New insights on the molecular features and electrophysiological properties of dinotefuran, imidacloprid and acetamiprid neonicotinoid insecticides

Structural features and hydrogen-bond interactions of dinotefuran (DIN), imidacoloprid (IMI) and acetamiprid (ACE) have been investigated experimentally through analyses of new crystal structures and observations in structural databases, as well as by Density Functional Theory quantum chemical calculations. Several conformations are observed experimentally in the solid state, highlighting the large flexibility of these compounds. This feature is confirmed by the theoretical calculations in the gas phase, the numerous and different energetic minima of the three neonicotinoids being located within a 10kJ/mol range. Comparisons of the observed and simulated data sheds light on the hydrogen-bond (HB) strength of the functional group at the tip of the electronegative fragment of each pharmacophore (NO(2) for DIN and IMI and CN for ACE). This effect originates in the \u27push-pull\u27 nature of these fragments and the related extensive electron delocalization. Molecular electrostatic potential calculations provide a ranking of the two fragments of the three neonicotinoid in terms of HB strength. Thus, the NO(2) group of DIN is the strongest HB acceptor of the electronegative fragment, closely followed by the cyano group of ACE. These two groups are significantly more potent than the NO(2) group of IMI. With respect to the other fragments of the three neonicotinoids, the nitrogen atom of the pyridine of IMI and ACE are stronger HB acceptors than the oxygen atom of the furanyl moiety of DIN. Finally, compared to electrophysiological studies obtained from cockroach synaptic and extrasynaptic receptors, DIN appears more effective than IMI and ACE because it strongly increases dose-dependently the ganglionic depolarisation and the currents amplitudes. These data suggest that DIN, IMI and ACE belong to two subgroups which act differently as agonists of insect nicotinic receptors

The representation of alkalinity and the carbonate pump from CMIP5 to CMIP6 Earth system models and implications for the carbon cycle

Ocean alkalinity is critical to the uptake of atmospheric carbon in surface waters and provides buffering capacity towards the associated acidification. However, unlike dissolved inorganic carbon (DIC), alkalinity is not directly impacted by anthropogenic carbon emissions. Within the context of projections of future ocean carbon uptake and potential ecosystem impacts, especially through Coupled Model Intercomparison Projects (CMIPs), the representation of alkalinity and the main driver of its distribution in the ocean interior, the calcium carbonate cycle, have often been overlooked. Here we track the changes from CMIP5 to CMIP6 with respect to the Earth system model (ESM) representation of alkalinity and the carbonate pump which depletes the surface ocean in alkalinity through biological production of calcium carbonate and releases it at depth through export and dissolution. We report an improvement in the representation of alkalinity in CMIP6 ESMs relative to those in CMIP5, with CMIP6 ESMs simulating lower surface alkalinity concentrations, an increased meridional surface gradient and an enhanced global vertical gradient. This improvement can be explained in part by an increase in calcium carbonate (CaCO3) production for some ESMs, which redistributes alkalinity at the surface and strengthens its vertical gradient in the water column. We were able to constrain a particulate inorganic carbon (PIC) export estimate of 44–55 Tmol yr−1 at 100 m for the ESMs to match the observed vertical gradient of alkalinity. Reviewing the representation of the CaCO3 cycle across CMIP5/6, we find a substantial range of parameterizations. While all biogeochemical models currently represent pelagic calcification, they do so implicitly, and they do not represent benthic calcification. In addition, most models simulate marine calcite but not aragonite. In CMIP6, certain model groups have increased the complexity of simulated CaCO3 production, sinking, dissolution and sedimentation. However, this is insufficient to explain the overall improvement in the alkalinity representation, which is therefore likely a result of marine biogeochemistry model tuning or ad hoc parameterizations. Although modellers aim to balance the global alkalinity budget in ESMs in order to limit drift in ocean carbon uptake under pre-industrial conditions, varying assumptions related to the closure of the budget and/or the alkalinity initialization procedure have the potential to influence projections of future carbon uptake. For instance, in many models, carbonate production, dissolution and burial are independent of the seawater saturation state, and when considered, the range of sensitivities is substantial. As such, the future impact of ocean acidification on the carbonate pump, and in turn ocean carbon uptake, is potentially underestimated in current ESMs and is insufficiently constrained.</p

Weight change during chemotherapy changes the prognosis in non metastatic breast cancer for the worse

<p>Abstract</p> <p>Background</p> <p>Weight change during chemotherapy is reported to be associated with a worse prognosis in breast cancer patients, both with weight gain and weight loss. However, most studies were conducted prior to the common use of anthracycline-base chemotherapy and on North American populations with a mean BMI classified as overweight. Our study was aimed to evaluate the prognostic value of weight change during anthracycline-based chemotherapy on non metastatic breast cancer (European population) with a long term follow-up.</p> <p>Methods</p> <p>Patients included 111 women diagnosed with early stage breast cancer and locally advanced breast cancer who have been treated by anthracycline-based chemotherapy regimen between 1976 and 1989. The relative percent weight variation (WV) between baseline and postchemotherapy treatment was calculated and categorized into either weight change (WV > 5%) or stable (WV < 5%). The median follow-up was 20.4 years [19.4 - 27.6]. Cox proportional hazard models were used to evaluate any potential association of weight change and known prognostic factors with the time to recurrence and overall survival.</p> <p>Results</p> <p>Baseline BMI was 24.4 kg/m2 [17.1 - 40.5]. During chemotherapy treatment, 31% of patients presented a notable weight variation which was greater than 5% of their initial weight.</p> <p>In multivariate analyses, weight change (> 5%) was positively associated with an increased risk of both recurrence (RR 2.28; 95% CI: 1.29-4.03) and death (RR 2.11; 95% CI: 1.21-3.66).</p> <p>Conclusions</p> <p>Our results suggest that weight change during breast-cancer chemotherapy treatment may be related to poorer prognosis with higher reccurence and higher mortality in comparison to women who maintained their weight.</p

Contribution of agronomy to land management issues - A comparison of five PhD thesis

An introductory literature review highlights the growing attention within the processes taking place at farming region and landscape scale beside the classical spatial scales at cultivated/experimental plot level. This recent evolution in agronomy finds its origin in newly emerging land management issues. Meanwhile, geography and other disciplines are stressing the need for a greater integration of multifunctional agricultural activities into the decision-making processes at the various levels of land management, such as provinces, municipalities or watersheds. This requires also that studies on farmland management include explicitly the different environmental and social contexts influencing farming activities. In this paper we aim to analyse how recent agronomic oriented research are facing and supporting various land management issues. We have compared five interdisciplinary PhD theses examining their definitions and methods of analysis for: the farming system, the local land management issues at stake, the spatial scale selected for the study, the stakeholders’ involvement and the interaction with other disciplines. Common issues which emerged from this comparison are delivery of agro-environmental services, sustainable land management and landscape conservation. Multiple spatial levels were considered, which included at least one administrative unit of policy decision/implementation. Consequently, the explicit (re)definition of some agronomic concepts and methods was needed. Regarding the interdisciplinary framework, the theses have stressed the interactions among agronomy, geography and ecology. All theses aimed at delivering tools for decision-making support, mainly in the form of cartography. Nevertheless the participation of local stakeholders was generally included as a final step; herewith the settings of stakeholders’ involvement were various. In conclusion, we discuss how the produced knowledge has enhanced the land management issues in local planning tools. On these bases, we stress finally the issues at stake to strengthen the roles and contributions of agronomic oriented education and research to agricultural land management and development

Plan concerté de la Trame Verte et Bleue du Val d’Authion : penser un paysage de l’écologie pour et par les habitants

International audienc

Knowledge Gaps in Quantifying the Climate Change Response of Biological Storage of Carbon in the Ocean

This is the final version. Available on open access from Wiley via the DOI in this recordData Availability Statement: Full anonymized results of the community survey are available as part of the Supplementary Information (Data Set S1 in Supporting Information S1) and in Henson et al. (2024).The ocean is responsible for taking up approximately 25% of anthropogenic CO2 emissions and stores >50 times more carbon than the atmosphere. Biological processes in the ocean play a key role, maintaining atmospheric CO2 levels approximately 200 ppm lower than they would otherwise be. The ocean's ability to take up and store CO2 is sensitive to climate change, however the key biological processes that contribute to ocean carbon storage are uncertain, as are how those processes will respond to, and feedback on, climate change. As a result, biogeochemical models vary widely in their representation of relevant processes, driving large uncertainties in the projections of future ocean carbon storage. This review identifies key biological processes that affect how ocean carbon storage may change in the future in three thematic areas: biological contributions to alkalinity, net primary production, and interior respiration. We undertook a review of the existing literature to identify processes with high importance in influencing the future biologically-mediated storage of carbon in the ocean, and prioritized processes on the basis of both an expert assessment and a community survey. Highly ranked processes in both the expert assessment and survey were: for alkalinity—high level understanding of calcium carbonate production; for primary production—resource limitation of growth, zooplankton processes and phytoplankton loss processes; for respiration—microbial solubilization, particle characteristics and particle type. The analysis presented here is designed to support future field or laboratory experiments targeting new process understanding, and modeling efforts aimed at undertaking biogeochemical model development.Natural Environment Research Council (NERC