Gold(I)-N-Heterocyclic Carbene Synthons in Organometallic Synthesis.

The prominent role of gold-N-heterocyclic carbene (NHC) complexes in numerous research areas such as homogeneous (photo)catalysis, medicinal chemistry and materials science has prompted organometallic chemists to design gold-based synthons that permit access to target complexes through simple synthetic steps under mild conditions. In this review, the main gold-NHC synthons employed in organometallic synthesis are discussed. Mechanistic aspects involved in their synthesis and reactivity as well as applications of gold-NHC synthons as efficient pre-catalysts, antitumor agents and/or photo-emissive materials are presented.

Lunar eclipses illuminate timing and climate impact of medieval volcanism.

Explosive volcanism is a key contributor to climate variability on interannual to centennial timescales1. Understanding the far-field societal impacts of eruption-forced climatic changes requires firm event chronologies and reliable estimates of both the burden and altitude (that is, tropospheric versus stratospheric) of volcanic sulfate aerosol2,3. However, despite progress in ice-core dating, uncertainties remain in these key factors4. This particularly hinders investigation of the role of large, temporally clustered eruptions during the High Medieval Period (HMP, 1100-1300 CE), which have been implicated in the transition from the warm Medieval Climate Anomaly to the Little Ice Age5. Here we shed new light on explosive volcanism during the HMP, drawing on analysis of contemporary reports of total lunar eclipses, from which we derive a time series of stratospheric turbidity. By combining this new record with aerosol model simulations and tree-ring-based climate proxies, we refine the estimated dates of five notable eruptions and associate each with stratospheric aerosol veils. Five further eruptions, including one responsible for high sulfur deposition over Greenland circa 1182 CE, affected only the troposphere and had muted climatic consequences. Our findings offer support for further investigation of the decadal-scale to centennial-scale climate response to volcanic eruptions.

250 years of flood frequency and discharge in an ungauged Corsican mountain catchment: A dendrogeomorphic reconstruction.

The primary goal of paleoflood hydrology is to estimate the frequency and magnitude of past floods. Botanical evidence, and particularly scars on trees, has been used repeatedly as paleostage indicators to reconstruct peak discharges and flood height. Yet, these reconstructions depend on the presence of visible scars on tree stems which tend to be masked as trees grow older. Here, we estimated flood magnitude using an alternative approach based on growth disturbances in tree-ring series, tree positions and the minimal discharge necessary to submerge the root collar of a tree as estimated by hydraulic modeling. We tested the reliability of this newly developed approach by using the traditional scar-based reconstruction as a benchmark. To this end, we sampled 60 trees showing evidence of flood damage on their stems along a 787-m long segment of the Asco river (Corsica, France). Based on 440 growth disturbances dated in tree-ring series, we reconstructed 28 floods between 1759 and 2020 and 18 during the 20th century. Using the two-dimensional Iber hydraulic model and detailed topographic data of the study site obtained from UAV imagery, we estimated that peak discharges of the 28 reconstructed events ranged between 10 and 210 m3s-1, with 200 m3s-1 being considered as the threshold for extreme floods. Not only do the scar-based and root collar submersion approaches yield similar results, findings are also clearly in line with the sparse information available from historical archives and short gauge station records on past floods. The unprecedented length and depth of the record presented here opens new avenues for climate change and flood impact research.

Access to Azetidines via Gold Mediated Energy Transfer Photocatalysis.

The area of energy transfer photocatalysis to generate four-membered rings is experiencing an unprecedented level of activity. Here, we report an operationally simple method toward azetidines from 2-isoxasoline-3-carboxylates and alkenes, using [Au(cbz)(NHC)] complexes as photocatalysts. The procedure enables the reaction for a wide range of substrates. Mechanistic studies confirm the energy transfer pathway. This contribution adds to the earlier reported use of these gold catalysts as a potentially versatile tool in energy transfer chemistry and catalysis.

Current Siberian heating is unprecedented during the past seven millennia.

The Arctic is warming faster than any other region on Earth. Putting this rapid warming into perspective is challenging because instrumental records are often short or incomplete in polar regions and precisely-dated temperature proxies with high temporal resolution are largely lacking. Here, we provide this long-term perspective by reconstructing past summer temperature variability at Yamal Peninsula - a hotspot of recent warming - over the past 7638 years using annually resolved tree-ring records. We demonstrate that the recent anthropogenic warming interrupted a multi-millennial cooling trend. We find the industrial-era warming to be unprecedented in rate and to have elevated the summer temperature to levels above those reconstructed for the past seven millennia (in both 30-year mean and the frequency of extreme summers). This is undoubtedly of concern for the natural and human systems that are being impacted by climatic changes that lie outside the envelope of natural climatic variations for this region.

Energy transfer (EnT) photocatalysis enabled by gold-N-heterocyclic carbene (NHC) complexes.

We present the use of gold sensitizers [Au(SIPr)(Cbz)] (PhotAu 1) and [Au(IPr)(Cbz)] (PhotAu 2) as attractive alternatives to state-of-the-art iridium-based systems. These novel photocatalysts are deployed in [2 + 2] cycloadditions of diallyl ethers and N-tosylamides. The reactions proceed in short reaction times and in environmentally friendly solvents. [Au(SIPr)Cbz] and [Au(IPr)(Cbz)] have higher triplet energy (E T) values (66.6 and 66.3 kcal mol-1, respectively) compared to commonly used iridium photosensitizers. These E T values permit the use of these gold complexes as sensitizers enabling energy transfer catalysis involving unprotected indole derivatives, a substrate class previously inaccessible with state-of-the-art Ir photocatalysts. The photosynthesis of unprotected tetracyclic spiroindolines via intramolecular [2 + 2] cycloaddition using our simple mononuclear gold sensitizer is readily achieved. Mechanistic studies support the involvement of triplet-triplet energy transfer (TTEnT) for both [2 + 2] photocycloadditions.

Simple synthesis of [Ru(CO3)(NHC)(p-cymene)] complexes and their use in transfer hydrogenation catalysis.

A novel, efficient and facile protocol for the synthesis of a series of [Ru(NHC)(CO3)(p-cymene)] complexes is reported. This family of Ru-NHC complexes was obtained from imidazol(in)ium tetrafluoroborate or imidazolium hydrogen carbonate salts in moderate to excellent yields, employing sustainable weak base. The ruthenium complexes were successfully utilized in the transfer hydrogenation of ketones as highly active multifunctional catalysts.

A simple synthesis of [RuCl2(NHC)(p-cymene)] complexes and their use in olefin oxidation catalysis.

A simple and efficient synthetic route to [RuCl2(NHC)(p-cymene)] and [Ru(CO3)(NHC)(p-cymene)] complexes making use of a weak base, under aerobic conditions, is reported. This method enables access to a series of NHC-ruthenium compounds with moderate to good yields under mild conditions. The Ru pre-catalysts were successfully used in olefin oxidation catalysis at low catalyst loading and reach complete conversion in short times.

A general protocol for the synthesis of Pt-NHC (NHC = N-heterocyclic carbene) hydrosilylation catalysts.

A general, user-friendly synthetic route to [Pt(NHC)(L)Cl2] and [Pt(NHC)(dvtms)] (L = DMS, Py; DMS = dimethyl sulfide, dvtms = divinyltetramethylsiloxane, Py = pyridine) complexes has been developed. The procedure is applicable to a wide range of ligands and enables facile synthetic access to key Pt(0)- and Pt(ii)-NHC complexes used in hydrosilylation catalysis.

Climatic and societal impacts of a "forgotten" cluster of volcanic eruptions in 1108-1110 CE.

Recently revised ice core chronologies for Greenland have newly identified one of the largest sulfate deposition signals of the last millennium as occurring between 1108 and 1113 CE. Long considered the product of the 1104 CE Hekla (Iceland) eruption, this event can now be associated with substantial deposition seen in Antarctica under a similarly revised chronology. This newly recognized bipolar deposition episode has consequently been deemed to reveal a previously unknown major tropical eruption in 1108 CE. Here we show that a unique medieval observation of a "dark" total lunar eclipse attests to a dust veil over Europe in May 1110 CE, corroborating the revised ice-core chronologies. Furthermore, careful evaluation of ice core records points to the occurrence of several closely spaced volcanic eruptions between 1108 and 1110 CE. The sources of these eruptions remain unknown, but we propose that Mt. Asama, whose largest Holocene eruption occurred in August 1108 CE and is credibly documented by a contemporary Japanese observer, is a plausible contributor to the elevated sulfate in Greenland. Dendroclimatology and historical documentation both attest, moreover, to severe climatic anomalies following the proposed eruptions, likely providing the environmental preconditions for subsistence crises experienced in Western Europe between 1109 and 1111 CE.

Understanding existing and designing novel synthetic routes to Pd-PEPPSI-NHC and Pd-PEPPSI-PR3 pre-catalysts.

The reaction mechanism leading to the formation of cross-coupling palladium pre-catalysts of the PEPPSI family was investigated. Two intermediates were isolated and proved to be both suitable synthons to the pre-catalysts, with one permitting the design of a novel and greener user-friendly synthetic route. In light of this mechanistic understanding, the traditional one-pot method was shown to be possible using stoichiometric amounts of throw-away ligand, which represents a considerable synthetic improvement over the wasteful "in pyridine" approach.

Recent flood hazards in Kashmir put into context with millennium-long historical and tree-ring records.

In September 2014, the Kashmir valley (north-west India) experienced a massive flood causing significant economic losses and fatalities. This disaster underlined the high vulnerability of the local population and raised questions regarding the resilience of Kashmiris to future floods. Although the magnitude of the 2014 flood has been considered unprecedented within the context of existing measurements, we argue that the short flow series may lead to spurious misinterpretation of the probability of such extreme events. Here we use a millennium-long record of past floods in Kashmir based on historical and tree-ring records to assess the probability of 2014-like flood events in the region. Our flood chronology (635 CE-nowadays) provides key insights into the recurrence of flood disasters and propels understanding of flood variability in this region over the last millennium, showing enhanced activity during the Little Ice Age. We find that high-impact floods have frequently disrupted the Kashmir valley in the past. Thus, the inclusion of historical records reveals large flood hazard levels in the region. The newly gained information also underlines the critical need to take immediate action in the region, so as to reduce the exposure of local populations and to increase their resilience, despite existing constraints in watershed management related to the Indus Water Treaty.

The Eldgjá eruption: timing, long-range impacts and influence on the Christianisation of Iceland.

The Eldgjá lava flood is considered Iceland's largest volcanic eruption of the Common Era. While it is well established that it occurred after the Settlement of Iceland (circa 874 CE), the date of this great event has remained uncertain. This has hampered investigation of the eruption's impacts, if any, on climate and society. Here, we use high-temporal resolution glaciochemical records from Greenland to show that the eruption began in spring 939 CE and continued, at least episodically, until at least autumn 940 CE. Contemporary chronicles identify the spread of a remarkable haze in 939 CE, and tree ring-based reconstructions reveal pronounced northern hemisphere summer cooling in 940 CE, consistent with the eruption's high yield of sulphur to the atmosphere. Consecutive severe winters and privations may also be associated with climatic effects of the volcanic aerosol veil. Iceland's formal conversion to Christianity dates to 999/1000 CE, within two generations or so of the Eldgjá eruption. The end of the pagan pantheon is foretold in Iceland's renowned medieval poem, VÇ«luspá ('the prophecy of the seeress'). Several lines of the poem describe dramatic eruptive activity and attendant meteorological effects in an allusion to the fiery terminus of the pagan gods. We suggest that they draw on first-hand experiences of the Eldgjá eruption and that this retrospection of harrowing volcanic events in the poem was intentional, with the purpose of stimulating Iceland's Christianisation over the latter half of the tenth century.

Imprisoned in the Cretan mountains: How relict Zelkova abelicea (Ulmaceae) trees cope with Mediterranean climate.

We investigate the sensitivity of the relict, endemic Cretan tree species Zelkova abelicea (Lam.) Boiss. (Ulmaceae) to several climate variables (temperature, precipitation and drought). For this purpose, we establish the first centennial tree-ring chronology for the species, and the first ever tree-ring chronology for a broadleaved species on Crete. We demonstrate the strong sensitivity of Z. abelicea towards precipitation and drought in late spring to early summer and the absence of a significant response to abundant precipitation occurring during winter or early spring. Whereas the late spring sensitivity is strong and consistent through time, the species seems to be experiencing a loss of signal towards early summer conditions since the 1970s, interpreted as an earlier cessation of cambial activity due to the increase in summer drought conditions on Crete. However, despite a reduced vegetative period, no significant decrease in radial growth of Z. abelicea was observed in the tree-ring series for the last decades, thus highlighting the capacity of Z. abelicea to withstand changing environmental conditions.

Impacts of regional climatic fluctuations on radial growth of Siberian and Scots pine at Mukhrino mire (central-western Siberia).

Ring width (TRW) chronologies from Siberian (Pinus sibirica) and Scots (Pinus sylvestris) pine trees were sampled at Mukhrino - a large mire complex in central-western Siberia - to evaluate the impacts of hydroclimatic variability on tree growth over the last three centuries. For this purpose, we compared climate-growth correlation profiles from trees growing on peat soils with those growing on adjacent mineral soils. Tree growth at both peat and mineral soils was positively correlated to air temperature during the vegetation period. This finding can be explained by (i) the positive influence of temperature on plant physiological processes (i.e. growth control) during the growing season and (ii) the indirect impact of air temperatures on water table fluctuations. We observe also a strong link between TRW and the winter Palmer Drought Severity Index (PDSI), especially in Siberian pine, reflecting the isolating effect of snow and limited freezing damage in roots. Significant negative relations were, by contrast, observed between bog TRW chronologies and hydroclimatic indices during spring and summer; they are considered an expression of the negative impacts of high water levels and moist peat soils on root development. Some unusually old bog pines - exhibiting >500 growth rings - apparently colonized the site at the beginning of the Little Ice Age, and therefore seem to confirm that (i) peat conditions may have been drier in Siberia than in most other regions of western Europe during this period. At the same time, the bog trees also point to (ii) their strong dependence on surface conditions.

Electronic cigarette: use and perceptions among French military nurses in 2013.

AIMS: Paramedical personnel are exposed to tobacco smoking. Electronic cigarettes (e-cigarettes) may be considered as a lower-risk substitute for cigarettes. The aim of the study was to estimate the prevalence of e-cigarette use, the motives for use and the perceptions among French military nurses. METHODS: A cross-sectional survey, using self-administered questionnaires, was conducted in 2013 among 300 students and instructors of the French school of military paramedical personnel. Prevalences of e-cigarette use among smokers and nonsmokers were compared using logistic regressions adjusted on age and gender. RESULTS: The prevalence of smoking was 40% among the 200 responders. E-cigarette current use prevalence was 25% (6% daily users), without significant difference according to gender and age. Tobacco smokers reported significantly more e-cigarette current use (51% vs7%). Motives for e-cigarette use reported by smokers were curiosity (48%), intention to reduce tobacco consumption (43%) or to quit smoking (8%). Among users of both tobacco and e-cigarettes, 48% reported a significant decrease in tobacco consumption following e-cigarette initiation (average decrease of 5-10 cigarettes smoked per day; p <0.001). Both tobacco smokers and nonsmokers (88%) estimated that e-cigarette use was potentially harmful for health, but it was perceived as less harmful than tobacco by 46%. CONCLUSIONS: E-cigarette use among military nurses follows the trends observed in the general population in terms of prevalence and motives. E-cigarettes, which are seen as an attractive alternative to cigarettes, may contribute to a reduction in tobacco use among healthcare workers.

Source of the great A.D. 1257 mystery eruption unveiled, Samalas volcano, Rinjani Volcanic Complex, Indonesia.

Polar ice core records attest to a colossal volcanic eruption that took place ca. A.D. 1257 or 1258, most probably in the tropics. Estimates based on sulfate deposition in these records suggest that it yielded the largest volcanic sulfur release to the stratosphere of the past 7,000 y. Tree rings, medieval chronicles, and computational models corroborate the expected worldwide atmospheric and climatic effects of this eruption. However, until now there has been no convincing candidate for the mid-13th century "mystery eruption." Drawing upon compelling evidence from stratigraphic and geomorphic data, physical volcanology, radiocarbon dating, tephra geochemistry, and chronicles, we argue the source of this long-sought eruption is the Samalas volcano, adjacent to Mount Rinjani on Lombok Island, Indonesia. At least 40 km(3) (dense-rock equivalent) of tephra were deposited and the eruption column reached an altitude of up to 43 km. Three principal pumice fallout deposits mantle the region and thick pyroclastic flow deposits are found at the coast, 25 km from source. With an estimated magnitude of 7, this event ranks among the largest Holocene explosive eruptions. Radiocarbon dates on charcoal are consistent with a mid-13th century eruption. In addition, glass geochemistry of the associated pumice deposits matches that of shards found in both Arctic and Antarctic ice cores, providing compelling evidence to link the prominent A.D. 1258/1259 ice core sulfate spike to Samalas. We further constrain the timing of the mystery eruption based on tephra dispersal and historical records, suggesting it occurred between May and October A.D. 1257.