipid profiling methods, such as fatty acid and lipid class analysis, with untargeted liquid chromatography-mass spectrometry (LC-MS) lipidomics. The approach used here enabled the identification of 770 lipid molecules from 23 different lipid classes in BMG. BMT, which consists of billions of spermatocytes, had greater amounts of cell membrane and membrane lipid components such as FA18:0, C20 polyunsaturated fatty acids (PUFA), free sterols (ST), ceramide phosphoethanolamines (CerPE), ceramide aminoethylphosphonates (CAEP), cardiolipins (CL), glycerophosphocholines (PC), glycerophosphoethanolamines (PE) and glycerophosphoserines (PS). In BMO, saturated fatty acids (FA14:0 and FA16:0), monounsaturated fatty acids (MUFA) and other storage components such as C18-PUFA accumulated in triradylglycerolipids (TG) and alkyldiacylglycerols (neutral plasmalogens, TG O-), which, together with terpenes, wax esters and cholesterol esters, make up most of oocytes yolk reserves. BMO also had higher levels of ceramides (Cer) and generally alkyl/alkenyl glycerophospholipids (mainly plasmanyl/plasmenyl PC), suggesting a role for these lipids in vitellogenesis. Non-methylene interrupted dienoic fatty acids (NMID FA), typically found in plasmalogens, were the only membrane-forming PUFA predominantly detected in BMO. The results of this study are of great importance for clarifying the lipid composition of BMG and provide an important basis for future studies on the reproductive physiology of these organisms.

Radiologic Imaging of the In Vivo Position of the New Supraglottic Airway Device Spritztube® in an Adult Patient-A Case Report.

Spritztube® is a new supraglottic airway device that allows either extraglottic ventilation or orotracheal intubation with the same device. The aim of the present report is to provide the first radiologic images of the Spritztube in situ in a living human and to assess the depth of insertion and its anatomical relationships in vivo. We present the case of a 55-year-old man who was admitted to our centre to perform an interventional neuroradiological procedure. We obtained and analysed radiologic images of the head and neck of an adult patient to ascertain the position of the cuffs of the Spritztube relative to different anatomic structures. The insertion and depth of the device, correct tip positioning, effects of the distal and proximal cuffs on adjacent soft tissues, and the position of the pharyngeal cuff from the cranial to the hyoid bone were evaluated. Our report shows that Spritztube could be helpful in maintaining an adequate airway during radiologic procedures.

Spawning induction and larval rearing in the thinlip gray mullet (Chelon ramada): The use of the slow release gonadotropin releasing hormone analog (GnRHa) preparation, leuprorelin acetate.

The thinlip gray mullet (Chelon ramada) belongs to the Mugilidae family, it is a low-trophic, euryhaline species adapted to a wide range of environmental conditions. As such, it represent a candidate to diversify aquaculture production toward more sustainable species. Nonetheless, several bottlenecks have to be overcome before production is undertaken at commercial scale. Indeed, C. ramada mature females do not spawn without hormonal treatments in captivity. This report describes the use of the gonadotropin releasing hormone analog (GnRHa), leuprorelin acetate as an effective single-dose inducer of spawning in this species. Wild mature females (n = 10; 29 ± 1 cm total length, TL and 199 ± 20 g body weight, BW) exhibiting protruded papilla and bulging abdomen, presenting vitellogenic oocytes (diameters higher than 657 µm) and fluent males (n = 21; 28 ± 1 cm TL and 181 ± 80 g BW) were treated with a single injection of leuprorelin acetate. Breeders spawned more than 500,000 eggs with a mean fertilization and hatching rate of 92 ± 3 and 91.4 ± 0.4 %, respectively. Larvae grew according to the equation y = 2.6841e0.044x, mean survival rate at 19 dph was 13.8 ± 1.5 %. Mean SGR% day-1 slightly decreased concomitantly with tail flexion, probably for a greater investment on ontogenic development rather than growth. Present results suggest that mature C. ramada presents easily recognizable reproductive traits, adapts without difficulty to captive conditions, and can be easily induced to spawn administrating a single dose of leuprorelin acetate. The protocol used in our study resulted in high fertilization and hatching rates, as well as promising larval survival minimizing broodstock stress.

Evidence of multiple genome duplication events in Mytilus evolution.

BACKGROUND: Molluscs remain one significantly under-represented taxa amongst available genomic resources, despite being the second-largest animal phylum and the recent advances in genomes sequencing technologies and genome assembly techniques. With the present work, we want to contribute to the growing efforts by filling this gap, presenting a new high-quality reference genome for Mytilus edulis and investigating the evolutionary history within the Mytilidae family, in relation to other species in the class Bivalvia. RESULTS: Here we present, for the first time, the discovery of multiple whole genome duplication events in the Mytilidae family and, more generally, in the class Bivalvia. In addition, the calculation of evolution rates for three species of the Mytilinae subfamily sheds new light onto the taxa evolution and highlights key orthologs of interest for the study of Mytilus species divergences. CONCLUSIONS: The reference genome presented here will enable the correct identification of molecular markers for evolutionary, population genetics, and conservation studies. Mytilidae have the capability to become a model shellfish for climate change adaptation using genome-enabled systems biology and multi-disciplinary studies of interactions between abiotic stressors, pathogen attacks, and aquaculture practises.

The Spritztube: A New Device for the Extraglottic Intubation of Rabbits.

The Spritztube (ST) is an extraglottic airway device developed for humans. The aim of the study was to design an ST for rabbits and to evaluate its feasibility. The study was divided into two phases. Phase I: anatomical study on 12 rabbit cadavers to design 2 STs (8 and 10 Ch, external diameter) for rabbits. Phase II: fourteen privately owned rabbits were anaesthetised, and intubation was attempted using a ST. Tube size, the method for confirming the correct positioning, the number of attempts, the time needed for the correct positioning of the ST and complications were recorded. The ST placement was feasible in all rabbits. The positioning of the ST was completed in 2.1 ± 1 attempts in 43 ± 21.4 s. A correct placement was confirmed by the visualisation of the proximal cuff at visual inspection of the oral cavity (14/14), by the detection of the airflow (9/14 rabbits) and by the visualisation of a capnographic wave (14/14 rabbits). Only one rabbit developed respiratory distress after the ST placement. The results of the present study allowed designing a ST specific for rabbits which was used a supraglottic airway device for the maintenance of isoflurane anaesthesia in spontaneously breathing rabbits.

Farmed Mussels: A Nutritive Protein Source, Rich in Omega-3 Fatty Acids, with a Low Environmental Footprint.

The world's ever-growing population presents a major challenge in providing sustainable food options and in reducing pressures on the Earth's agricultural land and freshwater resources. Current estimates suggest that agriculture contributes ~30% of global greenhouse gas (GHG) emissions. Additionally, there is an increased demand for animal protein, the production of which is particularly polluting. Therefore, the climate-disrupting potential of feeding the planet is likely to substantially worsen in the future. Due to the nutritional value of animal-based protein, it is not a simple solution to recommend a wholesale reduction in production/consumption of animal proteins. Rather, employing strategies which result in the production of low carbon animal protein may be part of the solution to reduce the GHGs associated with our diets without compromising diet quality. We suggest that farmed mussels may present a partial solution to this dilemma. Mussel production has a relatively low GHG production and does not put undue pressure on land or fresh water supplies. By drawing comparisons to other protein sources using the Australian Food and Nutrient Database and other published data, we demonstrate that they are a sustainable source of high-quality protein, long-chain omega-3 fatty acids, phytosterols, and other key micronutrients such as B-12 and iron. The aim of this review is to summarise the current knowledge on the health benefits and potential risks of increasing the consumption of farmed mussels.

Phylogenetic analysis of the caspase family in bivalves: implications for programmed cell death, immune response and development.

BACKGROUND: Apoptosis is an important process for an organism's innate immune system to respond to pathogens, while also allowing for cell differentiation and other essential life functions. Caspases are one of the key protease enzymes involved in the apoptotic process, however there is currently a very limited understanding of bivalve caspase diversity and function. RESULTS: In this work, we investigated the presence of caspase homologues using a combination of bioinformatics and phylogenetic analyses. We blasted the Crassostrea gigas genome for caspase homologues and identified 35 potential homologues in the addition to the already cloned 23 bivalve caspases. As such, we present information about the phylogenetic relationship of all identified bivalve caspases in relation to their homology to well-established vertebrate and invertebrate caspases. Our results reveal unexpected novelty and complexity in the bivalve caspase family. Notably, we were unable to identify direct homologues to the initiator caspase-9, a key-caspase in the vertebrate apoptotic pathway, inflammatory caspases (caspase-1, - 4 or - 5) or executioner caspases-3, - 6, - 7. We also explored the fact that bivalves appear to possess several unique homologues to the initiator caspase groups - 2 and - 8. Large expansions of caspase-3 like homologues (caspase-3A-C), caspase-3/7 group and caspase-3/7-like homologues were also identified, suggesting unusual roles of caspases with direct implications for our understanding of immune response in relation to common bivalve diseases. Furthermore, we assessed the gene expression of two initiator (Cg2A, Cg8B) and four executioner caspases (Cg3A, Cg3B, Cg3C, Cg3/7) in C. gigas late-larval development and during metamorphosis, indicating that caspase expression varies across the different developmental stages. CONCLUSION: Our analysis provides the first overview of caspases across different bivalve species with essential new insights into caspase diversity, knowledge that can be used for further investigations into immune response to pathogens or regulation of developmental processes.

Flash flood simulation and valve behavior of Mytilus galloprovincialis measured with Hall sensors.

Mussels close their shell as a protective strategy and the quantification of this behavioral marker may represent an alarm signal when they are exposed to environmental stressors. In the present study, we investigated the ability of the Mediterranean mussel Mytilus galloprovincialis to recover and then the resilience or inertia of valve activity after a pulsing exposition to diverse levels of salinity (5, 10, 20, and 35 PSU as reference value). The trial simulated an event of drastic and sudden reduction of seawater salinity thus mimicking an event of flash flood from intense rain. Valve gaping and movements were measured in continuous cycle for 10 days using a customized magneto-electric device which uses Hall sensors. Results showed that under normal conditions of salinity (35 PSU), the general pattern of valve movements was a continuously open state with sporadic spikes indicating a closing motion. At salinity of 5, PSU mussels reacted by closing their valves, leading to a 77% mortality on the 4th day. At salinity of 10, PSU animals were observed with closed valves for the entire duration of the exposure and no mortality occurred, they showed a significant reduction in the valve activity once the reference value of salinity was re-established. In contrast, salinity of 20 PSU did not trigger a significant behavioral response. Interestingly, there no define rhythms of valve movements were recorded during salinity challenges.

Cloning and characterisation of NMDA receptors in the Pacific oyster, Crassostrea gigas (Thunberg, 1793) in relation to metamorphosis and catecholamine synthesis.

Bivalve metamorphosis is a developmental transition from a free-living larva to a benthic juvenile (spat), regulated by a complex interaction of neurotransmitters and neurohormones such as L-DOPA and epinephrine (catecholamine). We recently suggested an N-Methyl-D-aspartate (NMDA) receptor pathway as an additional and previously unknown regulator of bivalve metamorphosis. To explore this theory further, we successfully induced metamorphosis in the Pacific oyster, Crassostrea gigas, by exposing competent larvae to L-DOPA, epinephrine, MK-801 and ifenprodil. Subsequently, we cloned three NMDA receptor subunits CgNR1, CgNR2A and CgNR2B, with sequence analysis suggesting successful assembly of functional NMDA receptor complexes and binding to natural occurring agonists and the channel blocker MK-801. NMDA receptor subunits are expressed in competent larvae, during metamorphosis and in spat, but this expression is neither self-regulated nor regulated by catecholamines. In-situ hybridisation of CgNR1 in competent larvae identified NMDA receptor presence in the apical organ/cerebral ganglia area with a potential sensory function, and in the nervous network of the foot indicating an additional putative muscle regulatory function. Furthermore, phylogenetic analyses identified molluscan-specific gene expansions of key enzymes involved in catecholamine biosynthesis. However, exposure to MK-801 did not alter the expression of selected key enzymes, suggesting that NMDA receptors do not regulate the biosynthesis of catecholamines via gene expression.

Bivalves are NO different: nitric oxide as negative regulator of metamorphosis in the Pacific oyster, Crassostrea gigas.

BACKGROUND: Nitric oxide (NO) is presumed to be a regulator of metamorphosis in many invertebrate species, and although NO pathways have been comparatively well-investigated in gastropods, annelids and crustaceans, there has been very limited research on the effects of NO on metamorphosis in bivalve shellfish. RESULTS: In this paper, we investigate the effects of NO pathway inhibitors and NO donors on metamorphosis induction in larvae of the Pacific oyster, Crassostrea gigas. The nitric oxides synthase (NOS) inhibitors s-methylisothiourea hemisulfate salt (SMIS), aminoguanidine hemisulfate salt (AGH) and 7-nitroindazole (7-NI) induced metamorphosis at 75, 76 and 83% respectively, and operating in a concentration-dependent manner. Additional induction of up to 54% resulted from exposures to 1H-[1,2,4]Oxadiazole[4,3-a]quinoxalin-1-one (ODQ), an inhibitor of soluble guanylyl cyclase, with which NO interacts to catalyse the synthesis of cyclic guanosine monophosphate (cGMP). Conversely, high concentrations of the NO donor sodium nitroprusside dihydrate in combination with metamorphosis inducers epinephrine, MK-801 or SMIS, significantly decreased metamorphosis, although a potential harmful effect of excessive NO unrelated to metamorphosis pathway cannot be excluded. Expression of CgNOS also decreased in larvae after metamorphosis regardless of the inducers used, but intensified again post-metamorphosis in spat. Fluorescent detection of NO in competent larvae with DAF-FM diacetate and localisation of the oyster nitric oxide synthase CgNOS expression by in-situ hybridisation showed that NO occurs primarily in two key larval structures, the velum and foot. cGMP was also detected in the foot using immunofluorescent assays, and is potentially involved in the foot's smooth muscle relaxation. CONCLUSION: Together, these results suggest that the NO pathway acts as a negative regulator of metamorphosis in Pacific oyster larvae, and that NO reduction induces metamorphosis by inhibiting swimming or crawling behaviour, in conjunction with a cascade of additional neuroendocrine downstream responses.

Lipidomics analysis of juveniles' blue mussels (Mytilus edulis L. 1758), a key economic and ecological species.

Blue mussels (Mytilus edulis L. 1758) are important components of coastal ecosystems and in the economy of rural and coastal areas. The understanding of their physiological processes at key life stages is important both within food production systems and in the management of wild populations. Lipids are crucial molecules for bivalve growth, but their diversity and roles have not been fully characterised. In this study, traditional lipid profiling techniques, such as fatty acid (FA) and lipid class analysis, are combined to untargeted lipidomics to elucidate the lipid metabolism in newly settled spat fed on a range of diets. The evaluated diets included single strains treatments (Cylindrotheca fusiformis CCAP 1017/2 -CYL, Isochrysis galbana CCAP 927/1- ISO, Monodopsis subterranean CCAP 848/1 -MONO, Nannochloropsis oceanica CCAP 849/10- NANNO) and a commercial algae paste (SP). Spat growth was influenced by the diets, which, according to their efficacy were ranked as follows: ISO>NANNO/CYL>SP>MONO. A higher triacylglycerols (TG) content, ranging from 4.23±0.82 µg mgashfree Dry weight (DW)-1 at the beginning of the trial (T0) to 51±15.3 µg mgashfreeDW-1 in ISO, characterised significant growth in the spat, whereas, a reduction of TG (0.3±0.08 µg mgashfreeDW-1 in MONO), mono unsaturated FA-MUFA (from 8.52±1.02 µg mgFAashfreeDW-1 at T0 to 2.81±1.02 µg mgFAashfreeDW-1 in MONO) and polyunsaturated FA-PUFA (from 17.57±2.24 µg mgFAashfreeDW-1 at T0 to 6.19±2.49 µg mgFAashfreeDW-1 in MONO) content characterised poor performing groups. Untargeted lipidomics evidenced how the availability of dietary essential PUFA did not influence only neutral lipids but also the membrane lipids, with changes in lipid molecular species in relation to the essential PUFA provided via the diet. Such changes have the potential to affect spat production cycle and their ability to respond to the surrounding environment. This study evidenced the advantages of coupling different lipid analysis techniques, as each technique disclosed relevant information on nutritional requirements of M. edulis juveniles, expanding the existing knowledge on the physiology of this important species.

Laryngeal Mask Airway Supreme vs. the Spritztube tracheal cannula in anaesthetised adult patients: A randomised controlled trial.

BACKGROUND: The Spritztube is a new supraglottic airway device combining the ability to allow extraglottic ventilation of the lungs with the opportunity to perform fibreoptic-assisted intubation. OBJECTIVES: To compare the Spritztube tracheal cannula with the Laryngeal Mask Airway Supreme (LMA-S) in anaesthetised adult patients. DESIGN: A single-centre, randomised controlled study. SETTING: Tertiary hospital. PATIENTS: Mechanically ventilated patients undergoing elective surgery in the supine position under general anaesthesia were included. Main exclusion criteria were a history of, or predicted, difficult airway management according to SIAARTI guidelines and absence of written informed consent. INTERVENTIONS: Patients received the LMA-S or Spritztube tracheal cannula to facilitate ventilation of the lungs. MAIN OUTCOME MEASURES: Successful placement (primary outcome), time required for insertion, number of attempts, subjective assessment of ease of insertion, safety and incidence of complications were recorded. RESULTS: One hundred and sixty seven patients were allocated to the LMA-S or Spritztube group, respectively, a total of 334 patients. In the LMA-S group, the device insertion failed in nine patients, compared with none in the Spritztube group (P = 0.002). Spritztube insertion was easy in 100% of cases compared with 94.6% of the cases in the LMA-S group (P = 0.03). The number of attempts was significantly higher with the LMA-S compared with the Spritztube (P = 0.0007), whereas the insertion times were comparable (P = 0.06). Except for the incidence of blood-staining, which was higher in the LMA-S group (P = 0.01), the number of complications was comparable in the two groups. CONCLUSION: The Spritztube was as effective as the LMA-S in maintaining the airway with all patients being successfully ventilated without difficulty. The success rate of achieving a patent airway was comparable between the groups, with a similar occurrence of complications. TRIAL REGISTRATION: NCT03443219.

Microplastics uptake and egestion dynamics in Pacific oysters, Magallana gigas (Thunberg, 1793), under controlled conditions.

Microplastics debris (<5 mm) are increasingly abundant in the marine environment, therefore, potentially becoming a growing threat for different marine organisms. Through aquatic animals, these can enter in the human food chain, and can be perceived as a risk for consumers' health. Different studies report the presence of particles in marketable shellfish including the world wide commercially grown Pacific oyster Magallana gigas (Thunberg, 1793). The aim of this study is to examine the potential risk of microplastics entering in the human food chain through this shellfish species, investigating the dynamics of the uptake, egestion (faeces) and rejection (pseudofaeces) of microplastics in Pacific oysters under controlled conditions. M. gigas collected from a farm in the San Teodoro lagoon (Italy), were exposed to 60 fluorescent orange polystyrene particles L-1 of known sizes (100, 250 and 500 µm). The uptake of each particle size was 19.4 ±â€¯1.1%, 19.4 ±â€¯2% and 12.9 ±â€¯2% respectively. After exposure M. gigas were left to depurate for 72 h, during which 84.6 ±â€¯2% of the particles taken up were released whilst 15.4 ±â€¯2% were retained inside the shell cavity. No microplastic particles were found in the animals' soft tissues. The results of this study, suggest that depuration is an effective method to reduce presence of large microplastic particles, in the size range 100-500 µm, in M. gigas. Importantly, the data suggests that the burden that could theoretically be up taken by consumers from these shellfish is negligible when compared to other routes.

Mussel Consumption as a "Food First" Approach to Improve Omega-3 Status.

Numerous United Kingdom and European Union expert panels recommend that the general adult population consumes ~250 mg of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) per day through the consumption of one portion of oily fish per week. The long-chain omega-3 fatty acids EPA and DHA are only found in appreciable amounts in marine organisms. Increasing oily fish consumption conflicts with sustaining fisheries, so alternative dietary sources of EPA and DHA must be explored. Mussels are high in omega-3 polyunsaturated fatty acids (PUFAs) and a good source of essential amino acids. Therefore, we aimed to investigate the impact of introducing mussels as a protein source in the lunchtime meal three times per week for two weeks on the omega-3 status of free-living participants. Following an initial two-week monitoring period, 12 participants (eight male and four female) attended the nutrition laboratory three times per week for two weeks. Each participant received a personalised lunch constituting one-third of their typical daily calorie consumption with ~20% of the calories supplied as cooked mussels. A portion of cooked mussels from each feeding occasion was tested for total omega-3 content. The mean ± SD mussel EPA + DHA content was 518.9 ± 155.7 mg/100 g cooked weight, meaning that each participant received on average 709.2 ± 252.6 mg of EPA + DHA per meal or 304.0 ± 108.2 mg of EPA + DHA per day. Blood spot analysis revealed a significant increase in the omega-3 index (week 1 = 4.27 ± 0.81; week 4 = 5.07 ± 1.00) and whole blood EPA content during the study (%EPA week 1 = 0.70 ± 0.0.35; %EPA week 4 = 0.98 ± 0.35). Consuming mussels three times per week for two weeks as the protein source in a personalised lunchtime meal is sufficient to moderately improve the omega-3 index and whole blood DHA + EPA content in young healthy adults.

New diagnostic SNP molecular markers for the Mytilus species complex.

The development of diagnostic markers has been a long-standing interest of population geneticists as it allows clarification of taxonomic uncertainties. Historically, there has been much debate on the taxonomic status of species belonging to the Mytilus species complex (M. edulis, M. galloprovincialis and M. trossulus), and whether they are discrete species. We analysed reference pure specimens of M. edulis, M. galloprovincialis and M. trossulus, using Restriction site associated DNA (RAD) sequencing and identified over 6,000 SNP markers separating the three species unambiguously. We developed a panel of diagnostic SNP markers for the genotyping of Mytilus species complex as well as the identification of hybrids and interspecies introgression events in Mytilus species. We validated a panel of twelve diagnostic SNP markers which can be used for species genotyping. Being able to accurately identify species and hybrids within the Mytilus species complex is important for the selective mussel stock management, the exclusion of invasive species, basic physiology and bio-diversity studies.

Biosynthesis of Polyunsaturated Fatty Acids in Sea Urchins: Molecular and Functional Characterisation of Three Fatty Acyl Desaturases from Paracentrotus lividus (Lamark 1816).

Sea urchins are broadly recognised as a delicacy and their quality as food for humans is highly influenced by their diet. Lipids in general and the long-chain polyunsaturated fatty acids (LC-PUFA) in particular, are essential nutrients that determine not only the nutritional value of sea urchins but also guarantee normal growth and reproduction in captivity. The contribution of endogenous production (biosynthesis) of LC-PUFA in sea urchins remained unknown. Using Paracentrotus lividus as our model species, we aimed to characterise both molecularly and functionally the repertoire of fatty acyl desaturases (Fads), key enzymes in the biosynthesis of LC-PUFA, in sea urchins. Three Fads, namely FadsA, FadsC1 and FadsC2, were characterised. The phylogenetic analyses suggested that the repertoire of Fads within the Echinodermata phylum varies among classes. On one hand, orthologues of the P. lividus FadsA were found in other echinoderm classes including starfishes, brittle stars and sea cucumbers, thus suggesting that this desaturase is virtually present in all echinoderms. Contrarily, the FadsC appears to be sea urchin-specific desaturase. Finally, a further desaturase termed as FadsB exists in starfishes, brittle stars and sea cucumbers, but appears to be missing in sea urchins. The functional characterisation of the P. lividus Fads confirmed that the FadsA was a Δ5 desaturase with activity towards saturated and polyunsaturated fatty acids (FA). Moreover, our experiments confirmed that FadsA plays a role in the biosynthesis of non-methylene interrupted FA, a group of compounds typically found in marine invertebrates. On the other hand, both FadsC desaturases from P. lividus showed Δ8 activity. The present results demonstrate that P. lividus possesses desaturases that account for all the desaturation reactions required to biosynthesis the physiological essential eicosapentaenoic and arachidonic acids through the so-called "Δ8 pathway".

Fatty acid profiles during gametogenesis in sea urchin (Paracentrotus lividus): effects of dietary inputs on gonad, egg and embryo profiles.

The effects of dietary fatty acids on the composition of Paracentrotus lividus gonads were investigated to determine whether dietary inputs affect their relative abundance during gametogenesis. Egg and embryo FA compositions were compared with that of mature gonads to understand how maternal FA is transferred to the offspring. Urchins were fed an experimental Pellet diet in comparison to brown Kelp (Laminaria digitata). FA profiles of diets, gonads, eggs and embryos revealed the presence in gonads of FA that was absent in the diets and/or higher in contents of some long-chain polyunsaturated fatty acid (LC-PUFA). Moreover, some unusual FA, such as non-methylene interrupted (NMI), was found in gonads, eggs and embryos, but not in the diets, suggesting that P. lividus may be capable of synthesizing this FA and accumulating them in the eggs. A description of gonad FA profiles during gametogenesis is reported for the first time and data suggest that eicosapentaenoic and docosahexaenoic acids are accumulated during gametogenesis, while arachidonic acid is highly regulated and is the only LC-PUFA clearly accumulated into the eggs along with NMI. Further studies are required to determine if maternal provisioning of FA has the potential to influence sea urchin production outputs and to increase hatchery profitability.

Rhodium-catalyzed asymmetric hydrogenation of olefins with PhthalaPhos, a new class of chiral supramolecular ligands.

A library of 19 binol-derived chiral monophosphites that contain a phthalic acid diamide group (PhthalaPhos) has been designed and synthesized in four steps. These new ligands were screened in the rhodium-catalyzed enantioselective hydrogenation of prochiral dehydroamino esters and enamides. Several members of the library showed excellent enantioselectivity with methyl 2-acetamido acrylate (6 ligands gave >97% ee), methyl (Z)-2-acetamido cinnamate (6 ligands gave >94% ee), and N-(1-phenylvinyl)acetamide (9 ligands gave >95% ee), whilst only a few representatives afforded high enantioselectivities for challenging and industrially relevant substrates N-(3,4-dihydronaphthalen-1-yl)-acetamide (96% ee in one case) and methyl (E)-2-(acetamidomethyl)-3-phenylacrylate (99% ee in one case). In most cases, the new ligands were more active and more stereoselective than their structurally related monodentate phosphites (which are devoid of functional groups that are capable of hydrogen-bonding interactions). Control experiments and kinetic studies were carried out that allowed us to demonstrate that hydrogen-bonding interactions involving the diamide group of the PhthalaPhos ligands strongly contribute to their outstanding catalytic properties. Computational studies carried out on a rhodium precatalyst and on a conceivable intermediate in the hydrogenation catalytic cycle shed some light on the role played by hydrogen bonding, which is likely to act in a substrate-orientation effect.

Supramolecular ligand-ligand and ligand-substrate interactions for highly selective transition metal catalysis.

The use of non covalent supramolecular ligand-ligand and ligand-substrate interactions in transition metal-catalysed transformations is a new, rapidly emerging area of research. Non-covalent interactions between monodentate ligands such as hydrogen bonding, coordinative bonding, ion pairing, π-π interactions and the formation of inclusion compounds, have been shown to impart higher activity and chemo-, regio-, and stereoselectivity to the corresponding transition metal complexes in a number of catalytic applications. Analogously, supramolecular ligand-substrate interactions, and particularly hydrogen bonding, have been used to direct the regio- and stereochemistry of several metal-catalysed reactions. The catalytic systems relying on supramolecular interactions are generally capable of self-assembling from simpler components in the environment where catalysis is to take place, and are therefore very well-suited for combinatorial catalyst discovery strategies and high-throughput screening.