HILIC-LC-MS/MS quantitative method for the cellular analysis of varying structures of gemini surfactants designed as nanomaterial drug carriers

Canada Foundation for Innovation; Natural Sciences and Engineering Research Council of CanadaDiquaternary gemini surfactants have successfully been used to form lipid-based nanoparticles that are able to compact, protect, and deliver genetic materials into cells. However, what happens to the gemini surfactants after they have released their therapeutic cargo is unknown. Such knowledge is critical to assess the quality, safety, and efficacy of gemini surfactant nanoparticles. We have developed a simple and rapid liquid chromatography electrospray ionization-tandem mass spectrometry (LC-ESI–MS/MS) method for the quantitative determination of various structures of gemini surfactants in cells. Hydrophilic interaction liquid chromatography (HILIC) was employed allowing for a short simple isocratic run of only 4 minutes. The lower limit of detection (LLOD) was 3 ng/mL. The method was valid to 18 structures of gemini surfactants belonging to two different structural families. A full method validation was performed for two lead compounds according to USFDA guidelines. The HILIC-MS/MS was compatible with the physicochemical properties of gemini surfactants that bear a permanent positive charge with both hydrophilic and hydrophobic elements within their molecular structure. In addition, an effective liquid-liquid extraction method (98% recovery) was employed surpassing previously used extraction methods. The analysis of nanoparticle-treated cells showed an initial rise in the analyte intracellular concentration followed by a maximum and a somewhat more gradual decrease of the intracellular concentration. The observed intracellular depletion of the gemini surfactants may be attributable to the bio­transformation into metabolites and exocytosis from the host cells. Obtained cellular data showed a pattern that grants additional investigations , evaluating metabolite formation and assessing the subcellular distribution of tested compounds

Gustoća naseljenosti i veličinska struktura ugrožene vrste školjkaša periske, Pinna nobilis (Linnaeus 1758), u plitkom dijelu zaljeva Maliakos, Grčka

A total of 346 live animals of the endangered species fan mussel Pinna nobilis (Linnaeus 1758) were recorded in situ in the shallow water zone (<2m) within two sites of the marine protected area “Natura 2000” of Maliakos Gulf (Central Hellas). Our results showed that the recorded length (from 11.89 to 72.51 cm) of the fan mussels corresponds to ages that cover the majority of the species life time. Population densities were comparable to the higher values recorded previously in the Mediterranean Sea. The spatial distribution of species was clumped. Estimated total mortality was close to estimated natural mortality indicating that fishing activity does not significantly affect the population density and mortality of fan mussel in the study area. Population densities were related to sediment type, the buried length of animals was related to both sediment type and sea grass leaves size.Ukupno 346 živih primjeraka ugrožene vrste školjkaša periske, Pinna nobilis (Linnaeus 1758), zabilježeno je in situ u plitkom moru (<2m) na dvije lokacije unutar morskog zaštićenog područja “Natura 2000” zaljeva Maliakos (središnja Grčka). Naši rezultati su pokazali da zabilježena duljina (od 11,89 do 72,51 cm) periski odgovara starosnoj dobi koja pokriva većinu životnog vijeka vrste. Gustoća naseljenosti bila je usporediva s većim vrijednostima zabilježenim u Sredozemnom moru. Prostorna raspodjela vrste bila je hrpičasta (grupna). Procjena ukupne smrtnosti bila je blizu procijenjene prirodne smrtnosti što ukazuje da ribolovna aktivnost ne utječe bitno na gustoću naseljenosti i smrtnost periske na istraživanom području. Dubina ukopavanja periske ovisila je o tipu sedimenta i visini (veličini) listića morske trave

Analysis of a Series of Chlorogenic Acid Isomers using Differential Ion Mobility and Tandem Mass Spectrometry

Canada Foundation for InnovationChlorogenic acids are among the most abundant phenolics found in the human diet. Of these, the mono-caffeoylquinic acids are the predominant phenolics found in fruits, such as apples and pears, and products derived from them. In this research, a comprehensive study of the electrospray ionization (ESI) tandem mass spectrometric (MS/MS) dissociation behavior of the three most common mono-caffeoylquinic acids, namely 5-O-caffeoylquinic acid (5-CQA), 3-O-caffeoylquinic acid (3-CQA) and 4-O-caffeoylquinic acid (4-CQA), were determined using both positive and negative ionization. All proposed structures of the observed product ions were confirmed with second-generation MS3 experiments. Similarities and differences between the dissociation pathways in the positive and negative ion modes are discussed, confirming the proposed structures and the established MS/MS fingerprints. MS/MS dissociation was primarily driven via the cleavage of the ester bond linking the quinic acid moiety to the caffeic acid moiety within tested molecules. Despite being structural isomers with the same m/z values and dissociation behaviors, the MS/MS data in the negative ion mode was able to differentiate the three isomers based on ion intensity for the major product ions, observed at m/z 191, 178 and 171. This differentiation was consistent among various MS instruments. In addition, ESI coupled with high-field asymmetric waveform ion mobility spectrometry-mass spectrometry (ESI-FAIMS-MS) was employed for the separation of these compounds for the first time. By combining MS/MS data and differential ion mobility, a method for the separation and identification of mono-caffeoylquinic in apple/pear juice samples was developed with a run time of less than one minute. It is envisaged that this methodology could be used to identify pure juices based on their chlorogenic acid profile (i.e., metabolomics), and could also be used to detect juice-to-juice adulteration (e.g., apple juice addition to pear juice)

An individual-based dataset of carbon and nitrogen isotopic data of Callinectes sapidus in invaded Mediterranean waters

[EN] Background The characterisation of functional traits of non-indigenous and invasive species is crucial to assess their impact within invaded habitats. Successful biological invasions are often facilitated by the generalist diet of the invaders which can modify their trophic position and adapt to new ecosystems determining changes in their structure and functioning. Invasive crustaceans are an illustrative example of such mechanisms since their trophic habits can determine important ecological impacts on aquatic food webs. The Atlantic blue crab Callinectes sapidus is currently established and considered invasive in the Mediterranean Sea where it has been recorded for the first time between 1947 and 1949. In the last decade, the blue crab colonised most of the eastern and central Mediterranean Sea and the Black Sea and it is currently widening its distribution towards the western region of the basin. New information Stable isotope analysis is increasingly used to investigate the trophic habits of invasive marine species. Here, we collated individual measures of the blue crab d C and d N values and of its potential invertebrate prey into a geo-referenced dataset. The dataset includes 360 records with 236 isotopic values of the blue crab and 224 isotopic data of potential prey collected from five countries and 12 locations between 2014 and 2019. This dataset allows the estimation of the trophic position of the blue crab within a variety of invaded ecosystems, as well as advanced quantitative comparisons of the main features of its isotopic niche.Di Muri, C.; Rosati, I.; Bardelli, R.; Cilenti, L.; Veli, DL.; Falco, S.; Vizzini, S.... (2022). An individual-based dataset of carbon and nitrogen isotopic data of Callinectes sapidus in invaded Mediterranean waters. Biodiversity Data Journal (Online). 10:1-12. https://doi.org/10.3897/BDJ.10.e775161121

Mapping of Greek Marine Finfish Farms and Their Potential Impact on the Marine Environment

The Greek marine aquaculture has a leading role in the Mediterranean mariculture industry, mainly in the export sector and its prominent contribution to the country&rsquo;s economy. In the present study, the spatial distribution of Greek finfish farming activity and its potential impact zones on the marine environment were estimated and mapped. The Greek coastline was scanned via Google Earth satellite images for the period of June 2016 to May 2017, with 433 fish farm cage arrays being detected. For each cage array, the zones at different distances corresponding to various type of impacts were mapped by means of GIS technologies. Seventy-five spatial clusters of cage arrays (sc) were revealed, including cage arrays with shown connectivity. As per the findings, Greek marine fish farming activity shows a high level of spatial aggregation but with a relative moderate intensity of impacts due to legal constraints, which play a crucial role in controlling the spatial distribution of activity at a local, regional, and national scale. The results reflect an important source of geodata, necessary for the spatial planning of activity, the monitoring of environmental impacts, and the research itself

Variaciones geográficas de la producción piscícola de la formación de marismas de Mesologi-Etolikó (Grecia occidental)

The Messolonghi-Etoliko lagoon is one of the largest lagoon system in the northern Mediterranean coast. This area contains six clearly distinct lagoons with different topographic and hydrological features. The fishery landings of the lagoons are based on the ontogenic and seasonal migrations of the species. The total annual fishery landings of the barrier fish traps are estimated as 195 mt and are mainly composed of 16 species belonging to 8 families. Eel (Anguilla anguilla), the four species of Mugilidae (Liza saliens, L. aurata, L. ramada and Mugil cephalus), the two species of Sparidae (Sparus aurata and Diplodus annularis) and one species of Mullidae (Mullus barbatus) represent more than 92% of the total annual landings. The composition of the fishery landings varies between lagoons. The cluster analysis showed three groups of lagoons. The first group comprised lagoons in which the landings were dominated by eel, the second group was dominated by Mugilidae species and S. aurata, and the third by L. ramada and M. cephalus. The diversity index of the fishery landings is fairly constant in time, except for the Etoliko lagoon, where repeated anoxic crises decreased the diversity index value to almost zero in 1992. All the landing series showed a dominant annual cycle. Two seasonal patterns of the fishery landings were observed and linked to the fish spawning behaviour and/or their reaction to environmental forcings. The first one concerns species caught from summer to early autumn and the second pattern concerns species trapped during their autumn to winter offshore migration.La formación de lagunas de Mesologi-Etolikó es una de las reservas naturales marinas más grandes de la franja septentrional del Mediterráneo. Este conjunto está compuesto por seis distintas marismas, con diferentes características topográficas e hidrográficas cada una de ellas. La producción piscícola de las marismas se basa en los movimientos estacionales de las especies hacia el mar. Del estudio del trampeo se concluye que los movimientos migratorios equivalen a 195 toneladas y se componen principalmente de 16 especies las cuales pertenecen a 8 familias: anguila (Anguilla anguilla), cuatro especies de Mugilidae (Liza saliens, L. aurata, L. ramada, y Mugil cephalus), dos especies de Sparidae (Sparus aurata y Diplodus annularis) y una especie de Mullidae (Mullus barbatus). Estas especies representan más del 92% de los desplazaminentos anuales. Estos varían entre las distintas marismas. El análisis cluster distingue tres tipos de marismas. El primer grupo incluye las marismas cuyos movimientos son principalmente de anguila; el segundo grupo de Mugilidae y de S. aurata, y el tercero con movimientos sobre todo de L. ramada y M. cephalus. Los desplazamientos de estas especies presentan un ciclo anual importante. Así mismo, se han observado dos clases de movimientos estacionales (en verano y a principios de invierno) que se asocian a los movimientos migratorios de estas especies hacia el mar para su reproducción y/o provocadas por consideraciones adversas

From Extermination to Conservation: Historical Records of Shark Presence during the Early and Development Phase of the Greek Fishery

The lack of historical data on shark presence, distribution, and status in the Eastern Mediterranean undermines efforts to manage and protect their populations. An exhaustive review of anecdotal references related to shark presence during the early and development phase of Greek fisheries (1883–1983) was conducted. In the early-20th century (1912), the first sighting of the presence of a dead shark was reported in the Ionian Sea. Later on, the presence of sharks gradually increased up to 1969, with most records being more frequent for the Aegean Sea, whereas the number of sharks being sighted declined leading up to the middle of 1980s. The increase in shark attacks during the mid-20th century led to a calling for culling of sharks in co-operation with the competent authorities promoting the permission to hunt sharks with firearms and offering rewards for killed individuals. A high number of these observations potentially resulted from shark attacks on people, whereas this is not currently evident. This is an indicator of the lower abundance of sharks in modern times and subsequently an alteration in the way that our current modern society is approaching the protection of such vulnerable species

Use of Local Ecological Knowledge on the Natural Recruitment of Bivalve Species of Commercial Exploitation in a Natura Area

The current study provides valuable insight into the ecological risks and decline of the bivalve fishery and biodiversity in the Amvrakikos Gulf over the last 50 years through a triangulation of information from in situ surveys and expert judgment, supplemented with historical archives. In situ sampling showed that bivalve species composition was a typical composition of benthic fauna consisting of the olive green cockle, Cerastoderma glaucum, the grooved carpet shell, Ruditapes decussatus, and the Mediterranean mussel, Mytilus galloprovincialis. Interviews confirmed the dramatic decrease in the abundance of striped venus clam, Chamelea gallina, and noble pen shell Pinna nobilis, both of which might be attributed to human-induced impacts, habitat degradation and climate change. Official data depicted a gradual reduction of bivalve catches since 1980 and massive degradation of the resources after 2000. As a result, the bivalve fishery was abandoned, having a negative impact on the local socio-economic community. The present study fills in a gap in knowledge for preserving species biodiversity that is critical to the health of the coastal environments

Istraživanje dužinsko-masenih odnosa za 10 komercijalnih vrsta riba kao mogućih indeksa trofičkih stanja obalnih laguna

Length-weight (L-W) relationships were estimated and compared for 10 commercially important fish species caught during September-December 2004 from two lagoons in the Ionian Sea based on similar length ranges. The median value of the exponent b of the L-W relationships was 3.091 and ranged from 2.444 to 3.536. The larger specimens of the mid-trophic level species (i.e. Sparus aurata, Diplodus annularis and D. sargus) were heavier at the same length in the less eutrophic lagoon. In contrast, most of the low-trophic level species (i.e. Mugilidae) did not show significant (P>0.05) differences of the L-W parameters between the studied lagoons. The estimated parameters of the L-W relationships for each species between the two lagoons in relation to their trophic state are also discussed. Our findings indicated that the L-W relationships of the mid-trophic level species may be possibly used as an index of the trophic state in lagoons.Dužinsko-maseni (LW) odnosi su procijenjeni i uspoređeni za 10 komercijalno važnih vrsta riba ulovljenih tijekom razdoblja rujan-prosinac 2004. godine iz dvije lagune u Jonskom moru na temelju raspona sličnih dužina. Medijan vrijednosti eksponenta b dužinsko-masenog odnosa je iznosio 3,091, a kretao se od 2,444 do 3,536. Veće jedinke, srednjeg trofičkog nivoa, vrsta Sparus aurata, Diplodus annularis i D. sargus su bile teže za istu duljinu ali u manje eutrofnim lagunama. Nasuprot tome, većina vrsta niskog trofičkog nivoa (tj. Mugilidae) nisu pokazali značajne razlike (P> 0,05) između parametara dužinsko masenog odnosa u istaživanim lagunama. Izračunati parametri dužinsko masenog odnosa za svaku vrstu između dviju laguna u odnosu na njihov trofički status se također raspravlja u ovom radu. Naši rezultati pokazuju da dužinsko maseni odnosi vrsta srednjeg trofičkog nivoa mogu eventualno poslužiti kao indeks trofičkog statusa u lagunama

Performance of the Cultured Mediterranean Mussel Mytilus galloprovincialis (Lamark 1819) after Summer Post-Harvest Reimmersion

Post-harvesting, handling and storage practices, particularly during the summer months, are crucial for mussel farms, as they induce stress, mortalities and affect overall performance and marketability. In the current work, Mediterranean farmed mussels, were stored into plastic net bags of different weights (7.5kg, 10 kg, 12.5 kg and 15 kg) and reimmersed into the farm sea water during summer 2012. The experiment was conducted under warm summer conditions in Mediterranean waters with temperature levels close to the upper tolerance limits of the mussels (28 degrees C). Mortality rates and condition index (CI) were calculated in all mussel bags at four sampling dates over a 46 days period. It is concluded that mussels graded-packed on bags (7.5-15 kg) could be preserved underwater for 25 days of re-immersion without significant mortality and CI losses