Synthesis, x-ray structure and anion binding properties of a cryptand-like hybrid calixpyrrole

The novel cryptand in/out-3, containing two tripyrrolemethane units briged by three 1,3- diisopropylidenbenzene arms was readily synthesized by a convergent three-step synthesis. It binds fluoride by inclusion with excellent selectivity with respect to a number of other tested anions. The structure of the free receptor and that of its fluoride complex were investigated in solution by NMR spectroscopy. The solid state X-ray structure of the free cryptand 3 was also determined

First macrobiota biomineralisation was environmentally triggered

Why large and diverse skeletons first appeared ca 550 Ma is not well understood. Many Ediacaran skeletal biota show evidence of flexibility, and bear notably thin skeletal walls with simple, non-hierarchical microstructures of either aragonite or high-Mg calcite. We present evidence that the earliest skeletal macrobiota, found only in carbonate rocks, had close soft-bodied counterparts hosted in contemporary clastic rocks. This includes the calcareous discoidal fossil Suvorovella, similar to holdfasts of Ediacaran biota taxa previously known only as casts and moulds, as well as tubular and vase-shaped fossils. In sum, these probably represent taxa of diverse affinity including unicellular eukaryotes, total group cnidarians and problematica. Our findings support the assertion that the calcification was an independent and derived feature that appeared in diverse groups where an organic scaffold was the primitive character, which provided the framework for interactions between the extracellular matrix and mineral ions. We conclude that such skeletons may have been acquired with relative ease in the highly saturated, high alkalinity carbonate settings of the Ediacaran, where carbonate polymorph was further controlled by seawater chemistry. The trigger for Ediacaran biomineralization may have been either changing seawater Mg/Ca and/or increasing oxygen levels. By the Early Cambrian, however, biomineralization styles and the range of biominerals had significantly diversified, perhaps as an escalating defensive response to increasing predation pressure. Indeed skeletal hardparts had appeared in clastic settings by Cambrian Stage 1, suggesting independence from ambient seawater chemistry where genetic and molecular mechanisms controlled biomineralization and mineralogy had become evolutionarily constrained

Room-Temperature Inter-Dot Coherent Dynamics in Multilayer Quantum Dot Materials

The full blossoming of quantum technologies requires the availability of easy-to-prepare materials where quantum coherences can be effectively initiated, controlled, and exploited, preferably at ambient conditions. Solid-state multilayers of colloidally grown quantum dots (QDs) are highly promising for this task because of the possibility of assembling networks of electronically coupled QDs through the modulation of sizes, inter-dot linkers, and distances. To usefully probe coherence in these materials, the dynamical characterization of their collective quantum mechanically coupled states is needed. Here, we explore by two-dimensional electronic spectroscopy the coherent dynamics of solid-state multilayers of electronically coupled colloidally grown CdSe QDs and complement it by detailed computations. The time evolution of a coherent superposition of states delocalized over more than one QD was captured at ambient conditions. We thus provide important evidence for inter-dot coherences in such solid-state materials, opening up new avenues for the effective application of these materials in quantum technologies

Whole Transcriptome Analysis of the Coral Acropora millepora Reveals Complex Responses to CO2-driven Acidification during the Initiation of Calcification

n/

Effects of ocean acidification on invertebrate settlement at volcanic CO<inf>2</inf> vents

We present the first study of the effects of ocean acidification on settlement of benthic invertebrates and microfauna. Artificial collectors were placed for 1 month along pH gradients at CO2 vents off Ischia (Tyrrhenian Sea, Italy). Seventy-nine taxa were identified from six main taxonomic groups (foraminiferans, nematodes, polychaetes, molluscs, crustaceans and chaetognaths). Calcareous foraminiferans, serpulid polychaetes, gastropods and bivalves showed highly significant reductions in recruitment to the collectors as pCO2 rose from normal (336-341 ppm, pH 8.09-8.15) to high levels (886-5,148 ppm) causing acidified conditions near the vents (pH 7.08-7.79). Only the syllid polychaete Syllis prolifera had higher abundances at the most acidified station, although a wide range of polychaetes and small crustaceans was able to settle and survive under these conditions. A few taxa (Amphiglena mediterranea, Leptochelia dubia, Caprella acanthifera) were particularly abundant at stations acidified by intermediate amounts of CO2 (pH 7. 41-7.99). These results show that increased levels of CO2 can profoundly affect the settlement of a wide range of benthic organisms. © 2010 Springer-Verlag

Operating Cabled Underwater Observatories in Rough Shelf-Sea Environments:A Technological Challenge

Cabled coastal observatories are often seen as future-oriented marine technology that enables science to conduct observational and experimental studies under water year-round, independent of physical accessibility to the target area. Additionally, the availability of (unrestricted) electricity and an Internet connection under water allows the operation of complex experimental setups and sensor systems for longer periods of time, thus creating a kind of laboratory beneath the water. After successful operation for several decades in the terrestrial and atmospheric research field, remote controlled observatory technology finally also enables marine scientists to take advantage of the rapidly developing communication technology. The continuous operation of two cabled observatories in the southern North Sea and off the Svalbard coast since 2012 shows that even highly complex sensor systems, such as stereo-optical cameras, video plankton recorders or systems for measuring the marine carbonate system, can be successfully operated remotely year-round facilitating continuous scientific access to areas that are difficult to reach, such as the polar seas or the North Sea. Experience also shows, however, that the challenges of operating a cabled coastal observatory go far beyond the provision of electricity and network connection under water. In this manuscript, the essential developmental stages of the "COSYNA Shallow Water Underwater Node" system are presented, and the difficulties and solutions that have arisen in the course of operation since 2012 are addressed with regard to technical, organizational and scientific aspects.</p

Framing and Context of the Report

The Intergovernmental Panel on Climate Change (IPCC) is the leading international body for assessing the science related to climate change. It provides policymakers with regular assessments of the scientific basis of human-induced climate change, its impacts and future risks, and options for adaptation and mitigation. This IPCC Special Report on the Ocean and Cryosphere in a Changing Climate is the most comprehensive and up-to-date assessment of the observed and projected changes to the ocean and cryosphere and their associated impacts and risks, with a focus on resilience, risk management response options, and adaptation measures, considering both their potential and limitations. It brings together knowledge on physical and biogeochemical changes, the interplay with ecosystem changes, and the implications for human communities. It serves policymakers, decision makers, stakeholders, and all interested parties with unbiased, up-to-date, policy-relevant information. Chapter 1: This special report assesses new knowledge since the IPCC 5th Assessment Report (AR5) and the Special Report on Global Warming of 1.5ºC (SR15) on how the ocean and cryosphere have and are expected to change with ongoing global warming, the risks and opportunities these changes bring to ecosystems and people, and mitigation, adaptation and governance options for reducing future risks. Chapter 1 provides context on the importance of the ocean and cryosphere, and the framework for the assessments in subsequent chapters of the report. All people on Earth depend directly or indirectly on the ocean and cryosphere. The fundamental roles of the ocean and cryosphere in the Earth system include the uptake and redistribution of anthropogenic carbon dioxide and heat by the ocean, as well as their crucial involvement of in the hydrological cycle. The cryosphere also amplifies climate changes through snow, ice and permafrost feedbacks. Services provided to people by the ocean and/or cryosphere include food and freshwater, renewable energy, health and wellbeing, cultural values, trade and transport. {1.1, 1.2, 1.5} Sustainable development is at risk from emerging and intensifying ocean and cryosphere changes. Ocean and cryosphere changes interact with each of the United Nations Sustainable Development Goals (SDGs). Progress on climate action (SDG 13) would reduce risks to aspects of sustainable development that are fundamentally linked to the ocean and cryosphere and the services they provide (high confidence1 ). Progress on achieving the SDGs can contribute to reducing the exposure or vulnerabilities of people and communities to the risks of ocean and cryosphere change (medium confidence). {1.1} Communities living in close connection with polar, mountain, and coastal environments are particularly exposed to the current and future hazards of ocean and cryosphere change. Coasts are home to approximately 28% of the global population, including around 11% living on land less than 10 m above sea level. Almost 10% of the global population lives in the Arctic or high mountain regions. People in these regions face the greatest exposure to ocean and cryosphere change, and poor and marginalised people here are particularly vulnerable to climate-related hazards and risks (very high confidence). The adaptive capacity of people, communities and nations is shaped by social, political, cultural, economic, technological, institutional, geographical and demographic factors. {1.1, 1.5, 1.6, Cross-Chapter Box 2 in Chapter 1} Ocean and cryosphere changes are pervasive and observedfrom high mountains, to the polar regions, to coasts, and intothe deep ocean. AR5 assessed that the ocean is warming (0 to700 m: virtually certain2; 700 to 2,000 m: likely), sea level is rising(high confidence), and ocean acidity is increasing (high confidence).Most glaciers are shrinking (high confidence), the Greenland andAntarctic ice sheets are losing mass (high confidence), sea ice extent inthe Arctic is decreasing (very high confidence), Northern Hemispheresnow cover is decreasing (very high confidence), and permafrosttemperatures are increasing (high confidence). Improvementssince AR5 in observation systems, techniques, reconstructions andmodel developments, have advanced scientific characterisationand understanding of ocean and cryosphere change, including inpreviously identified areas of concern such as ice sheets and AtlanticMeridional Overturning Circulation (AMOC). {1.1, 1.4, 1.8.1}Evidence and understanding of the human causes of climatewarming, and of associated ocean and cryosphere changes,has increased over the past 30 years of IPCC assessments (veryhigh confidence). Human activities are estimated to have causedapproximately 1.0ºC of global warming above pre-industrial levels(SR15). Areas of concern in earlier IPCC reports, such as the expectedacceleration of sea level rise, are now observed (high confidence).Evidence for expected slow-down of AMOC is emerging in sustainedobservations and from long-term palaeoclimate reconstructions(medium confidence), and may be related with anthropogenic forcingaccording to model simulations, although this remains to be properlyattributed. Significant sea level rise contributions from Antarctic icesheet mass loss (very high confidence), which earlier reports did notexpect to manifest this century, are already being observed. {1.1, 1.4}Ocean and cryosphere changes and risks by the end-of-century(2081?2100) will be larger under high greenhouse gas emissionscenarios, compared with low emission scenarios (very highconfidence). Projections and assessments of future climate, oceanand cryosphere changes in the Special Report on the Ocean andCryosphere in a Changing Climate (SROCC) are commonly basedon coordinated climate model experiments from the Coupled ModelIntercomparison Project Phase 5 (CMIP5) forced with RepresentativeConcentration Pathways (RCPs) of future radiative forcing. Currentemissions continue to grow at a rate consistent with a high emissionfuture without effective climate change mitigation policies (referredto as RCP8.5). The SROCC assessment contrasts this high greenhousegas emission future with a low greenhouse gas emission, highmitigation future (referred to as RCP2.6) that gives a two in threechance of limiting warming by the end of the century to less than 2oC above pre-industrial. {Cross-Chapter Box 1 in Chapter 1} Characteristics of ocean and cryosphere change include thresholds of abrupt change, long-term changes that cannot be avoided, and irreversibility (high confidence). Ocean warming, acidification and deoxygenation, ice sheet and glacier mass loss, and permafrost degradation are expected to be irreversible on time scales relevant to human societies and ecosystems. Long response times of decades to millennia mean that the ocean and cryosphere are committed to long-term change even after atmospheric greenhouse gas concentrations and radiative forcing stabilise (high confidence). Ice-melt or the thawing of permafrost involve thresholds (state changes) that allow for abrupt, nonlinear responses to ongoing climate warming (high confidence). These characteristics of ocean and cryosphere change pose risks and challenges to adaptation. {1.1, Box 1.1, 1.3} Societies will be exposed, and challenged to adapt, to changes in the ocean and cryosphere even if current and future efforts to reduce greenhouse gas emissions keep global warming well below 2ºC (very high confidence). Ocean and cryosphere-related mitigation and adaptation measures include options that address the causes of climate change, support biological and ecological adaptation, or enhance societal adaptation. Most ocean-based local mitigation and adaptation measures have limited effectiveness to mitigate climate change and reduce its consequences at the global scale, but are useful to implement because they address local risks, often have co-benefits such as biodiversity conservation, and have few adverse side effects. Effective mitigation at a global scale will reduce the need and cost of adaptation, and reduce the risks of surpassing limits to adaptation. Ocean-based carbon dioxide removal at the global scale has potentially large negative ecosystem consequences. {1.6.1, 1.6.2, Cross-Chapter Box 2 in Chapter 1} The scale and cross-boundary dimensions of changes in the ocean and cryosphere challenge the ability of communities, cultures and nations to respond effectively within existing governance frameworks (high confidence). Profound economic and institutional transformations are needed if climate-resilient development is to be achieved (high confidence). Changes in the ocean and cryosphere, the ecosystem services that they provide, the drivers of those changes, and the risks to marine, coastal, polar and mountain ecosystems, occur on spatial and temporal scales that may not align within existing governance structures and practices (medium confidence). This report highlights the requirements for transformative governance, international and transboundary cooperation, and greater empowerment of local communities in the governance of the ocean, coasts, and cryosphere in a changing climate. {1.5, 1.7, Cross-Chapter Box 2 in Chapter 1, Cross-Chapter Box 3 in Chapter 1} Robust assessments of ocean and cryosphere change, and the development of context-specific governance and response options, depend on utilising and strengthening all available knowledge systems (high confidence). Scientific knowledge from observations, models and syntheses provides global to local scale understandings of climate change (very high confidence). Indigenous knowledge (IK) and local knowledge (LK) provide context-specific and socio-culturally relevant understandings for effective responses and policies (medium confidence). Education and climate literacy enable climate action and adaptation (high confidence). {1.8, Cross-Chapter Box 4 in Chapter 1} Long-term sustained observations and continued modelling are critical for detecting, understanding and predicting ocean and cryosphere change, providing the knowledge to inform risk assessments and adaptation planning (high confidence). Knowledge gaps exist in scientific knowledge for important regions, parameters and processes of ocean and cryosphere change, including for physically plausible, high impact changes like high end sea level rise scenarios that would be costly if realised without effective adaptation planning and even then may exceed limits to adaptation. Means such as expert judgement, scenario building, and invoking multiple lines of evidence enable comprehensive risk assessments even in cases of uncertain future ocean and cryosphere changes.Fil: Abram, Nerilie. Australian National University; AustraliaFil: Gattuso, Jean Pierre. Centre National de la Recherche Scientifique; FranciaFil: Prakash, Anjal. Teri School Of Advanced Studies; IndiaFil: Cheng, Lijing. Chinese Academy Of Science; ChinaFil: Chidichimo, María Paz. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Ministerio de Defensa. Armada Argentina. Servicio de Hidrografía Naval. Departamento Oceanografía; ArgentinaFil: Crate, Susan. George Mason University; Estados UnidosFil: Enomoto, H.. National Polar Agency; JapónFil: Garschagen, M.. Technische Universitat München; AlemaniaFil: Gruber, N.. Swiss Federal Institute of Technology Zurich; SuizaFil: Harper, S.. University Of Alberta. Faculty Of Agricultural, Life And Environmental Sciences. Departament Of Agricultural, Food And Nutritional Science.; CanadáFil: Holland, Elisabeth. University Of South Pacific; FiyiFil: Kudela, Raphael Martin. University of California at San Diego. Scripps Institution of Oceanography; Estados UnidosFil: Rice, Jake. University of Toronto; CanadáFil: Steffen, Konrad. Swiss Federal Institute for Forest, Snow and Landscape Research; SuizaFil: Von Schuckmann, Karina. Mercator Ocean International; Franci

Default mode network modulation by psychedelics : a systematic review

Psychedelics are a unique class of drug that commonly produce vivid hallucinations as well as profound psychological and mystical experiences. A grouping of interconnected brain regions characterized by increased temporal coherence at rest have been termed the Default Mode Network (DMN). The DMN has been the focus of numerous studies assessing its role in self-referencing, mind wandering, and autobiographical memories. Altered connectivity in the DMN has been associated with a range of neuropsychiatric conditions such as depression, anxiety, post-traumatic stress disorder, attention deficit hyperactive disorder, schizophrenia, and obsessive-compulsive disorder. To date, several studies have investigated how psychedelics modulate this network, but no comprehensive review, to our knowledge, has critically evaluated how major classical psychedelic agents-lysergic acid diethylamide, psilocybin, and ayahuasca-modulate the DMN. Here we present a systematic review of the knowledge base. Across psychedelics there is consistent acute disruption in resting state connectivity within the DMN and increased functional connectivity between canonical resting-state networks. Various models have been proposed to explain the cognitive mechanisms of psychedelics, and in one model DMN modulation is a central axiom. Although the DMN is consistently implicated in psychedelic studies, it is unclear how central the DMN is to the therapeutic potential of classical psychedelic agents. This article aims to provide the field with a comprehensive overview that can propel future research in such a way as to elucidate the neurocognitive mechanisms of psychedelics

Aerosols in atmospheric chemistry and biogeochemical cycles of nutrients

Atmospheric aerosols have complex and variable compositions and properties. While scientific interest is centered on the health and climatic effects of atmospheric aerosols, insufficient attention is given to their involvement in multiphase chemistry that alters their contribution as carriers of nutrients in ecosystems. However, there is experimental proof that the nutrient equilibria of both land and marine ecosystems have been disturbed during the Anthropocene period. This review study first summarizes our current understanding of aerosol chemical processing in the atmosphere as relevant to biogeochemical cycles. Then it binds together results of recent modeling studies based on laboratory and field experiments, focusing on the organic and dust components of aerosols that account for multiphase chemistry, aerosol ageing in the atmosphere, nutrient (N, P, Fe) emissions, atmospheric transport, transformation and deposition. The human-driven contribution to atmospheric deposition of these nutrients, derived by global simulations using past and future anthropogenic emissions of pollutants, is put into perspective with regard to potential changes in nutrient limitations and biodiversity. Atmospheric deposition of nutrients has been suggested to result in human-induced ecosystem limitations with regard to specific nutrients. Such modifications favor the development of certain species against others and affect the overall functioning of ecosystems. Organic forms of nutrients are found to contribute to the atmospheric deposition of the nutrients N, P and Fe by 20%–40%, 35%–45% and 7%–18%, respectively. These have the potential to be key components of the biogeochemical cycles since there is initial proof of their bioavailability to ecosystems. Bioaerosols have been found to make a significant contribution to atmospheric sources of N and P, indicating potentially significant interactions between terrestrial and marine ecosystems. These results deserve further experimental and modeling studies to reduce uncertainties and understand the feedbacks induced by atmospheric deposition of nutrients to ecosystems