Exploring micropollutants in polar environments based on non-target analysis using LC-HRMS.

The routine use of chemicals in polar regions contributes to unexpected occurrence of micropollutants, with sewage discharge as a prominent pollution source. The aim of this study was to identify and quantify micropollutants in polar environments near potential point sources using non-target analysis (NTA) with liquid chromatography high-resolution mass spectrometry. Seawater samples were collected from Ny-Ålesund, Svalbard and Marian Cove, King George Island, in 2023. We tentatively identified 32 compounds with NTA, along with 105 homologous series substances. Of these, 18 substances were confirmed, and 13 were quantified using the internal standard method. Most quantified substances in the Ny-Ålesund, including caffeine, naproxen, and polyethylene glycols (PEGs), exhibited concentrations ranged from 0.9 to 770,000 ng/L. In Marian Cove, the analysis predominantly detected acetaminophen, with concentrations ranging from 13 to 35 ng/L. The findings underscore the presence and spatial distribution of emerging micropollutants resulting from wastewater discharge in polar regions.

Manganese reduction and associated microbial communities in Antarctic surface sediments.

The polar regions are the fastest warming places on earth. Accelerated glacial melting causes increased supply of nutrients such as metal oxides (i.e., iron and manganese oxides) into the surrounding environment, such as the marine sediments of Potter Cove, King George Island/Isla 25 de Mayo (West Antarctic Peninsula). Microbial manganese oxide reduction and the associated microbial communities are poorly understood in Antarctic sediments. Here, we investigated this process by geochemical measurements of in situ sediment pore water and by slurry incubation experiments which were accompanied by 16S rRNA sequencing. Members of the genus Desulfuromusa were the main responder to manganese oxide and acetate amendment in the incubations. Other organisms identified in relation to manganese and/or acetate utilization included Desulfuromonas, Sva1033 (family of Desulfuromonadales) and unclassified Arcobacteraceae. Our data show that distinct members of Desulfuromonadales are most active in organotrophic manganese reduction, thus providing strong evidence of their relevance in manganese reduction in permanently cold Antarctic sediments.

Four statistical frameworks for assessing an immune correlate of protection (surrogate endpoint) from a randomized, controlled, vaccine efficacy trial.

A central goal of vaccine research is to characterize and validate immune correlates of protection (CoPs). In addition to helping elucidate immunological mechanisms, a CoP can serve as a valid surrogate endpoint for an infectious disease clinical outcome and thus qualifies as a primary endpoint for vaccine authorization or approval without requiring resource-intensive randomized, controlled phase 3 trials. Yet, it is challenging to persuasively validate a CoP, because a prognostic immune marker can fail as a reliable basis for predicting/inferring the level of vaccine efficacy against a clinical outcome, and because the statistical analysis of phase 3 trials only has limited capacity to disentangle association from cause. Moreover, the multitude of statistical methods garnered for CoP evaluation in phase 3 trials renders the comparison, interpretation, and synthesis of CoP results challenging. Toward promoting broader harmonization and standardization of CoP evaluation, this article summarizes four complementary statistical frameworks for evaluating CoPs in a phase 3 trial, focusing on the frameworks' distinct scientific objectives as measured and communicated by distinct causal vaccine efficacy parameters. Advantages and disadvantages of the frameworks are considered, dependent on phase 3 trial context, and perspectives are offered on how the frameworks can be applied and their results synthesized.

Bridging of Cove Regions: A Strategy for Realizing Persistently Chiral Double Heterohelicenes with Attractive Luminescent Properties.

The racemization of chiral organic compounds is a common chemical phenomenon. However, it often poses configurational-stability issues to the application of this class of compounds. Achieving chiral organic compounds without the risk of racemization is fascinating, but it is challenging due to a lack of strategies. Here, we reveal the cove-regions bridging strategy for achieving persistently chiral multi-helicenes (incapable of racemization), based on the synthesized proof-of-concept double hetero[4]helicenes featuring macrocycle structures with a small 3D cavity. Additionally, we demonstrate that the strategy is also effective in tuning the electronic structures of multi-helicenes, resulting in a conversion from luminescence silence into thermally activated delayed fluorescence (TADF) for the present system. Furthermore, red circularly polarized TADF based on small double [4]helicene systems is achieved for the first time using this strategy. The disclosed cove-regions bridging strategy provides an opportunity to modulate the electronic structures and luminescent properties of multi-helicenes without concern for racemization, thus significantly enhancing the structural and property diversity of multi-helicenes for various applications.

The glacier melting process is an invisible barrier to the development of Antarctic subtidal macroalgal assemblages.

Ecological macroalgal succession in glacier-free areas has remained at the pioneer seral stage despite six decades of glacial retreat at Marian Cove, King George Island, Antarctica. With the rapid melting of glaciers in the West Antarctic Peninsula owing to global warming, a massive amount of meltwater is flowing into the coast, creating marine environmental gradients such as turbidity, water temperature, and salinity. This study examined the spatial and vertical distributions (up to a depth of 25 m) of macroalgal assemblages from nine sites in Maxwell Bay and Marian Cove. The macroalgal assemblages were analyzed for six sites located 0.2, 0.8, 1.2, 2.2, 3.6, and 4.1 km away from the glacier, including three sites where the glacial retreat history of Marian Cove could be estimated. To investigate the effects of meltwater, differences in the coastal environment were analyzed based on data collected from five stations located 0.4, 0.9, 3.0, 4.0, and 5.0 km away from the glacier. The macroalgal assemblages and marine environment were divided into two groups-inside and outside the cove-based on the region 2-3 km away from the glacier, which has been ice-free since 1956 and shows significant differences. In the three sites near the glacier front, Palmaria decipiens was dominant, and three to four species were distributed, whereas in the two sites outside the cove, nine and 14 species appeared, respectively, similar to the assemblage of the other three sites in Maxwell Bay. Palmaria decipiens, a representative opportunistic pioneer species in Antarctica, is dominant because of its physiological adaptation despite the high turbidity and low water temperature of the glacier front. This study shows that macroalgal assemblages in Antarctic fjord-like coves respond to glacial retreat and are valuable in understanding the macroalgal succession in Antarctica.

Seasonal variation of inorganic carbon parameters and air-sea exchange of CO2 in Marian Cove, King George Island, Western Antarctic Peninsula.

Inorganic carbon parameters were observed in Marian Cove, King George Island, Western Antarctic Peninsula, to assess the impact of the Antarctic coastal regions on air-sea CO2 exchange. The variations in total alkalinity (TA) and dissolved inorganic carbon (DIC) were caused by ice melting, formation, and biological activities. The net annual air-sea CO2 flux (5.6 ± 11.8 mmol m-2 d-1) indicated that Marian Cove was a CO2 source in the atmosphere, suggesting the opposite role of the Antarctic coastal regions to the Southern Ocean in CO2 flux estimates. Finally, this study identified the controlling factors of the annual variation of TA and DIC for the first time through direct field observations in King George Island. This study indicated that Antarctic coastal regions can act as a CO2 source to the atmosphere. Thus, further investigations and continuous monitoring are required in the coastal areas to improve our understanding of global carbon cycles.

Hydrogenated cove-edge aluminum nitride nanoribbons for ultrascaled resonant tunneling diode applications: a computational DFT study.

While synthesizing quasi-one-dimensional nanoribbons, there is a finite probability that edges have cove-edge defects. This paper focuses on the structural, electronic, and transport properties of cove-edge aluminum nitride nanoribbons (AlNNR) using density functional theory and the non-equilibrium Green's function (NEGF) method. The cove-edge AlNNRs are thermodynamically stable and exhibit metallic behavior. Interestingly, the calculated current-voltage characteristics of the cove-edge AlNNR-based nanodevices show negative differential resistance (NDR). The H-AlN-Cove nanodevice exhibits high peak-to-valley current ratio (PVCR) of the order of 107. The calculated PVCR of the H-AlN-Cove nanodevice is 106times higher than that of the silicene nanoribbon (SiNR) and graphene nanoribbon (GNR), and 104times higher than that of the phosphorene nanoribbon (PNR) and arsenene nanoribbons (ANR)-based devices respectively. The NDR feature with high PVCR provides a prospect for the cove-edge AlNNR in nanodevice applications.

Odor emission rate of a municipal solid waste sanitary landfill during different operation stages before final closure.

This study investigated the odor emission rate from different areas of a municipal solid waste landfill. The surface odor emission rate (SOER) of eight odorous compound groups were determined by flux chamber method. The SOER of working face, seams of daily cover, membrane surface of daily cover, seams of temporary cover, membrane surface of temporary cover, seams of intermediate cover, membrane surface of intermediate cover were 138.34, 49.83, 13.56, 90.35, 14.48, 4.05, and 8.14 µg/(m2·s), respectively. Therefore, odor emission hotspots were at seams of daily and temporary cover areas. Converting the odor emissions at emission hotspots to the entire membrane cover surface, the average SOER of working face, daily cover area, temporary cover area and intermediate cover area were 138.34, 17.95, 22.43, and 6.24 µg/(m2·s), respectively. Combined with the size of each landfill area, the total odor emissions of the four above areas of a landfill zone were 830, 108, 1346, and 5175 mg/s, respectively, suggesting the necessity to control the odor emission of membrane cover stages especially for large-scale landfills. In terms of odor components, alcohols (38.7 %), sulfur compounds (22.9 %) and aldehydes (15.7 %) were major odorous groups.

Ultraviolet - Chlorine combined treatment efficiency to eliminate Naegleria fowleri in artificial surf lagoons.

Naegleria. fowleri, a protozoa belonging to the free-living amoeba group, is the causative agent of a central nervous system affecting disease that is fatal in more than the 95% of the reported cases. This parasite can be found in warm water bodies such as lakes, rivers or inadequately disinfected swimming pools. On the other hand, chlorination and UV light treatment are two of the most extensively used disinfection methods in recreational water facilities. In this study the effect of chlorination and UV light on N. fowleri trophozoites was studied in a close water circuit with the aim to assess the efficacy of this disinfection methods in large pools. The obtained results showed that the chlorination was able to decrease the number of viable cells despite the elimination was not totally achieved. Nonetheless, the combination of the UV light with the chlorination allowed the complete removal of the N. fowleri trophozoites from the water in experimental testing conditions.

Effect of Intertidal Elevation at Tsuyazaki Cove, Fukuoka, Japan on Survival Rate of Horseshoe Crab Tachypleus tridentatus Eggs.

Physical factors affecting the survival of Tachypleus tridentatus eggs were investigated by translocating their eggs between the high intertidal zone and the low intertidal zone of a known spawning site. The mean egg survival rates per day were highest in the mid intertidal zone (45.1%±25.4%) and the lowest in the low intertidal zone (13.3%±27.6%). Differences in the elevation, air exposure time, and water content of the spawning ground were significant factors determining the egg survival rates. Excessive or insufficient air exposure time resulted in inadequate water content at higher and lower intertidal zones and could reduce egg survival. On the other hand, moderate saturation and dehydration were repeated with each tidal movement in the mid intertidal zone. This dynamic is considered as one of the crucial factors for the survival of eggs and is considered optimal for spawning. Therefore, the protection of the mid intertidal zone is imperative for maximizing the egg survival rate in Tsuyazaki Cove where almost all suitable nesting sites have disappeared due to coastal development. By protecting these optimal sites for spawning and recovering other optimal sites on suitable beaches, a positive contribution can be made to future management and conservation. The study also suggests that translocating eggs from marginal to optimal spawning sites might be a recovery strategy for this globally endangered species.

Humoral Immunogenicity of the mRNA-1273 Vaccine in the Phase 3 Coronavirus Efficacy (COVE) Trial.

BACKGROUND: Messenger RNA (mRNA)-1273 vaccine demonstrated 93.2% efficacy against coronavirus disease 2019 (COVID-19) in the Coronavirus Efficacy (COVE) trial. The humoral immunogenicity results are now reported. METHODS: Participants received 2 mRNA-1273 (100 µg) or placebo injections, 28 days apart. Immune responses were evaluated in a prespecified, randomly selected per-protocol immunogenicity population (n = 272 placebo; n = 1185 mRNA-1273). Serum binding antibodies (bAbs) and neutralizing antibodies (nAbs) to severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2)-spike protein were assessed at days 1, 29, and 57 by baseline SARS-CoV-2-negative (n = 1197) and SARS-CoV-2-positive (n = 260) status, age, and sex. RESULTS: SARS-CoV-2-negative vaccinees had bAb geometric mean AU/mL levels of 35 753 at day 29 that increased to 316 448 at day 57 and nAb inhibitory dilution 50% titers of 55 at day 29 that rose to 1081 at day 57. In SARS-CoV-2-positive vacinees, the first mRNA-1273 injection elicited bAb and nAb levels that were 11-fold (410 049) and 27-fold (1479) higher than in SARS-CoV-2-negative vaccinees, respectively, and were comparable to levels after 2 injections in uninfected participants. Findings were generally consistent by age and sex. CONCLUSIONS: mRNA-1273 elicited robust serologic immune responses across age, sex, and SARS-CoV-2 status, consistent with its high COVID-19 efficacy. Higher immune responses in those previously infected support a booster-type effect. Clinical Trials Registration. NCT04470427.

Cove-Edged Hexa-peri-hexabenzo-bis-peri-octacene: Molecular Conformations and Amplified Spontaneous Emission.

The bottom-up synthesis of an unprecedentedly large cove-edged nanographene, hexa-peri-hexabenzo-bis-peri-octacene (HBPO), is reported in this work. Chiral high-performance liquid chromatography and density functional theory (DFT) calculations revealed multiple conformations in solution. Two different molecular conformations, "waggling" and "butterfly", were found in crystals by X-ray crystallography, and the selectivity of conformations could be tuned by solvents. The optoelectronic properties of HBPO were investigated by UV/Vis absorption and fluorescence spectroscopies, cyclic voltammetry, and DFT calculations. The contorted geometry and branched alkyl groups suppress the aggregation of HBPO in solution, leading to a high fluorescence quantum yield of 79 %. The optical-gain properties were explored through transient absorption and amplified spontaneous emission spectroscopies, which enrich the choices of edge structures for potential applications in laser cavities.

Comparative efficacy of two pyrethroid-piperonyl butoxide nets (Olyset Plus and PermaNet 3.0) against pyrethroid resistant malaria vectors: a non-inferiority assessment.

BACKGROUND: Pyrethroid-PBO nets were conditionally recommended for control of malaria transmitted by mosquitoes with oxidase-based pyrethroid-resistance based on epidemiological evidence of additional protective effect with Olyset Plus compared to a pyrethroid-only net (Olyset Net). Entomological studies can be used to assess the comparative performance of other brands of pyrethroid-PBO ITNs to Olyset Plus. METHODS: An experimental hut trial was performed in Cové, Benin to compare PermaNet 3.0 (deltamethrin plus PBO on roof panel only) to Olyset Plus (permethrin plus PBO on all panels) against wild pyrethroid-resistant Anopheles gambiae sensu lato (s.l.) following World Health Organization (WHO) guidelines. Both nets were tested unwashed and after 20 standardized washes compared to Olyset Net. Laboratory bioassays were also performed to help explain findings in the experimental huts. RESULTS: With unwashed nets, mosquito mortality was higher in huts with PermaNet 3.0 compared to Olyset Plus (41% vs. 28%, P < 0.001). After 20 washes, mortality declined significantly with PermaNet 3.0 (41% unwashed vs. 17% after washing P < 0.001), but not with Olyset Plus (28% unwashed vs. 24% after washing P = 0.433); Olyset Plus induced significantly higher mortality than PermaNet 3.0 and Olyset Net after 20 washes. PermaNet 3.0 showed a higher wash retention of PBO compared to Olyset Plus. A non-inferiority analysis performed with data from unwashed and washed nets together using a margin recommended by the WHO, showed that PermaNet 3.0 was non-inferior to Olyset Plus in terms of mosquito mortality (25% with Olyset Plus vs. 27% with PermaNet 3.0, OR = 1.528, 95%CI = 1.02-2.29) but not in reducing mosquito feeding (25% with Olyset Plus vs. 30% with PermaNet 3.0, OR = 1.192, 95%CI = 0.77-1.84). Both pyrethroid-PBO nets were superior to Olyset Net. CONCLUSION: Olyset Plus outperformed PermaNet 3.0 in terms of its ability to cause greater margins of improved mosquito mortality compared to a standard pyrethroid net, after multiple standardized washes. However, using a margin of non-inferiority defined by the WHO, PermaNet 3.0 was non-inferior to Olyset Plus in inducing mosquito mortality. Considering the low levels of mortality observed and increasing pyrethroid-resistance in West Africa, it is unclear whether either of these nets would demonstrate the same epidemiological impact observed in community trials in East Africa.

Lues venerea at Warrane, Sydney Cove 1788-1828.

Historical writings of the growth of the Colony at Sydney Cove, Warrane, offered limited insight into the deprivations endured by sufferers of the 18th century canker, lues venerea, syphilis. Despite Governor Arthur Phillip's well-meaning precautions, the disease effortlessly accompanied the First Fleet, rapidly spread among the Colonial inhabitants and very soon spilled over to the indigenous Cadigal clansmen. Sporadic reporting by early Sydney diarists delineated the unstoppable course of the advancing affliction.

Efficacy of Fludora® Fusion (a mixture of deltamethrin and clothianidin) for indoor residual spraying against pyrethroid-resistant malaria vectors: laboratory and experimental hut evaluation.

BACKGROUND: A new generation of IRS insecticides which can provide improved and prolonged control of pyrethroid-resistant malaria vector populations are being developed. Fludora® Fusion is a new IRS insecticide containing a mixture of deltamethrin and clothianidin, a neonicotinoid. METHODS: The efficacy of Fludora® Fusion IRS was evaluated over 11-12 months on concrete and mud substrates in laboratory bioassays and experimental huts against wild free-flying pyrethroid-resistant Anopheles gambiae (sensu lato) in Cové, Benin. A comparison was made with the two active ingredients of the mixture; clothianidin and deltamethrin, applied alone. CDC bottle bioassays were also performed to investigate resistance to clothianidin in the wild vector population. RESULTS: Fludora® Fusion induced > 80% laboratory cone bioassay mortality with both susceptible and pyrethroid-resistant An. gambiae (s.l.) for 7-9 months on concrete block substrates and 12 months on mud block substrates. The vector population at the experimental hut site was fully susceptible to clothianidin in CDC bottle bioassays. Overall mortality rates of wild free-flying pyrethroid-resistant An. gambiae (s.l.) entering the experimental huts during the 11-month trial were < 15% with deltamethrin and significantly higher with Fludora® Fusion (69-71%) and clothianidin alone (72-78%). Initial high experimental hut mortality rates with Fludora® Fusion (> 80%) only declined by 50% after 8 months. Monthly in situ wall cone bioassay mortality of susceptible mosquitoes was > 80% for 9-12 months with Fludora® Fusion and clothianidin alone. Fludora® Fusion induced significantly higher levels of early exiting of mosquitoes compared to clothianidin alone (55-60% vs 37-38%, P < 0.05). CONCLUSIONS: Indoor residual spraying with Fludora® Fusion induced high and prolonged mortality of wild pyrethroid-resistant malaria vectors for 7-10 months mostly due to the clothianidin component and substantial early exiting of mosquitoes from treated huts due to the pyrethroid component. Fludora® Fusion is an important addition to the current portfolio of IRS insecticides with the potential to significantly reduce transmission of malaria by pyrethroid-resistant mosquito vectors.

Distribution and Control of Bacterial Community Composition in Marian Cove Surface Waters, King George Island, Antarctica during the Summer of 2018.

Marian Cove is experiencing some of the most rapid environmental changes in the Antarctic region; however, little is known about the response of bacterial communities to these changes. The main purpose of this study was to investigate the spatial variation of physical‒biogeochemical‒bacterial community features in the Marian Cove surface waters and the environmental parameters governing the spatial variation in the bacterial community composition during the summer of 2018. The Marian Cove surface waters are largely composed of two different characteristics of water masses: relatively low-temperature, -salinity, and -nutrient surface glacier water (named SGW) and relatively high-temperature, -salinity, and -nutrient surface Maxwell Bay water (named SMBW). The SGW bacterial communities were dominated by unclassified Cryomorphaceae, Sedimenticola, and Salibacter genera, while the SMBW bacterial communities were dominated by Sulfitobacter, Arcobacter, and Odoribacter genera. Spatial variations in bacterial community composition were mainly attributed to physical and biogeochemical characteristics, suggesting that the bacterial community composition of the Marian Cove surface waters is mainly determined by environmental characteristics. These findings provide a foundation to improve the understanding of bacterial community variations in response to a rapidly changing Marian Cove in the Antarctic.

Atomistic Modelling of Size-Dependent Mechanical Properties and Fracture of Pristine and Defective Cove-Edged Graphene Nanoribbons.

Cove-edged graphene nanoribbons (CGNR) are a class of nanoribbons with asymmetric edges composed of alternating hexagons and have remarkable electronic properties. Although CGNRs have attractive size-dependent electronic properties their mechanical properties have not been well understood. In practical applications, the mechanical properties such as tensile strength, ductility and fracture toughness play an important role, especially during device fabrication and operation. This work aims to fill a gap in the understanding of the mechanical behaviour of CGNRs by studying the edge and size effects on the mechanical response by using molecular dynamic simulations. Pristine graphene structures are rarely found in applications. Therefore, this study also examines the effects of topological defects on the mechanical behaviour of CGNR. Ductility and fracture patterns of CGNR with divacancy and topological defects are studied. The results reveal that the CGNR become stronger and slightly more ductile as the width increases in contrast to normal zigzag GNR. Furthermore, the mechanical response of defective CGNRs show complex dependency on the defect configuration and distribution, while the direction of the fracture propagation has a complex dependency on the defect configuration and position. The results also confirm the possibility of topological design of graphene to tailor properties through the manipulation of defect types, orientation, and density and defect networks.

Indoor spraying with chlorfenapyr (a pyrrole insecticide) provides residual control of pyrethroid-resistant malaria vectors in southern Benin.

BACKGROUND: New classes of insecticides with novel modes of action, which can provide effective and prolonged control of insecticide-resistant malaria vector populations, are urgently needed for indoor residual spraying. Such insecticides can be included in a rotation plan to manage and prevent further development of resistance in mosquito vectors of malaria. Chlorfenapyr, a novel pyrrole insecticide with a unique mode of action, is being developed as a long-lasting IRS formulation. METHODS: The efficacy of several formulations of chlorfenapyr alone and as mixtures with alpha-cypermethrin were evaluated in an experimental hut trial against wild pyrethroid-resistant Anopheles gambiae sensu lato in Cové, Benin, in an attempt to identify the most effective and long-lasting formulations for IRS. The trial lasted 12 months. A comparison was made with alpha-cypermethrin and bendiocarb formulations. CDC bottle bioassays were performed to investigate cross-resistance to chlorfenapyr in the local vector population. RESULTS: Mortality rates in World Health Organization (WHO) cylinder bioassays were < 5% with pyrethroids due to high levels of pyrethroid resistance, but > 95% with bendiocarb thus confirming susceptibility to carbamates in the vector population. CDC bottle bioassays showed no cross-resistance between pyrethroids and chlorfenapyr. Overall mortality of free-flying mosquitoes entering the experimental huts over the 12-month trial was 4% with alpha-cypermethrin and 12% with bendiocarb. The chlorfenapyr solo-formulations induced significantly higher levels of mortality (38-46%) compared to the bendiocarb (12% P < 0.001) and to the mixture formulations (18-22%, P < 0.05). The original Sylando 240SC formulation of chlorfenapyr was more efficacious than all other novel chlorfenapyr formulations tested. Bendiocarb induced > 80% mortality in the first month, but this declined sharply to < 20% by the third month while the mortality rates achieved with the chlorfenapyr formulations (38-46%) were persistent lasting 7-10 months. The mixtures induced significantly lower percentage mortality than chlorfenapyr-solo formulations. Wall cone bioassays only showed mortality rates that were consistent with chlorfenapyr IRS treated huts when the exposure time was increased to 2 h. CONCLUSION: Indoor residual spraying with chlorfenapyr (Sylando® 240SC) provides moderate but prolonged control of pyrethroid-resistant malaria vectors compared to pyrethroid and bendiocarb IRS. Wall cone bioassays on chlorfenapyr-treated walls required longer exposure times of 2 h than the customary 30 min indicating that WHO guidelines on residual cone bioassays need to be more insecticide-specific.

Cove-Edged Nanographenes with Localized Double Bonds.

The efficient synthesis and electronic properties of two large-size cove-edged nanographenes (NGs), CN1 and CN2, are presented. X-ray crystallographic analysis reveals a contorted backbone for both molecules owing to the steric repulsion at the inner cove position. Noticeably, the dominant structures of these molecules contain four (for CN1) or six (for CN2) localized C=C double bonds embedded in nine (for CN1) or twelve (for CN2) aromatic sextet rings according to Clar's formula, which is supported by bond length analysis and theoretical (NICS, ACID) calculations. Furthermore, Raman spectra exhibit a band associated with the longitudinal CC stretching mode of olefinic double bonds. Owing to the existence of the additional olefinic bonds, both compounds show a small band gap (1.84 eV for CN1 and 1.37 eV for CN2). They also display moderate fluorescence quantum yield (35 % for CN1 and 50 % for CN2) owing to the contorted geometry, which can suppress aggregation in solution.

Ocean freshening and acidification differentially influence mortality and behavior of the Antarctic amphipod Gondogeneia antarctica.

The Western Antarctic Peninsula (WAP) has experienced rapid atmospheric and ocean warming over the past few decades and many marine-terminating glaciers have considerably retreated. Glacial retreat is accompanied by fresh meltwater intrusion, which may result in the freshening and acidification of coastal waters. Marian Cove (MC), on King George Island in the WAP, undergoes one of the highest rates of glacial retreat. Intertidal and shallow subtidal waters are likely more susceptible to these processes, and sensitive biological responses are expected from the organisms inhabiting this area. The gammarid amphipod Gondogeneia antarctica is one of the most abundant species in the shallow, nearshore Antarctic waters, and it occupies an essential ecological niche in the coastal marine WAP ecosystem. In this study, we tested the sensitivity of G. antarctica to lowered salinity and pH by meltwater intrusion following glacial retreat. We exposed G. antarctica to four different treatments combining two salinities (34 and 27 psu) and pH (8.0 and 7.6) levels for 26 days. Mortality, excluding cannibalized individuals, increased under low pH but decreased under low salinity conditions. Meanwhile, low salinity increased cannibalism, whereas low pH reduced food detection. Shelter use during the daytime decreased under each low salinity and pH condition, indicating that the two stressors act as disruptors of amphipod behavior. Under low salinity conditions, swimming increased during the daytime but decreased at night. Although interactions between low salinity and low pH were not observed during the experiment, the results suggest that each stressor, likely induced by glacial melting, causes altered behaviors in amphipods. These environmental factors may threaten population persistence in Marian Cove and possibly other similar glacial embayments.