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International audience; High-precision triple oxygen isotope data on 40 water samples (5–10 923 m in depth) collected at the Challenger Deep of the Mariana Trench are reported in this study. The analyses at Laboratoire des Sciences du Climat et l’Environnement yield mean isotope values δ18O = −0.084 ± 0.224‰, δ17O = −0.061 ± 0.117‰, and 17O-excess = −17 ± 5 per meg, with standard deviations reported at 1σ. The range of δ18O (from −0.480 to 0.544‰) falls within records of the Global Seawater Oxygen-18 Database at the Mariana Trench. The average 17O-excess value at the Mariana Trench is more negative than the average 17O-excess value of −5 ± 4 (1σ) per meg in the only prior data set including deep ocean samples. The slope (λ) of the three-isotope plot of Mariana Trench water is 0.521 ± 0.003 (1σ), lower than λ of 0.528 ± 0.001 (1σ) for ocean water in the prior study. The new data set matches the prediction of the ocean isotope mass balance model, suggesting that it may represent a more appropriate ocean endmember for triple oxygen isotope thermometry. The 17O-excess of ocean water with respect to Vienna Standard Mean Ocean Water (VSMOW) is recognized to be a necessary correction in quantifying gross oxygen productivity of euphotic regions and relative humidity of moisture source regions.

Stable isotopes of hydrogen, carbon and oxygen are used to investigate numerous physical and chemical processes in the water and inorganic carbon cycles. Measuring and comparing natural isotopic variations requires reliable primary reference materials and consistent data treatment. However, these reference materials have changed over time, while advances in technology have led to better constrained isotopic compositions of the reference materials. In this Technical Review, we provide an overview of the historical evolution of such materials, and explain their relationships across time and isotopic scales. Recommendations are provided for the measurement and reporting of isotopic compositions against the consensual VPDB and VSMOW scales in light of the newest carbonate and water reference materials distributed by the International Atomic Energy Agency. Stable isotope fractionation factors and their temperature dependence in processes specific to the water cycle (2H, 18O, 17O) and the CO2–water–carbonate system (13C, 18O) are described, including for carbonate clumped isotope thermometry. Propagation of errors is also addressed for a consistent reporting of real uncertainties of isotopic measurements and calculations. Lastly, current gaps in knowledge on the behaviour of stable isotopes in the water cycle and the CO2–water–carbonate system are highlighted for future studies. The use of isotopes has provided key insights into the Earth system, but their use can be fraught with experimental and theoretical pitfalls. This Technical Review explains the use of and fractionation factors associated with hydrogen, carbon and oxygen isotopes in water cycle and CO2–carbonate–water system studies.

International audience; Heteroarylsilyl cations elaborated from a quinoline skeleton have been prepared from the corresponding silanes and their structures studied by 1 H, 29 Si, and 15 N NMR. DOSY experiments and DFT calculations were also carried out showing that the silyl cation center is stabilized intramolecularly by the quinoline nitrogen atom (N1), forming a highly strained and quasi planar 4-membered ring. Oxygenated and nitrogenated substituents at the C4 position on the quinoline ring were shown to reinforce the Si-N1 interaction through a p- conjugation. The Lewis acidity of this class of silylium was finally determined using Müller's nitrilium method.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) spike pseudotyped virus (PSV) assays are widely used to measure neutralization titers of sera and of isolated neutralizing Abs (nAbs). PSV neutralization assays are safer than live virus neutralization assays and do not require access to biosafety level 3 laboratories. However, many PSV assays are nevertheless somewhat challenging and require at least 2 d to carry out. In this study, we report a rapid (

Ecosystems integrity and services are threatened by anthropogenic global changes. Mitigating and adapting to these changes require knowledge of ecosystem functioning in the expected novel environments, informed in large part through experimentation and modelling. This paper describes 13 advanced controlled environment facilities for experimental ecosystem studies, herein termed ecotrons, open to the international community. Ecotrons enable simulation of a wide range of natural environmental conditions in replicated and independent experimental units while measuring various ecosystem processes. This capacity to realistically control ecosystem environments is used to emulate a variety of climatic scenarios and soil conditions, in natural sunlight or through broad‐spectrum lighting. The use of large ecosystem samples, intact or reconstructed, minimizes border effects and increases biological and physical complexity. Measurements of concentrations of greenhouse trace gases as well as their net exchange between the ecosystem and the atmosphere are performed in most ecotrons, often quasi continuously. The flow of matter is often tracked with the use of stable isotope tracers of carbon and other elements. Equipment is available for measurements of soil water status as well as root and canopy growth. The experiments ran so far emphasize the diversity of the hosted research. Half of them concern global changes, often with a manipulation of more than one driver. About a quarter deal with the impact of biodiversity loss on ecosystem functioning and one quarter with ecosystem or plant physiology. We discuss how the methodology for environmental simulation and process measurements, especially in soil, can be improved and stress the need to establish stronger links with modelling in future projects. These developments will enable further improvements in mechanistic understanding and predictive capacity of ecotron research which will play, in complementarity with field experimentation and monitoring, a crucial role in exploring the ecosystem consequences of environmental changes., Experimentation and modelling are necessary to predict ecosystem functioning under future environments and to develop mitigating and adapting strategies. This paper describes 13 advanced controlled environment facilities, called ecotrons, open to the international community. An ecotron comprises a set of replicated enclosures designed to host ecosystems samples and enable realistic simulations of above‐ and belowground environmental conditions, while simultaneously and automatically measuring ecosystem processes. The characteristics of these infrastructures are given as well as examples of collaborative projects hosted so far.

The isotopic compositions of oxygen (δ18O) and hydrogen (δ2H) are widely used to locate the geo- graphical origin of biological remains or manufactured products. In this paper, we analyse the distributions of δ18O and δ2H in tap waters sampled across France, and in precipitation interpolated with the Online Isotopes in Precipitation Calculator and modelled with the isotope-enabled ECHAM6-wiso model. Our aim is to provide isoscapes usable in archaeology and forensics and evaluate whether the modelled data could be surrogates for measured ones. The δ18O and δ2H in the 396 tap waters sampled varied spatially within a range of 10‰ and 77‰, respectively. Their consistent distributions followed rules summarized by the effects of altitude and dis- tance from the coast. Their variations along the year were small. Therefore, the database provides a solid ref- erence for δ18O and δ2H of the water supply system at the regional scale. The areas with the most uncommon oxygen and hydrogen isotopic compositions (Atlantic coast south of Brittany and the highest elevations in the Alps) are the most accurately traceable areas in provenancing studies. The isotopic compositions of modelled precipitation have the same spatial distributions but different absolute values from those of tap waters. There- fore, our results favour the use of statistical isoscapes rather than general circulation model-based isoscapes in provenancing studies.

Cyclic silylated chalconium borates 13[B(C6F5)4] and 14[B(C6F5)4] with peri‐acenaphthyl and peri‐naphthyl skeletons were synthesized from unsymmetrically substituted silanes 3, 4, 6, 7, 9 and 10 using the standard Corey protocol (Chalcogen Ch=O, S, Se, Te). The configuration at the chalcogen atom is trigonal pyramidal for Ch=S, Se, Te, leading to the formation of cis‐ and trans‐isomers in the case of phenylmethylsilyl cations. With the bulkier tert‐butyl group at silicon, the configuration at the chalcogen atoms is predetermined to give almost exclusively the trans‐configurated cyclic silylchalconium ions. The barriers for the inversion of the configuration at the sulfur atoms of sulfonium ions 13 c and 14 a are substantial (72–74 kJ mol−1) as shown by variable temperature NMR spectroscopy. The neighboring group effect of the thiophenyl substituent is sufficiently strong to preserve chiral information at the silicon atom at low temperatures., The Corey reaction of acenaphthyl‐ and naphthyl‐based chiral silanes allows the synthesis of silylchalconium ions with control of the stereochemistry at the chalcogen atom (shown here for the sulfonium ion). The chalcogen neighboring group effect on the silyl cation is sufficiently strong to conserve the stereochemistry in a consecutive nucleophilic attack.

International audience; Urethane synthesis via oxidative decarboxylation of oxamic acids under mild electrochemical conditions is reported. This simple phosgene-free route to urethanes involves an in situ generation of isocyanates by anodic oxidation of oxamic acids in an alcoholic medium. The reaction is applicable to a wide range of oxamic acids, including chiral ones, and alcohols furnishing the desired urethanes in a one-pot process without the use of a chemical oxidant.

The structure determination of a series of biphenylsilyloxonium cations through NMR and XRD studies, supported by DFT calculations was carried out, allowing to get insights into the origin of the oxygen pyramidalization in biphenyl and binaphthylsilyl oxoniums. Low barrier of inversion in the oxygenyl series points toward a key role of the biaryl axis in the inversion of configuration at the oxygen center.

Despite the ubiquity of singlet carbenes in chemistry, their utility as true monomeric building blocks for the synthesis of functional organic polymers has been underexplored. In this work, we exploit the capability of purposely designed mono- and bis-acyclic amino(aryl)carbenes to selectively dimerize as a general strategy to access diaminoalkenes and hitherto unknown amino-containing poly(p-phenylene vinylene)s (N-PPV’s). The unique selectivity of the dimerization of singlet amino(aryl)carbenes, relative to putative C-H insertion pathways, is rationalized by DFT calculations. Of particular interest, unlike classical PPV’s, the presence of amino groups in α-position of C=C double bonds in N-PPV’s allows their physico-chemical properties to be manipulated in different ways by a simple protonation reaction. Hence, depending on the nature of the amino group (iPr2N vs. piperidine), either a complete loss of conjugation or a blue-shift of the maximum of absorption is observed, as a result of the protonation at different sites (nitrogen vs. carbon). Overall, this study highlights that singlet bis-amino(aryl)carbenes hold great promise to access functional polymeric materials with switchable properties, through a proper selection of their substitution pattern., Despite the ubiquity of singlet carbenes in chemistry, their utility as true monomeric building blocks for the synthesis of functional organic polymers has been underexplored. Here the authors show mono- and bis-acyclic amino(aryl)carbenes selectively dimerize to form diaminoalkenes and hitherto unknown amino-containing poly(p-phenylene vinylene)s.

We propose a novel scheme for the expansion and comb densification of gain-switched optical frequency combs (GS-OFC). The technique entails mutual injection locking of two gain-switched lasers with a common master to generate a wider bandwidth OFC. Subsequently, the OFC is further expanded and/or densified using a phase modulator with optimum drive conditions. We experimentally demonstrate the generation of an OFC with 45 highly correlated lines separated by 6.25 GHz with an expansion factor ~3. In addition, operating in comb densification mode, the channel spacing of the OFC is tuned from 6.25 GHz to 390.625 MHz. Finally, a detailed characterization of the lines, across the entire expanded comb, is reported highlighting the excellent spectral purity with linewidths of ~40 kHz, a relative intensity noise better than −152 dB/Hz, and a high degree of phase correlation between the comb lines. The proposed method is simple, highly flexible and the architecture is suitable for photonic integration, all of which make such an OFC extremely attractive for the employment in a multitude of applications.

International audience; Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C + [B(C6F5)4]as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes.

The membrane-proximal external region (MPER) of HIV-1 envelope glycoprotein (Env) can be targeted by neutralizing antibodies of exceptional breadth. MPER antibodies usually have long, hydrophobic CDRH3s, lack activity as inferred germline precursors, are often from the minor IgG3 subclass, and some are polyreactive, such as 4E10. Here we describe an MPER broadly neutralizing antibody from the major IgG1 subclass, PGZL1, which shares germline V/D-region genes with 4E10, has a shorter CDRH3, and is less polyreactive. A recombinant sublineage variant pan-neutralizes a 130-isolate panel at 1.4 μg/ml (IC50). Notably, a germline revertant with mature CDR3s neutralizes 12% of viruses and still binds MPER after DJ reversion. Crystal structures of lipid-bound PGZL1 variants and cryo-EM reconstruction of an Env-PGZL1 complex reveal how these antibodies recognize MPER and viral membrane. Discovery of common genetic and structural elements among MPER antibodies from different patients suggests that such antibodies could be elicited using carefully designed immunogens., Here, the authors identify a broadly neutralizing antibody from an HIV-infected person that recognizes the membrane-proximal external region (MPER) of HIV envelope glycoprotein (Env) and has a short CDRH3 and low polyreactivity. Structural analysis shows how the antibody binds the MPER and Env on the viral membrane.

A general access to the spiroimine skeleton of gymnodimine and spirolides is described, relying on the construction of the cyclohexene fragment using an enantiocontrolled Diels-Alder reaction, the installation of the all-carbon quaternary stereocenter through a stereocontrolled alkylation or aldolisation and the elaboration of the lateral chains at C7 and C22 using Wittig-Horner olefinations. The spiroimine core of gymnodimine is made available through a 16-step linear sequence in a 21 % overall yield.

The Southern Ocean (SO) is a key region for ocean-atmosphere CO2 exchanges, as it witnesses significant changes in physical and biological pump dynamics. While numerous studies have highlighted the central role of reinvigorated SO upwelling behind rapid increases in atmospheric CO2 during glacial terminations, a very few studies have yet focused on the impact of the Biological Carbon Pump and more specifically of the Carbonate Counter Pump (CCP) that, contrary to the Soft Tissue Pump, participates to increase the concentration of dissolved CO2 in oceanic surface waters and thus, in the atmosphere.Amongst the last 9 interglacials, Marine Isotope Stage (MIS) 11 (~ 400 ka) is the longest interglacial of the past 800,000 years, characterised by a ~30 ka-long plateau with atmospheric CO2 hovering around 280 ppm. Reconstructions of past global biosphere productivity based on Δ17O of O2 measurements on air bubbles trapped in ice cores, show that MIS 11 registers the strongest global biosphere productivity (~ 20% higher) compared to the other 8 interglacials (Brandon et al., 2020; Yang et al., EGU21) Meanwhile, marine sedimentary records suggest strong carbonate production and export. Studying the detailed variations of the CCP during this specific period can therefore be useful to better understand its relationship with biospheric productivity changes and to better constraint its impacts on atmospheric CO2.As calcifying organisms, coccolithophores and planktonic foraminifera represent the major producers of CaCO3 in pelagic environments and are therefore useful tools to reconstruct past variations in the CCP strength. Here, we calibrate CaXRF and CaCO3 signals from marine core MD04-2718 located in the Indian sector of the SO (48°53 S; 65°57 E) in terms of coccolith and planktonic carbonate production and export signals over the last 800 ka, with a focus on the interval MIS 12 to MIS 10. We compare our results with published micropaleontological and geochemical records from the subantarctic zone (SAZ) in order to reconstruct past changes in CCP efficiency and circulation at the SO scale and understand their relationships with atmospheric CO2 patterns.We show an increase in CCP efficiency during interglacial periods, with an exceptional high carbonate export production during MIS 11. We demonstrate that enhanced CCP efficiency at the beginning of MIS 11 is likely the consequence of both higher SST conditions and nutrient contents in the upper water column of the SAZ, that increase coccolithophore and planktonic foraminifera productions, thanks to the southward migration of SO fronts and the reinvigoration of southern upwelling. While the sharp increase in atmospheric CO2 during Termination V seems correlated with the reinvigoration of the SO upwelling, enhanced CCP at the beginning of MIS 11 might have greatly reduced the efficiency of the biological pump, impacting the CO2 flux from the ocean to the atmosphere. The strong global biological productivity registered during this interval might have permitted to sustain the 30 ka-long plateau of atmospheric CO2 that characterize this time interval.

High precision measurements of triple isotopic composition of oxygen in the air trapped in ice cores is a useful tool to infer the global gross biosphere productivity in the past. The isotopic composition of oxygen is influenced by many physical, chemical and biological processes during consumption and production of oxygen by the oceanic and terrestrial biosphere. For an accurate quantification of the past biosphere productivity, it is thus important to determine the different fractionation processes occurring in the biosphere during respiration and photosynthesis processes.We present here quantification of fractionation coefficients associated with δ180 and the D170 of 02 during respiration and photosynthesis within the terrestrial biosphere. The experimental set-up relies on closed biological chambers in which all the environmental parameters are controlled and measured. Triple isotopic composition of oxygen is regularly measured through sampling of small aliquots at a low frequency (4 h to 4 days). Seven 2-month long experiments were performed in order to check the reproducibility of our set-up and quantify uncertainty on the determination of the fractionation coefficients.In order to improve our set-up for future experiments using different plants, we also present perspectives for a continuous measurement of the isotopic composition of oxygen using optical spectroscopy (Optical Feedback Cavity Enhanced Absorption Spectroscopy (OF-CEAS) technique). This instrument is currently being characterized and we will present its current performances.Triple isotopic composition of oxygen in the atmospheric dioxygen to reconstruct the dynamic of global biosphere productivity in the past from measurements in biological chambers.

Elicitation of broadly neutralizing antibodies (bnAbs) is a major challenge in HIV vaccine development, because unmutated precursors to bnAbs are rare and typically do not bind the wildtype HIV Envelope glycoprotein (Env) trimers. One strategy to initiate bnAb type responses is to use germline-targeting immunogens that have high affinity to bnAb-class precursor B cells, then shepherd affinity maturation with booster immunogens that successively look more similar to native Env. Here, we demonstrate in a rare VRC01gHL (inferred germline of bnAb VRC01) B cell precursor model in mouse, starting from a physiological 1 in 1 million VRC01 gHL precursor frequency, a single immunization with a germline targeting soluble Env trimer can generate a significant number of high affinity bnAb-class somatic hypermutations (SHM). Notably, deletions in the light chain complementarity determining region 1 were observed in multiple germinal center (GC) B cell clones after a single immunization. Many of the GC-derived VRC01gHL antibodies developed binding to the wildtype Env trimer without an N276 glycan. Antibodies elicited after a single priming immunization neutralized several N276 glycan-deficient tier-2 HIV strains. These results are encouraging for germline-targeting Env trimer vaccine designs, demonstrating it can be possible to accumulate substantial SHM, including indels, and functional bnAb features after a single immunization.

Using new and previously published CO2 data from the EPICA Dome C ice core (EDC), we reconstruct a new high-resolution record of atmospheric CO2 during Marine Isotope Stage (MIS) 6 (190 to 135 ka) the penultimate glacial period. Similar to the last glacial cycle, where high-resolution data already exists, our record shows that during longer North Atlantic (NA) stadials, millennial CO2 variations during MIS 6 are clearly coincident with the bipolar seesaw signal in the Antarctic temperature record. However, during one short stadial in the NA, atmospheric CO2 variation is small ( ∼5 ppm) and the relationship between temperature variations in EDC and atmospheric CO2 is unclear. The magnitude of CO2 increase during Carbon Dioxide Maxima (CDM) is closely related to the NA stadial duration in both MIS 6 and MIS 3 (60–27 ka). This observation implies that during the last two glacials the overall bipolar seesaw coupling of climate and atmospheric CO2 operated similarly. In addition, similar to the last glacial period, CDM during the earliest MIS 6 show different lags with respect to the corresponding abrupt CH4 rises, the latter reflecting rapid warming in the Northern Hemisphere (NH). During MIS 6i at around 181.5± 0.3 ka, CDM 6i lags the abrupt warming in the NH by only 240± 320 years. However, during CDM 6iv ( 171.1± 0.2 ka) and CDM 6iii ( 175.4± 0.4 ka) the lag is much longer: 1290± 540 years on average. We speculate that the size of this lag may be related to a larger expansion of carbon-rich, southern-sourced waters into the Northern Hemisphere in MIS 6, providing a larger carbon reservoir that requires more time to be depleted.

High precision measurements of triple isotopic composition of oxygen in water is a useful tool to infer the dynamic of past hydrological cycle when measured in ice core together with δ18O and δD. In particular, the triple isotopic composition of oxygen in water provides information on the climatic conditions of the evaporative sources. In parallel, it has been shown that the triple isotopic composition of oxygen in the atmospheric dioxygen can be a useful tracer of the global biosphere productivity and hence reconstruct the dynamic of the global biosphere productivity in the past from measurements performed in the air bubbles. Measuring triple isotopic composition of oxygen both in the water and in the atmospheric dioxygen trapped in bubbles in ice cores is thus a strong added value to study the past variability of water cycle and biosphere productivity in parallel to climate change.Here, we first present new laboratory experiments performed in closed biological chambers to show how the triple isotopic composition of oxygen in atmospheric dioxygen can be used for quantification of the biosphere productivity with determination of fractionation coefficients. Then, we present new records of triple isotopic composition of oxygen in water and O2 trapped in bubbles from the EPICA Dome C ice core over the deglaciations of the last 800 ka.

During the last 800,000 years, atmospheric CO2 concentrations have varied with an amplitude of more than 100 ppm, with the fastest increases registered during deglaciations. The mechanisms behind the increases of CO2 are still discussed since several parameters are involved. Biological productivity on land and in the ocean played a major role in the variations of atmospheric CO2. Particularly, productivity variations in the Southern Ocean along deglaciations are key because changes in the efficiency of the Soft Tissue Pump (STP) and the Carbonate Counter Pump (CCP) in the Subantarctic Zone significantly impact the exchanges between ocean and atmospheric reservoirs. As calcifying organisms, coccolithophores and planktonic foraminifera represent the major producers of CaCO3 and are therefore good tools to reconstruct past variations of CCP.Among the last 9 deglaciations, Termination V registers the strongest global productivity (20% higher) compared to the other 8 interglacial periods. Associated with the Mid-Brunhes event, it is followed by the warm MIS 11, the longest interglacial (~ 30 ka). MIS 11 also registers a strong carbonate production in the ocean, most probably favoured by the low eccentricity during this period. Studying the variations of the CCP during this specific period of time is therefore important to better understand its relation with biospheric productivity changes and its impact on atmospheric CO2.Here we present micropaleontological (coccoliths and foraminifera) and geochemical (CaCO3) data from marine core MD04-2718, located in the Indian sector of the Southern Ocean (48°53 S; 65°57 E) throughout Termination V and MIS 11, that we compared with other productivity data from the Southern Ocean as well as reconstruction of global biospheric productivity data (Δ17O of O2). Results show that coccolith and foraminifera abundances and masses increase during Termination V and MIS 11. The good correlation between variations of CaCO3 in the sediment and calcite mass from coccoliths and foraminifera shells proves that exported CaCO3 is essentially of planktonic origin and reveals that CCP significantly increases over this period.We suggest that the strengthening of CCP through the increase in production and export of calcite associated to coccolith and foraminifera in the Southern Ocean may have contributed to increase the atmospheric CO2 during Termination V and MIS 11, while the strong biological productivity registered during this period would have permitted to maintain the CO2 level relatively low

The oxygen isotope signature of leaf water is used to trace several processes at the soil-plant-atmosphere interface. During photosynthesis, it is transferred to the oxygen isotope signature of atmospheric CO2 and O2, which can be used for reconstructing past changes in gross primary production. The oxygen isotope signature of leaf water additionally imprints leaf organic and mineral compounds, such as phytoliths, used as paleoclimate and paleovegetation proxies when extracted from sedimentary materials.Numerous experimental and modelling studies were dedicated to constrain the main parameters responsible for changes in the δ18O of leaf water. Although these models usually correctly depict the main trends of 18O-enrichment of the leaf water when relative humidity decreases, the calculated absolute values often depart from the observed ones by several ‰. Moreover, the δ18O of leaf water absorbed by plants is dependent on the δ18O value of meteoric and soil waters that can vary by several ‰ at different space and time scales. These added uncertainties make our knowledge of the parameters responsible for changes in the δ18O of leaf water and phytoliths flawed.Changes in the triple oxygen isotope composition of leaf water, expressed by the 17O-excess, are controlled by fewer variables than changes in δ18O. In meteoric water the 17O-excess varies slightly as it is weakly affected by temperature or phase changes during air mass transport. This makes the soil water fed by meteoric water and the atmospheric vapour in equilibrium with meteoric water changing little from a place to another. Hence the 17O-excess of leaf water is essentially controlled by the evaporative fractionation. The latest depends on the ratio of vapor pressure in the air to vapor pressure in the stomata intercellular space, close to relative humidity. Leaf water evaporative fractionation can lead to 17O-excess negative values that can exceed most of surficial water ones.Here we present the outcomes of several recent growth chamber and field studies, for the purpose of i) refining the grass leaf water and phytoliths δ18O and 17O-excess modelling, ii) assessing whether the δ18O and 17O-excess of grass leaf water can be reconstructed from phytoliths, and iii) examining the precision of the 17O-excess of phytoliths as a new proxy for past changes in continental atmospheric relative humidity. Atmospheric continental relative humidity is an important climate parameter poorly constrained in global climate models. A model-data comparison approach, applicable beyond the instrumental period, is essential to progress on this issue. However, there is currently a lack of proxies allowing quantitative reconstruction of past continental relative humidity. The 17O-excess signature of phytoliths could fill this gap.

BNAbs of VH1-69 germline origin from a Chinese patient recognize the V3 glycan supersite via a disulfide-locked long HCDR3 loop., An oligomannose patch around the V3 base of HIV-1 envelope glycoprotein (Env) is recognized by multiple classes of broadly neutralizing antibodies (bNAbs). Here, we investigated the bNAb response to the V3 glycan supersite in an HIV-1–infected Chinese donor by Env-specific single B cell sorting, structural and functional studies, and longitudinal analysis of antibody and virus repertoires. Monoclonal antibodies 438-B11 and 438-D5 were isolated that potently neutralize HIV-1 with moderate breadth, are encoded by the VH1-69 germline gene, and have a disulfide-linked long HCDR3 loop. Crystal structures of Env-bound and unbound antibodies revealed heavy chain–mediated recognition of the glycan supersite with a unique angle of approach and a critical role of the intra-HCDR3 disulfide. The mechanism of viral escape was examined via single-genome amplification/sequencing and glycan mutations around the N332 supersite. Our findings further emphasize the V3 glycan supersite as a prominent target for Env-based vaccine design.

The photosensitized p-anisaldehyde-mediated addition of sulfonylcyanides onto the π-system of cyclobutenes is shown to afford highly functionalized cyclobutanes in high yields and diastereocontrol. The homochiral cyclobutene precursors are accessible on multigram scale in two steps through an asymmetric [2 + 2] cycloaddition/vinyl thioether reduction sequence. The enantiopure cyclobutylnitriles can be elaborated further through SmI2-mediated ring opening or converted into new enantiopure cyclobutenes through base-mediated sulfone elimination.

Pyridine- and quinoline-stabilized silyl cations have been prepared, and their structure in condensed phases unambiguously assigned using 1H, 13C, 15N, 29Si, and 1H DOSY NMR as well as X-ray diffra...

20dB gain in C-band with only 5.3W of pump is achieved with an all-fiberized 12-core Er/Yb doped fiber amplifier. This result is a first step towards SDM transmission including power efficient amplifiers and ROADM.

International audience; A new efficient strategy to access benzylic carbamates through C-H activation is reported. The use of a catalytic amount of Cu(I)/diimine ligand in combination with NFSI ((PhSO2)2NF) or F-TEDA-PF6 as oxidants and H2NCO2R as an amine source, direct leads to the C-N bond formation at benzylic position. The mild reaction conditions, and broad substrate scope make this transformation a useful method for a late-stage incorporation of the ibiquitous carbamate fragment onto hydrocarbons.

International audience; The formation of 3-methyl-2,4-nonanedione (MND) during red wine aging can contribute to the premature evolution of aroma, characterized by the loss of fresh fruit and development of dried fruit flavors. The identification of two new hydroxy ketones, 2-hydroxy-3-methylnonan-4-one (syn- and anti-ketol diastereoisomers) and 3-hydroxy-3-methyl-2,4-nonanedione (HMND), prompted the investigation of the precursors and pathways through which MND is produced and evolves. An HS-SPME-GC-MS method was optimized for their quantitation in numerous must and wine samples, providing insight into the evolution of MND, HMND, and ketols through alcoholic fermentation and wine aging. Alcoholic fermentation resulted in a significant decrease in MND and HMND and the simultaneous appearance of ketol diastereoisomers. The analysis of 167 dry red wines revealed significant increases in MND and anti-ketol contents through aging and a significant positive correlation between MND and anti-ketols. Additional experiments demonstrated that ketols are precursors to MND during red wine oxidation.

The atmospheric processes determining the isotopic composition of precipitation on the Antarctic plateau are yet to be fully understood, as well as the post-depositional processes altering the snow pristine isotopic signal. Improving the comprehension of these physical mechanisms is of crucial importance for interpreting the isotopic records from ice cores drilled in the low accumulation area of Antarctica, e.g., the upcoming Beyond EPICA drilling at Little Dome C.Up to now, few records of the isotopic composition of precipitation in Antarctica are available, most of them limited in time or sampling frequency. Here we present a 9-year long δ18O and δD record (2008-2016) of precipitation at Concordia base, East Antarctica. The snow is collected daily on a raised platform (1 m), positioned in the clean area of the station; the precipitation collection is still being carried out each year by the winter over personnel.A significant positive correlation between isotopes in precipitation and 2-m air temperature is observed at both seasonal and interannual scale; the lowest temperature and isotopic values are usually recorded during winters characterized by a strongly positive Southern Annular Mode index.To improve the understanding of the mechanisms governing the isotopic composition of precipitation, we compare the isotopic data of Concordia samples with on-site observations, meteorological data from the Dome C AWS of the University of Wisconsin-Madison, as well as with high-resolution simulation results from the isotope-enabled atmospheric general circulation models ECHAM5-wiso and ECHAM6-wiso, nudged with the ERA-Interim and ERA5 reanalyses respectively.

This review is an update on tris(trimethylsilyl)silane, TTMSS, in organic chemistry, focusing on the advancements of the past decade. The overview includes a wide range of chemical processes and synthetic strategies under different experimental conditions, including functional group insertion and transformations, as well as preparation of complex molecules, natural products, polymers, surfaces, and new materials. These results reveal how TTMSS has matured over the past 30 years, and they further establish its value as a free radical reagent with widespread academic and industrial applications.

Background and purpose: We evaluated the concordance of results from two sets of nonclinical cardiovascular safety studies on pitolisant. Experimental approach: Nonclinical studies envisaged both in the ICH S7B guideline and Comprehensive in vitro Proarrhythmia Assay (CiPA) initiative were undertaken. CiPA-initiative studies included in vitro ion channels and stem cell-derived human ventricular myocyte studies as well as in silico modelling of results to simulate human ventricular electrophysiology. ICH S7B-recommended studies included in vitro hERG studies, in vivo dog study with follow-up investigations in rabbit Purkinje fibres and in vivo studies in the Carlsson rabbit proarrhythmia model. Key results: Both sets of nonclinical studies consistently excluded pitolisant from having clinically relevant QT-liability or proarrhythmic potential. CiPA studies revealed pitolisant to have modest calcium channel blocking and late I Na reducing activities at high concentrations, which resulted in reduction of dofetilide-induced early after-depolarisations (EADs) by pitolisantin ICH S7B studies. Studies in stem cell-derived human cardiomyocytes with dofetilide or E-4031 given alone and in combination with pitolisant confirmed these properties. In silico modelling confirmed that the measured ion channel effects are consistent with results from both the stem cell-derived cardiomyocyte and rabbit Purkinje fibre studies and categorised pitolisant as a drug with low torsadogenic potential. The results from the two sets of nonclinical studies correlated well with two clinical QT studies. Conclusions and implications: Our experience supports the CiPA initiative but suggests that sponsors should consider investigating drug effects on EADs and the use of proarrhythmia models when the results from CiPA studies are ambiguous.

There is increasing evidence that the circadian clock is a significant driver of photosynthesis that becomes apparent when environmental cues are experimentally held constant. We studied whether the composition of photosynthetic pigments is under circadian regulation, and whether pigment oscillations lead to rhythmic changes in photochemical efficiency. To address these questions, we maintained canopies of bean and cotton, after an entrainment phase, under constant (light or darkness) conditions for 30-48 h. Photosynthesis and quantum yield peaked at subjective noon, and non-photochemical quenching peaked at night. These oscillations were not associated with parallel changes in carbohydrate content or xanthophyll cycle activity. We observed robust oscillations of Chl a/b during constant light in both species, and also under constant darkness in bean, peaking when it would have been night during the entrainment (subjective nights). These oscillations could be attributed to the synthesis and/or degradation of trimeric light-harvesting complex II (reflected by the rhythmic changes in Chl a/b), with the antenna size minimal at night and maximal around subjective noon. Considering together the oscillations of pigments and photochemistry, the observed pattern of changes is counterintuitive if we assume that the plant strategy is to avoid photodamage, but consistent with a strategy where non-stressed plants maximize photosynthesis.

International audience; Free-radical alkenylation of a range of alkyl iodides has been carried out leading to the desired olefins in moderate to good yields under mild conditions. The process is initiated by an aryl radical which abstracts the iodide from the alkyl iodide to form a C-centered radical intermediate, the addition of which onto a vinylsulfone providing the final vinylsulfone. The aryl radical is generated in situ through a single-electron transfer from an electron donor-acceptor complex (EDA) formed between a diaryliodonium salt (Ph2I + − PF6-) and triethylamine.

Continental relative humidity (RH) is a key-climate parameter. However, there is a lack of quantitative RH proxies suitable for climate model-data comparisons. Recently, a combination of climate chamber and natural transect calibrations laid the groundwork for examining the robustness of the triple oxygen isotope composition (δ18O, δ17O) of phytoliths as a new proxy for past changes in RH. However, it was recommended that besides RH, additional factors that may impact δ18O and δ17O of plant water and phytoliths be examined. Here, the effects of leaf anatomy, leaf development stage and day/night alternations are addressed from the growth of the grass species F. arundinacea in climate chambers. Plant water and phytoliths are analyzed in δ18O and δ17O. Silicification patterns are examined using light and scanning electron observation of phytoliths. The isotope data show the increasing contribution of evaporated epidermal water to the bulk leaf water, from sheath to proximal and apical leaf blade. However, despite this isotope heterogeneity, δ18O and δ17O of the bulk leaf water can be predicted by the Craig and Gordon model, in the given experimental conditions (high RH). Regarding phytoliths, their forming water (mainly epidermal) is, as expected, more impacted by evaporation than the bulk leaf water. This discrepancy increases from sheath to proximal and apical blade and can be explained by the steepening of the radial concentration gradient of evaporated water along the leaf. However, we show that because most of silica polymerizes in epidermal long cells of the apical blade of the leaves, the δ18O and δ17O of bulk grass phytoliths should not be impacted by the diversity in grass anatomy. The data additionally show that most of silica polymerizes at the end of the leaf elongation stage and at the transition towards leaf senescence. Thus, climate conditions at that time should be considered when interpreting δ18O and δ17O of phytoliths from the natural environment. At least, no light/dark effect was detected on the δ18O and δ17O signature of plant water and phytoliths of F. arundinacea. However, when day/night alternations are characterized by significant changes in RH, the lowest RH conditions favoring evaporation and silica polymerization should be considered when calibrating the phytolith proxy. This study contributes to the identification of the parameters driving the δ18O and δ17O of bulk grass phytoliths. It additionally brings elements to further understand and model the δ18O and δ17O of grass leaf water, which influences the isotope signal of several processes at the soil/plant/atmosphere interface.

A palladium-mediated double oxidative amination reaction on cyclohexa-2,5-dienes has been developed, leading to the tetracyclic indoline skeleton of aspidosperma and strychnos alkaloids. The allyl-palladium intermediate, generated after the double oxidative amination, could be trapped by an internal nucleophile to allow the construction of 3 rings in a single step. Approaches to the synthesis of strychnine and mossambine is finally reported.

Four-component coupling reactions between xanthogenates, alkenes, CO, and sulfonyl oxime ethers were studied. In the presence of hexabutylditin, working as a propagating radical reagent, the chain reaction proceeds, as expected, taking into account reagents polarities, affording the corresponding functionalized α-keto oximes. Although yields are modest, this rare one-pot four-component process is easy to carry out and the resulting compounds, bearing multiple functionalities, have the potential for further elaboration.

International audience; The generation of carbamoyl radicals, followed by their addition to heteroarenes, was performed under mild conditions through a metal-free photocatalyzed decarboxylation of oxamic acids. The process has been applied to the carbamoylation of heteroaromatic bases using α-aminoacid-derived oxamic acids, leading to the corresponding amides without racemization.